Circular polarizer, organic electroluminescence display device, display device

Abstract

The present invention provides a circular polarizer, an organic electroluminescence display device, and an optical device that, when applied to an organic EL display device (particularly, a curved display and a high aspect ratio automotive display), can suppress color tone non-uniformity in the tilt direction and, furthermore, is less likely to occur over time due to color tone non-uniformity in the tilt direction. The circular polarizer of the present invention is a circular polarizer comprising a polarizer and a phase difference film laminated on the surface side of one of the polarizers, wherein the water content of the phase difference film is 1.8% or less, and the circular polarizer and an aluminum sheet are laminated so that the phase difference film in the circular polarizer faces the aluminum sheet, and when the chromaticity a* and chromaticity b* are measured at the entire azimuth angle of 40° from the normal direction of the circular polarizer of the laminated structure, the absolute value of chromaticity a* and the absolute value of chromaticity b* are 10 or less at any azimuth angle, and when the reflectance is measured at the entire azimuth angle of 40° from the normal direction of the circular polarizer of the laminated structure, the reflectance is 3.0% or less at any azimuth angle.

Description

Technology Field

[0001] The present invention relates to a circular polarizing plate, an organic electroluminescence display device, and a display device. Background Technology

[0002] Recently, for white light, which is a composite wave containing a mixture of visible light, the development of polarizers capable of producing the same effect for all wavelengths (so-called broadband polarizers) is underway. In particular, due to the demand for thinning devices to which polarizers are applied, thinning of the phase difference layer included in the polarizer is also required.

[0003] In response to such requirements, for example, in Example 9 of Patent Document 1, a polymerizable liquid crystal compound with reverse wavelength dispersibility is used as the polymerizable compound used to form the optical anisotropic layer, and a phase difference plate is disclosed having a heterogeneous optical anisotropic layer exhibiting a predetermined optical property laminated thereon. Prior art literature

[0004] International Publication No. 2018 / 216812 The problem to be solved

[0005] The inventors examined a polarizer having an optically anisotropic layer obtained by polymerizing a polymerizable liquid crystal composition containing the compound (polymerizable liquid crystal compound) described in Patent Document 1, and confirmed that when a device to which this polarizer is applied is observed from an oblique direction, a change in color tone occurs depending on the azimuth angle, or in other words, color tone non-uniformity occurs (hereinafter, the occurrence of color tone non-uniformity when the azimuth angle is changed by observing from an oblique direction as described above will be simply described as "color tone non-uniformity occurs in the oblique direction"). In particular, the above problem was significantly observed when applied to curved displays or high aspect ratio automotive displays.

[0006] In addition, considering the long-term use of various devices, it is required that color tone non-uniformity when observed from an inclined direction does not occur over time.

[0007] The present invention aims to provide a circular polarizer that can suppress color tone non-uniformity in the tilt direction when applied to an organic EL display device (particularly, a curved display and a high aspect ratio automotive display), and also makes it difficult for color tone non-uniformity in the tilt direction to occur over time.

[0008] In addition, the present invention has the objective of providing an organic electroluminescence display device and a display device. means of solving the problem

[0009] The inventors have found that the above problem can be solved by the following configuration.

[0010] (1) A circular polarizing plate comprising a polarizer and a phase difference film laminated on one surface side of the polarizer,

[0011] The moisture content of the phase difference film is 1.8% or less, and

[0012] Chromaticity a at the total azimuth angle of a polar angle of 40° from the normal direction of the circular polarizer of the obtained laminate, by laminating a circular polarizer and an aluminum sheet such that the phase difference film in the circular polarizer faces the aluminum sheet. * and chromaticity b * When measuring, the chromaticity a at any azimuth angle * The absolute value of and chromaticity b * The absolute value of is 10 or less, and

[0013] A circular polarizer having a reflectance of 3.0% or less at any azimuth angle when the reflectance is measured at a total azimuth angle of 40° from the normal direction of the laminated circular polarizer.

[0014] (2) The phase difference film is a circular polarizing plate described in (1), comprising an optical anisotropic layer (B) formed by fixing a rod-shaped liquid crystal compound that is twist-oriented with the thickness direction as the helical axis.

[0015] (3) The phase difference film is a circular polarizer described in (1) or (2) comprising a negative uniaxial optical anisotropic layer (A).

[0016] (4) A circular polarizing plate described in any one of (1) to (3), having a phase difference film thickness of 30 μm or less.

[0017] (5) A circular polarizing plate described in any one of (1) to (4), wherein the phase difference film is formed by stacking three layers of optical anisotropic layers.

[0018] (6) A circular polarizing plate described in any one of (1) to (5), wherein the phase difference film is formed by stacking three layers of an optical anisotropic layer formed by fixing an oriented liquid crystal compound.

[0019] (7) A polarizer is formed using a composition containing a polymerizable liquid crystal compound, and

[0020] A circular polarizer described in any one of (1) to (6), having a polarizer thickness of 8 μm or less.

[0021] (8) An organic electroluminescence display device having a circular polarizing plate as described in any one of (1) to (7).

[0022] (9) A display device having a circular polarizing plate as described in any one of (1) to (7),

[0023] A display device in which a circular polarizing plate is arranged to follow the curved surface of the display device. Effects of the invention

[0024] According to the present invention, when applied to an organic EL display device (e.g., a curved display and a high aspect ratio automotive display), color tone non-uniformity in the tilt direction can be suppressed, and furthermore, a circular polarizing plate can be provided in which color tone non-uniformity in the tilt direction is less likely to occur over time.

[0025] In addition, according to the present invention, an organic electroluminescence display device and a display device can be provided. Brief explanation of the drawing

[0026] FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the circular polarizer of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of the circular polarizer of the present invention. Figure 3 is a diagram illustrating the definitions of polar angle and azimuth angle. Specific details for implementing the invention

[0027] The present invention will be described in detail below. Additionally, in this specification, a numerical range indicated by "~" refers to a range that includes the values ​​described before and after "~" as lower and upper limits. First, the terms used in this specification will be explained.

[0028] Unless otherwise noted, the in-plane lagging axis is defined as 550 nm.

[0029] In the present invention, Re(λ) and Rth(λ) respectively represent in-plane retardation and thickness direction retardation at wavelength λ. Unless otherwise specified, wavelength λ is 550 nm.

[0030] In the present invention, Re(λ) and Rth(λ) are values ​​measured at wavelength λ using an AxoScan (manufactured by Axometrics). By inputting the average refractive index ((nx+ny+nz) / 3) and film thickness (d(μm)) into the AxoScan,

[0031] Ground axis direction (°)

[0032] Re(λ)=R0(λ)

[0033] Rth(λ)=((nx+ny) / 2-nz)×d

[0034] is calculated.

[0035] In addition, R0(λ) is displayed as a value calculated by AxoScan, but it refers to Re(λ).

[0036] In this specification, the refractive indices nx, ny, and nz are measured using an Abbe refractometer (NAR-4T, manufactured by Atago Corporation) and a sodium lamp (λ=589 nm) as the light source. Additionally, when measuring wavelength dependence, the multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Corporation) can be measured in combination with an interference filter.

[0037] In addition, values ​​from the Polymer Handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films may be used. The values ​​of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).

[0038] In this specification, the term "light" means active light or radiation, and means, for example, the emission spectrum of a mercury lamp, far ultraviolet represented by an excimer laser, extreme ultraviolet (EUV light: Extreme Ultraviolet), X-rays, ultraviolet rays, and electron beams (EB: Electron Beam), etc.

[0039] Among them, ultraviolet rays are desirable.

[0040] In this specification, "visible light" refers to light of 380 to 780 nm. Also, in this specification, unless specifically noted regarding the measurement wavelength, the measurement wavelength is 550 nm.

[0041] Furthermore, in this specification, the relationship of angles (e.g., "orthogonal," "parallel," etc.) is defined to include the range of error permissible in the technical field to which the present invention belongs. Specifically, this means being within a range of less than ±10° of the strict angle, and the error from the strict angle is preferably within a range of ±5° or less, and more preferably within a range of ±3° or less.

[0042] In this specification, the vertical orientation of a rod-shaped liquid crystal compound refers to a state in which the long axis of the rod-shaped liquid crystal compound is arranged perpendicular to the surface of the layer and also in the same orientation.

[0043] Here, "vertical" does not strictly require being vertical, but rather refers to an orientation in which the angle of inclination between the average molecular axis of the rod-shaped liquid crystal compound within the layer and the layer surface is 70° or greater.

[0044] Also, the term "same bearing" does not strictly require that the bearings be identical, but rather means that when the bearings of the ground axis are measured at any 20 locations, the maximum difference in the ground axis bearings among the 20 locations (the difference between the two ground axis bearings that have the maximum difference among the 20 ground axis bearings) is less than 10°.

[0045] In this specification, the vertical orientation of a disc-shaped liquid crystal compound refers to a state in which the disc axis of the disc-shaped liquid crystal compound is arranged perpendicular to the surface of the layer and also in the same orientation.

[0046] Here, "vertical" does not strictly require being vertical, but rather refers to an orientation in which the angle of inclination between the disc plane of the disc-shaped liquid crystal compound within the layer and the surface of the layer is 70 to 90°.

[0047] In addition, the term "same orientation" does not strictly require that the orientations be identical, but rather means that when the orientation of the ground axis within the plane is measured at any 20 locations within the plane, the maximum difference in the orientation of the ground axis within the plane among the 20 locations (the difference between the two orientations within the plane where the difference is maximum among the 20 orientations within the plane) is less than 10°.

[0048] In the present specification, the optical anisotropic layer may be a layer exhibiting a predetermined optical property, and, for example, is preferably a layer formed by fixing the orientation state of an oriented liquid crystal compound.

[0049] In addition, the "fixed" state is a state in which the orientation of the liquid crystal compound is supported. Specifically, it is more preferable that the layer has no fluidity in the temperature range of 0 to 50°C, or -30 to 70°C under harsher conditions, and that the fixed orientation shape is stably maintained without causing a change in the orientation shape due to external force or external force.

[0050] Circular polarizer

[0051] As a feature of the circular polarizer of the present invention, when a laminate obtained by laminating a circular polarizer onto an aluminum sheet is observed from a predetermined direction, the chromaticity a * , chromaticity b * and the fact that the reflectance is within a predetermined range can be cited.

[0052] The polymerizable liquid crystal compound exhibiting reverse wavelength dispersion used in Patent Document 1 has excellent frontal reflection performance, but has a problem in that the reflectance increases at a specific azimuth angle in the oblique direction, causing color tone non-uniformity in the oblique direction. In contrast, the circular polarizer of the present invention solves the above problem by using a phase difference film that satisfies a specific characteristic.

[0053] (One embodiment of a circular polarizer)

[0054] As shown in FIG. 1, a circular polarizer (10) which is an embodiment of the present invention comprises a polarizer (3) and a phase difference film (1). The phase difference film (1) has an optical anisotropic layer (A) (1a), an optical anisotropic layer (B) (1b), and an optical anisotropic layer (C) (1c) in that order. The polarizer (3) is positioned on the opposite side of the optical anisotropic layer (C) (1c) of the phase difference film (1).

[0055] The optical anisotropic layer (A)(1a) is an optical anisotropic layer exhibiting negative uniaxiality, and details will be described later.

[0056] The optical anisotropic layer (B)(1b) is a layer formed by fixing a rod-shaped liquid crystal compound that is twist-oriented with the thickness direction as the helical axis, and details will be described later.

[0057] The optical anisotropic layer (C) (1c) is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound, and details will be described later.

[0058] (Different embodiments of circular polarizers)

[0059] As shown in FIG. 2, a circular polarizer (20), which is a different embodiment of the present invention, comprises a polarizer (3) and a phase difference film (2). The phase difference film (2) has an optical anisotropic layer (A) (2a), an optical anisotropic layer (C) (2c), and an optical anisotropic layer (B) (2b) in that order. The polarizer (3) is positioned on the opposite side of the optical anisotropic layer (B) (2b) of the phase difference film (2).

[0060] The optical anisotropic layer (A)(2a) is an optical anisotropic layer exhibiting negative uniaxiality, and details will be described later.

[0061] The optical anisotropic layer (B)(2b) is a layer formed by fixing a rod-shaped liquid crystal compound that is twist-oriented with the thickness direction as the helical axis, and details will be described later.

[0062] The optical anisotropic layer (C) (2c) is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound, and details will be described later.

[0063] The thickness of the circular polarizer is not particularly limited, but is preferably 80 μm or less, more preferably 60 μm or less, and more preferably 40 μm or less. In addition, the lower limit of the thickness of the circular polarizer is not particularly limited, but is preferably 1 μm or more.

[0064] Chromaticity a at a total azimuth angle of 40° polar angle from the normal direction of the circular polarizer of a laminate obtained by laminating a circular polarizer and an aluminum sheet such that the phase difference film in the circular polarizer faces the aluminum sheet (hereinafter also simply referred to as "specific laminate"). * and chromaticity b * When measuring, the chromaticity a at any azimuth angle * The absolute value of and chromaticity b * The absolute value of is 10 or less. The above characteristics will be explained using drawings.

[0065] In FIG. 3, a specific laminate (40) formed by laminating a circular polarizer (10) and an aluminum sheet (30) is shown. As shown in FIG. 3, the circular polarizer (10) is composed of a polarizer (3) and a phase difference film (1), and the phase difference film (1) is arranged to face the aluminum sheet (30).

[0066] Next, first, the polar angle and azimuth angle will be explained based on Figure 3.

[0067] In FIG. 3, the plane (main surface, a plane perpendicular to the thickness direction) of the circular polarizer (10) is defined as the xy plane, and the y-axis direction is defined as the absorption axis of the polarizer (3). Therefore, in FIG. 3, the y-axis direction serves as the reference for an azimuth angle of 0°. As shown in FIG. 3, the angle θ formed by the vector v1 and the z-axis is defined as the polar angle (the angle formed with the normal direction of the circular polarizer (10), and the angle φ formed by the projection of the vector v1 onto the xy plane and the y-axis (the absorption axis of the polarizer (3)) is defined as the azimuth angle. That is, the polar angle refers to the angle formed by the normal direction of the circular polarizer (10). Also, the azimuth angle represents the angle formed by the absorption axis of the polarizer (3).

[0068] Therefore, a polar angle of 40° means an angle where θ in Fig. 3 is 40°. Also, for example, an azimuth angle of 45° means an angle where φ in Fig. 3 is 45°.

[0069] In addition, in the present invention, when indicating the azimuth angle, the counterclockwise direction is indicated as a positive value based on the absorption axis direction of the polarizer (3) when viewed from the side of the circular polarizer of a specific laminate. Therefore, in FIG. 3, when the azimuth angle is 45°, it means an azimuth rotated 45° counterclockwise from the reference y-axis.

[0070] Chromaticity a at the entire azimuth angle (0~360°) with a polar angle of 40° from the normal direction of the circular polarizer among the specific laminated bodies described above * When measuring, the chromaticity a at any azimuth angle * The absolute value of is 10 or less. That is, observed from the side of the circular polarizer in a specific laminate, with a polar angle of 40° from the normal direction of the circular polarizer in the specific laminate, and while changing the azimuth angle in the range of 0 to 360°, the chromaticity a at each azimuth angle position * The colority a obtained when measuring * It means that the absolute values ​​of are all 10 or less.

[0071] The above color a* The absolute value of is preferably 9 or less, and more preferably 8 or less, in order to provide a more superior effect of the present invention. The lower limit is not particularly limited, but 0 may be used.

[0072] Also, chromaticity b at the entire azimuth angle (0~360°) with a polar angle of 40° from the normal direction of the circular polarizer among the specific laminated bodies described above. * When measuring, the chromaticity b at any azimuth angle * The absolute value of is 10 or less. That is, observed from the side of the circular polarizer in a specific laminate, with a polar angle of 40° from the normal direction of the circular polarizer in the specific laminate, and while changing the azimuth angle in the range of 0 to 360°, the chromaticity b at each azimuth angle position * The colorimetric value b obtained when measuring * It means that the absolute values ​​of are all 10 or less.

[0073] The above color b * The absolute value of is preferably 9 or less, and more preferably 8 or less, in order to provide a more superior effect of the present invention. The lower limit is not particularly limited, but 0 may be used.

[0074] The above color a * and chromaticity b * is L standardized by the International Commission on Illumination (CIE). * a * b * In a color system, it represents chromaticity, which indicates hue and saturation.

[0075] The above color a * and chromaticity b * As a method for measuring, a spectrophotometer (manufactured by Konica Minolta) is placed at a predetermined position (predetermined polar angle, predetermined azimuth angle) on the side of the circular polarizer of a specific laminate, and the chromaticity a under a fluorescent lamp * and chromaticity b * Methods for measuring can be cited.

[0076] In addition, when the reflectance is measured at the entire azimuth angle (0 to 360°) with a polar angle of 40° from the normal direction of the circular polarizer of the specific laminate described above, the reflectance at any azimuth angle is 3.0% or less. That is, it means that when observing from the side of the circular polarizer in the specific laminate, and changing the azimuth angle from the normal direction of the circular polarizer in the specific laminate to a polar angle of 40° in the range of 0 to 360°, and measuring the reflectance at each azimuth angle position, the reflectance obtained is 3.0% or less.

[0077] The above reflectance is preferably 2.5% or less, and more preferably 2.0% or less, in order to provide a more superior effect of the present invention. The lower limit is not particularly limited, but 0% may be used.

[0078] As a method for measuring the reflectance above, a detector is placed at a polar angle of 40° from the normal direction of a circular polarizer of a specific laminate, and incident light is incident from a polar angle of 40° at an azimuth angle 180° different from the azimuth angle at which the detector is placed, and the procedure of measuring the reflectance with the detector is performed in the range of azimuth angles 0 to 360° to measure the reflectance at each azimuth angle.

[0079] In addition, the above reflectance refers to the reflectance with visual sensitivity correction in the wavelength range of 400 to 750 nm. More specifically, it refers to the reflectance with visual sensitivity correction according to JIS Z 8701.

[0080] In addition, when performing the above measurement, instead of a specific laminate, a standard plate (Konica Minolta white calibration plate CS-A5) is used to determine the reflectance based on the reflected light measured in the above procedure.

[0081] The aluminum sheet used to form the above-mentioned characteristic laminate is a sheet having an aluminum foil on the outermost layer, and may be composed of aluminum foil alone, or may be a laminate comprising a support and an aluminum foil disposed on the support.

[0082] In the case where the aluminum sheet is a laminate comprising a support and an aluminum foil disposed on the support, the type of support is not particularly limited and may be a resin substrate.

[0083] The reflectance of the aluminum sheet alone is preferably 80 to 90%.

[0084] Polarizer

[0085] A polarizer is any component that has the function of converting natural light into specific linear polarization, and an example is an absorption-type polarizer.

[0086] There are no particular restrictions on the type of polarizer, and commonly used polarizers may be used; examples include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers are generally manufactured by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and stretching it.

[0087] In addition, a protective film may be placed on one or both sides of the polarizer.

[0088] In addition, as described in WO2019 / 131943 and Japanese Patent Publication No. 2017-083843, a coating type polarizer may be used by coating using a liquid crystal compound and a dichroic organic dye (for example, a dichroic azo dye used in the light-absorbing anisotropic film described in WO2017 / 195833) instead of using polyvinyl alcohol as a binder.

[0089] This coating-type polarizer is a technology that orients dichroic organic pigments by utilizing the orientation of liquid crystal compounds. As described in Japanese Patent Publication No. 2012-083734, it is desirable from the perspective of increasing the degree of orientation if the polymerizable liquid crystal compound exhibits smectic properties. Alternatively, as described in WO2018 / 186503, crystallizing the pigment is also desirable from the perspective of increasing the degree of orientation. WO2019 / 131943 describes a structure of a polymeric liquid crystal that is desirable for increasing the degree of orientation.

[0090] A polarizer that aligns a dichroic organic pigment using the orientation of a liquid crystal without performing stretching has the following characteristics. It has many advantages, such as being able to be made very thin with a thickness of about 0.1 to 8 μm, being resistant to cracking when folded or having small thermal deformation as described in Japanese Patent Publication No. 2019-194685, and having excellent durability even in a polarizer with high transmittance exceeding 50% as described in Japanese Patent Publication No. 6483486.

[0091] By leveraging these advantages, it can be applied to applications requiring high brightness or small, lightweight dimensions, fine optical systems, molding into curved surfaces, and flexible parts. Of course, when a polarizer is fabricated on a support, it is also possible to transfer the polarizer onto a predetermined substrate and peel off the support to use only the polarizer.

[0092] In terms of having the above-described features, the circular polarizer of the present invention is preferably formed using a composition containing a polymerizable liquid crystal compound and uses a polarizer having a thickness of 8 μm or less. More specifically, the composition preferably includes a polymerizable liquid crystal compound and a dichroic organic pigment. The type of polymerizable liquid crystal compound is not particularly limited, and examples include polymerizable liquid crystal compounds used when producing the phase difference film described later (e.g., rod-shaped liquid crystal compounds having polymerizable groups).

[0093] From the perspective of saving power, the transmittance of the polarizer (visual sensitivity correction single-body transmittance) is preferably 40% or more, more preferably 44% or more, and more preferably 50% or more.

[0094] Phase difference film

[0095] The moisture content of the phase difference film in the circular polarizer of the present invention is 1.8% or less. If the moisture content of the phase difference film is within the above range, the desired effect is obtained. Among these, 1.5% or less is preferred, and 1.0% or less is more preferred, as the effect of the present invention is superior. The lower limit is not particularly limited, but is often 0% or more.

[0096] The moisture content of the phase difference film is a value measured after humidifying for more than 24 hours under an environment of 25°C and 60% relative humidity, and the moisture content is measured by the Karl Fischer method.

[0097] The phase difference film among the circular polarizers of the present invention is not particularly limited in its composition as long as it is a circular polarizer that satisfies the aforementioned chromaticity a*, chromaticity b*, and reflectance within a predetermined range.

[0098] Among them, in order to have a more superior effect of the present invention, the phase difference film preferably comprises an optical anisotropic layer formed by fixing a rod-shaped liquid crystal compound that is twist-oriented with the thickness direction as a helical axis (corresponding to the optical anisotropic layer (B) shown in FIGS. 1 and 2).

[0099] In addition, for a more superior effect of the present invention, the phase difference film preferably comprises an optical anisotropic layer exhibiting negative uniaxiality (corresponding to the optical anisotropic layer (A) shown in FIGS. 1 and 2).

[0100] In addition, for the superior effect of the present invention, the phase difference film is preferably a phase difference film formed by stacking three layers of optical anisotropic layers, and more preferably a phase difference film formed by stacking three layers of optical anisotropic layers formed by fixing an oriented liquid crystal compound.

[0101] In particular, as shown in FIGS. 1 and 2 above, the phase difference film preferably comprises three optical anisotropic layers: an optical anisotropic layer (A), an optical anisotropic layer (B), and an optical anisotropic layer (C).

[0102] In the following, specific examples are described mainly regarding the composition of the optical anisotropic layer (A) to the optical anisotropic layer (C).

[0103] In the phase difference film, at least one of the optical anisotropic layer (A) and the optical anisotropic layer (B) and the optical anisotropic layer (C) are directly laminated, and the optical anisotropic layer (C) comprises a photo-oriented polymer having photo-oriented groups, and it is preferable that the photo-oriented polymer having photo-oriented groups is present on the surface of the optical anisotropic layer (C) that contacts the optical anisotropic layer (A) or the optical anisotropic layer (B).

[0104] Here, the surface of the optical anisotropic layer (C) that is in contact with the optical anisotropic layer (A) or the optical anisotropic layer (B) refers to a surface layer region extending from the interface between the optical anisotropic layer (C) and the optical anisotropic layer (A) or the optical anisotropic layer (B) to 20 nm in the thickness direction of the optical anisotropic layer (C), and is hereinafter also abbreviated as "surface layer C".

[0105] In addition, the presence of the photooriented polymer in the surface layer C of the optical anisotropic layer (C) can be confirmed, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS). Furthermore, the TOF-SIMS method may employ the method described in "Selected Textbook of Surface Analysis Technology: Secondary Ion Mass Spectrometry" edited by the Japanese Society for Surface Science and Technology, published by Maruzen Co., Ltd. (1999).

[0106] Specifically, when a photo-oriented polymer having photo-oriented groups is present on the surface of the optical anisotropic layer (C) that contacts the optical anisotropic layer (A) or the optical anisotropic layer (B), fragments originating from the photo-oriented groups are detected near the interface between the optical anisotropic layer (C) and the optical anisotropic layer (A) or the optical anisotropic layer (B).

[0107] In addition, the compositional distribution in the thickness direction of the optical anisotropic layer (C) and the optical anisotropic layer (A) or the optical anisotropic layer (B) is analyzed by repeating ion beam irradiation and TOF-SIMS measurements from the air interface side of any one of the optical anisotropic layers. In addition, the ion beam irradiation and TOF-SIMS measurements are performed by analyzing the composition of the region from the surface to 1 to 2 nm in the thickness direction, and then proceeding to analyze the composition of the next surface region by further analyzing the composition of the region from 1 to several hundred nm in the thickness direction.

[0108] And, the distribution of the photo-oriented polymer in the thickness direction of the optical anisotropic layer (C) is analyzed by measuring the secondary ion intensity derived from the unit having the photo-oriented group.

[0109] Examples of types of ion beams include ion beams produced by an argon gas cluster ion gun (Ar-GCIB gun).

[0110] (Optical Anisotropic Layer (A))

[0111] The optical anisotropic layer (A) is an optical anisotropic layer exhibiting negative uniaxiality.

[0112] The in-plane retardation at a wavelength of 550 nm of the optical anisotropic layer (A) is preferably 140 to 220 nm, and is more preferably 150 to 200 nm in that the effect of the present invention is superior.

[0113] The angle formed by the in-plane ground axis of the optical anisotropic layer (A) and the absorption axis of the polarizer is not particularly limited, but in order to provide a more superior effect of the present invention, as a preferred embodiment, 40 to 100° is preferred, 50 to 85° is more preferred, and 65 to 85° is more preferred. Also, as another preferred embodiment, 5 to 60° is preferred, 5 to 50° is more preferred, and 5 to 25° is more preferred.

[0114] In one embodiment when the optical anisotropic layer (A) is formed in a long shape, the angle θ1 formed by the longitudinal direction and the in-plane ground axis of the optical anisotropic layer (A) is not particularly limited, but is preferably 40 to 85°, more preferably 50 to 85°, and more preferably 65 to 85°.

[0115] In addition, from the perspective of being able to reduce the thickness of the optical anisotropic layer (A), it is preferable that the optical anisotropic layer (A) be a layer formed using a liquid crystal compound, and it is more preferable that the optical anisotropic layer be formed by fixing an oriented liquid crystal compound.

[0116] More specifically, the optical anisotropic layer (A) is preferably a layer formed using a disc-shaped liquid crystal compound, and more preferably a layer formed by fixing a vertically oriented disc-shaped liquid crystal compound.

[0117] There are no particular limitations on the types of liquid crystal compounds. Generally, liquid crystal compounds can be classified into rod-shaped types (rod-shaped liquid crystal compounds) and disc-shaped types (discotic liquid crystal compounds) based on their shape. Additionally, liquid crystal compounds can be classified into low-molecular-weight types and high-molecular-weight types. A high-molecular-weight type generally refers to one with a degree of polymerization of 100 or more (Polymer Physics and Phase Transition Dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound may be used, but it is preferable to use a rod-shaped liquid crystal compound. Two or more rod-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a discotic liquid crystal compound, may be used.

[0118] In addition, as a rod-shaped liquid crystal compound, for example, one described in claim 1 of Japanese Patent Publication No. Hei 11-513019 or paragraphs 0026 to 0098 of Japanese Patent Publication No. 2005-289980 may be preferably used.

[0119] As a discotic liquid crystal compound, for example, those described in paragraphs 0020 to 0067 of Japanese Patent Publication No. 2007-108732 or paragraphs 0013 to 0108 of Japanese Patent Publication No. 2010-244038 may be preferably used.

[0120] It is desirable for the liquid crystal compound to have a polymerizable group.

[0121] The type of polymerizable group having a liquid crystal compound is not particularly limited, and a functional group capable of addition polymerization reaction is preferred, a polymerizable ethylenically unsaturated group or a cyclic polymerizable group is more preferred, and a (meth)acryloyl group, a vinyl group, a styryl group, or an allyl group is more preferred.

[0122] The liquid crystal compound may be a liquid crystal compound with net wavelength dispersion or a liquid crystal compound with reverse wavelength dispersion, but if the liquid crystal compound is a liquid crystal compound with net wavelength dispersion, it is preferable in that the manufacturing cost of the film is reduced and durability is improved.

[0123] In this specification, a liquid crystal compound with net wavelength dispersion refers to a case where, when measuring the in-plane retardation (Re) value in the visible light range of an optically anisotropic layer fabricated using this liquid crystal compound, the Re value decreases as the measurement wavelength increases. On the other hand, a liquid crystal compound with inverse wavelength dispersion refers to a case where, when measuring the Re value in the same way, the Re value increases as the measurement wavelength increases.

[0124] The optical anisotropic layer (A) may be a polymer film containing a resin with negative intrinsic birefringence.

[0125] A resin with negative intrinsic birefringence is one in which the direction perpendicular to the elongation direction becomes the ground axis. In other words, a resin with negative intrinsic birefringence is one in which the refractive index in the elongation direction is smaller than the refractive index in the direction orthogonal to it.

[0126] In addition, as resins with negative intrinsic birefringence, examples include polystyrene-based polymers comprising homopolymers of styrene or styrene derivatives (e.g., polystyrene, fluorinated polystyrene) and copolymers of styrene or styrene derivatives and any monomer; polyacrylonitrile polymers; (meth)acrylic-based polymers such as polymethyl methacrylate; polyester-based resins; or polypolymers of the same; and cellulose compounds such as cellulose esters. More specifically, examples include polymethyl methacrylate, polystyrene, fluorinated polystyrene, polyvinyl naphthalene, and fumaric acid ester-based resins.

[0127] The thickness of the optical anisotropic layer (A) is not particularly limited, but when the optical anisotropic layer (A) is a layer formed using a disc-shaped liquid crystal compound, 0.5 to 5 μm is preferred and 0.5 to 2 μm is more preferred in terms of the balance between thinness and handling.

[0128] (Optical Anisotropic Layer (B))

[0129] The optical anisotropic layer (B) is a layer formed by fixing a rod-shaped liquid crystal compound that is twist-oriented with the thickness direction as the helical axis. It is preferable that the layer be formed by fixing a chiral nematic phase having a so-called helical structure. Furthermore, when forming the phase, it is preferable to use a mixture of a liquid crystal compound exhibiting a nematic liquid crystal phase and a chiral agent described later.

[0130] In addition, the meaning of the "fixed" state is as described above.

[0131] The value of the product Δnd of the refractive index anisotropy Δn of the optical anisotropy layer (B) measured at a wavelength of 550 nm and the thickness d of the optical anisotropy layer (B) is not particularly limited, but 140 to 220 nm is preferred, 150 to 210 nm is more preferred in that hue non-uniformity is more suppressed, and 160 to 200 nm is more preferred.

[0132] In addition, refractive index anisotropy Δn refers to the refractive index anisotropy of the optical anisotropy layer.

[0133] The above method for measuring Δnd is performed using Axometrics’ AxoScan (polarimeter) device and the company’s device analysis software.

[0134] The twist angle of the liquid crystal compound (twist angle in the orientation direction of the liquid crystal compound) is preferably in the range of 90±30° (within the range of 60 to 120°), more preferably in the range of 90±20° (within the range of 70 to 110°) in order to further suppress color non-uniformity, and more preferably in the range of 90±10° (within the range of 80 to 100°).

[0135] In addition, the torsional angle is measured using Axometrics' AxoScan (polarimeter) device and the company's device analysis software.

[0136] Furthermore, the twisting orientation of the liquid crystal compound is intended to twist the liquid crystal compound from one main surface of the optical anisotropic layer (B) to the other main surface of the optical anisotropic layer (B) with the thickness direction of the optical anisotropic layer (B) as the axis. Accordingly, the orientation direction of the liquid crystal compound (in-plane ground axis direction) differs depending on the position in the thickness direction of the optical anisotropic layer (B).

[0137] The thickness of the optical anisotropic layer (B) is not particularly limited, but in terms of the balance between thinness and handling, 0.5 to 5 μm is preferred, and 0.5 to 2 μm is more preferred.

[0138] It is preferable that the in-plane ground axis of the optical anisotropic layer (A) and the in-plane ground axis of the optical anisotropic layer (B) on the surface of the optical anisotropic layer (A) are parallel. Therefore, when the optical anisotropic layer (A) and the optical anisotropic layer (B) are long, it is preferable that the angle formed by the in-plane ground axis of the optical anisotropic layer (B) on the surface of the optical anisotropic layer (A) and the longitudinal direction corresponds to the above-described θ1.

[0139] In addition, it is preferable that the in-plane ground axis on the surface of the optical anisotropic layer (B) on the side of the optical anisotropic layer (A) and the in-plane ground axis on the surface of the optical anisotropic layer (B) opposite to the side of the optical anisotropic layer (A) form the twist angle described above (within the range of 90±30°). Among these, it is preferable that the in-plane ground axis on the surface of the optical anisotropic layer (B) opposite to the side of the optical anisotropic layer (A) rotates clockwise by a predetermined angle (within the range of 90±30°) with respect to the in-plane ground axis on the surface of the optical anisotropic layer (B) on the side of the optical anisotropic layer (A).

[0140] The type of liquid crystal compound used to form the optical anisotropic layer (B) is not particularly limited, and the compounds exemplified as liquid crystal compounds used to form the optical anisotropic layer (A) may be used.

[0141] Various known chiral agents can be used as chiral agents for forming twisted orientation of liquid crystal compounds. Chiral agents have the function of inducing a helical structure of liquid crystal compounds. Since the sense or pitch of the helix induced by chiral compounds varies depending on the compound, they can be selected according to the purpose.

[0142] As a chiral agent, known compounds may be used, but it is preferable that they have a cinnamonyl group. Examples of chiral agents include compounds described in the Handbook of Liquid Crystal Devices (Chapter 3, Paragraph 4-3, Chiral Agents for TN and STN, p. 199, edited by the 142nd Committee of the Society for the Promotion of Science in Japan, 1989), and Japanese Published Patent Application No. 2003-287623, Japanese Published Patent Application No. 2002-302487, Japanese Published Patent Application No. 2002-080478, Japanese Published Patent Application No. 2002-080851, Japanese Published Patent Application No. 2010-181852 and Japanese Published Patent Application No. 2014-034581, etc.

[0143] Chiral agents generally contain non-uniform carbon atoms, but axial non-uniform compounds or axial non-uniform compounds that do not contain non-uniform carbon atoms may also be used as chiral agents. Examples of axial non-uniform compounds or axial non-uniform compounds include binaphthyl, helicene, paracyclophane, and derivatives thereof. Chiral agents may have polymerizable groups.

[0144] In cases where both the chiral agent and the liquid crystal compound have polymerizable groups, a polymer having repeating units derived from the polymerizable liquid crystal compound and repeating units derived from the chiral agent can be formed by the polymerization reaction of the polymerizable chiral agent and the polymerizable liquid crystal compound. In this embodiment, it is preferable that the polymerizable group of the polymerizable chiral agent is of the same type as the polymerizable group of the polymerizable liquid crystal compound. Accordingly, it is preferable that the polymerizable group of the chiral agent be an unsaturated polymerizable group, an epoxy group, or an aziridinyl group, more preferable that it be an unsaturated polymerizable group, and particularly preferable that it be an ethylenically unsaturated polymerizable group.

[0145] Also, the chiral agent may be a liquid crystal compound.

[0146] As chiral agents, isosorbide derivatives, isomannide derivatives, and binaphyl derivatives are preferred. As isosorbide derivatives, commercially available products such as BASF's LC-756 may be used.

[0147] In the optical anisotropic layer (B), the content of the chiral agent is preferably 0.01 to 200 mol% with respect to the total molar amount of the liquid crystal compound, and more preferably 1 to 30 mol%.

[0148] The optical anisotropic layer (B) may include other materials other than the material described above.

[0149] Other materials may include, for example, surfactants, orientation control agents, and polymers used in the method for manufacturing the optically anisotropic layer (B) described later.

[0150] (Optical Anisotropic Layer (C))

[0151] The optical anisotropic layer (C) is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound.

[0152] Due to its utility as a compensation layer for a circular polarizer or a display device, the layer formed by fixing a vertically oriented rod-shaped liquid crystal compound is preferably a positive C plate, and the layer formed by fixing a horizontally oriented disc-shaped liquid crystal compound is preferably a negative C plate.

[0153] Here, the positive C plate and the negative C plate are defined as follows.

[0154] When the refractive index in the direction of the ground axis within the film plane (the direction in which the refractive index within the plane is maximum) is nx, the refractive index in the direction orthogonal to the ground axis within the plane is ny, and the refractive index in the thickness direction is nz, the positive C plate satisfies the relationship of Equation (C1), and the negative C plate satisfies the relationship of Equation (C2). Additionally, the positive C plate has a negative Rth value, and the negative C plate has a positive Rth value.

[0155] Equation (C1) nz>nx≒ny

[0156] Equation (C2) nz <nx≒ny

[0157] In addition, the above "≒" includes not only cases where the two are completely identical, but also cases where the two are substantially identical.

[0158] "Substantially identical" means that, for example, the absolute value of (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, and is also included in "nx≒ny".

[0159] The in-plane retardation at a wavelength of 550 nm of the optical anisotropic layer (C) is not particularly limited, but 0 to 10 nm is preferred, and 0 to 5 nm is more preferred in that tone non-uniformity is further suppressed.

[0160] In the case where the optical anisotropic layer (C) is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound, the retardation in the thickness direction at a wavelength of 550 nm of the optical anisotropic layer (C) is preferably -140 to -20 nm, more preferably -130 to -30 nm, and more preferably -120 to -40 nm.

[0161] In the case where the optical anisotropic layer (C) is a layer formed by fixing a horizontally oriented disc-shaped liquid crystal compound, the retardation in the thickness direction at a wavelength of 550 nm of the optical anisotropic layer (C) is preferably 20 to 140 nm, more preferably 30 to 130 nm, and more preferably 40 to 120 nm.

[0162] As for the upper limit of the thickness of the phase difference film, it is preferably 30 μm or less, more preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. As for the lower limit of the thickness of the phase difference film, it is preferably 1 μm or more. In addition, the thickness of the phase difference film refers to the thickness including the adhesive when the optical anisotropic layer is laminated with an adhesive or the like.

[0163] Other Absences

[0164] The circular polarizer may include other components.

[0165] The circular polarizer may include a substrate.

[0166] As for the substrate, a transparent substrate is preferred. In addition, a transparent substrate is intended to be a substrate having a transmittance of visible light of 60% or more, and a transmittance of 80% or more is preferred, and 90% or more is more preferred.

[0167] The retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the substrate is not particularly limited, but -110 to 110 nm is preferred, and -80 to 80 nm is more preferred.

[0168] The in-plane retardation value (Re(550)) at a wavelength of 550 nm of the substrate is not particularly limited, but is preferably 0 to 50 nm, more preferably 0 to 30 nm, and more preferably 0 to 10 nm.

[0169] As a material for forming the substrate, a polymer with excellent optical performance, transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy is preferred.

[0170] Polymer films that can be used as substrates include, for example, cellulose acylate films (e.g., cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butylate film, and cellulose acetate propionate film), polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyethersulfone films, polyacrylic films such as polymethyl methacrylate, polyuretaine films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth)acrylnitrile films, and films of polymers having a dicyclic structure (norbornene-based resin (Aton: trade name, manufactured by JSR), amorphous polyolefin (Zeonex: trade name, manufactured by Nippon Zeon))).

[0171] Among these, as the material for the polymer film, triacetylcellulose, polyethylene terephthalate, or a polymer having a cycloaliphatic structure is preferred, and triacetylcellulose is more preferred.

[0172] The substrate may contain various additives (e.g., optical anisotropy modifiers, wavelength dispersion modifiers, fine particles, plasticizers, UV inhibitors, degradation inhibitors, and release agents, etc.).

[0173] The thickness of the substrate is not particularly limited, but 10 to 200 μm is preferred, 10 to 100 μm is more preferred, and 20 to 90 μm is more preferred. In addition, the substrate may be composed of a plurality of stacked layers. To improve adhesion with a layer provided thereon, the surface of the substrate may be subjected to surface treatment (e.g., glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment).

[0174] In addition, an adhesive layer (undercoating layer) may be provided on the substrate.

[0175] In addition, a polymer layer mixed with 5 to 40 mass% of inorganic particles having an average particle size of about 10 to 100 nm as a solid content mass ratio may be disposed on one side of the substrate to impart sliding properties during the conveying process or to prevent adhesion between the back surface and the surface after winding.

[0176] The substrate may be a so-called branched support. That is, after carrying out the manufacturing method of the present invention, the substrate may be peeled off from the optical anisotropic layer.

[0177] In addition, rubbing treatment may be performed directly on the surface of the substrate. That is, a substrate that has undergone rubbing treatment may be used. The direction of the rubbing treatment is not particularly restricted, and the optimal direction is appropriately selected depending on the direction in which the liquid crystal compound is to be oriented.

[0178] For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment process for LCDs (liquid crystal displays) can be applied. That is, a method can be used to obtain alignment by rubbing the surface of a substrate in a certain direction using paper, gauze, felt, rubber, nylon fibers, or polyester fibers.

[0179] An alignment layer may be disposed on the substrate.

[0180] The alignment film can be formed by means such as rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having microgrooves, or accumulation of an organic compound (e.g., ω-tricosanic acid, dioctadecylmethylammonium chloride, methyl stearate) by the Langmuir-Blodgett method (LB film).

[0181] In addition, an alignment film is known in which an alignment function is generated by the application of an electric field, the application of a magnetic field, or light irradiation (preferably polarized light).

[0182] In addition, the circular polarizer may have an adhesive layer placed between each layer. Examples of the adhesive layer include known adhesive layers and adhesive layers.

[0183] As described in Japanese Patent Publication No. Hei 11-149015, generally, for each layer forming a stacked waveplate or circular polarizer, it is desirable to adjust the refractive index of the adhesive or pressure-sensitive adhesive in order to suppress reflection by controlling the refractive index between the layers. The difference in refractive index with the adhesive target is preferably 0.1 or less, more preferably 0.08 or less, even more preferably 0.06 or less, and most preferably 0.03 or less.

[0184] When placed between layers of an optical anisotropic layer using polymerizable liquid crystals, high-refractive index adhesives or pressure-sensitive adhesives may be used.

[0185] To increase the refractive index, it is also desirable to use high-refractive index monomers or high-refractive index metal microparticles.

[0186] As a high-refractive index monomer, it is desirable to have a benzene ring skeleton in the molecule. As monofunctional monomers having a benzene ring backbone in the molecule, for example, ethoxylated O-phenylphenol (meth)acrylate, O-phenylphenol glycidyl ether (meth)acrylate, paracumyl phenoxyethylene glycol (meth)acrylate, 2-methacryloyloxyethyl phthalate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxypropyl phthalate, phenoxyethyl (meth)acrylate, EO-modified phenol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, phenylglycidyl ether (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, Examples include nonylphenoxypolyethylene glycol (meth)acrylate, ECH-modified phenoxy(meth)acrylate, benzyl(meth)acrylate, vinylcarbazole, etc.

[0187] Examples of components constituting the inorganic particles include metal oxides, metal nitrides, metal oxynitrides, and metal elements. Examples of metal atoms included in the metal oxides, metal nitrides, metal oxynitrides, and metal elements include titanium atoms, silicon atoms, aluminum atoms, cobalt atoms, and zirconium atoms. Specific examples of inorganic particles include inorganic oxide particles such as alumina particles, alumina hydrate particles, silica particles, zirconia particles, and clay minerals (e.g., smectite). From the perspective of refractive index, fine particles of zirconium oxide are preferred. The refractive index can be adjusted to a predetermined level by varying the amount of inorganic fine particles. When zirconium oxide is used as the main component, the average particle size of the inorganic fine particles in the layer is preferably 1 to 120 nm, more preferably 1 to 60 nm, and even more preferably 2 to 40 nm.

[0188] Method for manufacturing a circular polarizer and a phase difference film

[0189] The manufacturing method of the circular polarizer described above is not particularly limited, and known methods may be adopted. For example, a method of laminating a polarizer and a phase difference film may be used. When laminating, an adhesive layer may be used as needed.

[0190] In addition, the method for manufacturing the phase difference film described above is not particularly limited, and known methods may be adopted. In particular, the method for manufacturing the phase difference film described above can be carried out continuously from roll to roll.

[0191] For example, an optical anisotropic layer (A) to an optical anisotropic layer (C) exhibiting specific optical properties can be manufactured, and the optical anisotropic layer and the substrate (e.g., a long substrate) can be laminated in a specific order with an adhesive layer (e.g., an adhesive layer or an adhesive layer) interposed therebetween to manufacture a phase difference film.

[0192] In addition, a phase difference film may be manufactured by sequentially producing optical anisotropic layers (A) to optical anisotropic layers (C) on a substrate using the polymerizable liquid crystal composition described below. For example, an optical anisotropic layer (C) may be formed by applying a polymerizable liquid crystal composition on a substrate, then applying a polymerizable liquid crystal composition on the optical anisotropic layer (C) to form an optical anisotropic layer (B), and further applying a polymerizable liquid crystal composition on the optical anisotropic layer (B) to form an optical anisotropic layer (A).

[0193] In addition, the method of laminating the optical anisotropic layer described above and the method of forming an optical anisotropic layer using a polymerizable liquid crystal composition may be combined. More specifically, a method may be used to form an optical anisotropic layer (C) by applying a polymerizable liquid crystal composition on a substrate, then forming an optical anisotropic layer (B) by applying a polymerizable liquid crystal composition on the optical anisotropic layer (C) to obtain a laminate, and then further laminating the laminate with an optical anisotropic layer (A) that was separately manufactured to produce a phase difference film.

[0194] Below, the manufacturing method of each layer is described in detail.

[0195] Below, each component will be described in detail.

[0196] The optical anisotropic layer (A) to the optical anisotropic layer (C) included in the phase difference film is preferably a layer that fixes an oriented liquid crystal compound.

[0197] In addition, the optically anisotropic layer produced in the present invention is preferably a layer formed by fixing a liquid crystal compound having a polymerizable group (a rod-shaped liquid crystal compound or a discotic liquid crystal compound having a polymerizable group) by polymerization or the like.

[0198] It is preferable that the above optical anisotropic layers (A) to (C) each be formed using a polymerizable liquid crystal composition. More specifically, it is preferable to form a composition layer by applying a polymerizable liquid crystal composition, orienting a liquid crystal compound within the composition layer, and then performing a curing treatment to form a predetermined optical anisotropic layer.

[0199] A polymerizable liquid crystal composition is a composition comprising a liquid crystal compound having a polymerizable group. Various components included in the polymerizable liquid crystal composition will be described in detail later.

[0200] The above procedure will be explained in detail below.

[0201] The procedure for forming the composition layer described above is not particularly limited, and, for example, a method of applying a polymerizable liquid crystal composition onto a substrate and performing a drying treatment as necessary may be cited.

[0202] The coating method is not particularly limited and may include, for example, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, and die coating.

[0203] The film thickness of the composition layer is not particularly limited, but 0.1 to 20 μm is preferred, 0.2 to 15 μm is more preferred, and 0.5 to 10 μm is more preferred.

[0204] Next, an orientation treatment is performed on the formed composition layer to orient the polymerizable liquid crystal compound in the composition layer.

[0205] Orientation treatment can be performed by drying the coating film at room temperature or by heating the coating film. In the case of thermotropic liquid crystal compounds, the liquid crystal phase formed by the orientation treatment can generally be transformed by a change in temperature or pressure. In the case of lyotropic liquid crystal compounds, it can also be transformed by a compositional ratio such as the amount of solvent.

[0206] In addition, the conditions for heating the composition layer are not particularly limited, but the heating temperature is preferably 50 to 250°C, more preferably 50 to 150°C, and the heating time is preferably 10 seconds to 10 minutes.

[0207] In addition, after heating the composition layer, the coating film may be cooled as needed before the curing treatment (light irradiation treatment) described later. The cooling temperature is preferably 20 to 200°C, and more preferably 30 to 150°C.

[0208] Next, a curing treatment is performed on the composition layer oriented with the polymerizable liquid crystal compound.

[0209] The method of curing treatment performed on a composition layer oriented with a polymerizable liquid crystal compound is not particularly limited, and examples include light irradiation treatment and heat treatment. Among these, light irradiation treatment is preferred from the perspective of manufacturability, and ultraviolet irradiation treatment is more preferred.

[0210] The irradiation conditions for light irradiation treatment are not specifically limited, but 50–1000 mJ / cm² 2 The amount of irradiation is desirable.

[0211] The atmosphere during light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferred.

[0212] In addition, although the above describes a method of forming a composition layer by applying a polymerizable liquid crystal composition, a separate composition layer may also be formed and transferred onto a predetermined substrate.

[0213] The polymerizable liquid crystal composition used above includes a liquid crystal compound having the polymerizable group described above, and other components used as needed (e.g., chiral agents, polymerization initiators, polymerizable monomers, surfactants, polymers, photo-aligned polymers, and solvents, etc.).

[0214] The content of the liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, but for ease of controlling the orientation state of the liquid crystal compound, it is preferable to have 60 mass% or more and 70 mass% or more with respect to the total solid content in the polymerizable liquid crystal composition. The upper limit is not particularly limited, but it is preferable to have 99 mass% or less and 97 mass% or less.

[0215] In addition, the term "solid component" refers to a component capable of forming an optically anisotropic layer from which the solvent has been removed, and is considered a solid component even if its nature is in a liquid phase.

[0216] As described above, the polymerizable liquid crystal composition may include components other than the liquid crystal compound.

[0217] For example, the polymerizable liquid crystal composition may include a polymerization initiator. When the polymerizable liquid crystal composition includes a polymerization initiator, the polymerization of the liquid crystal compound having a polymerizable group proceeds more efficiently.

[0218] Examples of polymerization initiators include known polymerization initiators, photopolymerization initiators, and thermal polymerization initiators, and photopolymerization initiators are preferred.

[0219] The content of the polymerization initiator in the polymerizable liquid crystal composition is not particularly limited, but with respect to the total solid content in the polymerizable liquid crystal composition, 0.01 to 20 mass% is preferred, and 0.5 to 10 mass% is more preferred.

[0220] The polymerizable liquid crystal composition may include a chiral agent.

[0221] The types of chiral agents are not particularly limited, and known chiral agents may be cited.

[0222] The content of the chiral agent in the polymerizable liquid crystal composition is not particularly limited, but with respect to the total solid content in the polymerizable liquid crystal composition, 0.01 to 20 mass% is preferred, and 0.3 to 10 mass% is more preferred.

[0223] The polymerizable liquid crystal composition may include a polymerizable monomer that is different from a liquid crystal compound having a polymerizable group. Examples of polymerizable monomers include radical polymerizable compounds and cationic polymerizable compounds, and polyfunctional radical polymerizable monomers are preferred. Examples of polymerizable monomers include the polymerizable monomers described in paragraphs 0018 to 0020 of Japanese Patent Publication No. 2002-296423.

[0224] The content of the polymerizable monomer in the polymerizable liquid crystal composition is not particularly limited, but is preferably 1 to 50 mass% with respect to the total mass of the liquid crystal compound, and more preferably 5 to 30 mass%.

[0225] The polymerizable liquid crystal composition may include a surfactant. As surfactants, conventionally known alkyl ether compounds, silicon compounds, or fluorine compounds may be used, and fluorine compounds are preferred. Specifically, examples include compounds described in paragraphs 0028 to 0056 of Japanese Patent Publication No. 2001-330725 and compounds described in paragraphs 0069 to 0126 of Japanese Patent Application No. 2003-295212.

[0226] The polymerizable liquid crystal composition may include a polymer. As a polymer, a cellulose ester may be used. As a cellulose ester, the one described in paragraph 0178 of Japanese Patent Publication No. 2000-155216 may be used.

[0227] The content of the polymer in the polymerizable liquid crystal composition is not particularly limited, but is preferably 0.1 to 10 mass% with respect to the total mass of the liquid crystal compound, and more preferably 0.1 to 8 mass%.

[0228] In addition to the above, the polymerizable liquid crystal composition may also include an additive (orientation control agent) that promotes horizontal or vertical orientation in order to make the liquid crystal compound horizontally or vertically oriented.

[0229] The polymerizable liquid crystal composition may include a photo-aligned polymer. A photo-aligned polymer is a polymer having photo-aligned groups. When the photo-aligned polymer has repeating units having fluorine atoms or silicon atoms represented by Formula (1) or Formula (2) described later, or when the photo-aligned polymer is a split-type photo-aligned polymer, when a composition layer is formed using the polymerizable liquid crystal composition, the photo-aligned polymer tends to be localized on the surface of the composition layer. In an optically anisotropic layer formed using such a composition layer, since the photo-aligned polymer is localized near the surface, a surface shape having a predetermined orientation regulating force is formed when a photo-alignment treatment is performed. As a result, a desired optically anisotropic layer can be manufactured by additionally applying the polymerizable liquid crystal composition onto the optically anisotropic layer without providing a separate alignment film.

[0230] A photooriented group having a photooriented polymer refers to a group having a photooriented function in which rearrangement or anisotropic chemical reactions are induced by irradiation with anisotropic light (e.g., plane-polarized light), and for the reason that the uniformity of orientation is excellent and thermal stability and chemical stability are also good, a photooriented group in which at least one of dimerization and isomerization occurs by the action of light is preferred.

[0231] Specifically, suitable examples of groups that are dimerized by the action of light include, for instance, groups having a framework of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, and benzophenone derivatives.

[0232] Meanwhile, as a group that isomerizes by the action of light, specifically, for example, a group having the backbone of at least one compound selected from the group consisting of azobenzene compounds, stilbene compounds, spiropyran compounds, cinnamic acid compounds, and hydrazono-β-keto ester compounds can be suitably cited.

[0233] Among these photo-aligning groups, it is preferable that the group selected from the group consisting of cinnamoyl groups, azobenzene groups, chalconeyl groups, and coumarin groups is selected, for the reason that the liquid crystal alignment of the optical anisotropic layer formed on the upper layer of the optical anisotropic layer containing the photo-aligning polymer is better even with a small amount of exposure light.

[0234] It is preferable that the photooriented polymer is a photooriented polymer comprising a repeating unit having a photooriented group and a repeating unit having a fluorine atom or a silicon atom.

[0235] In addition, for the reason that the liquid crystal orientation of the optical anisotropic layer formed on the upper layer of the optical anisotropic layer including the photo-oriented polymer is improved, the photo-oriented polymer is preferably a photo-oriented polymer (hereinafter also abbreviated as "cleavage-type photo-oriented polymer") having a repeating unit A that has a cleavage group that is decomposed by the action of at least one selected from the group consisting of light, heat, acid, and base to generate a polar group, and the repeating unit A has a cleavage group in a side chain and also has a fluorine atom or a silicon atom on the terminal side of the cleavage group of the side chain.

[0236] Here, the term "polar group" included in the repeating unit A refers to a group having at least one heteroatom, and specifically, examples include a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a nitro group, an ammonium group, and a cyano group. Among these, a hydroxyl group, a carbonyl group, or a carboxyl group is preferred.

[0237] Also, "a cleavage group that generates a polar group" refers to a group that generates the aforementioned polar group through cleavage, but in the present invention, it also includes a group that reacts with oxygen molecules after radical cleavage to generate a polar group.

[0238] Examples of such photo-oriented polymers include the photo-oriented polymers described in paragraphs 0014 to 0049 of Patent Document 1 (International Publication No. 2018 / 216812), and the contents of these paragraphs are incorporated by reference into this specification.

[0239] For example, by including a photo-aligned polymer in the optical anisotropic layer (C), a polymerizable liquid crystal composition that forms the optical anisotropic layer (B) can be applied on the optical anisotropic layer (C) without applying a separate alignment layer, thereby forming an optical anisotropic layer (B) in which the liquid crystal compound is oriented. That is, the optical anisotropic layer (C) and the optical anisotropic layer (A) or (B) can be directly laminated.

[0240] Other examples of photooriented polymers comprising repeating units having fluorine atoms or silicon atoms suitably include a copolymer having repeating units having fluorine atoms or silicon atoms represented by the following formula (1) or formula (2) and repeating units having photooriented groups (hereinafter also abbreviated as “specific copolymer”).

[0241] In addition, the repeating unit having a fluorine atom or a silicon atom represented by the following formula (1) or formula (2) is a repeating unit that includes a cleavage group that is decomposed by the action of at least one selected from the group consisting of light, heat, acid and base to generate a polar group.

[0242] [Chemical Formula 1]

[0243]

[0244] In the above equations (1) and (2), r and s each independently represent an integer greater than or equal to 1.

[0245] Also, R B1 and R B2 Each represents, independently, a hydrogen atom or a substituent.

[0246] Also, Y 1 and Y 2 is, respectively, -O-, or -NR Z - indicates. However, R Z represents a hydrogen atom or a substituent.

[0247] Also, L B1 represents a connector of r+1.

[0248] Also, L B2 represents the s+1 linker.

[0249] Also, B1 represents the group represented by the following equation (B1). provided that * in the following equation (B1) is L B1 Indicates the joint position with, and if r is an integer greater than or equal to 2, multiple B1s may each be the same or different.

[0250] Also, B2 represents the group represented by the following equation (B2). provided that * in the following equation (B2) is L B2 Indicates the joint position with, and if s is an integer greater than or equal to 2, multiple B2s may each be the same or different.

[0251] [Chemical Formula 2]

[0252]

[0253] In the above equations (B1) and (B2), * indicates the joining position.

[0254] Also, n represents an integer greater than or equal to 1. However, multiple n may be the same or different.

[0255] Also, m represents an integer greater than or equal to 2.

[0256] Also, R b1 It represents a hydrogen atom or a substituent.

[0257] Also, R b2 , R b3 , and, R b4 Each represents, independently, a hydrogen atom or a substituent. provided that the two Rs b3 Silver may be combined with each other to form rings, and multiple R b2 are, respectively, may be identical or different, and multiple R b3 Each may be the same or different, and multiple R b4 Each can be the same or different.

[0258] Also, L b1 represents an n+1-fold connector. provided that plural L b1 Each may be the same or different.

[0259] Also, L b2 represents the m+1 linker.

[0260] Also, Z represents an aliphatic hydrocarbon group having a fluorine atom or an organosiloxane group. However, the aliphatic hydrocarbon group may have an oxygen atom, and the plurality of Zs may each be the same or different.

[0261] In the above equation (1), R B1 As the substituents represented here, known substituents may be cited. Among them, an alkyl group having 1 to 12 carbon atoms is preferred, and a methyl group is more preferred.

[0262] Among the above equation (1), Y 1 , respectively, -O-, or -NR Z - indicates, R Z represents a hydrogen atom or a substituent. R Z As substituents, known substituents may be used, and a methyl group is preferred. Y 1 It is preferable to represent -O- or -NH-, and more preferable to represent -O-.

[0263] Among the above equation (1), L B1 ...represents an r+1 valence linker. As an r+1 valence linker, it is preferable to have a hydrocarbon group having 1 to 24 carbon atoms that may have substituents, wherein some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms, and an aliphatic hydrocarbon group that may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable. As an r+1 valence linker, a linker having 2 to 3 valence is preferred, and a linker having 2 valence is more preferable.

[0264] In the above formula (1), r represents an integer greater than or equal to 1. Among these, from the perspective of composite suitability, an integer of 1 to 3 is preferred, an integer of 1 to 2 is more preferred, and 1 is more preferred.

[0265] In the above equation (2), R B2As substituents represented by , known substituents may be used. Among these, an alkyl group having 1 to 12 carbon atoms is preferred, and a methyl group is more preferred.

[0266] Among the above equation (2), Y 2 is, -O-, or, -NR Z - indicates. However, R Z represents a hydrogen atom or a substituent. R Z As substituents, known substituents may be used, and a methyl group is preferred. Y 2 It is preferable to represent -O- or -NH-, and more preferable to represent -O-.

[0267] Among the above equation (2), L B2 ... represents an s+1 linker. As for the s+1 linker, it is preferable to have a hydrocarbon group having 1 to 24 carbon atoms that may have a substituent, wherein a portion of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms, and an aliphatic hydrocarbon group that may include an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.

[0268] As a connector for s+1, a connector for 2 is preferred.

[0269] In the above equation (2), s represents an integer greater than or equal to 1. Among these, an integer of 1 to 2 is preferred from the perspective of composite suitability, and 1 is more preferred.

[0270] In the above equation (B1), R b1 As the substituent shown here, an aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferred, an alkyl group having 1 to 12 carbon atoms is more preferred, and a methyl group is even more preferred. R b1 It is preferable that silver be a substituent.

[0271] In the above equation (B1), R b2As substituents represented by , known substituents may be cited, and R in the above formula (B1) b1 Groups exemplified by substituents of can be cited. Also, R b2 It is preferable to represent a hydrogen atom.

[0272] Among the above equation (B1), L b1 The linker represents an n+1 valence linker, and as the n+1 valence linker, it is preferably an n+1 valence hydrocarbon group having 1 to 24 carbon atoms that may have substituents, wherein some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms, and more preferably an aliphatic hydrocarbon group that may contain oxygen atoms or nitrogen atoms having 1 to 10 carbon atoms.

[0273] As for the n+1 linker, a linker with 2 to 4 values ​​is preferred, a linker with 2 to 3 values ​​is more preferred, and a linker with 2 values ​​is more preferred.

[0274] In the above formula (B1), n ​​represents an integer greater than or equal to 1. Among these, from the perspective of composite suitability, an integer from 1 to 5 is preferred, an integer from 1 to 3 is more preferred, and 1 is more preferred.

[0275] In the above formulas (B1) and (B2), Z represents an aliphatic hydrocarbon group having a fluorine atom or an organosiloxane group. However, the aliphatic hydrocarbon group may have an oxygen atom, and the plurality of Zs may each be the same or different.

[0276] Examples of aliphatic hydrocarbon groups having a fluorine atom include a fluorine atom-containing alkyl group, a group in which one or more of the -CH2- constituting the fluorine atom-containing alkyl group are substituted with -O-, and a fluorine atom-containing alkenyl group. The number of carbon atoms of the aliphatic hydrocarbon group having a fluorine atom is not particularly limited, but is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10.

[0277] The number of fluorine atoms included in the aliphatic hydrocarbon group having fluorine atoms is not particularly limited, and is preferably 1 to 30, more preferably 5 to 25, and more preferably 7 to 20.

[0278] In the above equation (B2), R b3 and R b4 As substituents represented by , known substituents may be cited, and R in the above formula (B1) b1 The group exemplified by the substituents represented by this can be cited. Also, R b3 Silver, 2 Rb 3 It is desirable that these combine with each other to form a ring, and two Rb 3 It is more preferable that these combine to form a cyclohexane ring. Also, R b4 It is preferable to represent a hydrogen atom.

[0279] Among the above formula (B2), L b2 represents the m+1 linker.

[0280] As for the m+1 linker, it is preferable to have a hydrocarbon group having 1 to 24 carbon atoms that may have substituents, wherein some of the carbon atoms constituting the hydrocarbon group may be substituted with heteroatoms, and an aliphatic hydrocarbon group that may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable. As for the m+1 linker, a linker having 3 to 4 valence is preferable, and a linker having 4 valence is more preferable.

[0281] In the above formula (B2), m represents an integer greater than or equal to 2. Among these, an integer of 2 to 4 is preferred from the perspective of composite suitability, and an integer of 2 to 3 is more preferred.

[0282] Specific examples of a repeating unit including the element represented by the above formula (B1) include repeating units represented by the following formulas B-1 to B-22, and specific examples of a repeating unit including the element represented by the above formula (B2) include repeating units represented by the following formulas B-23 to B-24.

[0283] [Chemical Formula 3]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292] The content of repeating units having fluorine atoms or silicon atoms represented by formula (1) or formula (2) in the photooriented polymer is not particularly limited, and for the reason that the effect of suppressing wind non-uniformity is improved, 15 to 75 mass% is preferred with respect to the total repeating units of the photooriented polymer, 20 to 50 mass% is more preferred, and 25 to 45 mass% is more preferred.

[0293] The structure of the main chain of the repeating unit having a photooriented group is not particularly limited and may include known structures, for example, a framework selected from the group consisting of (meth)acrylic, styrene, siloxane, cycloolefin, methylpentene, amide, and aromatic esters is preferred.

[0294] Among these, a framework selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin types is more preferred, and a (meth)acrylic framework is more preferred.

[0295] Specific examples of repeating units having photo-oriented groups include the following.

[0296] [Chemical Formula 4]

[0297]

[0298] [Chemical Formula 5]

[0299]

[0300] [Chemical Formula 6]

[0301]

[0302] [Chemical Formula 7]

[0303]

[0304] [Chemical Formula 8]

[0305]

[0306] [Chemical Formula 9]

[0307]

[0308] The content of repeating units having photo-aligning groups in the photo-aligning polymer is not particularly limited, and for the reason that the liquid crystal orientation of the optical anisotropic layer formed on the upper layer is improved, 5 to 60 mass% is preferred with respect to the total repeating units of the photo-aligning polymer, 10 to 50 mass% is more preferred, and 15 to 40 mass% is even more preferred.

[0309] A specific copolymer may have additional repeating units having crosslinkable groups in addition to repeating units having fluorine atoms or silicon atoms and repeating units having photo-oriented groups as represented by the above-described formula (1) or formula (2).

[0310] The types of crosslinking groups are not particularly limited, and known crosslinking groups may be used. Among them, epoxy groups, epoxycyclohexyl groups, oxetaneyl groups, acryloyl groups, methacryloyl groups, vinyl groups, styryl groups, and allyl groups may be used.

[0311] The structure of the main chain of the repeating unit having a crosslinking group is not particularly limited and may include known structures, for example, a framework selected from the group consisting of (meth)acrylic, styrene, siloxane, cycloolefin, methylpentene, amide, and aromatic esters is preferred.

[0312] Among these, a framework selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin types is more preferred, and a (meth)acrylic framework is more preferred.

[0313] Specific examples of repeating units having a crosslinking group include the following.

[0314] [Chemical Formula 10]

[0315]

[0316] The content of repeating units having crosslinkable groups in a specific copolymer is not particularly limited, and for the reason that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is improved, 10 to 60 mass% is preferred with respect to the total repeating units of the photooriented polymer, and 20 to 50 mass% is more preferred.

[0317] Examples of monomers (radical polymerizable monomers) that form other repeating units other than those mentioned above include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0318] The synthesis method of the photooriented polymer is not particularly limited, and, for example, can be synthesized by mixing a monomer forming a repeating unit having a fluorine atom or a silicon atom represented by the above-described formula (1) or formula (2), a monomer forming a repeating unit having the above-described photoreactive group, and any other monomer forming a repeating unit, and polymerizing them in an organic solvent using a radical polymerization initiator.

[0319] The weight average molecular weight (Mw) of the photo-aligned polymer is not particularly limited, but for the reason that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is better, it is preferable that it be 25,000 or more, 25,000 to 500,000 is more preferable, 25,000 to 300,000 is more preferable, and 30,000 to 150,000 is particularly preferable.

[0320] Here, the weight-average molecular weight of the photooriented polymer and surfactant is a value measured by gel penetration chromatography (GPC) under the conditions shown below.

[0321] · Solvent (Eluent): THF (Tetrahydrofuran)

[0322] · Device Name: TOSOH HLC-8320GPC

[0323] · Column: Use three connected TOSOH TSKgel Super HZM-H (4.6mm × 15cm).

[0324] · Column temperature: 40℃

[0325] · Sample concentration: 0.1 mass%

[0326] · Flow rate: 1.0 ml / min

[0327] · Calibration Curve: Calibration curves were used based on 7 samples of TOSOH-based TSK standard polystyrene ranging from Mw=2,800,000 to 1,050 (Mw / Mn=1.03 to 1.06).

[0328] Organic EL Display Device

[0329] The organic EL display device of the present invention has the circular polarizer described above. Typically, the circular polarizer is provided on the organic EL display panel of the organic EL display device. That is, the organic EL display device of the present invention has an organic EL display panel and the circular polarizer described above.

[0330] As an example of an organic EL display device, it has an organic EL display panel, a phase difference film, and a polarizer in this order.

[0331] An organic EL display panel is a member having a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer formed between a pair of electrodes, an anode and a cathode, and in addition to the light-emitting layer, may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a protective layer, and each of these layers may have a different function. Various materials may be used for forming each layer.

[0332] <<Display Device>>

[0333] The above-described circular polarizer may also be used in various display devices having a curved surface. For example, it may be used in rollable displays having a curved surface, automotive displays, lenses for sunglasses, and lenses for goggles for image display devices.

[0334] The circular polarizer of the present invention contributes to the improvement of designability because it can be laminated onto a curved surface or integrally molded with a resin. Since the organic EL display device using the circular polarizer of the present invention can suppress color tone non-uniformity in the tilt direction, it is preferable to use it in curved displays or automotive displays.

[0335] It is also desirable to use the optical system for on-board displays such as head-up displays, optical systems such as AR glasses and VR glasses, and optical sensors such as LiDAR, facial authentication systems, and polarization imaging. Furthermore, it is desirable to use the circular polarizer of the present invention by arranging it to follow the curved surface in a display device having a curved surface.

[0336] Examples

[0337] The features of the present invention are explained in more detail below through examples and comparative examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.

[0338] <Example 1>

[0339] (Fabrication of cellulose acylate film (substrate))

[0340] The following composition was introduced into a mixing tank and stirred, and then heated at 90°C for 10 minutes. Afterward, the obtained composition was filtered through a filter paper with an average pore diameter of 34 μm and a sintered metal filter with an average pore diameter of 10 μm to prepare a dope. The solid content of the dope is 23.5 mass%, the amount of plasticizer added is a ratio to the cellulose acylate, and the solvent of the dope is methylene chloride / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0341] -------------------------------------------------------------

[0342] Cellulose acylate dope

[0343] -------------------------------------------------------------

[0344] 100 parts by mass of cellulose acylate (acetyl substitution degree 2.86, viscosity average degree of polymerization 310)

[0345] 6.0 parts by mass of sugar ester compound 1 (represented in chemical formula (S4))

[0346] 2.0 parts by mass of sugar ester compound 2 (represented in chemical formula (S5))

[0347] 0.1 parts by mass of silica particle dispersion (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.)

[0348] Solvents (methylene chloride / methanol / butanol)

[0349] -------------------------------------------------------------

[0350] [Chemical Formula 11]

[0351]

[0352] [Chemical Formula 12]

[0353]

[0354] The dope prepared above was flexible using a drum film machine. The dope was flexible from the die to come into contact with a metal support cooled to 0°C, and then the obtained web (film) was peeled off from the drum. In addition, the drum was made of SUS.

[0355] After peeling the obtained flexible web (film) from the drum, it was dried for 20 minutes inside a tenter device at 30–40°C during film transport, using a tenter device in which both ends of the web are clipped with clips. Subsequently, the web was post-dried by zone heating while being conveyed via roll transport. After knurling was performed on the obtained web, it was wound up.

[0356] The thickness of the obtained cellulose acylate film was 40 μm, the in-plane retardation Re (550) at a wavelength of 550 nm was 1 nm, and the thickness direction retardation Rth (550) at a wavelength of 550 nm was 26 nm.

[0357] (Alkaline saponification treatment)

[0358] The aforementioned cellulose acylate film is passed through a dielectric heating roll at a temperature of 60°C to raise the film surface temperature to 40°C, and then an alkaline solution of the composition shown below is applied to the band surface of the film using a bar coater at a rate of 14 ml / m² 2It was coated and conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Company Limited, heated to 110℃. Subsequently, using the same bar coater, pure water was applied at 3 ml / m² 2 Coated. Subsequently, after repeating washing with a fountain coater and dehydration with an air knife three times, the film was dried by being conveyed to a drying zone at 70°C for 10 seconds, and an alkali saponified cellulose acylate film was produced.

[0359] -------------------------------------------------------------

[0360] alkaline solution

[0361] -------------------------------------------------------------

[0362] 4.7 parts by mass of potassium hydroxide

[0363] 15.8 parts by mass of water

[0364] 63.7 parts by mass of isopropanol

[0365] Surfactant: C 14 H 29 O(CH2CH2O) 20 H 1.0 parts by mass

[0366] 14.8 parts by mass of propylene glycol

[0367] -------------------------------------------------------------

[0368] (Formation of orientation layer)

[0369] An alignment film coating solution of the following composition was continuously applied to the surface of the cellulose acylate film that had undergone alkali saponification treatment using a #14 wire bar. It was dried for 60 seconds with hot air at 60°C, and additionally for 120 seconds with hot air at 100°C.

[0370] -------------------------------------------------------------

[0371] Orientation film coating solution

[0372] -------------------------------------------------------------

[0373] 10 parts by mass of the following polyvinyl alcohol

[0374] 371 parts by mass of water

[0375] 119 parts by mass of methanol

[0376] 0.5 parts by mass of glutaraldehyde (crosslinking agent)

[0377] 0.175 parts by mass of citric acid ester (manufactured by Sankyo Kagaku Co., Ltd.)

[0378] -------------------------------------------------------------

[0379] (Polyvinyl alcohol)

[0380] [Chemical Formula 13]

[0381]

[0382] (Formation of the optical anisotropic layer (A))

[0383] A continuous rubbing treatment was performed on the orientation film prepared above. At this time, the length direction of the long film and the conveying direction are parallel, and the angle formed by the length direction of the film (conveying direction) and the rotation axis of the rubbing roller is set to 76°. If the length direction of the film (conveying direction) is set to 90° and the clockwise direction is represented as a positive value with the film width direction as the reference (0°) when observed from the film side, the rotation axis of the rubbing roller is at -14°. In other words, the position of the rotation axis of the rubbing roller is the position rotated 76° clockwise with respect to the length direction of the film when observed from the film side.

[0384] On the above-mentioned rubbing-treated alignment film, a composition (1a) for forming an optically anisotropic layer containing a disc-shaped liquid crystal compound of the following composition was applied using a die applicator to form a composition layer. Subsequently, the obtained composition layer was heated with hot air at 110°C for 2 minutes to dry the solvent and to age the alignment of the disc-shaped liquid crystal compound. Subsequently, the obtained composition layer was subjected to UV irradiation (500 mJ / cm²) at 80°C. 2 ) was performed, and the orientation of the liquid crystal compound was immobilized to form an optical anisotropic layer (1a) corresponding to the optical anisotropic layer (A).

[0385] The thickness of the optical anisotropic layer (1a) was 1.1 μm. Also, the in-plane retardation at a wavelength of 550 nm was 168 nm. It was confirmed that the average angle of inclination of the disc surface of the disc-shaped liquid crystal compound with respect to the film surface was 90°, and that it was oriented perpendicularly with respect to the film surface. Also, the angle of the in-plane ground axis of the optical anisotropic layer (1a) was parallel to the rotation axis of the rubbing roller, and when the width direction of the film was set to 0° (the length direction was 90° in the counterclockwise direction and -90° in the clockwise direction), the in-plane ground axis was -14° when viewed from the side of the optical anisotropic layer (1a).

[0386] -------------------------------------------------------------

[0387] Composition for forming an optical anisotropic layer (1a)

[0388] -------------------------------------------------------------

[0389] 1 80 parts by mass of the following disc-shaped liquid crystal compound

[0390] 20 parts by mass of the following disc-shaped liquid crystal compound 2

[0391] 0.55 parts by mass of the following orientation film interface orientation agent 1

[0392] 0.1 parts by mass of the following fluorine-containing compound A

[0393] 0.05 parts by mass of the following fluorine-containing compound B

[0394] 0.21 parts by mass of the following fluorine-containing compound C

[0395] Ethylene oxide modified trimethylolpropane triacrylate

[0396] (V#360, manufactured by Osaka Yuki Kagaku Co., Ltd.) 10 mass parts

[0397] 3.0 parts by mass of photopolymerization initiator (Irgacure 907, BASF)

[0398] 200 parts by mass of methyl ethyl ketone

[0399] -------------------------------------------------------------

[0400] Disc-shaped liquid crystal compound 1

[0401] [Chemical Formula 14]

[0402]

[0403] Disc-shaped liquid crystal compound 2

[0404] [Chemical Formula 15]

[0405]

[0406] Orientation film interface orientation agent 1

[0407] [Chemical Formula 16]

[0408]

[0409] Fluorine-containing compound A

[0410] [Chemical Formula 17]

[0411]

[0412] The above a and b represent the content (mass%) of each repeating unit relative to the total repeating unit, where a represents 90 mass% and b represents 10 mass%.

[0413] Fluorine-containing compound B (the values ​​in each repeating unit represent the content (mass%) relative to the total repeating units, and the content of the repeating unit on the left was 32.5 mass%, and the content of the repeating unit on the right was 67.5 mass%.)

[0414] [Chemical Formula 18]

[0415]

[0416] Fluorine-containing compound C (the values ​​in each repeating unit represent the content (mass%) relative to the total repeating units, and the content of the repeating unit on the left was 25 mass%, the content of the repeating unit in the middle was 25 mass%, and the content of the repeating unit on the right was 50 mass%.)

[0417] [Chemical Formula 19]

[0418]

[0419] (Formation of a stack of optical anisotropic layer (C) and optical anisotropic layer (B))

[0420] (Formation of the optical anisotropic layer (1c))

[0421] On the cellulose acylate film prepared above, a composition (1c) for forming an optically anisotropic layer containing a rod-shaped liquid crystal compound of the following composition was applied using a die applicator to form a composition layer. Then, both ends of the film were supported, and a cooling plate (9°C) was installed on the side of the film where the composition layer was formed, at a distance of 5 mm from the film, and a heater (75°C) was installed on the side opposite to the film where the composition layer was formed, at a distance of 5 mm from the film, and dried for 2 minutes.

[0422] Next, heating with hot air at 60°C for 1 minute, and while purging with nitrogen to maintain an oxygen concentration of 100 ppm or less, using a 365 nm UV-LED at an irradiation dose of 100 mJ / cm² 2 Ultraviolet rays were irradiated. After that, an optically anisotropic layer (1c) was formed by annealing at 120°C for 1 minute with hot air.

[0423] UV light (ultra-high pressure mercury lamp; UL750; HOYA) passed through a wire grid polarizer at room temperature to the obtained optical anisotropic layer (1c) at 7.9 mJ / cm² 2 By irradiating (wavelength: 313 nm), an optically anisotropic layer (1c) with orientation control capability was formed on the surface.

[0424] In addition, the film thickness of the formed optical anisotropic layer (1c) was 0.5 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the thickness direction retardation Rth at a wavelength of 550 nm was -68 nm. The average angle of inclination of the rod-shaped liquid crystal compound with respect to the film plane in the long axis direction was 90°, and it was confirmed that it is oriented perpendicularly to the film plane.

[0425] In this way, an optical anisotropic layer (1c) corresponding to the optical anisotropic layer (C) was formed.

[0426] -------------------------------------------------------------

[0427] Composition for forming an optical anisotropic layer (1c)

[0428] -------------------------------------------------------------

[0429] 100 parts by mass of the following rod-shaped liquid crystal compound (A)

[0430] Polymerizable monomer (A-400, manufactured by Shin-Nakamura Kagaku High School) 4.0 parts by mass

[0431] 5.0 parts by mass of the following polymerization initiator S-1 (oxime type)

[0432] 3.0 parts by mass of the following photogenerative D-1

[0433] 2.0 parts by mass of the following polymer M-1

[0434] 2.0 parts by mass of the following vertical orientation agent S01

[0435] 2.0 parts by mass of the following photooriented polymer A-1

[0436] 0.2 parts by mass of the following surfactant B-1

[0437] 42.3 parts by mass of methyl ethyl ketone

[0438] 627.5 parts by mass of methyl isobutyl ketone

[0439] -------------------------------------------------------------

[0440] Rod-shaped liquid crystal compound (A) (hereinafter, mixture of compounds)

[0441] [Chemical Formula 20]

[0442]

[0443] Polymerization initiator S-1

[0444] [Chemical Formula 21]

[0445]

[0446] Mineral generator D-1

[0447] [Chemical Formula 22]

[0448]

[0449] Polymer M-1

[0450] [Chemical Formula 23]

[0451]

[0452] Vertical orientation agent S01

[0453] [Chemical Formula 24]

[0454]

[0455] Photooriented polymer A-1 (The numbers listed in each repeating unit represent the content (mass%) of each repeating unit relative to the total repeating units, and were 43 mass%, 27 mass%, and 30 mass% starting from the repeating unit on the left. Also, the weight-average molecular weight was 69,800.)

[0456] [Chemical Formula 25]

[0457]

[0458] Surfactant B-1 (weight average molecular weight was 2200.)

[0459] [Chemical Formula 26]

[0460]

[0461] (Formation of the optical anisotropic layer (1b))

[0462] Next, an optical anisotropic layer forming composition (1b) containing a rod-shaped liquid crystal compound of the following composition was applied to the optical anisotropic layer (1c) prepared above using a die applicator, and heated with hot air at 80°C for 60 seconds. Subsequently, UV irradiation (500 mJ / cm²) was applied to the obtained composition layer at 80°C. 2 ) and fixed the orientation of the liquid crystal compound to form an optical anisotropic layer (1b) corresponding to the optical anisotropic layer (B).

[0463] The thickness of the optical anisotropic layer (1b) was 1.2 μm, the Δnd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was 81°. When the width direction of the film is 0° (length direction is 90°), the alignment axis angle of the liquid crystal compound when viewed from the side of the optical anisotropic layer (1b) was 14° on the air side and 95° on the side in contact with the optical anisotropic layer (1c).

[0464] In addition, the alignment axis angle of the liquid crystal compound included in the optical anisotropic layer is indicated by observing the substrate from the surface side of the optical anisotropic layer with the width direction of the substrate set to 0° as the reference, and representing it as negative when clockwise (right rotation) and positive when counterclockwise (left rotation).

[0465] In addition, the twist angle of the liquid crystal compound is expressed as negative when the alignment axis direction of the liquid crystal compound on the substrate side (inner side) is clockwise (right rotation) and positive when it is counterclockwise (left rotation), based on the alignment axis direction of the liquid crystal compound on the surface side (front side) when observing the substrate from the surface side of the optical anisotropic layer.

[0466] -------------------------------------------------------------

[0467] Composition for forming an optical anisotropic layer (1b)

[0468] -------------------------------------------------------------

[0469] 100 parts by mass of the above rod-shaped liquid crystal compound (A)

[0470] Ethylene oxide modified trimethylolpropane triacrylate

[0471] (V#360, manufactured by Osaka Yuki Kagaku Co., Ltd.) 4 mass parts

[0472] 3 parts by mass of photopolymerization initiator (Irgacure 819, BASF)

[0473] 0.60 parts by mass of the following left-hand torsional chiral material (L1)

[0474] 0.08 parts by mass of the above fluorine-containing compound C

[0475] 156 parts by mass of methyl ethyl ketone

[0476] -------------------------------------------------------------

[0477] Left twist chirality (L1)

[0478] [Chemical Formula 27]

[0479]

[0480] According to the above procedure, a laminate (1c-1b) was fabricated in which an optical anisotropic layer (1c) and an optical anisotropic layer (1b) were directly laminated on a long cellulose acylate film. Additionally, by examining the surface of the side of the optical anisotropic layer (1c) that contacts the optical anisotropic layer (1b) using the method described above, it was confirmed that a photo-oriented polymer is present.

[0481] (Formation of a stack of optical anisotropic layer (A), optical anisotropic layer (B) and optical anisotropic layer (C))

[0482] The surface side of the optical anisotropic layer (1a) formed on the above-made long cellulose acylate film and the surface side of the optical anisotropic layer (1b) of the above-made laminate (1c-1b) formed on the above-made long cellulose acylate film were continuously bonded using a UV-curing adhesive.

[0483] Next, the cellulose acylate film on the side of the optical anisotropic layer (1a) was peeled off to expose the surface that was in contact with the cellulose acylate film of the optical anisotropic layer (1a). In this way, a phase difference film (1c-1b-1a) was obtained in which the optical anisotropic layer (1c), the optical anisotropic layer (1b), and the optical anisotropic layer (1a) were laminated in this order on a long cellulose acylate film. The thickness of the phase difference film (1c-1b-1a) was 4.0 μm. The water content of the obtained phase difference film (1c-1b-1a) was 0.8%. The in-plane ground axis of the surface of the optical anisotropic layer (1b) on the side of the optical anisotropic layer (1a) and the in-plane ground axis of the optical anisotropic layer (1a) were parallel.

[0484] (Fabrication of Linear Polarizer 1)

[0485] The surface of a support of a cellulose triacetate film TJ25 (manufactured by Fujifilm: thickness 25 μm) was subjected to alkali saponification treatment. Specifically, the support was immersed in a sodium hydroxide aqueous solution with a ratio of 1.5 at 55°C for 2 minutes, then washed in a water bath at room temperature, and further neutralized using sulfuric acid with a ratio of 0.1 at 30°C. After neutralization, the support was washed in a water bath at room temperature and further dried with hot air at 100°C to obtain a polarizer protection film.

[0486] A roll-shaped polyvinyl alcohol (PVA) film with a thickness of 60 μm was continuously stretched in the longitudinal direction in an aqueous iodine solution and dried to obtain a polarizer with a thickness of 13 μm. The luminous sensitivity correction single transmittance of the polarizer was 43%. At this time, the absorption axis direction and the longitudinal direction of the polarizer coincided.

[0487] A straight polarizer 1 was fabricated by laminating the polarizer protection film onto one side of the above polarizer using the following PVA adhesive.

[0488] (Preparation of PVA adhesive)

[0489] A PVA adhesive was prepared by dissolving 100 parts by mass of a polyvinyl alcohol-based resin having acetoacetyl groups (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%) and 20 parts by mass of methylolmelamine in pure water under a temperature condition of 30°C, and adjusting the solid content concentration to 3.7 mass% to an aqueous solution.

[0490] (Production of circular polarizers)

[0491] The surface of the optical anisotropic layer (1a) of the above-made long-length phase difference film (1c-1b-1a) and the surface of the polarizer (the side opposite to the polarizer protection film) of the above-made long-length linear polarizer 1 were continuously laminated using a UV-curing adhesive. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (1c) was peeled off to expose the side that was in contact with the cellulose acylate film of the optical anisotropic layer (1c).

[0492] In this way, a circular polarizer (P1) consisting of a phase difference film (1c-1b-1a) and a linear polarizer was fabricated. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (1a), an optical anisotropic layer (1b), and an optical anisotropic layer (1c) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (1a) was 76°. Also, with the width direction set to 0° of the reference, the alignment axis angle of the liquid crystal compound on the side of the optical anisotropic layer (1b) to the optical anisotropic layer (1a) was 14° and coincided with the ground axis direction of the optical anisotropic layer (1a). The thickness of the circular polarizer was 43 μm.

[0493] In addition, the alignment axis angle of the liquid crystal compound included in the optical anisotropic layer is indicated by observing the substrate from the surface side of the polarizer with the width direction of the linear polarizer set to 0° as the reference, and showing negative when clockwise (rightward rotation) and positive when counterclockwise (leftward rotation).

[0494] <Example 2>

[0495] (Formation of orientation layer)

[0496] A photoalignment film forming material described in Example 1 of WO2016 / 002722 was applied to the long cellulose acylate film prepared above. Then, the film was hardened by heating it to 125°C with hot air. Subsequently, the obtained film was irradiated with 313 nm polarized ultraviolet light to produce a photoalignment film.

[0497] (Formation of the optical anisotropic layer (B))

[0498] On the photoalignment film prepared above, an optically anisotropic layer forming composition (1b) containing a rod-shaped liquid crystal compound of the above composition was applied using a die applicator, and heated with hot air at 80°C for 60 seconds. Subsequently, UV irradiation (500 mJ / cm²) was applied to the obtained composition layer at 80°C. 2 ) was performed, and the orientation of the liquid crystal compound was immobilized to form an optical anisotropic layer (2b) corresponding to the optical anisotropic layer (B).

[0499] The thickness of the optical anisotropic layer (2b) was 1.2 μm, the Δnd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was 81°. When the width direction of the film is 0° (length direction is 90°), the alignment axis angle of the liquid crystal compound when viewed from the side of the optical anisotropic layer (2b) was -76° on the air side and 5° on the side in contact with the cellulose acylate film.

[0500] In addition, the alignment axis angle of the liquid crystal compound included in the optical anisotropic layer is indicated by observing the substrate from the surface side of the optical anisotropic layer with the width direction of the substrate set to 0° as the reference, and representing it as negative when clockwise (right rotation) and positive when counterclockwise (left rotation).

[0501] In addition, the twist angle of the liquid crystal compound is expressed as negative when the alignment axis direction of the liquid crystal compound on the substrate side (inner side) is clockwise (right rotation) and positive when it is counterclockwise (left rotation), based on the alignment axis direction of the liquid crystal compound on the surface side (front side) when observing the substrate from the surface side of the optical anisotropic layer.

[0502] (Formation of a stack of optical anisotropic layer (C) and optical anisotropic layer (A))

[0503] (Formation of the optical anisotropic layer (2c))

[0504] In the formation of the optical anisotropic layer (1c) of Example 1, the same method was used except for changing the thickness of the composition layer, thereby forming an optical anisotropic layer (2c) having orientation control capability on the surface.

[0505] In addition, the film thickness of the formed optical anisotropic layer (2c) was 0.7 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the thickness direction retardation Rth at a wavelength of 550 nm was -96 nm. The average angle of inclination of the rod-shaped liquid crystal compound with respect to the film plane in the long axis direction was 90°, and it was confirmed that it is oriented perpendicularly to the film plane.

[0506] In this way, an optical anisotropic layer (2c) corresponding to the optical anisotropic layer (C) was formed.

[0507] (Formation of the optical anisotropic layer (2a))

[0508] Next, an optical anisotropic layer forming composition (2a) containing a rod-shaped liquid crystal compound of the following composition was applied onto the optical anisotropic layer (2c) prepared above using a die applicator, and heated with hot air at 80°C for 60 seconds. Subsequently, UV irradiation (500 mJ / cm²) was applied to the obtained composition layer at 80°C. 2 ) was performed, and the orientation of the liquid crystal compound was immobilized to form an optical anisotropic layer (2a) corresponding to the optical anisotropic layer (A).

[0509] The thickness of the optical anisotropic layer (2a) was 1.2 μm. Also, the retardation at a wavelength of 550 nm was 168 nm. The average inclination angle of the rod-shaped liquid crystal compound with respect to the film plane in the long axis direction was 0°, and it was confirmed that it is oriented horizontally with respect to the film plane. Also, when the width direction of the film is 0° (length direction is 90°), the ground axis was -76° when viewed from the side of the optical anisotropic layer (2a).

[0510] -------------------------------------------------------------

[0511] Composition for forming an optical anisotropic layer (2a)

[0512] -------------------------------------------------------------

[0513] 100 parts by mass of the above rod-shaped liquid crystal compound (A)

[0514] Ethylene oxide modified trimethylolpropane triacrylate

[0515] (V#360, manufactured by Osaka Yuki Kagaku Co., Ltd.) 4 mass parts

[0516] 3 parts by mass of photopolymerization initiator (Irgacure 819, BASF)

[0517] 0.08 parts by mass of the above fluorine-containing compound C

[0518] 156 parts by mass of methyl ethyl ketone

[0519] -------------------------------------------------------------

[0520] According to the above procedure, a laminate (2c-2a) was fabricated in which an optical anisotropic layer (2c) and an optical anisotropic layer (2a) were directly laminated on a long cellulose acylate film. Additionally, by examining the surface of the side of the optical anisotropic layer (2c) that contacts the optical anisotropic layer (2a) using the method described above, it was confirmed that a photo-oriented polymer is present.

[0521] (Formation of a laminate of optical anisotropic layer (A), optical anisotropic layer (C) and optical anisotropic layer (B), fabrication of a circular polarizer)

[0522] The surface of the optical anisotropic layer (2a) of the laminate (2c-2a) formed on the above-made long-length cellulose acylate film and the surface of the polarizer (the side opposite to the polarizer protection film) of the above-made long-length straight polarizer 1 were continuously laminated using a UV-curing adhesive. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (2c) was peeled off to expose the side of the optical anisotropic layer (2c) that was in contact with the cellulose acylate film.

[0523] The surface of the exposed optical anisotropic layer (2c) and the surface side of the optical anisotropic layer (2b) formed on the fabricated long cellulose acylate film were continuously bonded using a UV-curing adhesive. Subsequently, the cellulose acylate film on the optical anisotropic layer (2b) side was peeled off to expose the surface of the optical anisotropic layer (2b) that was in contact with the cellulose acylate film.

[0524] In this way, a circular polarizer (P2) consisting of an optical phase difference film (2b-2c-2a) and a linear polarizer 1 was fabricated. The thickness of the phase difference film (2b-2c-2a) was 4.0 μm. The water content of the obtained phase difference film (2b-2c-2a) was 0.8%. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (2a), an optical anisotropic layer (2c), and an optical anisotropic layer (2b) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (2a) was 14°. Also, with the width direction set to 0° of the reference, the alignment axis angle of the liquid crystal compound on the side of the optical anisotropic layer (2b) to the optical anisotropic layer (2c) was 76°, and coincided with the ground axis direction of the optical anisotropic layer (2a). The thickness of the circular polarizer was 43 μm.

[0525] In addition, the alignment axis angle of the liquid crystal compound included in the optical anisotropic layer is indicated by observing the substrate from the surface side of the polarizer with the width direction of the linear polarizer set to 0° as the reference, and showing negative when clockwise (rightward rotation) and positive when counterclockwise (leftward rotation).

[0526] <Comparative Example 1>

[0527] An optically anisotropic layer (1c) was formed on a long cellulose acylate film in the same manner as in Example 1.

[0528] Next, an optical anisotropic layer (1h) containing a reverse wavelength dispersed liquid crystal compound was formed on the above-described optical anisotropic layer (1c) using composition A-1 described in Example 9 of Patent Document 1. The retardation at a wavelength of 550 nm was 138 nm. It was confirmed that the average inclination angle of the reverse wavelength dispersed liquid crystal compound with respect to the film plane in the long axis direction was 0°, and that it was oriented horizontally with respect to the film plane. In addition, when the width direction of the film was set to 0° (length direction to 90°), the ground axis was 45° when viewed from the side of the optical anisotropic layer (1h).

[0529] In this way, an optical anisotropic layer (1c) containing a vertically oriented rod-shaped liquid crystal compound and an optical anisotropic layer (1h) containing a horizontally oriented inverse wavelength dispersion liquid crystal compound were directly stacked to produce a laminate.

[0530] A laminate comprising a linear polarizer 1 manufactured in the same manner as in Example 1, an optical anisotropic layer (1c) manufactured above, and an optical anisotropic layer (1h) was continuously laminated using a UV-curing adhesive such that the surface of the optical anisotropic layer (1h) and the surface of the polarizer of the linear polarizer 1 (the side opposite to the polarizer protection film) faced each other. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (1c) was peeled off to expose the side of the optical anisotropic layer (1c) that was in contact with the cellulose acylate film.

[0531] In this way, a circular polarizer made of a linear polarizer was manufactured. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (1h), and an optical anisotropic layer (1c) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (1h) was 45°.

[0532] <Comparative Example 2>

[0533] An optically anisotropic layer (1c) was formed on a long cellulose acylate film in the same manner as in Example 1.

[0534] Next, an optical anisotropic layer (2h) was formed on the optical anisotropic layer (1c) prepared above using the optical anisotropic layer forming composition (2a) above. The retardation at a wavelength of 550 nm was 138 nm. It was confirmed that the average inclination angle of the rod-shaped liquid crystal compound with respect to the film plane in the direction of the long axis was 0°, and that it was oriented horizontally with respect to the film plane. Also, when the width direction of the film was set to 0° (length direction to 90°), the ground axis was 45° when viewed from the side of the optical anisotropic layer (2h).

[0535] In this way, an optical anisotropic layer (1c) containing a vertically oriented rod-shaped liquid crystal compound and an optical anisotropic layer (2h) containing a horizontally oriented rod-shaped liquid crystal compound were directly stacked to produce a laminate.

[0536] A laminate comprising a straight polarizer 1 manufactured in the same manner as in Example 1, an optical anisotropic layer (1c) manufactured above, and an optical anisotropic layer (2h) was continuously laminated using a UV-curing adhesive such that the surface of the optical anisotropic layer (2h) and the surface of the polarizer of the straight polarizer 1 (the side opposite to the polarizer protection film) faced each other. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (1c) was peeled off to expose the side of the optical anisotropic layer (1c) that was in contact with the cellulose acylate film.

[0537] In this way, a circular polarizer made of a linear polarizer was manufactured. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (2h), and an optical anisotropic layer (1c) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (2h) was 45°.

[0538] <Comparative Example 3>

[0539] (Formation of the optical anisotropic layer (3h))

[0540] A continuous rubbing treatment was performed on the alignment layer placed on the cellulose acylate film used in the fabrication of the optical anisotropic layer A of Example 1. At this time, the length direction of the long film and the conveying direction are parallel, and the angle formed by the length direction of the film (conveying direction) and the rotation axis of the rubbing roller is set to 75°. If the length direction of the film (conveying direction) is set to 90° and the clockwise direction is expressed as a positive value with the film width direction as the reference (0°) when observed from the film side, the rotation axis of the rubbing roller is at 165°.

[0541] On the above-mentioned rubbing-treated alignment film, an optical anisotropic layer coating solution (1a) identical to that of Example 1 was applied using a die applicator to form an optical anisotropic layer (3h) corresponding to the optical anisotropic layer (A).

[0542] The thickness of the optical anisotropic layer (3h) was 2.0 μm. Also, the retardation at a wavelength of 550 nm was 250 nm. It was confirmed that the average inclination angle of the disc surface of the disc-shaped liquid crystal compound with respect to the film surface was 90°, and that it was oriented perpendicularly with respect to the film surface. Also, the angle of the ground axis of the optical anisotropic layer (3h) was parallel to the rotation axis of the rubbing roller, and if the width direction of the film was set to 0° (the length direction was 90° in the counterclockwise direction and -90° in the clockwise direction), the ground axis was 165° when viewed from the side of the optical anisotropic layer (3h).

[0543] (Formation of the optical anisotropic layer (4h))

[0544] A continuous rubbing treatment was performed on the alignment film placed on the cellulose acylate film used in the fabrication of the optical anisotropic layer A of Example 1. At this time, the longitudinal direction of the long film and the conveying direction were parallel, and the angle formed by the longitudinal direction of the film (conveying direction) and the rotation axis of the rubbing roller was set to 75°.

[0545] If the length direction (transport direction) of the film is set to 90° and the clockwise direction is expressed as a positive value with the film width direction as the reference (0°) when observed from the film side, the rotation axis of the rubbing roller is at 165°.

[0546] On the above-mentioned rubbing-treated alignment film, an optical anisotropic layer forming composition (1a) identical to that of Example 1 was applied using a die applicator to form an optical anisotropic layer (4h) corresponding to the optical anisotropic layer (A).

[0547] The thickness of the optical anisotropic layer (4h) was 0.8 μm. Also, the retardation at a wavelength of 550 nm was 120 nm. It was confirmed that the average inclination angle of the long axis of the rod-shaped liquid crystal compound with respect to the film plane was 0°, and that it was oriented horizontally with respect to the film plane. Also, the angle of the ground axis of the optical anisotropic layer (4h) was parallel to the rotation axis of the rubbing roller, and if the width direction of the film was 0° (the length direction was 90° in the counterclockwise direction and -90° in the clockwise direction), the ground axis was 105° when viewed from the side of the optical anisotropic layer (4h).

[0548] A linear polarizer 1 and a cellulose acylate film having an optical anisotropic layer (3h) arranged thereon, prepared in the same manner as in Example 1, were continuously laminated using a UV-curing adhesive such that the surface of the optical anisotropic layer (3h) and the surface of the polarizer of the linear polarizer 1 (the side opposite to the polarizer protection film) faced each other. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (3h) was peeled off to expose the side of the optical anisotropic layer (3h) that was in contact with the cellulose acylate film. The exposed surface of the optical anisotropic layer (3h) and the surface of the optical anisotropic layer (4h) formed on the above-prepared long cellulose acylate film were continuously laminated using a UV-curing adhesive. Subsequently, the cellulose acylate film on the side of the optical anisotropic layer (4h) was peeled off to expose the side of the optical anisotropic layer (4h) that was in contact with the cellulose acylate film.

[0549] In this way, a circular polarizer made of a linear polarizer was manufactured. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (3h), and an optical anisotropic layer (4h) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (3h) was 75°.

[0550] <Comparative Example 4>

[0551] Instead of the optical anisotropic layer (1c) of Example 1, a cellulose acylate film (3c) was produced in the same procedure as Example 15 of Japanese Patent Publication No. 2006-265309, except that stretching was not performed. Re and Rth were equivalent to those of the optical anisotropic layer (1c).

[0552] A cellulose acylate film (3c) was alkaline saponified to form an alignment layer, and then an optical anisotropic layer (3b) was formed. The optical anisotropic layer (3b) was prepared in the same way as the optical anisotropic layer (1b) of Example 1, except that the optical anisotropic layer (1c) of Example 1 was changed to the cellulose acylate film (3c) described above.

[0553] The surface side of the optical anisotropic layer (1a) produced in Example 1 and the surface side of the optical anisotropic layer (3b) produced above were continuously laminated using a UV-curing adhesive. After that, the cellulose acylate film on the optical anisotropic (1a) side was peeled off to obtain a phase difference film (3c-3b-1a). The water content of the obtained phase difference film was 2.1%, and the thickness was 303 μm.

[0554] The surface of the optical anisotropic layer (1a) of the above-made long-length phase difference film (3c-3b-1a) and the surface of the polarizer (the side opposite to the polarizer protection film) of the above-made long-length straight polarizer 1 were continuously laminated using a UV-curing adhesive.

[0555] In this way, a circular polarizer consisting of a phase difference film (3c-3b-1a) and a linear polarizer was fabricated. At this time, a polarizer protection film, a polarizer, an optical anisotropic layer (1a), an optical anisotropic layer (3b), and an optical anisotropic layer (3c) were stacked in this order, and the angle formed by the absorption axis of the polarizer and the ground axis of the optical anisotropic layer (1a) was 76°. Also, with the width direction set to 0° of the reference, the alignment axis angle of the liquid crystal compound on the side of the optical anisotropic layer (3b) to the optical anisotropic layer (1a) was 14°, and coincided with the ground axis direction of the optical anisotropic layer (1a). The thickness of the circular polarizer was 342 μm.

[0556] <Color and Reflectance Measurement>

[0557] A reflective substrate was fabricated by attaching aluminum foil to a 100 μm thick PET film using an adhesive sheet.

[0558] A circular polarizer prepared in the examples and comparative examples was placed on the aluminum foil side of the obtained reflective substrate, and a laminate (corresponding to a specific laminate) was obtained. In addition, the reflective substrate and the circular polarizer were laminated such that the phase difference film of the circular polarizer and the aluminum foil faced each other. Using a spectrophotometer (manufactured by Konica Minolta), the color chromaticity a at the entire azimuth angle (0–360°) with a polar angle of 40° from the normal direction of the circular polarizer of the laminate was observed from the side of the circular polarizer in the obtained laminate. * and chromaticity b * The reflectance was measured. In addition, following the procedure described above, the reflectance was measured at the entire azimuth angle (0 to 360°) with a polar angle of 40° from the normal direction of the circular polarizer of the laminate.

[0559] Furthermore, the above azimuth angle represents the angle formed by the absorption axis of the polarizer with respect to the absorption axis of the polarizer. Additionally, when representing the azimuth angle, when viewed from the circular polarizer side of the obtained laminate, the counterclockwise direction with respect to the direction of the polarizer's absorption axis is indicated as a positive value.

[0560] Fabrication of Organic EL Display Devices

[0561] (Mounting into a display device)

[0562] A Royole FlexPai equipped with an organic EL display panel (organic EL display element) was disassembled, and a circular polarizer was peeled off from the organic EL display device. Subsequently, the circular polarizer fabricated above was laminated to the panel side using a pressure-sensitive adhesive so that a protective film was placed on the outside of the isolated organic EL display panel, thereby fabricating an organic EL display device.

[0563] (Evaluation of display performance)

[0564] (Front direction)

[0565] A black mark was applied to the fabricated organic EL display device, and the color tone non-uniformity was evaluated by observing it from the front while the display was unfolded and under bright light, according to the following criteria. The results are shown in Table 1.

[0566] A: No color unevenness is noticeable (allowed)

[0567] B: Slight color unevenness is noticeable, but there are no usability issues (acceptable)

[0568] C: Color unevenness is noticeable, causing usability issues.

[0569] (Slope direction)

[0570] A black mark was applied to the fabricated organic EL display device, and the display was folded and placed under bright light. The color tone non-uniformity was evaluated based on the following criteria by observing the entire azimuth angle from the tilt direction. The results are shown in Table 1.

[0571] A: No color unevenness is noticeable (allowed)

[0572] B: Slight color unevenness is noticeable, but there are no usability issues (acceptable)

[0573] C: Color unevenness is noticeable, causing usability issues.

[0574] (Competition Evaluation)

[0575] After leaving the fabricated organic EL display device in an environment of 25°C and 10% relative humidity for 72 hours, a black display was applied to the organic EL display device, and the color tone non-uniformity was evaluated under bright light while the display was folded according to the following criteria. The results are shown in Table 1.

[0576] A: There was no change in the time.

[0577] B: There was a change in the competition.

[0578] In Table 1, in the column "Liquid crystal compound type," "disc-shaped" means that the optical anisotropic layer is a layer formed using a disc-shaped liquid crystal compound, "rod-shaped liquid crystal" means that the optical anisotropic layer is a layer formed using a rod-shaped liquid crystal compound, and "inverse dispersion liquid crystal" means that the optical anisotropic layer is a layer formed using an inverse wavelength dispersion liquid crystal compound.

[0579] In the "Orientation State" column, "Horizontal" means that the liquid crystal compound is horizontally oriented. "Twisted" means that the liquid crystal compound is twistedly oriented. "Vertical" means that the liquid crystal compound is vertically oriented.

[0580] In Table 1, the "Reflectance" column indicates the reflectance at the entire azimuth angle measured by the above <Color and Reflectance Measurement>, and "<X%"란 어느 방위각에서의 반사율이 X% 미만인 것을 의미하며, "> "Y%" means that the reflectance at any given azimuth angle exceeds Y%.

[0581] In Table 1, "a * "Ran is the chromaticity a at the entire azimuth angle measured by the above <chromaticity and reflectance measurement>." * Represents the absolute value of, and " <X"란 어느 방위각에서의 색도 a * It means that the absolute value of is less than X, and ">Y" means the chromaticity a at any given azimuth angle. * It means that the absolute value of is greater than Y.

[0582] In Table 1, "b * "Ran is the chromaticity b at the entire azimuth angle measured by the above <chromaticity and reflectance measurement>." * Represents the absolute value of, and " <X"란 어느 방위각에서의 색도 b * It means that the absolute value of is less than X, and ">Y" means the chromaticity b at any given azimuth angle. * It means that the absolute value of is greater than Y.

[0583] [Table 1]

[0584]

[0585] From the results shown in Table 1 above, it was confirmed that the circular polarizer of the present invention can suppress color tone non-uniformity in the frontal and oblique directions when used in an organic EL display device. In addition, the occurrence of color tone non-uniformity over time was also suppressed. On the other hand, the circular polarizer of the comparative example did not achieve the desired effect when used in an organic EL display device.

[0586] <Example 3>

[0587] In the same manner as in Example 1, a phase difference film (1c-1b-1a) was obtained in which an optical anisotropic layer (1c), an optical anisotropic layer (1b), and an optical anisotropic layer (1a) were laminated in this order on a long cellulose acylate film.

[0588] Next, a polarizer utilizing a dichroic organic dye and a polymerizable liquid crystal was prepared as a linear polarizer 3. The coating solution PA1 for forming an alignment layer, described later, was applied continuously via a wire bar onto a cellulose triacetate film TJ40 (manufactured by Fujifilm: thickness 40 μm). The substrate with the formed film was dried with hot air at 140°C for 120 seconds, and subsequently, polarized ultraviolet irradiation (10 mJ / cm²) was applied to the film. 2 By using an ultra-high pressure mercury lamp, a photo-aligned layer PA1 was formed, and a TAC film with the photo-aligned layer PA1 attached was obtained.

[0589] The film thickness of the photoalignment layer PA1 was 0.3 μm.

[0590] -------------------------------------------------------------

[0591] Coating solution PA1 for forming orientation layer

[0592] -------------------------------------------------------------

[0593] · 100.00 parts by mass of the following polymer PA-1

[0594] · 5.00 parts by mass of the following acid-generating agent PAG-1

[0595] · 0.005 parts by mass of the following acid-generating agent CPI-110TF

[0596] · 1220.00 parts by mass of xylene

[0597] · 122.00 parts by mass of methyl isobutyl ketone

[0598] -------------------------------------------------------------

[0599] Polymer PA-1

[0600] [Chemical Formula 28]

[0601]

[0602] Acid-generating agent PAG-1

[0603] [Chemical Formula 29]

[0604]

[0605] Acid-generating agent CPI-110F

[0606] [Chemical Formula 30]

[0607]

[0608] On the obtained photo-aligned layer PA1, the following composition P2 for forming a light-absorbing anisotropic layer was continuously applied via a wire bar to form a film P2.

[0609] Next, the coating P2 was heated at 140°C for 30 seconds, and then the coating P2 was cooled to room temperature (23°C).

[0610] Next, the obtained film P2 was heated at 90°C for 60 seconds and then cooled to room temperature.

[0611] Subsequently, using an LED (light emitting diode) lamp (center wavelength 365 nm) with an illuminance of 200 mW / cm² 2A light-absorbing anisotropic layer P2 was fabricated on a photo-aligned layer PA1 by irradiating for 2 seconds under the irradiation conditions. The molar content of radical polymerizable groups is 1.17 mmol / g.

[0612] The film thickness of the light-absorbing anisotropic layer P2 was 1.3 μm.

[0613] -------------------------------------------------------------

[0614] Composition P2 for forming a light-absorbing anisotropic layer

[0615] -------------------------------------------------------------

[0616] · 0.25 parts by mass of the following dichroic pigment D-4

[0617] · 0.36 parts by mass of the following dichroic pigment D-5

[0618] · 0.59 parts by mass of the following dichroic pigment D-6

[0619] · 2.21 parts by mass of the following polymer liquid crystal compound P-1

[0620] · 1.36 parts by mass of the following low molecular weight liquid crystal compound M-1

[0621] · Polymerization initiator

[0622] IRGACUREOXE-02 (BASF) 0.150 parts by mass

[0623] · 0.026 parts by mass of the following surfactant F-1

[0624] · 46.00 parts by mass of cyclopentanone

[0625] · Tetrahydrofuran 46.00 parts by mass

[0626] · 3.00 parts by mass of benzyl alcohol

[0627] -------------------------------------------------------------

[0628] Dichroic pigment D-4

[0629] [Chemical Formula 31]

[0630]

[0631] Dichroic pigment D-5

[0632] [Chemical Formula 32]

[0633]

[0634] Dichroic pigment D-6

[0635] [Chemical Formula 33]

[0636]

[0637] Polymer liquid crystal compound P-1

[0638] [Chemical Formula 34]

[0639]

[0640] Low molecular weight liquid crystal compound M-1

[0641] [Chemical Formula 35]

[0642]

[0643] Surfactant F-1

[0644] [Chemical Formula 36]

[0645]

[0646] A coating film was formed by continuously applying the following curing layer forming composition K1 onto the obtained light-absorbing anisotropic layer P2 using a wire bar.

[0647] Next, dry the coating film at room temperature, and then, use a high-pressure mercury lamp with an illuminance of 28 mW / cm² 2 A hardened layer K1 was fabricated on a light-absorbing anisotropic layer P2 by irradiating for 15 seconds under the irradiation conditions.

[0648] The film thickness of the hardened layer K1 was 0.05 μm.

[0649] -------------------------------------------------------------

[0650] Composition K1 for forming a hardened layer

[0651] -------------------------------------------------------------

[0652] · Mixture L1 of the following rod-shaped liquid crystal compound 2.61 parts by mass

[0653] · 0.11 parts by mass of the following modified trimethylolpropane triacrylate

[0654] · 0.05 parts by mass of the following photopolymerization initiator I-1

[0655] · 0.21 parts by mass of the following surfactant F-3

[0656] · 297 parts by mass of methyl isobutyl ketone

[0657] -------------------------------------------------------------

[0658] Mixture L1 of rod-shaped liquid crystal compounds (the numbers in the following formula represent mass %, and R represents a group bonded to an oxygen atom.)

[0659] [Chemical Formula 37]

[0660]

[0661] Modified trimethylolpropane triacrylate

[0662] [Chemical Formula 38]

[0663]

[0664] Photopolymerization initiator I-1

[0665] [Chemical Formula 39]

[0666]

[0667] Surfactant F-3

[0668] [Chemical Formula 40]

[0669]

[0670] The following oxygen blocking layer forming composition B2 was applied continuously via a wire bar onto the cured layer K1. Then, by drying with hot air at 100°C for 2 minutes, an oxygen blocking layer B2 with a thickness of 1.0 μm was formed on the cured layer K1, thereby producing a polarizing film containing a light-absorbing anisotropic layer P2.

[0671] The individual transmittance of the polarizing film for visual sensitivity correction was 43%.

[0672] -------------------------------------------------------------

[0673] Composition B2 for forming an oxygen barrier layer

[0674] -------------------------------------------------------------

[0675] · 3.80 parts by mass of the following modified polyvinyl alcohol

[0676] · Initiator Irg2959 0.20 parts by mass

[0677] · 70 parts by mass of water

[0678] · 30 parts by mass of methanol

[0679] -------------------------------------------------------------

[0680] Modified polyvinyl alcohol

[0681] [Chemical Formula 41]

[0682]

[0683] The oxygen blocking layer B2 side of the polarizing film and the polarizing plate protection film were attached using an adhesive sheet. Then, only TJ40 of the polarizing film was peeled off, and the peeled surface was continuously laminated with the surface of the optical anisotropic layer (1a) of the long-length phase difference film (1c-1b-1a) using a UV-curing adhesive. Subsequently, the cellulose acylate film of the optical anisotropic layer (1c) was peeled off to expose the surface that was in contact with the cellulose acylate film of the optical anisotropic layer (1c). In this way, a circular polarizing plate was manufactured. The thickness of the circular polarizing plate was 38 μm.

[0684] <Example 4>

[0685] A circular polarizer was fabricated in the same direction as in Example 3, except that the film thickness of the light-absorbing anisotropic layer P2 of Example 3 was 0.8 μm. The visual sensitivity correction single transmittance of the polarizing film was 45%. The thickness of the circular polarizer was 37 μm.

[0686] (Evaluation of display performance)

[0687] As a result of mounting the circular polarizer of Example 3 or 4 in an organic EL display device in the same manner as Example 1, display performance equivalent to that of Example 1 was confirmed. In addition, the overall thickness of the circular polarizer could be reduced, and the yield during irregular processing, such as for curved displays, could be improved.

[0688] <Example 5>

[0689] (Fabrication of a circular polarizer using high-refractive index adhesive)

[0690] The surface side of the optical anisotropic layer (1a) formed on a long cellulose acylate film prepared in the same manner as in Example 1, and the surface side of the optical anisotropic layer (1b) of the laminate (1c-1b) formed on the long cellulose acylate film prepared above, were continuously laminated using a UV-curing adhesive. As the UV-curing adhesive, an adhesive was used in which a high-refractive index monomer was added to an acrylic compound to control the refractive index after curing to 1.53. The difference between the refractive index averaged along the axial direction of adjacent optical anisotropic layers and the refractive index of the adhesive was within 0.08. A circular polarizer was prepared in the same manner as in Example 1, except for controlling the refractive index.

[0691] <Example 6>

[0692] A circular polarizer was fabricated in the same manner as in Example 1 using a UV-curing adhesive in which the refractive index after curing was controlled to 1.58, in the same way as in Example 5. The difference between the refractive index averaged along the axial direction of adjacent optical anisotropic layers and the refractive index of the adhesive was within 0.05.

[0693] <Example 7>

[0694] In the same manner as in Example 5, a UV-curing adhesive with a refractive index controlled to 1.53 was prepared. The surface of the optical anisotropic layer (1a) of the elongated phase difference film (1c-1b-1a) produced in Example 5 and the surface of the polarizer (the side opposite to the polarizer protection film) of the elongated linear polarizer 1 produced above were continuously laminated using the UV-curing adhesive with a cured refractive index controlled to 1.53. A circular polarizer was produced in the same manner as in Example 5. The difference between the average refractive index of the polarizer and the refractive index of the adhesive was within 0.05.

[0695] (Evaluation of display performance)

[0696] As a result of mounting the polarizers of Examples 5, 6, and 7 in an organic EL display device in the same manner as Example 1, display performance equivalent to that of Example 1 was confirmed. Explanation of the symbols

[0697] 1, 2 Phase difference film 10, 20 circular polarizers 1a, 2a Optical anisotropic layer (A) 1b, 2b Optical anisotropic layer (B) 1c, 2c Optical anisotropic layer (C) 3 polarizers 30 aluminum sheets 40 specific laminates

Claims

Claim 1 A circular polarizer comprising a polarizer and a phase difference film laminated on the surface side of one side of the polarizer, wherein the water content of the phase difference film is 1.8% or less, and the circular polarizer and the aluminum sheet are laminated such that the phase difference film in the circular polarizer faces the aluminum sheet, and the chromaticity a at a total azimuth angle of 40° polar angle from the normal direction of the circular polarizer obtained therefrom * and chromaticity b * When measuring, the chromaticity a at any azimuth angle * The absolute value of and chromaticity b * The absolute value of is 10 or less, and when the reflectance is measured at the entire azimuth angle of 40° from the normal direction of the circular polarizer of the laminate, the reflectance at any azimuth angle is 3.0% or less, and the phase difference film comprises an optical anisotropic layer (A), an optical anisotropic layer (B), and an optical anisotropic layer (C), wherein the optical anisotropic layer (A) is an optical anisotropic layer exhibiting negative uniaxiality, the optical anisotropic layer (B) is an optical anisotropic layer formed by fixing a rod-shaped liquid crystal compound twist-oriented with the thickness direction as a helical axis, and the optical anisotropic layer (C) is an optical anisotropic layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound, and the in-plane retardation of the optical anisotropic layer (A) at a wavelength of 550 nm is 140 to 220 nm, and the optical The value of the product Δnd of the refractive index anisotropy Δn of the anisotropic layer (B) and the thickness d of the optical anisotropic layer (B) is 140 to 220 nm, the twist angle of the twist-oriented rod-shaped liquid crystal compound is in the range of 90 ± 30°, the in-plane ground axis of the optical anisotropic layer (A) and the in-plane ground axis of the optical anisotropic layer (B) on the surface of the optical anisotropic layer (A) are parallel, and in the case where the optical anisotropic layer (C) is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound, the retardation in the thickness direction of the optical anisotropic layer (C) at a wavelength of 550 nm is -140 to -20 nm, and in the case where the optical anisotropic layer (C) is a layer formed by fixing a horizontally oriented disc-shaped liquid crystal compound, the thickness direction of the optical anisotropic layer (C) at a wavelength of 550 nm Circular polarizer with a retardation of 20–140 nm. Claim 2 A circular polarizer according to claim 1, wherein the thickness of the phase difference film is 30 μm or less. Claim 3 A circularly polarized plate according to claim 1, wherein the phase difference film is formed by stacking three layers of optical anisotropic layers. Claim 4 A circularly polarized plate according to claim 1, wherein the phase difference film is formed by stacking three layers of an optical anisotropic layer formed by fixing an oriented liquid crystal compound. Claim 5 A circular polarizer according to claim 1, wherein the polarizer is formed using a composition comprising a polymerizable liquid crystal compound, and the thickness of the polarizer is 8 μm or less. Claim 6 An organic electroluminescence display device having a circular polarizing plate as described in claim 1. Claim 7 A display device having a circular polarizing plate as described in claim 1, wherein the circular polarizing plate is arranged to follow a curved surface having the display device. Claim 8 delete Claim 9 delete

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