JP2013029552A - Optical film and stereoscopic image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical film having a patterned optical anisotropic layer capable of reducing crosstalk when incorporated into a stereoscopic image display device.SOLUTION: An optical film includes a pattern optical anisotropic layer 10 having a first retardation region 1 and a second retardation region 2. The first retardation region and the second retardation region are alternately arranged in the same plane, and are different from at least one of an in-plane slow axis direction and in-plane retardation. And a distance L between two adjacent boundaries among boundaries 3 between the first retardation regions and the second retardation regions is 1 mm to 50 mm.

Description

  The present invention relates to an optical film and a stereoscopic image display apparatus using the same.

The 3D image display device that displays a stereoscopic image requires an optical member for converting the right-eye image and the left-eye image into, for example, circularly polarized images in opposite directions. Such an optical member requires a pattern in which regions having different absorption axes of the polarizing film and slow axes of the retardation film are regularly arranged. Various patterns are known (Patent Documents 1 to 4).
In such a pattern, it is strongly demanded to reduce crosstalk.

Japanese Patent Laid-Open No. 10-90675 Japanese Patent Laid-Open No. 10-153707 JP 2009-193014 A JP 2007-71952 A

  The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide an optical film having a patterned optical anisotropic layer with reduced crosstalk.

As a result of intensive studies by the inventors of the present invention based on the above problems, the above problems can be solved by the following (1) and (18), preferably by the following (2) to (17) and (19). I found out.
(1) It has a first phase difference region and a second phase difference region, and the first phase difference region and the second phase difference region are alternately arranged in the same plane, and the first phase difference region And the second retardation region is different from each other in at least one of the in-plane slow axis direction and the in-plane retardation, and adjacent two of the boundary lines between the first retardation region and the second retardation region. The optical film which has a pattern optically anisotropic layer whose distance L between boundary lines is 1 mm-50 mm.
(2) The distance L between two adjacent boundary lines among the boundary lines of the first phase difference region and the second phase difference region and the width L1 of the boundary line satisfy the following formula (1): The optical film as described.
Formula (1) 100 <= L / L1 <= 5,000
(3) The optical film according to (1) or (2), wherein a black portion is disposed on at least one surface of the boundary line.
(4) The optical film according to any one of (1) to (3), further comprising a polarizing film.
(5) The optically anisotropic layer according to any one of (1) to (4), wherein the optically anisotropic layer is formed on a transparent support having Re (550) of 0 to 10 nm. the film.
(6) The optical film according to any one of (1) to (5), wherein the first retardation region and the second retardation region are formed in a stripe shape.
(7) The in-plane slow axes of the first retardation region and the second retardation region and the absorption axis of the polarizing film form an angle of ± 45 °, respectively. The optical film according to any one of 6).
(8) The optical film according to any one of (1) to (7), wherein in-plane slow axis directions of the first retardation region and the second retardation region are orthogonal to each other.
(9) The in-plane retardation Re (550) of the entire optical film having a wavelength of 550 nm is 110 to 160 nm in both the portion including the first retardation region and the portion including the second retardation region ( The optical film according to any one of 1) to (8).
(10) The optical film according to any one of (1) to (9), wherein any one of the layers constituting the optical film contains an ultraviolet absorber.
(11) The optical film according to any one of (1) to (10), wherein the patterned optically anisotropic layer is formed on an alignment film processed in one direction.
(12) The optical film according to (11), wherein the alignment film contains a photoacid generator.
(13) At least a part of the photoacid generator is decomposed, and the degrees of decomposition of the photoacid generator in regions corresponding to the first retardation region and the second retardation region of the alignment film are different from each other, The optical film as described in (12).
(14) An acidic compound generated from the photoacid generator or an ion thereof is present in at least a part of the optically anisotropic layer, and the first retardation region and the second retardation region of the optically anisotropic layer. The optical film as described in (12) or (13), wherein the ratio of the acidic compound or its anion contained therein is different from each other.
(15) The optical film according to any one of (11) to (14), wherein the alignment film is a rubbing alignment film that is rubbed in one direction.
(16) The first retardation region and the second retardation region are each formed from a composition containing a discotic liquid crystal compound having a polymerizable group as a main component, (1) to The optical film according to any one of (15).
(17) The optical film according to (16), wherein the discotic liquid crystal is fixed in a vertically aligned state.
(18) A three-dimensional image display device having the optical film according to any one of (1) to (17).
(19) The stereoscopic image display device according to (18), which has a color filter, and when a distance in a direction perpendicular to the film surface of the color filter and the patterned optically anisotropic layer is D, D A stereoscopic image display device in which / L is 2 or less.

  According to the present invention, it is possible to reduce the crosstalk of the stereoscopic image display device.

It is a top view which shows an example of the pattern optical anisotropic layer in this invention. It is sectional drawing which shows an example of the relationship between the pattern optically anisotropic layer and black part in this invention. It is sectional drawing which shows an example of the optical film of this invention. It is a conceptual diagram when the optical film of this invention is combined with the color filter. It is the schematic which shows an example of the relationship between the polarizing film and patterned optically anisotropic layer in this invention. It is the schematic which shows an example of the embodiment in the case of using combining the two optical films of this invention. It is the schematic which shows the state before and behind sliding a pattern optical anisotropic layer in the case of using combining the two optical films of this invention. It is a figure which shows the direction of the transmission axis of the polarizing film of the difference which bonds the optical film and liquid crystal cell which were created in the Example. FIG. 3 is a schematic diagram illustrating a pattern state in the first embodiment. The shape of the flexographic plate used in Example 5 is shown. The schematic of the structure of the flexographic printing apparatus used in Example 5 is shown. In Example 6, it is the schematic which shows the position of the mask for alignment film preparation, and the direction of the absorption axis of a wire grid polarizing film.

Hereinafter, the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, when there is no special mention about a measurement wavelength, a measurement wavelength is 550 nm.
Further, in the present specification, regarding the angle (for example, an angle such as “90 °”) and the relationship (for example, “orthogonal”, “parallel”, “crossing at 45 °”, etc.), the technical field to which the present invention belongs. The range of allowable error is included. For example, it means that the angle is within the range of strict angle ± 10 °, and the error from the strict angle is preferably 5 ° or less, and more preferably 3 ° or less.

[Re and Rth]
In the present specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.
When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (when there is no slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (11) and (12).
Formula (11)

The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In formula (11), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz represents the refractive index in the direction orthogonal to nx and ny. . d is the film thickness.

Formula (12): Rth = {(nx + ny) / 2−nz} × d
In formula (12), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. . d is the film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotating axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

The optical film of the present invention has a first retardation region and a second retardation region, and the first retardation region and the second retardation region are alternately arranged in the same plane, The first phase difference region and the second phase difference region are different from each other in at least one of the in-plane slow axis direction and the in-plane retardation, and are adjacent to each other between the boundary lines of the first phase difference region and the second phase difference region. The patterned optically anisotropic layer has a distance L between two boundary lines of 1 mm to 50 mm. The optical film of the present invention may consist only of a patterned optically anisotropic layer.
The stereoscopic image display device of the present invention has an optical film having the patterned optically anisotropic layer.

Hereinafter, the optical film of the present invention will be described in detail. FIG. 1 is a top view showing an example of the patterned optically anisotropic layer 10 of the present invention, where 1 is a first retardation region, 2 is a second retardation region, and 3 is a first retardation region. A boundary line that is a boundary of the second phase difference region is shown. The arrow has shown the direction of the slow axis of a 1st phase difference area | region and a 2nd phase difference area | region. The reference numerals in the drawings are common to the following drawings unless otherwise specified.
Further, FIG. 1 is a schematic diagram, and the relationship between the first phase difference region 1, the second phase difference region, and the boundary line 3 will be described in an easy-to-understand manner, and this is not the most appropriate dimension ratio. A preferable range of these dimensional ratios will be described later.

In FIG. 1, L indicates a distance between two adjacent boundary lines 3 and 3 which is a boundary line 3 which is a boundary between the first phase difference region and the second phase difference region. Here, the distance between the boundary lines 3 and 3 is the average surface in the thickness direction of the film at one end of one phase difference region, and the film of the end film on the side close to the phase difference region of the adjacent phase difference region. The shortest distance between the average surfaces in the thickness direction. Here, the average surface refers to a reference surface when the uneven surface is assumed to be a flat surface when the surface in the thickness direction at the end of the retardation region is an uneven surface.
In the present invention, L is 1 mm to 50 mm. In this way, crosstalk can be reduced by increasing the pitch width as compared with the prior art.

L1 means the width of the boundary line. The width of the boundary line is the average surface in the thickness direction at one end of one retardation region and the average surface in the direction of the thickness of the end of the retardation region adjacent to the retardation region on the side close to the retardation region. The shortest distance between. In the present invention, it is preferable that the distance L between the two adjacent boundary lines and the width L1 of the boundary line satisfy the following formula (1).
Formula (1) 100 <= L / L1 <= 5,000
Furthermore, it is preferable that 200 ≦ L / L1 ≦ 5,000, more preferably 400 ≦ L / L1 ≦ 5,000, and still more preferably 500 ≦ L / L1 ≦ 5,000. By setting such a ratio, the crosstalk tends to be further reduced.

  It is preferable that the first phase difference region and the second phase difference region have the same shape. Moreover, it is preferable that each arrangement | positioning is equal. The patterned optically anisotropic layer according to the present embodiment has a structure in which the first retardation regions and the second retardation regions are alternately arranged in the order of the stripes, but is not limited to the stripe shape. Absent. Moreover, in this embodiment, the stripe may be formed in the longitudinal direction of the optical film, or may be formed in a direction perpendicular to the longitudinal direction.

  In the present invention, the first retardation region and the second retardation region are characterized in that at least one of the in-plane slow axis direction and the in-plane retardation is different from each other.

  In the present invention, it is preferable that at least the in-plane slow axis directions of the first retardation region and the second retardation region are different from each other. The slow axis of the first retardation region and the slow axis of the second retardation region are each ± 45 ° with respect to an arbitrary side of the optical film (preferably, a stripe formed by the retardation region). It is preferable. The in-plane slow axis direction of the first phase difference region and the second phase difference region preferably has an angle difference of 70 to 110 °, more preferably an angle difference of 80 to 100 °, and 90 °. More preferably, it has an angular difference.

The in-plane retardation Re (550) at a wavelength of 550 nm in the first retardation region and the second retardation region is preferably 110 to 160 nm, more preferably 120 to 170 nm, and 125 to 140 nm. More preferably it is.
The total of Rth of the transparent support and Rth of the patterned optically anisotropic layer preferably satisfies | Rth | ≦ 20 nm. For this purpose, the transparent support should satisfy −150 nm ≦ Rth (630) ≦ 100 nm. preferable.

In the optical film of the present invention, a black portion is preferably provided on at least one surface of the boundary line. FIG. 2 is an example showing an embodiment in which a black portion is provided, and the black portion 4 is provided so as to cover the boundary line 3 of the optically anisotropic layer 10. By providing the black portion, the viewing angle dependency of the crosstalk in the direction perpendicular to the longitudinal direction of the black portion is improved.
The width of the black portion is appropriately set from the viewpoint of the luminance and the viewing angle of the crosstalk, and is preferably 0.1 to 0.7 times the boundary line distance L, and is 0.3 to 0.5 times. More preferably.

The optical film of the present invention preferably has a polarizing film. FIG. 3 is a schematic cross-sectional view showing an example of an embodiment in which the optical film of the present invention has a polarizing film. In FIG. 3, 10 is a patterned optical anisotropic layer, 11 is a transparent support, 12 is an alignment film, 13 is a polarizing film, and 14 is a polarizing film protective film. Thus, by providing the polarizing film 13, for example, a viewing-side polarizing plate of the stereoscopic image display device of the present invention can be configured. The transparent support 12 is usually a polymer film, and a film having a small birefringence is preferable. By adopting such a film, for example, right circularly polarized light and left circularly polarized light can be accurately realized according to the pattern optical anisotropic layer.
The alignment film 11 is provided for aligning the liquid crystal compound when a liquid crystal compound is used for the patterned optically anisotropic layer 10. Therefore, it may not be necessary depending on the method of forming the patterned optically anisotropic layer 10.
In this embodiment, the polarizing film protective film 14 is provided only on one surface of the polarizing film 13. This is because in the present embodiment, the transparent support 12 of the patterned optically anisotropic layer 10 serves as the other polarizing film protective film. Of course, it goes without saying that a polarizing film protective film may also be provided on the other surface of the polarizing film 13.
Further, although not shown, it goes without saying that a constituent layer such as an adhesive layer may be included.

In the image display element, as shown in FIG. 4, a glass substrate 15, an adhesive layer, a protective film, and the like are disposed between the patterned optical anisotropic layer 10 and the color filter layer 16 in addition to the polarizing film. When there is a distance (D) between the patterned optically anisotropic layer and the color filter layer, the image is tilted in a direction not parallel to the boundary line 3 of the patterned optically anisotropic layer and observed. When this happens, crosstalk occurs. For example, when viewed from the direction of the dotted arrow in FIG. 4, the direction is parallel to the boundary line 3 of the pattern, and when viewed from the direction of the solid arrow, the direction is not parallel to the boundary line. In FIG. 4, some components such as the adhesive layer are not shown.
This crosstalk observed from an oblique direction can be reduced by sufficiently reducing the distance D between the pattern optical anisotropic layer and the color filter layer in the ratio of the distance L between the pattern boundary lines, and D / L Is preferably 2 or less, more preferably 1 or less, still more preferably 0.8 or less, and even more preferably 0.5 or less. Since the distance D is usually several hundred μm to several mm, in order to reduce D / L, the distance L of the pattern boundary line of the patterned optical anisotropic layer is preferably 1 mm or more, more preferably 2 mm or more. Further, it is more preferably 5 mm or more, still more preferably 10 mm or more, and particularly preferably 20 mm or more. Since the image quality deteriorates if the distance L between the pattern boundaries of the pattern optical anisotropic layer is too large, 50 mm or less is preferable.
Here, the D distance is the shortest distance between the average surface of the color filter 16 near the pattern optical anisotropic layer 10 and the average surface of the pattern optical anisotropic layer 10 near the color filter. say.

In the present invention, it is preferable that in-plane slow axes of the first retardation region and the second retardation region form an angle of ± 45 ° with the absorption axis of the polarizing film 13, respectively. With such a configuration, right-handed circularly polarized light and left-handed circularly polarized light can be accurately realized. FIG. 5 shows the relationship between the absorption axis of the polarizing film 13 and the in-plane slow axis of the optically anisotropic layer 10. The absorption axis of the polarizing film 13 and the surface of the optically anisotropic layer 10 are shown in FIG. Each inner slow axis forms an angle of ± 45 °.
When two optical films of the present invention are used in combination, the absorption axis of the polarizing film of one optical film is orthogonal to the stripe, and the absorption axis of the polarizing film of the other optical film is parallel to the stripe. It is preferable to set so. Details of this point will be described later.

  Hereinafter, preferable materials and manufacturing methods of the constituent layers of the present invention will be described. Needless to say, the optical film of the present invention is not limited thereto.

<Pattern optical anisotropic layer>
The patterned optically anisotropic layer in the present invention preferably forms each retardation region by using a liquid crystal composition (preferably a composition containing a discotic liquid crystal compound), and has the same liquid crystal as the main component. Each retardation region is preferably formed using a curable liquid crystal composition, and each retardation region is preferably formed by pattern exposure.

  More specifically, the first aspect of forming the patterned optically anisotropic layer uses a plurality of actions that affect the alignment control of the liquid crystal, and then performs any action by external stimulation (such as heat treatment). In this method, the predetermined orientation control action is made dominant by disappearing. For example, the liquid crystal is brought into a predetermined alignment state by a combined action of the alignment control ability by the alignment film and the alignment control ability of the alignment control agent added to the liquid crystal composition, and is fixed in one retardation region. After forming, by external stimulus (heat treatment, etc.), one of the actions (for example, the action by the alignment control agent) disappears, and the other orientation control action (the action by the alignment film) becomes dominant, thereby other An alignment state is realized and fixed to form another retardation region. For example, a predetermined pyridinium compound or imidazolium compound is unevenly distributed on the surface of the hydrophilic polyvinyl alcohol alignment film because the pyridinium group or imidazolium group is hydrophilic. In particular, if the pyridinium group is further substituted with an amino group that is a substituent of an acceptor of a hydrogen atom, intermolecular hydrogen bonds are generated with polyvinyl alcohol, and are unevenly distributed on the surface of the alignment film at a higher density. At the same time, due to the effect of hydrogen bonding, the pyridinium derivative is aligned in the direction orthogonal to the main chain of polyvinyl alcohol, so that the orthogonal alignment of the liquid crystal is promoted with respect to the rubbing direction. Since the pyridinium derivative has a plurality of aromatic rings in the molecule, a strong intermolecular π-π interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the alignment film of the discotic liquid crystal. Induces orthogonal orientation near the interface. In particular, when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect. However, the effect is that when heated above a certain temperature, the hydrogen bond is broken, the density of the pyridinium compound or the like on the surface of the alignment film is lowered, and the action disappears. As a result, the liquid crystal is aligned by the regulating force of the rubbing alignment film itself, and the liquid crystal is in a parallel alignment state. Details of this method are described in Japanese Patent Application No. 2010-141345, the contents of which are incorporated herein by reference.

  The second mode for forming the patterned optically anisotropic layer is a mode using a pattern alignment film. In this embodiment, pattern alignment films having different alignment control capabilities are formed, and a liquid crystal composition is disposed thereon to align the liquid crystal. The alignment of the liquid crystal is regulated by the respective alignment control ability of the pattern alignment film, thereby achieving different alignment states. By fixing each alignment state, a phase difference region pattern corresponding to the alignment film pattern is formed. The pattern alignment film can be formed using a printing method, mask rubbing for the rubbing alignment film, mask exposure for the photo alignment film, or the like. Alternatively, the alignment film can be formed uniformly, and an additive that affects the alignment control ability (for example, the onium salt or the like) can be separately printed in a predetermined pattern to form the pattern alignment film. A method using a printing method is preferable in that large-scale equipment is not required and manufacturing is easy. Details of this method are described in Japanese Patent Application No. 2010-173077, the contents of which are incorporated herein by reference.

Moreover, you may use the said 1st and 2nd aspect together. An example is an example in which a photoacid generator is added to the alignment film. In this example, two or more types of retardation regions can be formed by adding a photoacid generator in the alignment film and turning on / off the exposure amount (exposure intensity).
That is, pattern exposure forms a region where the photoacid generator is decomposed and an acidic compound is generated, and a region where the photoacid generator is not decomposed and an acidic compound is not generated. The photoacid generator remains almost undecomposed in the unirradiated portion, and the interaction between the alignment film material, the liquid crystal, and the alignment control agent added as required dominates the alignment state, and the liquid crystal has its slow axis. Is oriented in a direction perpendicular to the rubbing direction. When the alignment film is irradiated with light and an acidic compound is generated, the interaction is no longer dominant, the rubbing direction of the rubbing alignment film dominates the alignment state, and the liquid crystal has its slow axis parallel to the rubbing direction. Parallel orientation. As the photoacid generator used for the alignment film, a water-soluble compound is preferably used. Details of this method are described in Japanese Patent Application No. 2010-289360, the contents of which are incorporated herein by reference.

As the method for producing the optical film of the present invention, particularly preferably,
1) forming an alignment film comprising a composition containing at least one photoacid generator on a transparent support;
2) A step of irradiating the alignment film with light under a photomask to decompose a photoacid generator in the light irradiation region and generating an acidic compound in the light irradiation region;
3) A step of forming a coating film by applying a kind of composition mainly composed of a liquid crystal having a polymerizable group on the alignment film,
4) The slow axis of the liquid crystal on the light irradiation region of the alignment film is aligned in the first direction at the temperature T ₁ ° C., and the slow axis of the liquid crystal on the unirradiated region of the alignment film is different from the first direction. Step 5 for orienting in the second direction 5) A first phase difference region in which the in-plane slow axis directions are different from each other by advancing a polymerization reaction at a temperature T ₂ (where T ₁ > T ₂ ) ° C. Forming a patterned optically anisotropic layer including a second retardation region;
In this order.

  In the above method, it is preferable to use an alignment film that has been subjected to an alignment treatment in one direction for the formation of the patterned optically anisotropic layer, and it is particularly preferable to use an alignment film that has been subjected to a rubbing treatment or a photo-alignment treatment. Most preferably, the rubbed alignment film is used. The alignment treatment can be performed between 1) step and 2) step, or between 2) step and 3) step. It is preferable to carry out between 1) process and 2) process.

  The rubbing alignment film develops alignment control ability by rubbing treatment. Usually, when liquid crystal is aligned on an alignment film that has been rubbed in one direction, the liquid crystal is aligned with its slow axis parallel or orthogonal to the rubbing direction. The alignment state is determined by one or more kinds of alignment film material, liquid crystal, and alignment control agent. As will be described later, in the present invention, the rubbing direction is obtained by decomposing the alignment film material and / or changing the alignment film interface uneven distribution property of the alignment controller due to the effect of the acidic compound generated by the ultraviolet irradiation of the alignment film. Thus, an alignment state in which the slow axis of the liquid crystal is orthogonally aligned and an alignment state in which the slow axis of the liquid crystal is aligned in parallel with the rubbing direction are realized. The shape and arrangement of the first and second retardation regions can be changed to a desired shape and arrangement pattern by selecting a photomask used in the step 2). In the aspect used for the image display apparatus for stereoscopic image display, the first and second phase difference regions are in a strip shape in which the lengths of the short sides of each other are substantially equal, and are alternately and repeatedly patterned. preferable.

In the method of the present invention, the slow axis of the liquid crystal on the light irradiation region of the alignment film is aligned in the first direction, and the slow axis of the liquid crystal on the unirradiated region of the alignment film is different from the first direction. Orient in the second direction. At least one kind of photoacid generator is decomposed by light irradiation, and there is a difference in the ratio of acidic compounds generated by the decomposition between the light irradiated part and the light non-irradiated part, thereby causing a difference in the alignment control ability of the alignment film. You can have it. An example is as follows.
In the unirradiated part, the photoacid generator remains almost undecomposed, and the interaction between the alignment film material, the liquid crystal, and the alignment control agent added as required dominates the alignment state, and the liquid crystal has a slow axis. Oriented in a direction perpendicular to the rubbing direction. When the alignment film is irradiated with ultraviolet rays and acidic compounds are generated, the interaction is no longer dominant, the rubbing direction of the rubbing alignment film controls the alignment state, and the liquid crystal is parallel with its slow axis parallel to the rubbing direction. Orient. The conditions for achieving these states vary depending on the materials / amounts used and the irradiation conditions, and cannot be determined in general. In the present invention, generation and diffusion of acidic compounds occur, so environmental conditions such as temperature and humidity and the irradiation amount contribute to pattern accuracy. For example, the rubbing treatment and the liquid crystal coating and orientation process are preferably performed under high humidity conditions. Specifically, the humidity is particularly preferably 40% or more, and more preferably 60% or more. It is also a preferred embodiment that a small amount of water is added to the liquid crystal composition used for forming the optically anisotropic layer.

In the above example, the coating liquid used in step 3) contains an alignment film interface alignment control agent, and the acidic compound generated in the light irradiation region of the alignment film in step 2) or its constituent ions controls the alignment film interface alignment. A difference in alignment control ability may be provided between the light irradiation region and the light non-irradiation region of the alignment film by reducing the alignment film interface uneven distribution of the agent. When an onium salt is used as the alignment control agent for the alignment layer interface, the disc-shaped liquid crystal can be aligned with the disc surface perpendicular to the rubbing axis and the disc surface perpendicular to the layer surface (ie, orthogonal vertical alignment). it can. On the light-irradiated region of the alignment film, the alignment film interface alignment control agent is unevenly distributed at the alignment film interface, and the disk-like liquid crystal is orthogonally aligned vertically. On the light irradiation region of the alignment film, the alignment film interface control agent is The uneven distribution property of the alignment film interface is reduced by the acidic compound generated by the decomposition of the photoacid generator or the ions constituting it, and the action of the alignment film interface alignment control agent is weakened. As a result, the orientation control ability expressed by the rubbing process becomes dominant, and the disc-like liquid crystal is oriented with the disc surface parallel to the rubbing axis and the disc surface perpendicular to the layer surface, that is, parallel perpendicular. Transition to the alignment state.
In this embodiment, the decrease in the alignment film interface alignment property of the alignment film interface alignment control agent is caused by ion exchange between the ions constituting the alignment film interface alignment control agent and the constituent ions of the acidic compound generated in the light irradiation region. May occur. For example, in an example using an onium salt such as a pyridinium compound and an imidazolium compound as an alignment film interface alignment control agent, the onium salt is unevenly distributed on the alignment film interface by anion exchange between the onium salt and an acidic compound generated in the light irradiation region. Sex may be reduced.

In step 2), an acidic compound is generated by irradiating with ultraviolet rays under a photomask. As described above, since generation and diffusion of an acidic compound occur with the decomposition of the photoacid generator, ultraviolet rays are preferably used for irradiation under a photomask, and unpolarized ultraviolet rays are more preferably used. Preferably has a peak at 200~250nm the irradiation wavelength, it is preferable to use a UV-C light source, the exposure amount is preferably 5~1000mJ / cm ² approximately, 5 to 100 mJ / cm ² about More preferably, it is about 5-50 mJ / cm < ² >. If the exposure amount is too small, a pattern cannot be formed. On the other hand, when the exposure amount is too large, the pattern resolution decreases due to the diffusion of the acidic compound. In order to improve the pattern resolution, exposure at room temperature is preferable.
The light irradiation conditions can be appropriately set according to the composition of the alignment film composition and the like, and are not limited to the above conditions.

In the step 5), the alignment state is preferably fixed by advancing the polymerization reaction of the polymerizable liquid crystal by light irradiation (for example, ultraviolet irradiation). Irradiation energy is preferably ^{10mJ / cm 2 ~10J / cm 2} , further preferably 25~800mJ / cm ^2. Illuminance is preferably 10 to 1,000 / cm ^2, more preferably 20 to 500 mW / cm ^2, further preferably 40~350mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In order to accelerate the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions. The light source is preferably a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp) or short arc discharge lamp (super-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Used.
In addition, since the polymerization reaction for fixing the alignment state proceeds rapidly, the alignment state of the optically anisotropic layer can be obtained even if the entire surface is irradiated with light in step 5) and the photoacid generator is decomposed at that stage. There is no impact on

5) of the alignment state in the step fixed, a temperature T ₂ ° C., 4) in relation to the orientation temperature T ₁ ° C. of the liquid crystal process, carried out at a temperature which satisfies T _1> T _2. If this condition is satisfied, it is possible to fix the alignment state while suppressing disturbance of the alignment state. The preferable temperature ranges of T1 ° C. and T2 ° C. vary depending on the material to be selected. Generally, T ₁ ° C is about 50 to about 150 ° C, and T ₂ ° C is about 20 to about 120 ° C. The difference between T ₁ and T ₂ is preferably about 10 to about 100 ° C.

Alignment film:
By the steps 1) and 2), an alignment film capable of realizing a patterned optically anisotropic layer is formed. Furthermore, it is preferable to perform an alignment treatment in one direction between the step 1) and the step 2) or between the step 2) and the step 3). It is preferable to carry out between 1) process and 2) process. The alignment treatment is preferably a rubbing treatment. That is, it is preferable to use a rubbing alignment film.
The “rubbing alignment film” that can be used in the present invention means a film that has been processed by rubbing so as to have alignment ability of liquid crystal molecules. The rubbing alignment film has an alignment axis that regulates alignment of liquid crystal molecules, and the liquid crystal molecules are aligned according to the alignment axis. In the present invention, the liquid crystal molecules are aligned so that the slow axis of the liquid crystal is parallel to the rubbing direction in the ultraviolet irradiation portion of the alignment film, and the slow axis of the liquid crystal molecules is in the rubbing direction in the unirradiated portion. The material of the alignment film, the acid generator, the liquid crystal, and the alignment control agent are selected so as to be orthogonally aligned.

  The rubbing alignment film generally contains a polymer as a main component. The polymer material for alignment film is described in many documents, and many commercially available products can be obtained. The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred. Polyvinyl alcohols having various saponification degrees exist. In the present invention, those having a saponification degree of about 85 to 99 are preferably used. Commercial products may be used. For example, “PVA103”, “PVA203” (manufactured by Kuraray Co., Ltd.) and the like are PVA having the above saponification degree. For the rubbing alignment film, reference can be made to the modified polyvinyl alcohol described in WO01 / 88574A1, page 43, line 24 to page 49, line 8, and paragraph Nos. [0071] to [0095] of Japanese Patent No. 3907735. The thickness of the rubbing alignment film is preferably from 0.01 to 10 μm, and more preferably from 0.01 to 1 μm.

The rubbing treatment can be generally performed by rubbing the surface of a film containing a polymer as a main component several times in a certain direction with paper or cloth. A general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
As a method for changing the rubbing density, a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).

In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this.
Between the rubbing density and the pretilt angle of the alignment film, there is a relationship in which the pretilt angle decreases as the rubbing density increases and the pretilt angle increases as the rubbing density decreases.
In order to bond a long polarizing film with an absorption axis in the longitudinal direction, an alignment film is formed on a support made of a long polymer film, and the direction is 45 ° to the longitudinal direction. It is preferable to perform a rubbing treatment continuously to form a rubbing alignment film.

  If possible (for example, when light irradiation for decomposing the photoacid generator and light irradiation for developing the photo-alignment function can be performed separately), a photo-alignment film may be used.

Photoacid generator:
The alignment film according to the present invention contains at least one photoacid generator. The photoacid generator is a compound that decomposes upon irradiation with light such as ultraviolet rays to generate an acidic compound. When the photoacid generator is decomposed by light irradiation to generate an acidic compound, the alignment control ability of the alignment film changes. The change in the orientation control ability here is included in the alignment film and the composition for forming an optically anisotropic layer disposed on the orientation film, even if it is specified as a change in the orientation control ability of the orientation film alone. It may be specified as a change in the orientation control ability achieved by the additive or the like, or may be specified as a combination thereof.
A discotic (discotic) liquid crystal to be described later may be in an orthogonal vertical alignment state by adding an onium salt. When the acid generated by decomposition and the onium salt are anion-exchanged, the uneven distribution at the interface of the alignment film of the onium salt may be reduced, the orthogonal vertical alignment effect may be reduced, and a parallel vertical alignment state may be formed. For example, when the alignment film is a polyvinyl alcohol-based alignment film, the ester portion may be decomposed by the generated acid, and as a result, the alignment film interface uneven distribution of the onium salt may be changed.

As the photoacid generator used for the alignment film, a water-soluble compound is preferably used. Examples of photoacid generators that can be used include Prog. Polym. Sci. , 23, 1485 (1998).
As the photoacid generator, pyridinium salts, iodonium salts and sulfonium salts are particularly preferably used. Preferable examples of the pyridinium salt, iodonium salt, and sulfonium salt include salts represented by the following general formulas.

In the formula, each R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Or a halogen atom. Y is a straight-chain alkyl group or branched alkyl group having 1 to 6 carbon atoms, a straight-chain alkoxy group or branched alkoxy group having 1 to 6 carbon atoms. X- represents a counter anion of a pyridinium salt, an iodonium salt or a sulfonium salt, and becomes an anion of an acidic compound generated by decomposition. Preferably PF ₆ ^- or BF ₄ ^- is. For example, X- is BF ₄ ^- from a is a photoacid generator, the acid HBF ₄ is generated by the decomposition, X- is PF ₆ ^- from a is a photoacid generator, HPF ₆ is generated.

In the formula, each R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Or a halogen atom. Y is a straight-chain alkyl group or branched alkyl group having 1 to 6 carbon atoms, a straight-chain alkoxy group or branched alkoxy group having 1 to 6 carbon atoms. X- represents a counter anion of a pyridinium salt, an iodonium salt or a sulfonium salt, and becomes an anion of an acidic compound generated by decomposition. Preferably PF ₆ ^- or BF ₄ ^- is. For example, X- is BF ₄ ^- from a is a photoacid generator, the acid HBF ₄ is generated by the decomposition, X- is PF ₆ ^- from a is a photoacid generator, HPF ₆ is generated.

  Although the specific example of the photo-acid generator which can be utilized for this invention below is shown, it is not limited to these.

  The composition used for forming the alignment film is preferably prepared as a coating solution. The solvent used for the preparation of the coating preferably contains water, more preferably contains 20% by mass or more, more preferably 50-80% by mass of water. By using a coating solution prepared with a water-containing solvent, elution of the support by the solvent can be suppressed or controlled when coating on the support.

  The content of each component in the alignment film composition can be appropriately set so that a stable alignment film can be formed. For example, the content of the alignment layer polymer material as the main component is 2.0 to 10.0 mass%, preferably 2.0 to 5.0 mass%, based on the total amount of the composition (including the solvent). It can be. The addition amount of the photoacid generator can be appropriately set within a range in which ion exchange with the counter anion of the onium salt described above can be performed, for example, 0.1 to 10.0% by mass with respect to the polymer material for alignment film, Preferably it can be 0.5-5.0 mass%. Moreover, the solvent amount in a composition can be 80-98 mass% with respect to the total amount of a composition, for example, Preferably it can be 90-97 mass%.

Pattern optical anisotropic layer:
In the step 3), a kind of composition mainly composed of a liquid crystal having a polymerizable group, which is prepared as a coating solution, is applied to a surface such as a rubbing-treated surface of the alignment film. The coating method is not particularly limited, curtain coating method, dip coating method, spin coating method, printing coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, gravure coating method, A known coating method such as a wire bar method may be used.

  In the step 4), for example, the liquid crystal is aligned with the slow axis of the liquid crystal perpendicular to and parallel to the rubbing direction. Thereby, the directions of the first and second in-plane slow axes are determined, and the first and second phase difference regions having the in-plane slow axes perpendicular to each other are formed. Furthermore, the optical properties (Re and Rth) of the optically anisotropic layer are determined by the alignment state of the liquid crystal in these steps. The optically anisotropic layer is preferably a λ / 4 plate, that is, an optically anisotropic layer having a function of converting linearly polarized light into circularly polarized light. There are various methods for forming an optically anisotropic layer having a function as a λ / 4 plate. One example is a method of fixing the slow axis of a rod-like liquid crystal compound having a polymerizable group to a state where it is horizontally aligned on the layer surface, or a state where the disc surface of the discotic liquid crystal is aligned vertically to the layer surface. It is a method of immobilization. More preferred is a method of fixing the discotic liquid crystal in a vertically aligned state.

An example of the composition used for forming the optically anisotropic layer is a liquid crystal composition containing at least one liquid crystal compound having a polymerizable group and at least one alignment control agent. In addition, a polymerization initiator and a sensitizer may be contained.
Hereinafter, each material will be described in detail.

[Liquid crystal compound having a polymerizable group]
Examples of the liquid crystal that can be used as the main raw material of the optically anisotropic layer of the present invention include rod-shaped liquid crystals and discotic liquid crystals. preferable.
Examples of the rod-like liquid crystal include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, World Patents (WO) 95/22586, 95/24455. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, No. 7-110469, No. 11-80081, No. 11-513019 And compounds described in each publication and specification such as Japanese Patent Application No. 2001-64627.

The low molecular rod-like liquid crystal compound is preferably a compound represented by the following general formula (X).
Formula (X)
^{Q 1 -L 1 -Cy 1 -L 2} - (Cy 2 -L 3) n -Cy 3 -L 4 -Q 2
In the formula, Q ¹ and Q ² each independently represent a polymerizable group, L ¹ and L ⁴ each independently represent a divalent linking group, and L ² and L ³ each independently represent a single bond or a divalent group. Represents a linking group, Cy ¹ , Cy ² and Cy ³ each independently represent a divalent cyclic group, and n is 0, 1 or 2.

In the formula, Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction.

  As the discotic liquid crystal that can be used as the main raw material of the optically anisotropic layer of the present invention, a compound having a polymerizable group is preferable as described above.

[Discotic liquid crystal compound]
Examples of discotic liquid crystal compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), azacrown type and phenylacetylene type macrocycles are included.

The discotic liquid crystal compound exhibits liquid crystallinity with a structure in which a linear alkyl group, an alkoxy group, or a substituted benzoyloxy group is radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule. Also included are compounds. The molecule or the assembly of molecules is preferably a compound having rotational symmetry and imparting a certain orientation.
When an optically anisotropic layer is formed from a discotic liquid crystal compound, the compound finally contained in the optically anisotropic layer no longer needs to exhibit liquid crystallinity. For example, a low-molecular discotic liquid crystal compound has a group that reacts with heat or light, and the group reacts with heat or light to polymerize or crosslink, thereby increasing the molecular weight. In the case where an optical layer is formed, the compound contained in the optically anisotropic layer may no longer have liquid crystallinity.

  Preferred examples of the discotic liquid crystal compound include paragraph number [0052] in JP-A-8-50206 and JP-A-2006-76992, and paragraph number [0040] in JP-A-2007-2220. To [0063]. For example, the compounds represented by the following general formulas (DI) and (DII) are preferable because they exhibit high birefringence. Further, among the compounds represented by the following general formulas (DI) and (DII), compounds showing discotic liquid crystallinity are preferable, and compounds showing a discotic nematic phase are particularly preferable. Details of the following compounds (definition of symbols in the formula and preferred ranges thereof) are specifically described in the above publication.

  In addition, preferable examples of the discotic liquid crystal compound include compounds described in JP-A-2005-301206.

[Onium salt compound (alignment control agent on alignment film)]
In the present invention, as described above, an onium salt is preferably added in order to realize vertical alignment of a liquid crystal compound having a polymerizable group, particularly a discotic liquid crystal having a polymerizable group. The onium salt is unevenly distributed at the alignment film interface and acts to increase the tilt angle of the liquid crystal molecules in the vicinity of the alignment film interface.

As the onium salt, a compound represented by the following general formula (1) is preferable.
General formula (1)
Z- (YL-) _n Cy ⁺ .X-
In the formula, Cy represents a 5- or 6-membered onium group, and L, Y, Z, and X represent L ²³ , L ²⁴ , Y ²² , Y ²³ , Z ²¹ , and X in the general formula (II) described later. It is synonymous, the preferable range is also the same, and n represents an integer of 2 or more.

  The 5- or 6-membered onium group (Cy) is preferably a pyrazolium ring, an imidazolium ring, a triazolium ring, a tetrazolium ring, a pyridinium ring, a pyrazinium ring, a pyrimidinium ring, or a triazinium ring, and particularly preferably an imidazolium ring or a pyridinium ring.

The 5- or 6-membered onium group (Cy) preferably has a group having an affinity for the alignment film material. The onium salt compound has a high affinity with the alignment film material at the portion where the acid generator is not decomposed (unexposed portion) and is unevenly distributed at the alignment film interface. On the other hand, in the portion where the acid generator is decomposed and an acidic compound is generated (exposed portion), the anion of the onium salt is ion-exchanged, the affinity is lowered, and the uneven distribution at the alignment film interface is lowered. Since the hydrogen bond can be in a bonded state or a state in which the bond has disappeared within the actual temperature range for aligning the liquid crystal (room temperature to about 150 ° C.), it is preferable to use the affinity due to the hydrogen bond. . However, it is not limited to this example.
For example, in an embodiment in which polyvinyl alcohol is used as the alignment film material, it preferably has a hydrogen bonding group in order to form a hydrogen bond with the hydroxyl group of polyvinyl alcohol. As a theoretical interpretation of hydrogen bonding, for example, H.H. Unneyama and K.M. There are reports in Morokuma, Journal of American Chemical Society, Vol. 99, pp. 1316-1332, 1977. Specific examples of hydrogen bonding include J.I. N. Examples include Israes Ativiri, Yasuo Kondo, Hiroyuki Oshima, Intermolecular Force and Surface Force, McGraw Hill, 1991, page 98, FIG. Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angewent Chemistry International Edition England, Vol. 34, p. 2311, 1995.

In addition to the hydrophilic effect of the onium group, the 5- or 6-membered onium group having a hydrogen bonding group enhances the surface unevenness of the alignment film interface by hydrogen bonding to the polyvinyl alcohol, and the polyvinyl alcohol main chain Promotes the function of imparting orthogonal orientation to the. Preferred hydrogen-bonding groups include amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl groups, benzimidazolyl groups, Pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil group, barbituric acid group And hydantoin group, maleic hydrazide group, isatin group, uramil group and the like. More preferred hydrogen bonding groups include amino groups and pyridyl groups.
For example, it is also preferable that a 5- or 6-membered onium ring contains an atom having a hydrogen bonding group, such as a nitrogen atom of an imidazolium ring.

  n is preferably an integer of 2 to 5, more preferably 3 or 4, and particularly preferably 3. A plurality of L and Y may be the same as or different from each other. When n is 3 or more, the onium salt represented by the general formula (1) has three or more 5- or 6-membered rings, so that the discotic liquid crystal has a strong intermolecular π-π interaction. Therefore, the vertical alignment of the discotic liquid crystal, particularly the orthogonal vertical alignment with respect to the polyvinyl alcohol main chain can be realized on the polyvinyl alcohol alignment film.

The onium salt represented by the general formula (1) is particularly preferably a pyridinium compound represented by the following general formula (2a) or an imidazolium compound represented by the following general formula (2b).
The compounds represented by the general formulas (2a) and (2b) are added mainly for the purpose of controlling the alignment at the alignment film interface of the discotic liquid crystal represented by the general formulas (I) to (IV). In addition, there is an effect of increasing the tilt angle in the vicinity of the alignment film interface of the molecules of the discotic liquid crystal.

In the formula, L ²³ and L ²⁴ each represent a divalent linking group.
L ²³ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH—, —N═. N-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O- CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO-AL-CO-O-. And AL is an alkylene group having 1 to 10 carbon atoms. L ²³ represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO- AL-CO-O- is preferable, a single bond or -O- is more preferable, and -O- is most preferable.

L ²⁴ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH— or —N═. N- is preferred, and -O-CO- or -CO-O- is more preferred. When m is 2 or more, it is more preferable that the plurality of L ²⁴ are alternately —O—CO— and —CO—O—.

R ²² is a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 1 to 20 carbon atoms.
When R ²² is a dialkyl-substituted amino group, two alkyl groups may be bonded to each other to form a nitrogen-containing heterocycle. The nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring. R ²³ is more preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 12 carbon atoms, and a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted group having 2 to 8 carbon atoms. Even more preferred is an amino group. When R ²³ is an unsubstituted amino group or a substituted amino group, the 4-position of the pyridinium ring is preferably substituted.

X is an anion.
X is preferably a monovalent anion. Examples of anions include halide ions (fluorine ions, chlorine ions, bromine ions, iodine ions) and sulfonate ions (eg, methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions).

Y ²² and Y ²³ are each a divalent linking group having a 5- or 6-membered ring as a partial structure.
The 5- or 6-membered ring may have a substituent. Preferably, at least one of Y ²² and Y ²³ is a divalent linking group having a 5- or 6-membered ring having a substituent as a partial structure. Y ²² and Y ²³ are preferably each independently a divalent linking group having a 6-membered ring which may have a substituent as a partial structure. The 6-membered ring includes an aliphatic ring, an aromatic ring (benzene ring) and a heterocyclic ring. Examples of the 6-membered aliphatic ring include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring. Examples of 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. Including. Another 6-membered ring or 5-membered ring may be condensed to the 6-membered ring.
Examples of the substituent include a halogen atom, cyano, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms. The substituent is preferably an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms. The number of substituents may be 2 or more. For example, when Y ²² and Y ²³ are a phenylene group, the number of carbon atoms of 1 to 4 is 1 to 12 (more preferably 1 to 6, more preferably 1 to The alkyl group of 3) may be substituted.

Here, m is 1 or 2, and is preferably 2. When m is 2, the plurality of Y ²³ and L ²⁴ may be the same as or different from each other.

Z ²¹ is halogen-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, phenyl substituted with an alkyl group having 1 to 10 carbon atoms, phenyl substituted with an alkoxy group having 2 to 10 carbon atoms, carbon atom An alkyl group having 1 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and 7 to 26 carbon atoms And a monovalent group selected from the group consisting of an arylcarbonyloxy group having 7 to 26 carbon atoms.
When m is 2, Z ²¹ is preferably cyano, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and is an alkoxy group having 4 to 10 carbon atoms. Is more preferable.
When m is 1, Z ²¹ is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an acyl-substituted alkyl group having 7 to 12 carbon atoms, or 7 carbon atoms. It is preferably an acyl-substituted alkoxy group of -12, an acyloxy-substituted alkyl group having 7-12 carbon atoms, or an acyloxy-substituted alkoxy group having 7-12 carbon atoms.

  The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

p is an integer of 1-10. It is particularly preferable that p is 1 or 2. C _p H _2p means a chain alkylene group which may have a branched structure. C _p H _2p is preferably a linear alkylene group (— (CH ₂ ) _p —).

In the formula (2b), R ³⁰ is a hydrogen atom or an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.

  Among the compounds represented by the formula (2a) or (2b), compounds represented by the following formula (2a ′) or (2b ′) are preferable.

In the formulas (2a ′) and (2b ′), the same symbols as those in the formula (2) have the same meaning, and the preferred ranges are also the same. L ²⁵ has the same meaning as L ²⁴ , and the preferred range is also the same. L ²⁴ and L ²⁵ are preferably —O—CO— or —CO—O—, L ²⁴ is preferably —O—CO—, and L ²⁵ is preferably —CO—O—.

R ²³ , R ²⁴ and R ²⁵ are each an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, more preferably 1 to 3). n ₂₃ is 0-4, n ₂₄ is 1 to 4, and n ₂₅ represents 0 to 4. In n ₂₃ and n ₂₅ is 0, n ₂₄ is preferably a 1-4 (more preferably 1-3).
R ³⁰ is preferably an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, more preferably 1 to 3).

  Specific examples of the compound represented by the general formula (1) include compounds described in [0058] to [0061] in JP-A-2006-113500.

Specific examples of the compound represented by the general formula (1) are shown below. However, the anion (X ⁻ ) was omitted in the following formula.

The compounds of the formulas (2a) and (2b) can be produced by a general method. For example, the pyridinium derivative of the formula (2a) is generally obtained by alkylating the pyridine ring (Menstokin reaction).
The addition amount of the onium salt does not exceed 5% by mass with respect to the liquid crystal compound, and is preferably about 0.1 to 2% by mass.

The onium salts represented by the general formulas (2a) and (2b) are unevenly distributed on the hydrophilic polyvinyl alcohol alignment film surface because the pyridinium group or the imidazolium group is hydrophilic. In particular, a pyridinium group is further substituted with an amino group which is a substituent of an acceptor of a hydrogen atom (in the general formulas (2a) and (2a ′), R ²² is an unsubstituted amino group or a carbon atom having 1 to 20 carbon atoms) When the amino group is substituted, intermolecular hydrogen bonds are generated with the polyvinyl alcohol, and it is unevenly distributed on the surface of the alignment film at a higher density, and due to the effect of the hydrogen bonds, the pyridinium derivative is a main chain of the polyvinyl alcohol. Alignment in a direction orthogonal to the direction of the liquid crystal promotes the orthogonal alignment of the liquid crystal with respect to the rubbing direction. Since the pyridinium derivative has a plurality of aromatic rings in the molecule, a strong intermolecular π-π interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the alignment film of the discotic liquid crystal. Induces orthogonal orientation near the interface. In particular, as represented by the general formula (2a ′), when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect.

  Further, when the onium salts represented by the general formulas (2a) and (2b) are used in combination, an anion exchange is performed with an acidic compound released from the photoacid generator by photolysis, and the hydrogen bond strength and hydrophilicity of the onium salt are changed. Changes, the uneven distribution at the interface of the alignment film is lowered, and the liquid crystal is aligned with its slow axis parallel to the rubbing direction to promote parallel alignment. This is because the onium salt is uniformly dispersed in the alignment film by salt exchange, the density on the surface of the alignment film is lowered, and the liquid crystal is aligned by the regulating force of the rubbing alignment film itself.

[Fluoroaliphatic group-containing copolymer (air interface orientation control agent)]
The fluoroaliphatic group-containing copolymer is added for the purpose of controlling the orientation of the liquid crystal at the air interface, and has the effect of increasing the tilt angle near the air interface of the liquid crystal molecules. Furthermore, applicability such as unevenness and repellency is also improved.
Examples of the fluoroaliphatic group-containing copolymer that can be used in the present invention include JP-A Nos. 2004-333852, 2004-333863, 2005-134484, 2005-179636, and 2005-181977. It can be used by selecting from the compounds described in each publication and specification. Particularly preferably, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy described in JP-A Nos. 2005-179636 and 2005-181977 and the specification thereof. {-OP (= O) (OH) ₂ }} and a polymer containing one or more hydrophilic groups selected from the group consisting of salts thereof in the side chain.
The addition amount of the fluoroaliphatic group-containing copolymer does not exceed 2% by mass relative to the liquid crystal compound, and is preferably about 0.1 to 1% by mass.

The fluoroaliphatic group-containing copolymer increases the uneven distribution at the air interface due to the hydrophobic effect of the fluoroaliphatic group, and provides a low surface energy field on the air interface side, and tilts liquid crystals, particularly discotic liquid crystals. The corner can be increased. And one or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy {—OP (═O) (OH) ₂ }} and salts thereof; In the side chain, a vertical alignment of the liquid crystal compound can be realized by charge repulsion between these anions and π electrons of the liquid crystal.

[solvent]
The composition used for forming the optically anisotropic layer is preferably prepared as a coating solution. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Polymerization initiator]
A composition containing a liquid crystal compound having a polymerizable group (for example, a coating solution) is brought into an alignment state exhibiting a desired liquid crystal phase, and then the polymerization reaction proceeds to fix the alignment state (of the above method). 5) Step). The immobilization is preferably performed by a polymerization reaction of a reactive group introduced into the liquid crystal compound. It is preferable to fix by a photopolymerization reaction by ultraviolet irradiation. The photopolymerization reaction may be either radical polymerization or cationic polymerization. Examples of radical photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Aciloin compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970). Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.

[Sensitizer]
In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like. Multiple photopolymerization initiators may be combined, and the amount used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. The light irradiation for the polymerization of the liquid crystal compound preferably uses ultraviolet rays.

[Other additives]
Apart from the polymerizable liquid crystal compound, the composition may contain a non-liquid crystalline polymerizable monomer. As the polymerizable monomer, a compound having a vinyl group, a vinyloxy group, an acryloyl group or a methacryloyl group is preferable. Note that it is preferable to use a polyfunctional monomer having two or more polymerizable reactive functional groups, for example, ethylene oxide-modified trimethylolpropane acrylate because durability is improved. Since the non-liquid crystalline polymerizable monomer is a non-liquid crystalline component, the addition amount thereof does not exceed 40 mass% with respect to the liquid crystal compound, and is preferably about 0 to 20 mass%.

  The thickness of the optically anisotropic layer formed in this manner is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

<Polarizing film>

  The optical film of the present invention preferably has a polarizing film. The polarizing film is preferably bonded to the surface of the optically anisotropic layer film (transparent support side surface) and the surface of the polarizing film. The rubbing direction of the alignment film of the retardation film of the present invention and the transmission axis of the polarizing film The crossing angle is preferably approximately 90 degrees and pasted. There is no need to be strictly 0 degrees, and an error of about ± 5 degrees that is allowed in manufacturing does not affect the effect of the present invention and is allowed. Further, as described above, a polarizing film protective film such as a cellulose acylate film is preferably bonded to the other surface of the polarizing film.

  Examples of the polarizing film include an iodine-based polarizing film, a dye-based polarizing film using a dichroic dye, and a polyene-based polarizing film, and any of them may be used in the present invention. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. For the method for producing the polarizing film, for example, the description of JP-A-2011-128584 can be referred to.

<Polarizing film protective film>
It is preferable to use a transparent polymer film for the protective film bonded to the surface of the polarizing film. “Transparent” means that the light transmittance is 80% or more. As the protective film, a cellulose acylate film, a polyolefin film containing polyolefin, and an acrylic film are preferable. Among the cellulose acylate films, a cellulose triacetate film is preferable. Of the polyolefin films, a polynorbornene film containing a cyclic polyolefin is preferable. The thickness of the protective film is preferably 20 to 500 μm, and more preferably 40 to 100 μm.

<Transparent support>
The optical film of the present invention has a transparent support. As the transparent support, it is preferable to use a member having little in-plane and thickness direction retardation.

  As a material for forming a transparent support that can be used in the present invention, a polymer excellent in optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, and the like is preferable. Any material may be used as long as it satisfies the above-described formula (I). Examples include polycarbonate polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin). Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfone polymers , Polyether ether ketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or polymers mixed with the above polymers Take an example. The polymer film of the present invention can also be formed as a cured layer of an ultraviolet-curable or thermosetting resin such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

  As a material for forming the transparent support, a thermoplastic norbornene resin can be preferably used. Examples of the thermoplastic norbornene-based resin include ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., and ARTON manufactured by JSR Corporation.

In addition, as a material for forming the transparent support, a cellulose polymer represented by triacetyl cellulose (hereinafter referred to as cellulose acylate), which has been conventionally used as a transparent protective film of a polarizing plate, is preferably used. I can do it.
Hereinafter, cellulose acylate will be described in detail mainly as an example of the transparent support, but it is obvious that the technical matters can be applied to other polymer films as well.

  Examples of cellulose as a cellulose acylate raw material include cotton linter and wood pulp (hardwood pulp, softwood pulp). Cellulose acylate obtained from any raw material cellulose can be used, and in some cases, a mixture may be used. Details of these raw material celluloses are, for example, the plastic material course (17) Fibrous resin (manufactured by Marusawa and Uda, Nikkan Kogyo Shimbun, published in 1970) and the Japan Institute of Technology Open Technical Report 2001-1745 (7-8 However, the present invention is not limited to the description.

  Cellulose acylate is obtained by acylating a hydroxyl group of cellulose, and the substituent can be any acetyl group having 2 carbon atoms in the acyl group to those having 22 carbon atoms. In the cellulose acylate of the present invention, the degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of binding of acetic acid and / or a fatty acid having 3 to 22 carbon atoms substituted with a hydroxyl group of cellulose is measured and substituted by calculation. You can get a degree. As a measuring method, it can carry out according to ASTM D-817-91.

  The degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of acyl substitution with a hydroxyl group of cellulose is preferably 2.50 to 3.00. Furthermore, the degree of substitution is preferably 2.75 to 3.00, and more preferably 2.85 to 3.00.

  Among the acetic acid and / or the fatty acid having 3 to 22 carbon atoms substituted for the hydroxyl group of cellulose, the acyl group having 2 to 22 carbon atoms may be an aliphatic group or an aromatic group, and is not particularly limited. It may be a mixture of more than one type. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. These preferred acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, Examples include oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl groups. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferable, and acetyl, propionyl and butanoyl are more preferable.

  Among the acyl substituents substituted on the hydroxyl group of cellulose described above, in the case of substantially consisting of at least two types of acetyl group / propionyl group / butanoyl group, the degree of substitution is 2.50 to 3.00. The optical anisotropy of the cellulose acylate film can be reduced. A more preferable degree of acyl substitution is 2.60 to 3.00, and more preferably 2.65 to 3.00. In addition, when the acyl substituent substituted for the hydroxyl group of cellulose consists only of acetyl groups, in addition to being able to reduce the optical anisotropy of the film, it is further compatible with additives and soluble in organic solvents to be used. From the viewpoint, the degree of substitution is preferably 2.80 to 2.99, more preferably 2.85 to 2.95.

The degree of polymerization of cellulose acylate is preferably 180 to 700 in terms of viscosity average degree of polymerization. In cellulose acetate, 180 to 550 is more preferable, 180 to 400 is further preferable, and 180 to 350 is particularly preferable. When the degree of polymerization is too high, the viscosity of the cellulose acylate dope solution becomes high, and film production becomes difficult due to casting. If the degree of polymerization is too low, the strength of the produced film will decrease. The average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Society, Vol. 18, No. 1, pages 105-120, 1962). This is described in detail in JP-A-9-95538.
Further, the molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) is small, and molecular weight distribution. Is preferably narrow. The specific value of Mw / Mn is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and most preferably 1.0 to 1.6. preferable.

  When the low molecular component is removed, the average molecular weight (degree of polymerization) increases, but the viscosity becomes lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent. In addition, when manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is within the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. When used in the production of the cellulose acylate of the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. . In general, cellulose acylate contains water and is known to have a moisture content of 2.5 to 5% by mass. In order to obtain the moisture content of cellulose acylate, it is necessary to dry the cellulose acylate, and the method is not particularly limited as long as the desired moisture content is achieved. The method for synthesizing these cellulose acylates of the present invention is described in detail on pages 7 to 12 in the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention). .

  Cellulose acylate can be used by mixing two or more different types of cellulose acylate as long as the substituent, substitution degree, polymerization degree, molecular weight distribution and the like are within the above-mentioned ranges.

For the production of a film used as a support, together with cellulose acylate, various additives (for example, compounds that reduce optical anisotropy, wavelength dispersion adjusting agents, fine particles, plasticizers, UV inhibitors, deterioration inhibitors, Release agents, optical property modifiers, etc.) can be used, and these are described below. Moreover, the addition time may be any in the dope preparation process (the preparation process of the cellulose acylate solution), but a step of adding and preparing an additive may be performed at the end of the dope preparation process.
By adjusting the addition amount of these additives, a cellulose acylate film satisfying 0 ≦ Re (550) ≦ 10 can be produced. By using the film as a support, the optical properties of the support can be improved. The Re of all the first and second retardation regions contained in the optical film of the present invention can be in the range of 110 nm ≦ Re (550) ≦ 165 nm with little influence. The Re value is preferably 120 ≦ Re (550) ≦ 145, and particularly preferably 130 ≦ Re (550) ≦ 145.

  Further, in relation to the optically anisotropic layer described later, since the total of Rth of the transparent support and Rth of the optically anisotropic layer (λ / 4 plate) satisfies | Rth | ≦ 20 nm, the transparent support Preferably satisfies −150 nm ≦ Rth (630) ≦ 100 nm.

It is a preferable embodiment that contains at least one compound that lowers the optical anisotropy of the cellulose acylate film.
The compound that reduces the optical anisotropy of the cellulose acylate film will be described. Optical anisotropy can be reduced by using a compound that suppresses the orientation of cellulose acylate in the film in the plane and in the film thickness direction. The compound that lowers the optical anisotropy is sufficiently compatible with cellulose acylate, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, when a plurality of planar functional groups such as aromatic groups are provided, a structure having these functional groups in a non-planar rather than the same plane is advantageous.

In order to produce a cellulose acylate film having a low retardation, among the compounds that reduce the optical anisotropy by inhibiting the cellulose acylate in the film from being oriented in the plane and in the film thickness direction as described above. A compound having an octanol-water partition coefficient (log P value) of 0 to 7 is preferred. A compound having a log P value of more than 7 is poor in compatibility with cellulose acylate, and tends to cause film turbidity or powder blowing. In addition, a compound having a log P value of less than 0 has high hydrophilicity, and thus may deteriorate the water resistance of the cellulose acetate film. A more preferable range for the logP value is 1 to 6, and a particularly preferable range is 1.5 to 5.
The octanol-water partition coefficient (log P value) can be measured by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29,). 163 (1989).), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984).) And the like are preferably used, but the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987). When the log P value of a certain compound varies depending on the measurement method or calculation method, it is preferable to determine whether or not the compound is within the range by the Crippen's fragmentation method. In addition, the value of logP described in this specification is determined by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

The compound that decreases the optical anisotropy may or may not contain an aromatic group. The compound that reduces the optical anisotropy preferably has a molecular weight of 150 or more and 3000 or less, more preferably 170 or more and 2000 or less, and particularly preferably 200 or more and 1000 or less. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.
The compound that reduces optical anisotropy is preferably a liquid at 25 ° C. or a solid having a melting point of 25 to 250 ° C., more preferably a liquid at 25 ° C. or a melting point of 25 to 200. C solid. Moreover, it is preferable that the compound which reduces optical anisotropy does not volatilize in the process of dope casting and drying of cellulose acylate film production.
The amount of the compound that reduces optical anisotropy is preferably 0.01 to 30% by mass, more preferably 1 to 25% by mass, and 5 to 20% by mass with respect to cellulose acylate. It is particularly preferred.
The compound that decreases the optical anisotropy may be used alone, or two or more compounds may be mixed and used in an arbitrary ratio.
The timing for adding the compound for reducing the optical anisotropy may be any time during the dope preparation process, or may be performed at the end of the dope preparation process.

  The compound that reduces the optical anisotropy is such that the average content of the compound in the portion from the surface on at least one side to 10% of the total film thickness is the average content of the compound in the center of the cellulose acylate film. 80-99% of the rate. The amount of the compound present can be determined, for example, by measuring the amount of the compound at the surface and in the center by a method using an infrared absorption spectrum described in JP-A-8-57879.

  Specific examples of the compound that reduces the optical anisotropy of the cellulose acylate film include, for example, the compounds described in [0035] to [0058] of JP-A-2006-199855, but are limited to these compounds. Is not to be done.

  Since the optical film of the present invention is arranged on the viewing side, it is easily affected by external light, particularly ultraviolet rays. Therefore, it is desirable to add an ultraviolet (UV) absorber to a polymer film or the like used as a transparent support.

  Among these, UV absorbers are compounds that have absorption in the ultraviolet region of 200 to 400 nm and reduce both | Re (400) -Re (700) | and | Rth (400) -Rth (700) | Preferably, it is good to use 0.01-30 mass% with respect to cellulose acylate solid content.

  In recent years, liquid crystal display devices such as televisions, notebook personal computers, and mobile portable terminals have been required to have excellent transmittance of optical members used in liquid crystal display devices in order to increase luminance with less power. In that respect, a compound having absorption in the ultraviolet region of 200 to 400 nm and reducing | Re (400) -Re (700) | and | Rth (400) -Rth (700) | When it is added, it is required that the spectral transmittance is excellent. In the cellulose acylate film of the present invention, the spectral transmittance at a wavelength of 380 nm is preferably 45% to 95%, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less.

  The UV absorber preferably has a molecular weight of 250 to 1000 from the viewpoint of volatility. More preferably, it is 260-800, More preferably, it is 270-800, Most preferably, it is 300-800. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.

  It is preferable that the UV absorber does not volatilize during the dope casting and drying process for producing the cellulose acylate film.

  Specific examples of the UV absorber for the cellulose acylate film include the compounds described in JP-A-2006-199855, [0059] to [0135].

  It is preferable to add fine particles as a matting agent to the cellulose acylate film. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable. The silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. Those having an average primary particle size as small as 5 to 16 nm are more preferred because they can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.

  These fine particles usually form secondary particles having an average particle diameter of 0.1 to 3.0 μm, and these fine particles are present as aggregates of primary particles in the film, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle size is preferably from 0.2 to 1.5 μm, more preferably from 0.4 to 1.2 μm, and most preferably from 0.6 to 1.1 μm. The primary and secondary particle sizes were determined by observing the particles in the film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

  As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and the coefficient of friction is maintained while keeping the turbidity of the optical film low. It is particularly preferable because it has a great effect of reducing the effect.

In order to obtain a cellulose acylate film having particles having a small secondary average particle size in the present invention, several methods are conceivable when preparing a fine particle dispersion. For example, a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and this fine particle dispersion is added to a small amount of a cellulose acylate solution separately prepared and stirred and dissolved. Further, a main cellulose acylate solution (dope solution) There is a way to mix. This method is a preferred preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser to make this fine particle additive solution, and mix this fine particle additive solution with the dope solution using an in-line mixer. There is also a way to do it. Although not limited to these methods, the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20% by mass. Most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent fine particles in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, more preferably 0.08 to 0.16 g per m ^3. Is most preferred.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  For the cellulose acylate film, in addition to the compound that optically reduces anisotropy and the UV absorber, various additives (for example, a plasticizer, an ultraviolet ray inhibitor, a deterioration inhibitor, and a release agent) depending on the application. , Infrared absorbers, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, as an infrared absorber, it describes in Unexamined-Japanese-Patent No. 2001-194522, for example. Further, the addition time may be any time in the dope production process, but it is preferable to add an additive at the end of the dope production process. Furthermore, the amount of each additive added is not particularly limited as long as the function is exhibited. Moreover, when a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, although it describes in Unexamined-Japanese-Patent No. 2001-151902 etc., these are techniques conventionally known. For these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.

  As for the plasticizer, some of the examples described later do not have a plasticizer added, but compounds that optically reduce anisotropy are compounds that exert an effect as a plasticizer. It goes without saying that in some cases it is not necessary to add a plasticizer.

  The cellulose acylate film is preferably produced by a solution casting method using a cellulose acylate solution. The method for dissolving the cellulose acylate solution (dope) is not particularly limited, and may be room temperature, and further, a cooling dissolution method or a high temperature dissolution method, and further a combination thereof. Regarding the preparation of the cellulose acylate solution, and further the steps of solution concentration and filtration accompanying the dissolving step, 22 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Institute of Invention). Production processes described in detail on pages 25 to 25 are preferably used.

  The dope transparency of the cellulose acylate solution is preferably 85% or more. More preferably, it is 88% or more, and more preferably 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose acylate dope solution. As a specific method for calculating the dope transparency, the dope solution was poured into a 1 cm square glass cell, and the absorbance at 550 nm was measured with a spectrophotometer (UV-3150, Shimadzu Corporation). Only the solvent was measured in advance as a blank, and the transparency of the cellulose acylate solution was calculated from the ratio with the absorbance of the blank.

As the method and equipment for producing the cellulose acylate film, a solution casting film forming method and a solution casting film forming apparatus used for producing a conventional cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. The both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder. Wind up to a predetermined length. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film as an optical member for an electronic display, which is the main use of the cellulose acylate film of the present invention, in addition to the solution casting film forming apparatus, the undercoat layer In many cases, a coating apparatus is added for surface processing of a film such as an antistatic layer, an antihalation layer, or a protective layer. These are described in detail on pages 25 to 30 in the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Inventions). Including), metal support, drying, peeling and the like, and can be preferably used in the present invention.
Moreover, 10-120 micrometers is preferable, as for the thickness of a cellulose acylate film, 20-100 micrometers is more preferable, and 30-90 micrometers is still more preferable.

  An example of the polymer film used as the transparent support is a low retardation film having Re of 0 to 10 nm and an absolute value of Rth of 20 nm or less.

[Humidity expansion coefficient]
The humidity expansion coefficient of the polymer film can be appropriately set depending on the combination with the thermal expansion coefficient, but is preferably 3.0 × 10 ^{−6 to} 500 × 10 ⁻⁶ /% RH, and 4.0 × 10. ^{−6 to} 100 × 10 ⁻⁶ /% RH is more preferable, 5.0 × 10 ⁻⁶ to 50 × 10 ⁻⁶ /% RH is more preferable, and 5.0 × 10 ⁻⁶ to 40 × 10 ⁻⁶ /%. RH is most preferred.
The thermal expansion coefficient can be measured according to ISO11359-2, and is calculated from the slope of the film length when the sample is heated from room temperature to 80 ° C. and then cooled from 60 ° C. to 50 ° C. can do.
When measuring the humidity expansion coefficient, a film sample having a length of 25 cm (measurement direction) and a width of 5 cm cut out with the direction in which the modulus of elasticity is maximized as the longitudinal direction is prepared, and pinned to the sample at intervals of 20 cm. After making holes and adjusting the humidity for 24 hours at 25 ° C. and 10% relative humidity, the distance between the pin holes is measured with a pin gauge (measured value is L ₀ ). Next, the sample is conditioned at 25 ° C. and a relative humidity of 80% for 24 hours, and the distance between the pin holes is measured with a pin gauge (measured value is L ₁ ). The humidity expansion coefficient is calculated by the following formula using these measured values.
Humidity expansion coefficient [/% RH] = {(L ₁ −L ₀ ) / L ₀ } / (R ₁ −R ₀ )

[Elastic modulus]
Although the elasticity modulus of the said polymer film is not specifically limited, 1-50 GPa is preferable, 5-50 GPa is more preferable, 7-20 GPa is still more preferable. The elastic modulus can be controlled by the type of polymer, the type and amount of additives, and stretching.
As for the elastic modulus, a film sample having a length of 150 mm and a width of 10 mm was prepared, and after humidity conditioning at 25 ° C. and a relative humidity of 60% for 24 hours, the initial sample length was 100 mm according to the standard of ISO527-3: 1995. It is the tensile modulus measured from the initial slope of the stress-strain curve measured at a speed of 10 mm / min. Although the elastic modulus generally differs depending on how the film sample is taken in the length direction and the width direction, in the present invention, a value obtained by preparing a film sample in the direction in which the elastic modulus is maximum is expressed as the elastic modulus of the present invention. When the elastic modulus in the direction where the speed of sound is maximum is E1, and the elastic modulus in the direction orthogonal to that is E2, the ratio (E1 / E2) reduces the dimensional change while maintaining the flexibility of the film. From the viewpoint, 1.1 to 5.0 is preferable, and 1.5 to 3.0 is more preferable.
In the present invention, the direction in which the speed of sound (sonic wave propagation speed) is maximized is that the film is conditioned at 25 ° C. and a relative humidity of 60% for 24 hours, and then an orientation measuring machine (SST-2500: manufactured by Nomura Corporation). ) Was used as the direction in which the propagation velocity of the longitudinal vibration of the ultrasonic pulse was maximized.

[Total light transmittance, haze]
In the present invention, the sample was conditioned at 25 ° C. and a relative humidity of 60% for 24 hours, and then the values measured using a haze meter (NDH 2000: manufactured by Nippon Denshoku Industries Co., Ltd.) were used as the total light transmittance and haze. It was.
The total light transmittance of the polymer film is preferably higher from the viewpoint of efficiently using the light from the light source and reducing the power consumption of the panel, specifically, it is preferably 85% or more. % Or more is more preferable, and it is still more preferable that it is 92% or more. Further, the haze of the film of the present invention is preferably 5% or less, more preferably 3% or less, further preferably 2% or less, still more preferably 1% or less, It is particularly preferable that it is 0.5% or less.

[Tear strength]
In the present invention, the tear strength (Elmendorf tear method) is obtained by cutting out a sample of 64 mm × 50 mm with the direction parallel to the slow axis of the film and the direction orthogonal thereto as the longitudinal direction, respectively, at 25 ° C. and 60% relative humidity. After adjusting the humidity for 2 hours, it was measured using a light load tear strength tester, and the smaller value was taken as the tear strength of the film.
The tear strength of the polymer film is preferably 3 to 50 g, more preferably 5 to 40 g, and still more preferably 10 to 30 g from the viewpoint of film brittleness.

[Film thickness]
The thickness of the polymer film is preferably 10 to 1000 μm, more preferably 40 to 500 μm, and particularly preferably 40 to 200 μm, from the viewpoint of reducing the manufacturing cost.

<Ultraviolet absorber>
In this invention, it is preferable that any layer which comprises an optical film contains a ultraviolet absorber. Furthermore, it is preferable that the layer closer to the viewing side than the optically anisotropic layer contains an ultraviolet absorber. The ultraviolet absorber is also preferably contained in the polarizing film protective film and / or the substrate film. As the ultraviolet absorber, a compound having absorption in the ultraviolet region of 200 to 400 nm and reducing both | Re (400) -Re (700) | and | Rth (400) -Rth (700) | of the film is preferable. . For example, 0.01-30 mass% can be added with respect to cellulose acylate solid content.
The ultraviolet absorber preferably has a molecular weight of 250 to 1000 from the viewpoint of volatility. More preferably, it is 260-800, More preferably, it is 270-800, Most preferably, it is 300-800. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.
Specific examples of the ultraviolet absorber include compounds described in JP-A-2006-199855, [0059] to [0135].

The optical film of the present invention can be used for various applications in addition to being used as a polarizing plate for 3D image display devices. For example, it can be used as an adjusting light system by using two optical films. In particular, it is preferably used as a window adjustment system.
For example, in the embodiment shown in FIG. 6, two optical films (1) and (2) are provided on the glass substrate 15, respectively. The optical film (1) is laminated | stacked in order of the glass substrate 15, the polarizing film protective film 14, the polarizing film 13, the transparent support body 11, and the pattern optical anisotropic layer 10. FIG. Here, the glass substrate 15 and the polarizing film protective film 14, and the transparent support 11 and the polarizing film 13 can be bonded together with an adhesive, for example (not shown). An alignment film may be included between the transparent support and the optically anisotropic layer 10. The absorption axis of the polarizing film of the optical film (1) is set so as to be orthogonal to the stripes of the patterned optical anisotropic layer 10. On the other hand, the optical film (2) is laminated | stacked in order of the glass substrate 15, the polarizing film protective film 14, the polarizing film 13 pattern, the optical anisotropic layer 10, and the transparent support body 11. FIG. Here, the glass substrate and the base film 11, and the patterned optical anisotropic layer 10 and the polarizing film can be bonded together with an adhesive, for example (not shown). An alignment film may be included between the transparent support and the optically anisotropic layer 10. The absorption axis of the polarizing film of the optical film (2) is set to be parallel to the stripes of the patterned optical anisotropic layer 10.
FIG. 7A shows an example of a state in which each retardation region of the patterned optical anisotropic layer of the film (2) is inverted. In this state, Re is the same and the slow axes are orthogonal, so that all areas are black. A state in which the pattern is slid (movable) by one area is shown in FIG. In the state of FIG. 7B, the first retardation region of the optical film (1) and the second retardation region of the optical film (2) have the same Re and the slow axis is parallel, so that the white display It becomes. Similarly, the second retardation region of the optical film (1) and the first retardation region of the optical film (2) are also displayed in white. Therefore, the two combined optical films can achieve different Re in each phase difference region of the pattern optical anisotropic layer by sliding in the film surface direction, and the light transmission can be adjusted.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
<Preparation of transparent support A>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acylate solution A.
────────────────────────────────────
Composition of Cellulose Acylate Solution A────────────────────────────────────
Cellulose acetate having a substitution degree of 2.86 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) ) 54 parts by mass 1-butanol 11 parts by mass ─────────────────────────────────────

The following composition was charged into another mixing tank, stirred while heating to dissolve each component, and an additive solution B was prepared.
────────────────────────────────────
Composition of additive solution B ─────────────────────────────────────
The following compound B1 (Re reducing agent) 40 parts by mass The following compound B2 (wavelength dispersion controlling agent) 4 parts by mass Methylene chloride (first solvent) 80 parts by mass Methanol (second solvent) 20 parts by mass ──────── ────────────────────────────

化合物Ｂ２

Compound B1

Compound B2

<< Preparation of transparent cellulose acetate support >>
A dope was prepared by adding 40 parts by mass of the additive solution B to 477 parts by mass of the cellulose acylate solution A and stirring sufficiently. The dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, and both ends in the width direction of the film are fixed with a pin tenter (the pin tenter described in FIG. 3 of JP-A-4-1009), and the solvent content is 3-5% by mass. In this state, the film was dried while maintaining an interval at which the stretching ratio in the transverse direction (direction perpendicular to the machine direction) was 3%. Then, it dried further by conveying between the rolls of a heat processing apparatus, and produced the 60-micrometer-thick cellulose acetate protective film (transparent support body A). Transparent support A did not contain an ultraviolet absorber, Re (550) was 0 nm, and Rth (550) was 12.3 nm.

<< Alkaline saponification treatment >>
The cellulose acetate transparent support A is passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature is raised to 40 ° C. Then, an alkali solution having the composition shown below is applied to one side of the film using a bar coater. The coating was applied at a coating amount of 14 ml / m ² , heated to 110 ° C., and conveyed for 10 seconds under a steam far infrared heater manufactured by Noritake Company Limited. Subsequently, 3 ml / m ^{2 of} pure water was applied using the same bar coater. Next, washing with a fountain coater and draining with an air knife were repeated three times, followed by transporting to a drying zone at 70 ° C. for 10 seconds and drying to prepare an alkali saponified cellulose acetate transparent support A.

────────────────────────────────────
Composition of alkaline solution (parts by mass)
────────────────────────────────────
Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight Surfactant SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H 1.0 part by weight Propylene glycol 14. 8 parts by mass ────────────────────────────────────

<Preparation of transparent support with rubbing alignment film>
A rubbing alignment film coating solution having the following composition was continuously applied with a # 8 wire bar to the saponified surface of the prepared support. The alignment film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, a stripe mask having a horizontal stripe width of 5.7 mm in the transmission portion and a horizontal stripe width of 5.7 mm in the shielding portion is disposed on the rubbing alignment film, and the illuminance in the UV-C region is 2.5 mW / well under room temperature air. Using a cm ² air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet light is irradiated for 4 seconds to decompose the photoacid generator and generate an acidic compound to form an alignment layer for the first retardation region. did. Thereafter, a rubbing treatment was performed once in one direction at 500 rpm while maintaining an angle of 45 ° with respect to the stripe of the stripe mask, and a transparent support with a rubbing alignment film was produced. The alignment film had a thickness of 0.5 μm.
────────────────────────────────────
Composition of coating solution for alignment film formation ────────────────────────────────────
3.9 parts by mass of polymer material for alignment film (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Photoacid generator (S-2) 0.1 parts by weight Methanol 36 parts by weight Water 60 parts by weight ──────────────────────────── ────────

Photoacid generator S-2

<Preparation of patterned optically anisotropic layer A>
The following coating liquid for optically anisotropic layer was applied at a coating amount of 4 ml / m ² using a bar coater. Next, after aging for 2 minutes at a film surface temperature of 110 ° C., it was cooled to 80 ° C. and irradiated with ultraviolet rays for 20 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm ^{2 in} the air. Then, the patterned optical anisotropic layer A was formed by fixing the orientation state. In the mask exposure portion (first retardation region), the discotic liquid crystal is vertically aligned with the slow axis direction parallel to the rubbing direction, and the unexposed portion (second retardation region) is orthogonally aligned perpendicularly. It was. The film thickness of the optically anisotropic layer was 0.9 μm, the distance L between the boundary lines of the pattern was 5.7 mm, and the width L1 of the boundary line was 10 μm.

────────────────────────────────────
Composition of coating solution for optically anisotropic layer ────────────────────────────────────
Discotic liquid crystal E-1 100 parts by mass alignment film interface alignment agent (II-1) 3.0 parts by mass air interface alignment agent (P-1) 0.4 parts by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 400 parts by weight ───────────────────────── ───────────

配向膜界面配向剤（II−１）

Discotic liquid crystal E-1

Alignment film interfacial alignment agent (II-1)

The first retardation region and the second retardation region of the formed patterned optical anisotropic layer A are each analyzed by TOF-SIMS (time-of-flight secondary ion mass spectrometry, TOF-SIMS V manufactured by ION-TOF). As a result, in the first retardation region and the second retardation region, the abundance ratio of the photoacid generator S-2 in the corresponding alignment layer is 8 to 92, and almost no S-2 is present in the first retardation region. It turns out that it has decomposed. Further, in the optically anisotropic layer, the anion BF ₄ ⁻ of the acid HBF ₄ generated from the cation of II-1 and the photoacid generator S-2 exists at the air interface in the first retardation region. Was confirmed. These ions were hardly observed at the air interface in the second retardation region, and it was found that II-1 cations and Br ⁻ were present in the vicinity of the alignment film interface. The abundance ratio of each ion at the air interface was 93: 7 for II-1 cations and 90:10 for BF ₄ ⁻ . From this, the alignment film interface aligning agent (II-1) is unevenly distributed at the alignment film interface in the second retardation region, but the uneven distribution is decreased in the first retardation region and diffused to the air interface. In the first retardation region, it can be understood that diffusion of the II-1 cation is promoted by anion exchange between the generated acid HBF ₄ and II-1.

  Polarization of either one of the two polarizing plates in which the slow axis of one of the first retardation region and the second retardation region is combined in the orthogonal position with the patterned optically anisotropic layer A The optically anisotropic layer is placed between the polarizing plates so as to be parallel to the axis, and a sensitive color plate having a phase difference of 530 nm is formed so that the slow axis forms an angle of 45 ° with the polarizing axis of the polarizing plate. I was on top. Next, the state where the optically anisotropic layer was rotated by + 45 ° was observed. As is clear from the observation results shown in FIG. 9, when the rotation is rotated by + 45 °, the slow axis of the first retardation region and the slow axis of the sensitive color plate are parallel to each other, so that the phase difference is more than 530 nm. It became larger and its color changed to darker shades. On the other hand, since the slow axis of the second phase difference region is orthogonal to the slow axis of the sensitive color plate, the phase difference is smaller than 530 nm, and the color is changed to a light and light portion.

(Evaluation of optically anisotropic layer)
After peeling off the produced optically anisotropic layer from the transparent support, the tilt angle of the discotic liquid crystal at the alignment film interface and the disco at the air interface according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments) The tilt angle of the tick liquid crystal, the direction of the slow axis, and Re and Rth were measured, respectively. The results are shown in Table 1. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

  From the results shown in Table 1, the discotic liquid crystal was mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and then unidirectional Then, a patterned optically anisotropic layer having a first retardation region and a second retardation region that are perpendicularly aligned and whose slow axes are orthogonal to each other is obtained by orienting on the alignment film subjected to the rubbing treatment. I can understand.

<Preparation of polarizing plate A>
TD80UL (manufactured by FUJIFILM Corporation, Re / Rth = 2/40 at 550 nm) was used as a protective film A for polarizing plate A, and this surface was subjected to alkali saponification treatment. It was immersed in a 1.5 N aqueous sodium hydroxide solution at 55 ° C. for 2 minutes, washed in a water bath at room temperature, and neutralized with 0.1 N sulfuric acid at 30 ° C. Again, it was washed in a water bath and further dried with hot air at 100 ° C.
Subsequently, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an iodine aqueous solution and dried to obtain a polarizing film having a thickness of 20 μm. Using a 3% aqueous solution of polyvinyl alcohol (manufactured by Kuraray, PVA-117H) as an adhesive, the above-described alkali saponified TD80UL and the same alkali saponified VA retardation film (manufactured by FUJIFILM Corporation, Re / Rth = 550 nm) 50/125) is sandwiched between the polarizing films so that their saponified surfaces are on the polarizing film side, and TD80UL and VA retardation film are protective films for the polarizing film A Was made. At this time, the angle formed by the slow axis of the retardation film and the transmission axis of the polarizing film was set to 45 °.

<Preparation of patterned polarizing plate A with optically anisotropic layer A>
The transparent support A surface of the prepared optically anisotropic layer A and the TD80UL surface of the polarizing plate A were bonded with an adhesive to prepare a patterned polarizing plate A with an optically anisotropic layer A. . At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 °.
<Production of stereoscopic display device A>
The polarizing plate on the viewer side of FLEXSCANS 2231 manufactured by Nanao Co., Ltd. is peeled off, and the VA retardation film side of the prepared polarizing plate A with optically anisotropic layer A and the liquid crystal cell are bonded together with an adhesive. Display device A was produced. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Further, the distance D between the patterned optically anisotropic layer and the color filter layer (CF) was 0.9 mm.

(Example 2)
<Transparent support B>
TD80UL (manufactured by FUJIFILM Corporation) was prepared and used as the transparent support B. The film thickness of TD80UL was 80 μm, contained an ultraviolet absorber, the in-plane retardation Re (550) was 2 nm, and the thickness direction retardation Rth (550) was 40 nm.

<Preparation of patterned optically anisotropic layer B>
The transparent support A was changed to the transparent support B, the rubbing alignment film coating solution was changed to the following composition, and the stripe mask width was changed to 2.85 mm. A patterned optically anisotropic layer B was prepared. The film thickness of the alignment film is 0.5 μm, the film thickness of the optically anisotropic layer is 0.9 μm, the distance L between the boundary lines of the pattern is 2.85 mm, and the width L1 of the boundary line Was 10 μm.

──────────────────────────────────────
Composition for alignment layer ──────────────────────────────────────
3.9 parts by mass of polymer material for alignment film (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Photoacid generator (I-33) 0.1 parts by weight Methanol 36 parts by weight Water 60 parts by weight ─────────────────────────── ──────────

Photoacid generator I-33

The first retardation region and the second retardation region of the formed patterned optically anisotropic layer B are each analyzed by TOF-SIMS (time-of-flight secondary ion mass spectrometry, TOF-SIMS V manufactured by ION-TOF). As a result, in the first retardation region and the second retardation region, the abundance ratio of the photoacid generator I-33 in the corresponding alignment layer is 10:90, and almost no I-33 is present in the first retardation region. It turns out that it has decomposed. In the optically anisotropic layer, the anion BF _{4 of} the acid HBF ₄ generated from the cation of the alignment film interface aligning agent (II-1) and the photoacid generator I-33 is formed at the air interface of the first retardation region. ^- it was confirmed that exists. These ions were hardly observed at the air interface in the second retardation region, and it was found that II-1 cations and Br ⁻ were present in the vicinity of the alignment film interface. The abundance ratio of each ion at the air interface was 93: 7 for II-1 cations and 90:10 for BF ₄ ⁻ . From this, the alignment film interface aligning agent (II-1) is unevenly distributed at the alignment film interface in the second retardation region, but the uneven distribution is decreased in the first retardation region and diffused to the air interface. In the first retardation region, it can be understood that diffusion of the II-1 cation is promoted by anion exchange between the generated acid HBF ₄ and II-1.

(Evaluation of optically anisotropic layer B)
After peeling off the produced optically anisotropic layer B from the transparent support B, the direction of the slow axis of the optically anisotropic layer was determined in the same manner as in Example 1. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the rubbing direction of the alignment film. From the results shown in Table 1, the discotic liquid crystal was mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and then unidirectional Then, a patterned optically anisotropic layer having a first retardation region and a second retardation region that are perpendicularly aligned and whose slow axes are orthogonal to each other is obtained by orienting on the alignment film subjected to the rubbing treatment. I can understand.

<Preparation of patterned polarizing plate B with optically anisotropic layer B>
TD80UL of the polarizing plate A with the patterned optically anisotropic layer A produced in Example 1 was changed to the patterned optically anisotropic layer B produced above, and the patterned optically anisotropic layer The B surface and the polyvinyl alcohol film surface of the polarizing plate A produced in Example 1 were bonded together with an adhesive to produce a patterned polarizing plate B with an optically anisotropic layer B. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer B and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device B>
Peel off the polarizing plate on the viewing side of FLEXSCANS 2231 manufactured by Nanao Co., Ltd., and paste the VA phase difference film for the polarizing plate B with the optically anisotropic layer B produced above and the liquid crystal cell through an adhesive to provide a three-dimensional display. Device A was made. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Example 3)
<Preparation of transparent support with rubbing alignment film>
A 4% aqueous solution of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. was applied to the surface of the transparent support A produced in Example 1 with a No. 12 bar and dried at 80 ° C. for 5 minutes. . Thereafter, one reciprocating rubbing treatment was performed in one direction at 400 rpm to produce a transparent support with a rubbing alignment film.

<Preparation of patterned optically anisotropic layer C>
After preparing the following composition for optically anisotropic layers, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid for optically anisotropic layers. The coating solution was applied and dried at a film surface temperature of 80 ° C. for 1 minute to obtain a liquid crystal phase and uniformly aligned, and then cooled to room temperature. Next, a stripe mask having a horizontal stripe width of 1.14 mm at the transmissive portion and a horizontal stripe width of 1.14 mm at the shielding portion is optically anisotropic while holding the stripe mask at 45 ° with respect to the rubbing direction. Alignment state is fixed by irradiating with UV light for 5 seconds using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 20 mW / cm ² under air. As a result, the first retardation region was formed. Subsequently, the film surface temperature was raised to 140 ° C., and after making it isotropic phase, the temperature was lowered to 100 ° C. and heated at that temperature for 1 minute for uniform orientation. After cooling to room temperature, the entire surface was irradiated at 20 mW / cm ² for 20 seconds to fix the orientation state, thereby forming a second retardation region. The slow axes of the first phase difference region and the second phase difference region are orthogonal, the film thickness is 0.9 μm, the distance L between the pattern boundary lines is 1.14 mm, and the width L1 of the boundary line Was 10 μm.

──────────────────────────────────────
Optically anisotropic layer composition ──────────────────────────────────────
Discotic liquid crystal E-2 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-2) 0.4 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 400 parts by weight ───────────────────────── ─────────────

Discotic liquid crystal E-2

(Evaluation of optically anisotropic layer)
After peeling off the produced optically anisotropic layer C from the transparent support A, the direction of the slow axis of the optically anisotropic layer was determined in the same manner as in Example 1. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the direction of the rubbing direction of the alignment film. From the results shown in Table 1, the discotic liquid crystal is aligned on a PVA rubbing alignment film rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature is changed. It can be understood that the patterned optically anisotropic layer having the first retardation region and the second retardation region having the vertical alignment and the slow axis orthogonal to each other can be obtained by performing the exposure.

<Preparation of patterned polarizing plate C with optically anisotropic layer C>
A polarizing plate C with a patterned optically anisotropic layer C was produced in the same manner as in Example 2, except that the patterned optically anisotropic layer B was changed to the patterned optically anisotropic layer C. .

<Production of stereoscopic display device C>
The polarizing plate on the viewer side of FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and the liquid crystal cell of the prepared polarizing plate C with the optically anisotropic layer C are bonded via an adhesive to provide a three-dimensional display. Device A was made. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

Example 4
<Preparation of patterned optically anisotropic layer D>
A patterned optically anisotropic layer D was prepared in the same manner as in Example 3 except that the optically anisotropic layer coating solution was changed to the following composition. The thickness of the optically anisotropic layer was 0.8 μm, the pattern boundary line distance L was 1.14 mm, and the boundary line width L1 was 10 μm.
──────────────────────────────────────
Composition for optically anisotropic layers ──────────────────────────────────────
Discotic liquid crystal E-3 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-1) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 parts by mass Methyl ethyl ketone 400 mass ──────────────────────────────────────

Discotic liquid crystal E-3

(Evaluation of optically anisotropic layer)
After peeling off the produced optically anisotropic layer D from the transparent support A, the direction of the slow axis of the optically anisotropic layer was determined in the same manner as in Example 1. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the rubbing direction of the alignment film. From the results shown in Table 1, the discotic liquid crystal is aligned on a PVA rubbing alignment film rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature is changed. It can be understood that the patterned optically anisotropic layer having the first retardation region and the second retardation region having the vertical alignment and the slow axis orthogonal to each other can be obtained by performing the exposure.

<Preparation of patterned polarizing plate D with optically anisotropic layer D>
A polarizing plate D with an optically anisotropic layer D patterned in the same manner as in Example 3 except that the patterned optically anisotropic layer C was changed to the patterned optically anisotropic layer D produced above. Produced. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer D and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device D>
The polarizing plate on the viewing side of the FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and the liquid crystal cell of the prepared polarizing plate D with the optically anisotropic layer D are bonded via an adhesive to provide a three-dimensional display. Device D was made. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Example 5)
<Preparation of transparent support with rubbing alignment film>
(1) Preparation of parallel alignment film (first alignment film) 4% water / methanol solution of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. on the surface of transparent support B prepared in Example 2 subjected to saponification treatment (PVA103 (4.0 g) dissolved in 72 g of water and 24 g of methanol, with a viscosity of 4.35 cp and a surface tension of 44.8 dyne) was applied with a No. 12 bar and dried at 80 ° C. for 5 minutes.

(2) Preparation of patterning orthogonal alignment film (second alignment film) 2.0 g of polyacrylic acid (Mw25000) manufactured by Wako Pure Chemical Industries, Ltd. 2.52 g of triethylamine / 1.12 g of water / 5.09 g of propanol / 3-methoxy-1 -It dissolved in 5.09g of butanol, and prepared the coating liquid.

  Next, as the flexographic plate, a synthetic rubber-like flexographic plate having irregularities having the shape shown in FIG. 10 was produced.

As the flexographic printing apparatus shown in FIG. 11, a flexiproof 100 (RK Print Coat Instruments Ltd. UK) was used. The anilox roller used was 400 cells / cm (volume: 3 cm ³ / m ² ). The flexographic plate was attached to a pressure drum of the flexoproof 100 with a pressure sensitive tape. After the parallel alignment film was affixed to the printing roller, the patterning orthogonal alignment film coating solution was put into a doctor blade, and the orthogonal alignment film was pattern-printed on the parallel alignment film at a printing speed of 30 m / min.

(3) Preparation of rubbing alignment layer After drying at 80 ° C. for 5 minutes, a reciprocating rubbing treatment was performed at 1000 rpm in a 45 ° direction with respect to the stripe line of the pattern to prepare a rubbing alignment layer.

<Preparation of patterned optically anisotropic layer D>
The coating solution for optical anisotropy prepared in Example 3 was applied, dried at a film surface temperature of 110 ° C. for 1 minute to obtain a liquid crystal phase, cooled to 80 ° C., and air-cooled at 160 W / cm in air. An attempt was made to fabricate a patterned optically anisotropic layer D by irradiating ultraviolet rays using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to fix the orientation state. The thickness of the optically anisotropic layer was 0.9 μm, the distance L between the pattern boundary lines was 2.85 mm, and the width L1 of the boundary line was 5 μm.

(Evaluation of optically anisotropic layer)
After peeling off the produced optically anisotropic layer from the transparent support B, the direction of the slow axis of the optically anisotropic layer was determined in the same manner as in Example 1. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the rubbing direction of the alignment film. From the results shown in Table 1, a PVA rubbing alignment film (first alignment film) / polyethylene obtained by rubbing a discotic liquid crystal in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer. By aligning and exposing on an acrylic acid-based rubbing alignment film (second alignment film), patterning is performed that has a first retardation region and a second retardation region that are vertically aligned and whose slow axes are orthogonal to each other. It can be understood that the obtained optically anisotropic layer is obtained.

<Preparation of patterned polarizing plate E with optically anisotropic layer E>
A polarizing plate E with an optically anisotropic layer E patterned in the same manner as in Example 3, except that the patterned optically anisotropic layer C was changed to the patterned optically anisotropic layer E produced above. Produced. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer E and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device E>
The polarizing plate on the viewing side of the FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and the liquid crystal cell of the polarizing plate E with the optically anisotropic layer E produced as described above are bonded via an adhesive to provide a three-dimensional display. Device D was made. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Example 6)
<Preparation of transparent support A with photo-alignment film>
A 1% aqueous solution of photoalignment material E-1 having the following structure was applied to the surface of the transparent support A produced in Example 1 that had been subjected to saponification treatment, and dried at 100 ° C. for 1 minute. The obtained coating film was irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm ² under air. At this time, as shown in FIG. 12A, a wire grid polarizer (Moxtek, ProFlux PPL02) is set in direction 1, and further mask A (transmission part horizontal stripe width 1.14 mm, shielding part The exposure was performed through a stripe mask having a horizontal stripe width of 1.14 mm. Thereafter, as shown in FIG. 12B, a wire grid polarizer is set in direction 2, and mask B (a stripe mask with a horizontal stripe width of 1.14 mm at the transmission portion and a horizontal stripe width of 1.14 mm at the shielding portion). ) To perform exposure. The distance between the exposure mask surface and the photo-alignment film was set to 200 μm. The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount was 1000 mJ / cm ² in the UV-A region.

<Preparation of patterned optically anisotropic layer F>
After preparing the following composition for optically anisotropic layers, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution. The coating solution is applied onto the transparent support A with a photo-alignment film, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, cooled to 75 ° C., and 160 W / cm ² under air. An attempt was made to produce a patterned optically anisotropic layer A by irradiating ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to fix the orientation state. The thickness of the optically anisotropic layer was 1.3 μm, the distance L between the boundary lines of the pattern was 1.14 mm, and the width L1 of the boundary line was 10 μm.

──────────────────────────────────────
Composition for optically anisotropic layers ──────────────────────────────────────
Rod-shaped liquid crystal (LC242, manufactured by BASF Corporation) 100 parts by mass horizontal alignment agent A 0.3 parts by mass photopolymerization initiator 3.3 parts by mass (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.1 parts by weight Methyl ethyl ketone 300 parts by weight ───────────────────────── ─────────────

Rod-like liquid crystal LC242: rod-like liquid crystal described in WO2010 / 090429A2

(Evaluation of optically anisotropic layer)
After peeling off the produced optically anisotropic layer from the transparent support A, the slow axis of either one of the first retardation region or the second retardation region of the two polarizing plates combined in an orthogonal position Insert between the polarizing plates so that either one of them is parallel to the polarization axis, and then add a sensitive color plate with a phase difference of 530 nm so that the slow axis forms an angle of 45 ° with the polarizing axis of the polarizing plate. It was placed on the anisotropic layer. Next, the state in which the optically anisotropic layer was rotated by + 45 ° was observed with a polarizing microscope (NECON ECLIPIE E600W POL). When rotated + 45 °, the slow axis of the first phase difference region and the slow axis of the sensitive color plate are parallel, so the phase difference is larger than 530 nm, and the color is blue (in the black and white drawing, the color is light and dark). The darker part). On the other hand, since the slow axis of the second phase difference region is orthogonal to the slow axis of the sensitive color plate, the phase difference is smaller than 530 nm, and the color changes to white (the light and shaded part in the black and white drawing). To do. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the direction of the exposure direction of the alignment film. From the results shown in Table 1, by aligning the rod-like liquid crystal on the photo-alignment film and exposing it, the first retardation region and the second position, which are horizontally oriented but the slow axis slightly deviates from orthogonal, are shown. It can be seen that a patterned optically anisotropic layer having a phase difference region is obtained. The factors causing the slow axis to deviate from orthogonal are considered to be due to (1) difficulty in adjusting the angle of the mask and (2) a large distance L between the pattern boundary lines.

  Next, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the rod-like liquid crystal at the alignment film interface, the tilt angle of the rod-like liquid crystal at the air interface, the direction of the slow axis, and Re, Each Rth was measured. The results are shown in Table 1. In the following table, horizontal represents a tilt angle of 0 ° to 20 °.

<Preparation of patterned polarizing plate F with optically anisotropic layer F>
A polarizing plate F with an optically anisotropic layer F patterned in the same manner as in Example 3 except that the patterned optically anisotropic layer C was changed to the patterned optically anisotropic layer F produced above. Produced. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer F and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device F>
The polarizing plate on the viewing side of FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and the liquid crystal cell of the above-prepared polarizing plate F with optically anisotropic layer F are bonded via an adhesive to provide a three-dimensional display. Device D was made. The direction of the absorption axis of the polarizing film 13 is as indicated by the arrow in FIG. The one pixel and the retardation region of the patterned optically anisotropic layer were accurately aligned and bonded. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Example 7)
<Preparation of transparent support G with rubbing alignment film>
A 4% aqueous solution of Kuraray's polyvinyl alcohol “PVA103” was applied to the surface of a Teijin Chemicals pure ace film with Re (550) of 138 nm and Rth (550) of 69 nm at a number 12 bar at 80 ° C. Dry for 5 minutes. Thereafter, a rubbing treatment was performed once in a direction parallel to the slow axis of Pure Ace at 400 rpm to produce a transparent support G with a rubbing alignment film. The thickness of the alignment film was 0.5 μm.

<Preparation of patterned optically anisotropic layer G>
After preparing a composition for an optically anisotropic layer having the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution for ½ wavelength. The coating solution was applied and dried at a film surface temperature of 80 ° C. for 1 minute to obtain a liquid crystal phase and uniformly aligned, and then cooled to room temperature. Next, a mask with a horizontal stripe width of 2.85 mm is placed on the substrate coated with the coating solution for 1/2 wavelength layer, and an air-cooled metal halide lamp (produced by Eye Graphics Co., Ltd.) of 20 mW / cm ² under air. The first retardation region was formed by irradiating with ultraviolet rays for 5 seconds and fixing the alignment state. Subsequently, the film surface temperature was raised to 140 ° C. to make it isotropic phase once, and then the whole surface was irradiated at 20 mW / cm ² for 20 seconds to fix the orientation state, thereby forming the second retardation region. . In this manner, a patterned half-wave layer was produced. The thickness of the optically anisotropic layer was 1.8 μm, the distance L between the boundary lines of the pattern was 2.85 mm, and the width L1 of the boundary line was 10 μm.

────────────────────────────────────────
Composition for optically anisotropic layer formation ------------------------------
Discotic liquid crystal E-4 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-1) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 parts by mass Methyl ethyl ketone 400 mass ─────────────────────────────────────────

(Evaluation of optically anisotropic layer)
When a similar optically anisotropic layer was separately formed on a glass substrate and Re at a measurement wavelength of 550 nm was measured, Re in the first retardation region was 275 nm, and the slow axis was parallel to the pure ace slow axis. And Re in the second retardation region was 0 nm. The total value of Re of the first retardation region and Re of the transparent support of the patterned optically anisotropic layer G is 413 nm, and the total value of Re of the second retardation region and Re of the transparent support is 138 nm. The slow axes of the first phase difference region and the second phase difference region were parallel. The tilt angle of the first phase difference region was 90 °.

<Preparation of black photosensitive composition for barrier rib preparation>
The black photosensitive composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 RPM for 10 minutes, Next, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-diethoxycarbonylmethylamino) -3 in the amounts shown in Table 1 '-Bromophenyl] -s-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes. . In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%
<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%
<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

(Preparation of patterned optically anisotropic layer G with black partition walls G)
The black photosensitive composition K1 which consists of a composition of the said Table 1 was apply | coated to the pure ace surface. Subsequently, prebaking was performed at 120 ° C. for 3 minutes to obtain a black photosensitive layer K1 having a thickness of 10 μm.

A mask was prepared in which the stripe width of the transmission part was 1.14 mm and the center line of the transmission part coincided with the pattern boundary line of the optically anisotropic layer G patterned.
The distance between the mask surface and the black photosensitive layer K1 is set to 200 μm so that the transmission center line of the mask coincides with the pattern boundary line of the optically anisotropic layer G, and the exposure amount is 300 mJ in a nitrogen atmosphere. The pattern was exposed at / cm2.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the black photosensitive layer K1, and then a KOH-based developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film) Shower development was performed at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa by Electronics Materials Co., Ltd., and a black partition was further formed on Pure Ace, which is a support for the patterned optically anisotropic layer G. A patterned optically anisotropic layer was obtained. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post exposure was performed at an exposure amount of 2000 mJ / cm 2 in the atmosphere to obtain a black having an optical density of 3.9. A partition was obtained. The width (B) of the black partition wall is 1.14 mm, the center line of B is precisely located at the pattern boundary of the patterned optically anisotropic layer G, and B is 0.4 times L It was wide.

<Preparation of patterned polarizing plate G with optically anisotropic layer G>
The support surface of WV-EA (manufactured by FUJIFILM Corporation) was subjected to alkali saponification treatment. It was immersed in a 1.5 N aqueous sodium hydroxide solution at 55 ° C. for 2 minutes, washed in a water bath at room temperature, and neutralized with 0.1 N sulfuric acid at 30 ° C. Again, it was washed in a water bath and further dried with hot air at 100 ° C.
Subsequently, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an iodine aqueous solution and dried to obtain a polarizing film having a thickness of 20 μm. The surface of the saponified WV-EA treated with alkali saponification is bonded to one side of the polarizing film using a 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) as an adhesive so that the surface is the polarizing film side. For this, the black partition wall B surface of the patterned optically anisotropic layer G was bonded with an adhesive. In this way, a polarizing plate G with a patterned optically anisotropic layer G, in which WV-EA and the optically anisotropic layer G are protective films for the polarizing film, was produced. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to 45 degrees.

<Production of stereoscopic display device G>
The three-dimensional display device G was manufactured by peeling off the pattern retardation plate and the front polarizing plate used in the circular polarizing glasses type 3D monitor W220S (manufactured by Hyundai) and bonding the polarizing plate prepared above. In the pasting, 4 pixels are used as one pixel of the right-eye or left-eye image (pixel distance is 1.14 mm), and the phase difference region of the optically anisotropic layer patterned with the one pixel is accurately set. The alignment was carried out in accordance with the above. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Comparative Example 1)
<Preparation of patterned optically anisotropic layer G>
A patterned optically anisotropic layer G was prepared in the same manner as in Example 1 except that the width of the stripe mask was changed to 285 μm. The film thickness of the alignment film is 0.5 μm, the film thickness of the optically anisotropic layer is 0.9 μm, the distance L between the pattern boundary lines is 285 μm, and the width L1 of the boundary line is 10 μm. Met.

(Evaluation of optically anisotropic layer G)
After peeling off the produced optically anisotropic layer G from the transparent support A, the direction of the slow axis of the optically anisotropic layer was determined in the same manner as in Example 1. Table 1 shows the relationship between the slow axis of the optically anisotropic layer and the rubbing direction of the alignment film. From the results shown in Table 1, the discotic liquid crystal was mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and then unidirectional Then, a patterned optically anisotropic layer having a first retardation region and a second retardation region that are perpendicularly aligned and whose slow axes are orthogonal to each other is obtained by orienting on the alignment film subjected to the rubbing treatment. I can understand.

<Preparation of patterned polarizing plate G with optically anisotropic layer G>
TD80UL of the polarizing plate G with the patterned optically anisotropic layer G produced in Example 1 was changed to the patterned optically anisotropic layer G produced above, and the patterned optically anisotropic layer The G surface and the polyvinyl alcohol film surface of the polarizing plate A prepared in Example 1 were bonded together with an adhesive to prepare a patterned polarizing plate G with an optically anisotropic layer G. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer B and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device G>
The polarizing plate on the viewing side of FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and liquid crystal cell of the above-prepared polarizing plate G with optically anisotropic layer G are bonded via an adhesive to provide a three-dimensional display. Device G was made. The direction of the absorption axis of the polarizing film 13 is as shown by the arrow in FIG. 8, and the bonding is performed accurately in the phase difference region of the optically anisotropic layer patterned with one pixel (pixel distance is 285 μm). Lamination was performed after alignment. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Comparative Example 2)
<Preparation of patterned optically anisotropic layer H>
A patterned optically anisotropic layer H was prepared in the same manner as in Example 6 except that the width of the stripe mask was changed to 285 μm. The thickness of the optically anisotropic layer was 1.3 μm, the distance L between the pattern boundary lines was 285 μm, and the width L1 of the boundary line was 10 μm.

(Evaluation of optically anisotropic layer H)
From the results shown in Table 1, by aligning the rod-like liquid crystal on the photo-alignment film and exposing it, the first retardation region and the second position, which are horizontally oriented but the slow axis slightly deviates from orthogonal, are shown. It can be seen that a patterned optically anisotropic layer having a phase difference region is obtained.

<Preparation of the polarizing plate H with the patterned optically anisotropic layer H>
TD80UL of the polarizing plate F with the patterned optically anisotropic layer F produced in Example 6 is changed to the patterned optically anisotropic layer H produced above, and the patterned optically anisotropic layer The H plane and the polyvinyl alcohol film surface of the polarizing plate A prepared in Example 1 were bonded together with an adhesive to prepare a patterned polarizing plate H with an optically anisotropic layer H. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer B and the absorption axis of the polarizing film was set to ± 45 °.

<Production of stereoscopic display device H>
The polarizing plate on the viewing side of the FLEXSCANS 2231 manufactured by NANAO is peeled off, and the VA retardation film and liquid crystal cell of the above-prepared polarizing plate G with optically anisotropic layer H are bonded via an adhesive to provide a three-dimensional display. Device H was made. The direction of the absorption axis of the polarizing film 13 is as shown by the arrow in FIG. 8, and the bonding is performed accurately in the phase difference region of the optically anisotropic layer patterned with one pixel (pixel distance is 285 μm). Lamination was performed after alignment. Moreover, the distance D of the optically anisotropic layer patterned from the color filter layer was 0.8 mm.

(Evaluation)
<Evaluation of stereoscopic display device>
A stereoscopic display device displaying a stereoscopic image in which images for right eye / left eye having parallax were alternately arranged was observed through 3D glasses from a polar angle of 0 degrees, and the degree of crosstalk was evaluated in seven stages. Subsequently, the observation was made from a polar angle of 45 ° with an azimuth angle of 0 ° and 180 °, and the same evaluation was made. Subsequently, observations were made from polar angles of 10 degrees with azimuth angles of 90 degrees and 270 degrees, and the same evaluation was performed. Evaluation was carried out in 7 stages from 7 (no crosstalk) to 1 (large crosstalk). The results are shown in Table 2.

<Evaluation of light resistance>
Using a light resistance test apparatus (super xenon weather meter SX120 type (long life xenon lamp), manufactured by Suga Test Instruments Co., Ltd.), irradiance 100 ± 25 W / m ² (wavelength 310 nm to 400 nm), test chamber temperature 35 ± Before and after the light resistance test 25 hr was performed according to JIS K 5600-7-5 under the conditions of 5 ° C., black panel temperature 50 ± 5 ° C., and relative humidity 65 ± 15%, The change and the change of the polarization degree of the polarizing plate were examined. A case where the rate of change was within 10% was marked with ◯, and a case where the rate of change was larger than that was marked with ×.

DESCRIPTION OF SYMBOLS 1 1st phase difference area | region 2 2nd phase difference area | region 3 Boundary line 4 Black part 10 Pattern optically anisotropic layer 11 Transparent support 12 Alignment film 13 Polarizing film 14 Polarizing film protective film 15 Glass substrate 16 Color filter 31 Flexo plate 32 Parallel alignment film (or orthogonal alignment film)
33 Orthogonal alignment film liquid for pattern printing (or parallel alignment film liquid for pattern printing)
40 flexographic printing apparatus 41 impression cylinder 42 printing pressure roller 43 anix roller 44 doctor blade

Claims (19)

Having a first phase difference region and a second phase difference region;
The first phase difference region and the second phase difference region are alternately arranged in the same plane,
The first retardation region and the second retardation region are different from each other in at least one of an in-plane slow axis direction and an in-plane retardation, and
The optical film which has a pattern optical anisotropic layer whose distance L between two adjacent boundary lines is 1 mm-50 mm among the boundary lines of a said 1st phase difference area | region and a 2nd phase difference area | region. 2. The optical according to claim 1, wherein a distance L between two boundary lines adjacent to each other and a width L <b> 1 of the boundary line satisfy the following expression (1) among boundary lines between the first phase difference region and the second phase difference region. the film.
Formula (1) 100 <= L / L1 <= 5,000 The optical film according to claim 1, wherein a black portion is disposed on at least one surface of the boundary line. Furthermore, it has a polarizing film, The optical film of any one of Claims 1-3 characterized by the above-mentioned. The optical film according to any one of claims 1 to 4, wherein the optically anisotropic layer is formed on a transparent support having Re (550) of 0 to 10 nm. The optical film according to claim 1, wherein the first retardation region and the second retardation region are formed in a stripe shape. The in-plane slow axis of each of the first retardation region and the second retardation region and the absorption axis of the polarizing film form an angle of ± 45 °, respectively. 2. An optical film according to item 1. The optical film according to claim 1, wherein in-plane slow axis directions of the first retardation region and the second retardation region are orthogonal to each other. The in-plane retardation Re (550) of the entire optical film having a wavelength of 550 nm is 110 to 160 nm in both the portion including the first retardation region and the portion including the second retardation region. 9. The optical film according to any one of 8 above. The optical film of any one of Claims 1-9 in which any layer which comprises the said optical film contains a ultraviolet absorber. The optical film according to claim 1, wherein the patterned optical anisotropic layer is formed on an alignment film processed in one direction. The optical film according to claim 11, wherein the alignment film contains a photoacid generator. The at least part of the photoacid generator is decomposed, and the degrees of decomposition of the photoacid generator in regions corresponding to the first retardation region and the second retardation region of the alignment film are different from each other. The optical film described in 1. In at least a part of the optically anisotropic layer, there is an acidic compound generated from the photoacid generator or ions thereof, and each in the first retardation region and the second retardation region of the optically anisotropic layer. The optical film according to claim 12 or 13, wherein the ratio of the acidic compound or anion thereof contained is different from each other. The optical film according to claim 11, wherein the alignment film is a rubbing alignment film that is rubbed in one direction. The said 1st phase difference area | region and the 2nd phase difference area | region are each formed from the composition which has as a main component the discotic liquid crystal compound which has a polymeric group, The any one of Claims 1-15 characterized by the above-mentioned. 2. The optical film according to item 1. The optical film according to claim 16, wherein the discotic liquid crystal is fixed in a vertically aligned state. The three-dimensional image display apparatus which has an optical film of any one of Claims 1-17. 19. The stereoscopic image display device according to claim 18, wherein a color filter is provided, and when a distance in a direction perpendicular to the film surface of the color filter and the patterned optically anisotropic layer is D, D / L is A stereoscopic image display device that is 2 or less.

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