JP2013164525A - Laminate and application of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel laminate having a patterned optical anisotropic layer useful for various purposes.SOLUTION: The laminate comprises: a polarizer; a first film; and a patterned optical anisotropic layer disposed on one surface of the first film. The patterned optical anisotropic layer includes a first retardation region and a second retardation region, in which the first retardation region and the second retardation region are arranged in the same plane and at least one of an in-plane slow axis direction and an in-plane retardation differs between the first retardation region and the second retardation region, and in boundary lines between the first retardation region and the second retardation region, a distance L between adjoining two boundary lines is 1 mm to 50 mm. The laminate includes a pigment portion having a width of 5 μm to 200 μm, disposed at least a position corresponding to the boundary portion between the first and second retardation regions adjoining to each other of the patterned optical anisotropic layer.

Description

  The present invention relates to a laminate useful for various uses such as an optical film for 3D display devices, and the use thereof.

About the optical member which has a pattern optical anisotropic layer, utilization to various uses is anticipated. For example, in a 3D image display device that displays a stereoscopic image, the optical member is used to convert a right-eye image and a left-eye image into circularly polarized images in opposite directions. For the production of the optical member, a pattern formation technique is required, and various types of pattern formation are known (Patent Documents 1 to 4).
When forming the patterned optically anisotropic layer, it is ideal that the phase difference regions having different optical characteristics are clearly switched in the plane, but it is difficult to completely eliminate the boundary between the phase difference regions. It is. The boundary part existing in the patterned optically anisotropic layer contributes to a reduction in properties required in various applications. For example, when used in a 3D image display device, it contributes to left and right crosstalk.

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

This invention makes it a subject to provide the novel laminated body which has a pattern optically anisotropic layer, and its use.
Moreover, the subject of 1 aspect of this invention is provision of the optical film for 3D image display apparatuses which contributes to reduction of the left-right crosstalk of the 3D image display apparatus.
Moreover, the subject of the other aspect of this invention is provision of the shutter member which is excellent in the light-and-dark light control characteristic, and is excellent also in the light control of an intermediate state.

Means for solving the above problems are as follows.
[1] A laminate including a polarizer, a first film, and a patterned optically anisotropic layer disposed on one surface of the first film,
The patterned optically anisotropic layer has a first retardation region and a second retardation region, and the first retardation region and the second retardation region are arranged in the same plane, The 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 of the boundary line between the first phase difference region and the second phase difference region, A pattern optical anisotropic layer having a distance L between two adjacent boundary lines of 1 mm to 50 mm; and a boundary portion between the first and second retardation regions adjacent to each other of the pattern optical anisotropic layer. A laminate having a pigment portion having a width of 5 μm to 200 μm arranged at a corresponding position.
[2] The laminate according to [1], wherein the pigment portion is disposed in contact with the surface of the patterned optically anisotropic layer.
[3] The laminate of [1] or [2], wherein at least one layer contains at least one ultraviolet absorber.
[4] The laminate according to any one of [1] to [3], wherein the first and second retardation regions have a stripe shape with a width L.
[5] The laminate according to any one of [1] to [4], wherein the in-plane slow axis of the first and second retardation regions and the transmission axis of the polarizer each form an angle of ± 45 °.
[6] The laminated body according to any one of [1] to [5], wherein the total value of in-plane retardation Re (550) at a wavelength of 550 nm of all members except the polarizer of the laminated body is 110 to 160 nm. .
[7] The laminate according to any one of [1] to [6], further including an alignment film that is aligned in one direction and adjacent to the patterned optically anisotropic layer.
[8] The laminate according to [7], wherein the alignment film is a rubbing alignment film that has been rubbed in one direction.
[9] The laminate according to any one of [1] to [8], wherein the patterned optically anisotropic layer is a layer formed from a composition containing a discotic liquid crystal having a polymerizable group as a main component.
[10] The laminate according to [9], wherein the discotic liquid crystal is fixed in a vertically aligned state.
[11] The laminate according to any one of [1] to [10], further including a second film, wherein the polarizer is disposed between the first and second films.
[12] The main component of the first film or the second film is selected from at least one of cellulose acylate, cyclic olefin, acrylic resin, polyethylene terephthalate resin, and polycarbonate resin. ] The laminated body in any one of.
[13] The laminate according to any one of [1] to [12], which is an optical film for a 3D display device.
[14] The laminate according to any one of [1] to [12] used as a shutter member.
[15] The laminate according to [14], wherein a single plate transmittance T ₁ (λ)% at a wavelength λnm satisfies the following formulas (1) and (2).
(1) 55% ≧ T (430) ≧ 38%
(2) 60% ≧ T (590) ≧ 42.5%
[16] The laminate of [14] or [15], wherein the single plate transmittance T ₁ (λ)% satisfies the following formula (3).
(3) 1.0 ≧ T (430) / T (590) ≧ 0.9
[17] The laminate according to any one of [14] to [16], wherein the orthogonal transmittance T ₂ (λ)% at the wavelength λnm satisfies the following formula (4).
(4) T ₂ (430)> 0.02%

ADVANTAGE OF THE INVENTION According to this invention, the novel laminated body which has a pattern optically anisotropic layer, and its use can be provided.
Moreover, according to one aspect of the present invention, it is possible to provide an optical film for a 3D image display device that contributes to the reduction of left-right crosstalk of the 3D image display device.
Moreover, according to the other aspect of this invention, the shutter member which is excellent in the light-and-dark light control characteristic and is excellent also in the light control of an intermediate state can be provided.

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 pigment | dye part in this invention. It is a cross-sectional schematic diagram of an example of the laminated body of this invention. It is a conceptual diagram when the laminated body of this invention is combined with a 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 a cross-sectional schematic diagram of the other example of the laminated body of this invention. It is the schematic which shows an example of the shutter member which uses two laminated bodies of this invention in combination. It is the schematic which shows the state before and behind sliding an optical pattern anisotropic layer about an example of the shutter member which uses two laminated bodies of this invention in combination. It is a cross-sectional schematic diagram of the rubber-like flexographic plate used in the examples. It is a schematic diagram of the flexographic printing apparatus used in the examples.

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.

1. Laminate A laminate comprising a polarizer, a first film, and a patterned optically anisotropic layer disposed on one surface of the first film,
The patterned optically anisotropic layer has a first retardation region and a second retardation region, and the first retardation region and the second retardation region are arranged in the same plane, The 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 of the boundary line between the first phase difference region and the second phase difference region, A pattern optical anisotropic layer having a distance L between two adjacent boundary lines of 1 mm to 50 mm; and a boundary portion between the first and second retardation regions adjacent to each other of the pattern optical anisotropic layer. The present invention relates to a laminate having a pigment portion having a width of 5 μm to 200 μm arranged at a corresponding position. In the present invention, the order of arrangement of the polarizer, the first film, and the patterned optically anisotropic layer is not particularly limited.

Hereinafter, embodiments of the laminate of the present invention will be described with reference to the drawings.
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. As described above, by widening the pitch width as compared with the prior art, a film suitable for a large screen or outdoor display can be supplied when used in a 3D display device. In addition, when used as a window shutter, moire can be reduced, and a system with little light leakage in a black display state can be provided.

The width L1 of the boundary line is the average in the direction of the thickness in the thickness direction at one end of one phase difference region and the thickness of the end of the phase difference region adjacent to the phase difference region near the phase difference region. The shortest distance between the faces. 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. With such a ratio, the crosstalk can be further reduced in the aspect used for the 3D display device, and the light and dark dimming property is further improved in the dark state in the aspect used for the shutter. A film with little light leakage can be provided.

  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 laminated body, 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 laminate (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.

In one embodiment of the present invention, the in-plane retardation Re (550) at a wavelength of 550 nm in the first retardation region and the second retardation region is preferably about λ / 4, specifically 110 each. It is preferably ˜160 nm, more preferably 120 to 170 nm, and still more preferably 125 to 140 nm.
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.

One feature of the laminate of the present invention is that it has a dye portion disposed at least at a position corresponding to a boundary portion of the first and second retardation regions adjacent to each other of the patterned optically anisotropic layer. . FIG. 2 is an example showing an embodiment in which a dye part is provided, and the dye part 4 is provided so as to cover the boundary line 3 of the optically anisotropic layer 10. By providing L in the above range and providing the dye portion, in the embodiment used in the 3D display device, the viewing angle dependency of the crosstalk in the direction perpendicular to the longitudinal direction of the dye portion is improved, and the mode for the shutter for the window Then, light and dark dimming properties are greatly improved. In particular, since light leakage during dark adjustment is easily visible to human eyes, light leakage during dark adjustment is extremely reduced. In addition, the said pigment | dye part is a part to which the light transmittance fell by containing a pigment | dye, and it is preferable that it is a black or a hue similar to it by including a 1 type, or 2 or more types of pigment | dye.
In the present invention, the width of the dye portion is appropriately set from the viewpoint of luminance and the viewing angle of crosstalk, and is 5 to 200 μm, preferably 10 to 150 μm, more preferably 10 to 100 μm, and still more preferably 15 to 75 μm. .

  FIG. 2 shows an example in which the dye portion 4 is formed on the surface of the patterned optically anisotropic layer. For example, the dye portion 4 is interposed between the alignment film used as desired and the patterned optically anisotropic layer. It may be formed. FIG. 2 shows an example in which the dye portion 4 is formed in contact with the surface of the patterned optical anisotropic layer. However, in the present invention, the dye portion is formed in contact with the patterned optical anisotropic layer. It is not essential. For example, in an embodiment having a support film that supports the patterned optically anisotropic layer, the dye portion is the back surface of the support film (the surface on which no optically anisotropic layer is formed), and the boundary It may be provided at a position corresponding to the line. Furthermore, the pigment portion is the surface of the polarizer protective film (which means that both the surface in contact with the polarizer and the opposite surface are included), and is formed at a position corresponding to the boundary line. May be.

The laminate of the present invention has a polarizer (sometimes referred to as a polarizing film). FIG. 3 is a schematic cross-sectional view of an example of the laminate of the present invention. 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 11 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 12 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 FIG. 3, the dye portion is omitted, but as described above, the dye portion is preferably formed in contact with the optical anisotropic layer 10, and the optical anisotropic layer 10, the alignment film 12, and the like. Between the optically anisotropic layer and the polarizing film 13.

In the mode used for the image display element, as shown in FIG. 4, between the patterned optical anisotropic layer 10 and the color filter layer 16, in addition to the polarizing film, a light transmissive substrate 15 such as a glass substrate, an adhesive When there is a distance (D) between the patterned optically anisotropic layer and the color filter layer as in the case where a layer, a protective film, etc. are arranged, the boundary line of the pattern of the patterned optically anisotropic layer When the image is tilted and observed in a direction not parallel to 3, 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 the laminate of the present invention is used in combination, the absorption axis of the polarizing film of one laminate is orthogonal to the stripe, and the absorption axis of the polarizing film of the other laminate is parallel to the stripe. It is preferable to set so. Details of this point will be described later.

  One embodiment of the present invention is a shutter member. When the laminate of the present invention is used as a shutter member, it is preferable because bright / dark dimming switching is clear and the appearance of the intermediate state is good. When L is less than 1 mm, the proportion of the pigment portion arranged in the patterned optically anisotropic layer increases, the light control state becomes dark, and the switching between light and dark becomes unclear. On the other hand, if L exceeds 50 mm, the shutter operating area when switching between light and dark light control becomes large, which may be undesirable for simple shutter applications.

A schematic cross-sectional view of an example of this embodiment is shown in FIG. In the figure, the same members as those in FIG. 3 are identified by the same reference numerals, and the description thereof is omitted.
The shutter member shown in FIG. 6 further includes a light transmissive substrate 15 made of a glass plate or a plastic substrate. The surface of the polarizing film protective film 14 of the laminate shown in FIG. 3 can be produced by bonding to the light transmissive substrate 15 using an adhesive. There is no restriction | limiting in particular about this adhesive, You may use an adhesive agent. Examples of adhesives that can be used include rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, Examples include acrylamide-based adhesives and cellulose-based adhesives.

  In the embodiment in which the shutter member laminate shown in FIG. 6 is used as a shutter member for windows, it is preferable that there is no tint in terms of comfort such as indoor space. The degree of the tint is affected by the characteristics of the polarizers to be laminated. For example, it has been found that when a polarizer generally used in a liquid crystal display device is used, there is a yellow tint. The yellowing of the window glass may impair the comfort of the indoor space. In addition, a light transmissive display may be mounted on a commercial building window such as a show window. However, an image displayed on the display may be colored to significantly reduce the display quality. .

  In addition, although the example which bonded the translucent board | substrate 15 to the outer surface of the polarizing film protective film 14 was shown in FIG. 6, arrangement | positioning of a translucent board | substrate is not limited to this example. The translucent substrate may be disposed between the polarizing film 13 and the patterned optically anisotropic layer 10. In the latter embodiment, a protective film for the polarizing film may be further disposed between the polarizing film and the translucent substrate.

In the technical field of display devices such as liquid crystal display devices, achieving an ideal black state is one of the technical problems. In order to achieve an ideal black, it is important to prevent light leakage at a short wavelength. Therefore, the single plate transmittance T ₁ (λ)% of the polarizing plate used in the liquid crystal display device is Generally, the following formula (i) is satisfied. In order to achieve an ideal black state, it is important to make the orthogonal transmittance T ₂ close to 0 (specifically, T ₂ should be less than 0.01%). In general, the single plate transmittance T ₁ % satisfies the following formula (ii).
(i) T ₁ (430) <38%
(ii) T ₁ (λvis) <42.5% (where λvis is an arbitrary wavelength in the visible light region)

In the aspect of the shutter member, coloration and light transmittance when used as a single plate are important characteristics. As a result of various studies by the present inventors, it has been found that coloring can be remarkably reduced by making the single-plate transmittance of short wavelength light higher than that of a polarizing plate used in a liquid crystal display device. Furthermore, coloring can be further reduced by making the single plate transmittance T ₁ in the visible light region lower than that of the polarizing plate used in the liquid crystal display device and making the orthogonal transmittance T ₂ higher than that of the polarizing plate. all right.

Specifically, in the laminate of the invention used as a shutter member (an embodiment including a translucent substrate), the single plate transmittance T ₁ (λ)% and the orthogonal transmittance T ₂ (λ %) Is preferably adjusted so as to satisfy the following formulas (1) to (4).
(1) 55% ≧ T ₁ (430) ≧ 38%
(2) 60% ≧ T ₁ (590) ≧ 42.5%
(3) 1.0 ≧ T ₁ (430) / T ₁ (590) ≧ 0.9
(4) T ₂ (430) ≧ 0.02%

Here, the single-plate transmittance T ₁ (λ)% means the ratio of light having a wavelength λ that passes through one laminate, and the orthogonal transmittance T ₂ (λ)% means a wavelength λ. This means the transmittance of the orthogonal position of the light. These can be measured by a spectrophotometer, and specifically, can be measured by an automatic polarizing film measuring apparatus “VAP-7070” (JASCO Corporation).

The expression (1) is a relational expression that specifies the range of the single-plate transmittance T ₁ of short wavelength light (for example, blue light) in the visible light range. From the viewpoint of the tinted reduction effect, the following expression (1) It is more preferable to satisfy '), and it is more preferable to satisfy the following formula (1 "). Further, the formula (2) is a single plate transmittance of center wavelength light (for example, green light) in the visible light range. It is a relational expression that specifies the range of T _1. From the viewpoint of the effect of reducing tinting, it is more preferable that the following expression (2 ′) is satisfied, and it is more preferable that the following expression (2 ″) is satisfied.
(1 ′) 55%> T ₁ (430)> 38.5%
(1 ”) 55%> T ₁ (430)> 39%
(2 ′) 60%> T ₁ (590)> 43%
(2 ″) 60%> T ₁ (590)> 45%

The equation (3) is a relational expression that specifies the ratio range of the single plate transmittance of blue light to the single plate transmittance of green light. From the viewpoint of the tinted reduction effect, T ₁ (430) / T ₁ (590) is preferably 0.91 to 0.98, and more preferably 0.91 to 0.95. Incidentally, as described above, in the polarizing plate is used on a standard display device, in order to reduce the color shift in the black state by the leakage of the short wavelength light, since the smaller the T ₁ (430), T ₁ (430) / T ₁ (590) is about 0.87.

  The formula (4) is a relational expression for specifying the transmittance at the orthogonal position, and is preferably 0.02% to 1.0% from the viewpoint of the tinted reduction effect, and is preferably 0.03 to 0. More preferably, it is 5%.

  As the light-transmitting substrate included in the laminate of this embodiment, a glass plate used for ordinary windows, and a plastic substrate such as an acrylic plate, a polycarbonate plate, or a polystyrene plate can be used. Although the preferable range of the thickness of the light-transmitting substrate varies depending on the application, it is generally 0.1 to 20 mm in a window for a building, and generally in a window for a vehicle such as an automobile, 1-10 mm.

  A shutter member can be configured by using two stacked bodies of the above-described aspect. When combining, it is preferable to laminate | stack so that a pattern optically anisotropic layer may be opposed (separated if desired). Moreover, it is preferable that the absorption axes of the polarizers included in each of the two laminated bodies to be combined are orthogonal to each other. Switching from the transmission mode to the light-shielding mode can be performed by, for example, an operation of sliding one of the stacked bodies by the width of the phase difference region of the pattern optical anisotropic layer, and includes the slide mechanism. Also good.

FIG. 7 shows a schematic cross-sectional view of an example of a shutter member in which two laminates having the aspect shown in FIG. 6 are combined. However, the pigment part, the support film 11 and the alignment film 12 were omitted. Moreover, the pattern shape of the pattern optical anisotropic layer 10 was also omitted.
In the embodiment shown in FIG. 7, the two laminates I and II of the aspect shown in FIG. 6 are laminated with the pattern optical anisotropic layer 10 facing each other and spaced apart. As shown in FIG. 5, the relationship between the in-plane slow axis of each retardation region of the patterned optically anisotropic layer 10 included in each laminate and the absorption axis of the polarizer 13 is ± 45 °. In addition, the absorption axes of the polarizers included in each polarizing plate are orthogonal to each other. For example, the absorption axis of one polarizer 13 is set to be orthogonal to the stripe of the patterned optical anisotropic layer 10, and the absorption axis of the other polarizer 13 is the stripe of the patterned optical anisotropic layer 10. Are set to be parallel to each other.

  As shown in FIG. 8A, in the state where the patterns of the patterned optically anisotropic layer 10 in the laminates I and II match, the linearly polarized light that has passed through the polarizer 13 of the laminate I has a slow axis. Since it passes through the two first phase difference regions or the two second phase difference regions having the same direction and a phase difference of λ / 4, it is converted into linearly polarized light rotated by 90 °. Since the absorption axes of the polarizer 13 included in each of the stacked bodies I and II are orthogonal to each other, the linearly polarized light is transmitted through the polarizer 13 of the stacked body II (transmission mode).

  On the other hand, as shown in FIG. 8B, when the laminate I is slid by the width of the retardation region and the patterns do not match, the linearly polarized light that has passed through the polarizer 13 of the laminate I has a slow axis. Since the directions are orthogonal to each other and pass through the first phase difference region and the second phase difference region having a phase difference of λ / 4, the polarization state is maintained without being affected by the phase difference. Since the absorption axes of the polarizer 13 included in each of the stacked bodies I and II are orthogonal to each other, the linearly polarized light is absorbed by the polarizer 13 of the stacked body II (light shielding mode).

  The shutter member can be used in various applications that require light control or light shielding properties. Specifically, for example, imaging fields such as cameras, VTRs, projector lenses, viewfinders, filters, prisms, and Fresnel lenses, lens fields such as optical disc pickup lenses such as CD players, DVD players, MD players, CDs, etc. Optical recording field for optical discs such as players, DVD players, MD players, liquid crystal light guide plates, liquid crystal display films such as polarizer protective films and retardation films, information equipment fields such as surface protective films, optical fibers, optical switches , Optical communication fields such as optical connectors, automotive headlights, tail lamp lenses, inner lenses, instrument covers, sunroofs, and other vehicle fields, eyeglasses, contact lenses, internal vision lenses, medical equipment such as medical supplies that require sterilization Field, road Transparent plate, a pair of glass lenses, lighting window and a carport, an illumination lens and light cover, architectural and construction materials such as building materials for sizing, can be suitably used for microwave cooking vessel (dishes) or the like. In particular, it can be used for windows for various buildings such as residential buildings such as ordinary houses and apartment houses, and commercial buildings such as office buildings. Moreover, it can be used not only for buildings but also for windows for vehicles such as automobiles.

Hereinafter, preferable materials and manufacturing methods of the respective constituent layers of the laminate of the present invention will be described. Needless to say, the laminate 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. 2010-141346, 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 laminate 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;
Are included 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 (ultra-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 alignment control ability here is included in the alignment film and the composition for forming an optically anisotropic layer disposed on the alignment film, even if it is specified as a change in the alignment control ability of the alignment 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. Further, 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%.

  Further, as another preferred example of the pattern alignment film used for forming the patterned optical anisotropic layer, a horizontal alignment film and an orthogonal alignment film were patterned in the same manner as the desired pattern optical anisotropic layer. A pattern alignment film is mentioned. The pattern alignment film includes, for example, a first alignment control region forming step of forming a first alignment control region made of the first composition on the transparent support, and a second composition different from the first composition. And a second alignment control region forming step of printing a second alignment control region made of the above composition in a pattern. In the above method, one of the first and second alignment control regions means a parallel alignment film, and the other means an orthogonal alignment film. The first alignment control region may be formed on the entire surface of the transparent support, or the first alignment control region may be formed on a partial region of the transparent support. In the former embodiment, the second alignment control region is printed in a pattern on a part of the first alignment control region. In the latter embodiment, the second alignment control region is the first alignment control region. Is printed in a pattern on a transparent support surface on which no is formed. For printing, for example, a flexographic printing method can be used. By aligning the pattern alignment film manufactured by this method in one direction (for example, rubbing), in one alignment control region, the major axis of the liquid crystal is parallel to the alignment processing direction and the other alignment In the control region, the orientation of the long axis of the liquid crystal can be controlled orthogonal to the orientation processing direction. The details of this method and the pattern alignment film produced by this method are described in Japanese Patent Application No. 2010-173077 (or PCT / JP2011 / 67255), and can be referred to.

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. Discotic liquid crystals are preferable, and as described above, discotic liquid crystals having a polymerizable group are more preferable. 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. Compounds are also included. 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 in a state where 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, Angelewan Chemistry International Edition England, Vol. 34, page 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 of the discotic liquid crystal at the alignment film interface, and the vicinity of the alignment film interface of the discotic liquid crystal molecules. Has the effect of increasing the tilt angle.

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 preferred 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 phenylene groups, the number of carbon atoms of 1 to 4 is 1 to 12 (more preferably 1 to 6, more preferably 1 to 6). 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. It is a polymer containing in the side chain one or more hydrophilic groups selected from the group consisting of {—OP (═O) (OH) ₂ } and salts thereof.
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. Furthermore, one or more hydrophilic groups selected from the group consisting of carboxyl group (—COOH), sulfo group (—SO ₃ H), phosphonoxy {—OP (═O) (OH) ₂ } and salts thereof When having a copolymer component contained in the side chain, 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.

Dye part:
The patterned optically anisotropic layer includes a boundary portion existing between the first and second retardation regions adjacent to each other. In this invention, it has the pigment | dye part arrange | positioned in the position corresponding to the said boundary part for the purpose of reducing the light leak etc. resulting from this boundary part existing. The dye portion is preferably present in at least one of the upper layer and the lower layer of the patterned optically anisotropic layer. There is no restriction | limiting in particular about the shape of a pigment | dye part, According to the shape of a 1st and 2nd phase difference area | region, a suitable shape is selected. For example, in an aspect in which the first and second retardation regions are formed as a stripe pattern, it is preferable to form a stripe-shaped dye portion at a position corresponding to the boundary portion.

  From the viewpoint of reducing light leakage, the pigment portion preferably has black or a hue similar to black, and preferably includes one or more pigments to have the hue. . Examples of usable dyes include dyes conventionally used for forming a black matrix of a color filter.

  The width | variety of the said pigment | dye part is 5-200 micrometers (preferably 10-150 micrometers). As described above, in the aspect in which the first and second retardation regions are formed as a stripe pattern, it is preferable to form a stripe-shaped dye portion having a width of 5 to 50 μm at a position corresponding to the boundary portion. . The method for forming the dye part is not particularly limited, and examples of a method that can stably form the dye part having the width at a predetermined position with high accuracy include a printing method and an ink jet method. An example of the printing method is a flexographic printing method.

<Polarizing film>
The laminate 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.

  In addition, in order to produce the laminated body of the aspect of the member for shutters in which the single plate transmittance and the orthogonal transmittance satisfy the characteristics of the above formulas (1) to (4), the polarization degree of the polarizer is set to a wavelength of 430 nm. It is preferably 99.8% or less when light is incident. The polarizer showing the degree of polarization can be produced by reducing the amount of iodine dyeing or reducing the overall draw ratio of polyvinyl alcohol in a normal polarizing plate production step. Moreover, in order to produce the laminated body which satisfy | fills the characteristic of said Formula (1)-(4), as a transparent substrate and the protective film of the polarizer used depending on necessity, the transmittance | permeability with a film single plate It is preferable to use those having an optical property of 90% or more.

<Polarizing film protective film and support film>
It is preferable to use a transparent polymer film for the protective film bonded to the surface of the polarizing film and the support film of the patterned optically anisotropic layer. “Transparent” means that the light transmittance is 80% or more. Moreover, as a support body film, it is preferable to use the member which hardly has an in-plane and thickness direction phase difference.

  As a material for forming a support film or the like 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 the protective film or support film, a film containing at least one selected from cellulose acylate, cyclic olefin, acrylic resin, polyethylene terephthalate resin, and polycarbonate resin as a main component is preferably used.

  Commercial products may also be used. For example, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Co., Ltd., or the like can be used. Various commercially available cellulose acylate films can also be used.

  Moreover, as the film, a film formed by any one of a solution casting method and a melt casting method can also be used. The thickness of the film is preferably 10 to 1000 μm, more preferably 40 to 500 μm, and particularly preferably 40 to 200 μm.

  There is no restriction | limiting in particular about the optical characteristic of the said film. From the viewpoint of reducing light leakage when observed from an oblique direction, the film is preferably an optically isotropic film, but is not limited to this embodiment. Specifically, a film having Re of 0 to 10 nm and an absolute value of Rth of 20 nm or less is preferable.

  In order to prevent the laminate of the present invention from being deteriorated by sunlight, any layer preferably contains an ultraviolet absorber. The ultraviolet absorber may be added in any layer. An example is an embodiment in which the protective film or the support film contains an ultraviolet absorber. As the ultraviolet absorber, it is preferable to use an ultraviolet absorber that has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less and absorbs visible light having a wavelength of 400 nm or more as much as possible from the viewpoint of light transmittance. In particular, the transmittance at a wavelength of 370 nm is desirably 20% or less, preferably 10% or less, and more preferably 5% or less. Examples of such ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and ultraviolet absorbing groups as described above. Examples thereof include, but are not limited to, polymer ultraviolet absorbing compounds. Two or more kinds of ultraviolet absorbers may be used.

When producing an ultraviolet absorber-containing film by a solution casting method, an ultraviolet absorber is added to the dope which is a solution of the main component polymer. The method of adding the ultraviolet absorber to the dope is alcohol, methylene chloride, dioxolane. It may be added after being dissolved in an organic solvent such as, or may be added directly into the dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and the main component polymer to disperse and then added to the dope.
In addition, about a cellulose acylate film, it is preferable to add a ultraviolet absorber especially and to improve light resistance.

  In this invention, the usage-amount of a ultraviolet absorber is 0.1-5.0 mass parts with respect to 100 mass parts of the main components of the said film, Preferably it is 0.5-2.0 mass parts, More preferably, it is 0.8- 2.0 parts by mass.

Dye part:
The laminate of the present invention has a dye portion disposed at a position corresponding to the boundary line of the width L1 existing between the first and second retardation regions adjacent to each other of the patterned optically anisotropic layer. Is a feature. The dye portion is preferably present in at least one of the upper layer and the lower layer of the patterned optically anisotropic layer. From the viewpoint of reducing light leakage, the pigment portion preferably has black or a hue similar to black, and preferably has one or two or more pigments. Examples of usable dyes include dyes conventionally used for forming a black matrix of a color filter. In addition, the said pigment | dye part can be formed on the said pattern optical anisotropic layer etc. using a printing method, for example, An example of the printing method is a flexographic printing method. Moreover, the said pigment | dye part can be formed with an inkjet system.

[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 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.

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 features of the present invention will be described more specifically with reference to examples and comparative 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. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Preparation and evaluation of 1.3D optical film for display device (1) Preparation of protective film and support film (CTA1 film)
The following CTA1 films were prepared.
A cellulose acylate solution (dope) having the following composition was prepared.
Dope composition:
Cellulose triacetate 100.0 parts by mass Triphenyl phosphate 7.8 parts by mass Biphenyl diphenyl phosphate 3.9 parts by mass Methylene chloride 272.0 parts by mass Methanol 93.0 parts by mass n Butanol 7.0 parts by mass UV absorber (below Of UV1, UV2 and UV3) 1.0 part by mass (UV1 / UV2 / UV3 = 0.2 / 0.4 / 0.4 (mass ratio))

A cellulose acylate film CTA1 film was produced by the solution casting method using the dope. The film forming conditions are the same as in Example 1 described in Japanese Patent No. 3974422. Some conditions are listed as follows.
Film forming speed: 60 m / min,
Layer structure: Single layer Support temperature: minus 5 ° C
Casting die temperature: 35 ° C
Moreover, the optical characteristics and film thickness of the obtained CTA1 film were as follows.
Optical characteristics: Re = 0 nm, Rth = 40 nm
Film thickness: 60 μm

(2) Preparation of patterned optically anisotropic film Preparation of patterned optically anisotropic film (film b) for Example 1:
The prepared CTA1 film was used as a support.

(Formation of pattern alignment film)
Formation of parallel alignment film (first alignment film):
On the surface of the support, a 4% water / methanol solution (PVA-103 (4.0 g)) of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. was dissolved in 72 g of water and 24 g of methanol. 44.8 dyne) was applied with a No. 12 bar and dried at 120 ° C. for 2 minutes. The thickness of the alignment film was 0.9 μm. The alignment film functions as a parallel alignment film.

Formation of orthogonal alignment film (second alignment film):
2.646 g of the following compound for orthogonal alignment films was dissolved in 0.658 g of triethylamine and 12 g of tetrafluoropropanol to prepare an orthogonal alignment film solution 1 for pattern printing.

As the flexographic plate, a synthetic rubber-like flexographic plate having irregularities with dimensions shown in FIG. 9 was prepared.
As the flexographic printing apparatus 50 shown in FIG. 10, a flexiproof 100 (RK Print Coat Instruments Ltd. UK) was used. The anilox roller 53 used a cell of 400 lines / cm (volume: 3 cm ³ / m ² ). A rubber-like flexographic plate 61 shown in FIG. 9 was bonded to the pressure drum 51 of the flexiproof 100 with a pressure sensitive tape (not shown). After pasting any one of the above support films (reference numeral 62 in FIG. 10) on the printing roller 52, the pattern printing orthogonal alignment film liquid (reference numeral 63 in FIG. 10) is applied to the doctor blade 54. Then, the orthogonal alignment film was pattern-printed on the parallel alignment film at a printing speed of 30 m / min (anilox roller pressure was 40, printing pressure roller pressure was 42, neither unit).

(Formation of pigment part (black stripe))
A black dye composition (manufactured by Dainippon Seika Co., Ltd., Hydrick FCG) was flexographically printed by the same method as the formation of the orthogonal alignment film. At this time, the width of the formed black stripe was as shown in the following table, and the black stripe was printed in a direction parallel to the orthogonal alignment film and on the boundary between the orthogonal alignment film and the parallel alignment film.

(Rubbing treatment for pattern alignment film with black stripes)
A rubbing process was performed at 1000 rpm for one reciprocation in the direction of 45 ° with respect to the stripe, and a support with a black stripe and a rubbing alignment film was produced.

(Formation of patterned optical anisotropic layer)
0.35 mL of the discotic liquid crystal composition 1 having the following composition was spin coated on the rubbed patterned alignment film with black stripes (2500 rpm, 10 seconds) and heated at 90 ° C. for UV irradiation (10 seconds) ) And cured, the alignment was confirmed with a microscope.
-Discotic liquid crystal composition 1
The following polymerizable liquid crystal 3 / the following polymerization initiator 2 / the following sensitizer 1 / the following pyridinium compound 1 / the following air interface aligning agent 2 / the following air interface aligning agent 3 (= 100: 3: 1: 2: 0.3: 0.5) MEK solution with a solid content of 20%

  The width of the first and second phase difference regions was 3 mm, and the boundary portion was shielded by black stripes and could not be observed. The width of the black stripes was 50 μm. Further, it was confirmed that the in-plane slow axes of the first and second retardation regions were ± 45 ° with respect to the longitudinal direction of the stripe pattern, and the discotic liquid crystal was vertically aligned in each region.

  In this way, a film b having a patterned optically anisotropic layer for Example 1 was produced. Re and Rth as a whole of the film b for Example 1, the film thickness, and the direction of the in-plane slow axis of the first and second retardation regions of the patterned optically anisotropic layer in the major axis direction, formed in stripes The width L of each phase difference region thus obtained is shown in the following table.

Production of patterned optically anisotropic film (film b) for Example 2:
In the production of the film b for Example 1, the pigment portion is the back surface (the surface on the side where the patterned optical anisotropic layer is not formed) of the support CTA1 film of the patterned optical anisotropic layer, and the first And the film b for Example 2 was produced like Example 1 except having formed in the position corresponding to the boundary part of a 2nd phase difference area | region. Re and Rth as a whole of the film b for Example 2, the film thickness, and the direction of the in-plane slow axis of the first and second retardation regions of the pattern optical anisotropic layer in the major axis direction, formed in stripes The width L of each phase difference region thus obtained is shown in the following table.

Production of patterned optically anisotropic film (film b) for Comparative Example 1:
In the production of the film b for Example 1, a film b for Comparative Example 1 was produced in the same manner as in Example 1 except that the pigment portion was not formed. Re and Rth as a whole of the film b for Example 2, the film thickness, and the direction of the in-plane slow axis of the first and second retardation regions of the pattern optical anisotropic layer in the major axis direction, formed in stripes The width L of each phase difference region thus obtained is shown in the following table.

(3) Production of patterned laminate with optically anisotropic layer The surface of the separately prepared CTA1 film was subjected to alkali saponification treatment.
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 alkali saponified CTA1 film (film a) was bonded to one side of a polarizing film using a 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) as an adhesive, and on the other side, the above prepared Example 1 was prepared. The CTA1 film surface of the film b for use was bonded through an adhesive. Thus, the laminated body with an optically anisotropic layer for Example 1 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.

  Except that the film b for Example 1 was replaced with the film b for Example 2 and the film b for Comparative Example 1, respectively, in the same manner as described above, the laminate with the optically anisotropic layer for Example 2 and the comparative example 1 were used. Each laminated body with an optically anisotropic layer was produced.

(4) Production of stereoscopic display device The pattern retardation plate and front polarizing plate used in the 3D monitor W220S (manufactured by Hyundai) with circularly polarized glasses are peeled off, and the laminates produced above are bonded together to produce a stereoscopic display. Each device was fabricated. 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.

(8) 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).
Example 1 in which the dye portion was formed in contact with the surface of the patterned optically anisotropic layer was the best, and the crosstalk evaluation was 7 in any direction (Evaluation A).
Example 2 in which the dye portion was formed on the back surface of the CTA1 film as the support film also had good crosstalk evaluation, but was slightly inferior to Example 1 and had polar angles of 90 and 270 degrees. The crosstalk evaluation when observed from the degree was 5 (evaluation B).
In Comparative Example 1 in which the dye portion was not formed, the crosstalk evaluation was 7 when the polar angle was 0 °, but the evaluation was 2 when the azimuth angle was 0 ° and the polar angle was 45 °, and the azimuth angle was 90 °. Evaluation was 3 at a polar angle of 10 degrees of 270 degrees, which was inferior to Examples 1 and 2 (Evaluation C).
The results are summarized in the table below.

In Example 1, except that the width of the dye portion was changed to 3 μm and 310 μm, respectively, a laminated body with an optically anisotropic layer patterned in the same manner was prepared and mounted on a stereoscopic image display device. As evaluated in the same manner, the crosstalk is not sufficiently improved for the former, which is inferior to that of Example 1. For the latter, the proportion occupied by the dye region portion is high, and the light transmittance is Compared with Example 1, it was inferior.
Further, except that the width of the dye portion was changed to 10 μm and 180 μm, respectively, a laminate with an optically anisotropic layer patterned in the same manner was prepared, mounted on a stereoscopic image display device, and similarly evaluated. However, it was found that display performance almost equivalent to that in Example 1 was obtained.

2. Production and evaluation of shutter member (1) Preparation of light-transmitting substrate A glass plate was prepared as a light-transmitting substrate.

(2) Preparation of Polarizer A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 65 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution in which the concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) was adjusted to about 20% and stretching. Thereafter, in the boric acid ester aqueous solution at 65 ° C., the total draw ratio was adjusted by adjusting the draw ratio. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and produced the polarizer. The thickness of the polarizer was about 20 μm.

(3) Production of patterned laminate with optically anisotropic layer Example 11:
One film b for Example 1 was prepared in the same manner as described above. However, the pigment portion was formed at a position corresponding to the boundary portion by an inkjet method using black ink. The width of the dye portion was 50 μm.
The surface of the CTA1 film prepared separately was subjected to alkali saponification treatment.
Subsequently, the above-mentioned alkali saponified CTA1 film (film a) was bonded to one side of the polarizer prepared above as an adhesive with a 3% aqueous solution of polyvinyl alcohol (PVA-117H made by Kuraray), and further to the other side. Attached the CTA1 film surface of the produced film b for Example 1 through an adhesive. This laminate was bonded to the surface of the glass plate using a SK2057 pressure sensitive adhesive manufactured by Soken Chemical Co., Ltd., to produce a laminate of shutter members for Example 11.

Example 12:
Film b for Example 1 was film b for Example 2 (however, the dye part was formed at a position corresponding to the boundary part by an ink jet method using black ink. The width of the dye part was 50 μm) A laminated body of shutter members for Example 12 was produced in the same manner as described above except that the above was changed.

Examples 13 and 14:
Two films b for comparative example 1 in which a pigment part is not formed were prepared.
Two films (film a) having a pigment portion formed on the surface of the separately prepared CTA1 film were prepared. In addition, when the pigment | dye part formed in the CTA1 film surface is bonded with the film b for Comparative Example 1 through a polarizer, it becomes a position corresponding to the boundary line of the first and second retardation regions of the film. Formed.
Example 13 was carried out in the same manner as the polarizing plate for Example 11, except that the CTA1 film (film a) on which the dye portion was formed was used and the film b for Comparative Example 1 was used instead of the film b for Example 1. Laminate plates of shutter members for and 14 were prepared. In the laminated body of the shutter member for Example 13, the surface on which the dye portion of the CTA1 film was formed was bonded with the polarizer side. In the laminated body of the shutter member for Example 14, the CTA1 film was laminated. The surface on which the dye portion was not formed was bonded to the polarizer side.

Example 15:
One film b for Comparative Example 1 in which no pigment portion was formed was prepared.
A pigment portion was formed on the surface of a separately prepared glass plate. In addition, the pigment | dye part formed in the glass plate surface was formed so that it might become a position corresponding to the boundary line of the 1st and 2nd phase difference area | region of the film b for Comparative Examples 1 bonded.
The surface of the separately prepared CTA1 film (film a) was subjected to alkali saponification treatment.
Subsequently, the alkali saponified CTA1 film was bonded to one side of the polarizer prepared above using a 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) as an adhesive, and the other side was prepared as described above. The CTA1 film surface of the comparative example 1 film b was bonded with an adhesive. This laminate was bonded to the surface of the glass plate on which the dye portion was formed using a SK2057 pressure sensitive adhesive made by Soken Chemical Co., Ltd., to produce a polarizing plate for Example 15.

Comparative Example 11:
A shutter member laminate for Comparative Example 11 was prepared in the same manner as in Example 11 except that the film b for Example 1 was replaced with the film b for Comparative Example 1.

(4) Evaluation For each of the laminates of the shutter members for Examples 11 to 15 and Comparative Example 11 produced above, the spectral transmittance was measured using an automatic polarizing film measuring device “VAP-7070” (JASCO Corporation). And measured at a measurement wavelength of 380 to 780 nm. The results are shown in the table below.

  Each of the laminates of the shutter members for Examples 11 to 15 and Comparative Example 11 produced above was combined as shown in FIG. 7 and slided as shown in FIG. The light property was evaluated. Light leakage in the front and oblique directions in the dark state, the appearance in the dark state, and the appearance in the intermediate state (L / 2; half the distance slide with respect to the distance L that is moved during the slide operation that brightens or darkens by the slide operation) And measuring the distance from the device where the state appears gray) was evaluated according to the following criteria.

Evaluate light and dark light control:
AA: There is no light leakage including the oblique direction.
A: There is no light leakage from the front, but light leaks slightly from an oblique direction.
B: Light leakage from the front is slight, but there is light leakage from an oblique direction.
C: Light leakage is large in both front and oblique directions.

Appearance evaluation during light dimming:
A: It looks transparent.
B: There is a slightly grayish part.
C: Light transmittance is low and looks grayish.

Appearance evaluation of intermediate state AA: It looks gray at a distance of 1 m.
A: It looks gray when it is more than 3m away.
B: Even if it is 5 m away, it does not look gray.

  The results are shown in the table below. As shown in the table below, even in the mode used for the shutter, the closer the pigment portion is to the pattern optical anisotropic layer, the better the characteristics, and the more the contact with the pattern optical anisotropic layer becomes. It can be understood that the most excellent characteristics are formed.

In Example 1, except that the width of the dye portion was changed to 3 μm and 310 μm, respectively, a laminated body with an optically anisotropic layer patterned in the same manner was prepared and mounted on a shutter member. As a result, the light leakage in the dark dimming state was inferior to that in Example 1 for the former, and the light transmittance in the light dimming state was insufficient for the latter. It was inferior.
Furthermore, except that the width of the dye portion was changed to 10 μm and 180 μm, respectively, a laminated body with an optically anisotropic layer patterned in the same manner was prepared, mounted on a shutter member, and evaluated in the same manner. It was found that display performance almost equivalent to that in Example 1 was obtained with any width.

3. Production and evaluation of shutter member (1) Production of protective film and support film (CTA1 film and CTA2 film)
A CTA1 film was produced in the same manner as described above.
A cellulose triacetate film was prepared in the same manner except that the UV agent was not added, and used as a CTA2 film.

(COP film)
“ZF14” manufactured by Nippon Zeon Co., Ltd. was prepared as a film containing a cyclic olefin polymer as a main component.

(2) Production of patterned optically anisotropic film As the support film for the patterned optically anisotropic layer, any one of the above CTA1, CTA2 and COP films is used, and the width L of the stripe pattern of the patterned optically anisotropic layer is as follows: Each pattern optically anisotropic film (film b in the table) was prepared in the same manner as described above with the changes shown in the table. In all cases, a dye portion having a width of 50 μm was formed in contact with the pattern optical anisotropic layer so as to cover the position corresponding to the boundary portion of the pattern.

(3) Production of patterned laminated body with optically anisotropic layer Except for changing the bonding position of the polarizing film, the protective film for polarizing film, or the glass plate, respectively, Each laminate was manufactured.
The polarizing film was the same as described above.
(4) Evaluation About the produced laminated body of each member for shutters, the spectral transmittance was measured at a measurement wavelength of 380 to 780 nm using an automatic polarizing film measuring device “VAP-7070” (JASCO Corporation). The results are shown in the table below.

  As shown in FIG. 7, the laminates of the shutter members prepared above were combined as shown in FIG. 7 and slid as shown in FIG. The light leakage in the front direction and the oblique direction in the dark state and the appearance in the dark state were evaluated based on the same criteria as above.

Light resistance evaluation:
About each laminated body, after irradiating the xenon lamp for 500 hours, the single-plate transmittance | permeability was measured, respectively, and the following references | standards evaluated.
A: The transmittance change was less than 10%.
B: The transmittance change was 10% or more and less than 30%.
C: The transmittance change was 30% or more.

From the above result, the position corresponding to the boundary portion of the first and second retardation regions having the pattern optical anisotropic layer whose distance L between two adjacent boundary lines is 1 mm to 50 mm and adjacent to each other. It can be understood that Examples having at least a dye portion arranged in the above are excellent in light and dark dimming properties and in an intermediate state.
On the other hand, in Comparative Example 21 in which L is less than 1 mm, the light dimming state is dark, the light / dark dimming switching is not clear, and the appearance of the intermediate state is inferior to that of the example.
Further, in Comparative Example 23 in which L exceeded 50 mm, the appearance of the intermediate state was significantly inferior compared to the Examples.

DESCRIPTION OF SYMBOLS 1 1st phase difference area | region 2 2nd phase difference area | region 3 Boundary part 4 Dye part 10 Pattern optically anisotropic layer 11 Transparent support body (1st film)
DESCRIPTION OF SYMBOLS 12 Alignment film 13 Polarizing film 14 Polarizing film protective film 15 Light transmissive substrate 16 Color filter layer

Claims (17)

A laminate comprising a polarizer, a first film, and a patterned optical anisotropic layer disposed on one surface of the first film,
The patterned optically anisotropic layer has a first retardation region and a second retardation region, and the first retardation region and the second retardation region are arranged in the same plane, The 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 of the boundary line between the first phase difference region and the second phase difference region, A pattern optical anisotropic layer having a distance L between two adjacent boundary lines of 1 mm to 50 mm; and a boundary portion between the first and second retardation regions adjacent to each other of the pattern optical anisotropic layer. A laminate having a pigment portion having a width of 5 μm to 200 μm arranged at a corresponding position. The laminate according to claim 1, wherein the dye portion is disposed in contact with the surface of the patterned optically anisotropic layer. The laminate according to claim 1 or 2, wherein at least one layer contains at least one ultraviolet absorber. The laminate according to any one of claims 1 to 3, wherein the first and second retardation regions have a stripe shape with a width L. The laminate according to any one of claims 1 to 4, wherein an in-plane slow axis of each of the first and second retardation regions and a transmission axis of the polarizer each form an angle of ± 45 °. The laminated body according to any one of claims 1 to 5, wherein a total value of in-plane retardation Re (550) of a wavelength of 550 nm of all members excluding the polarizer of the laminated body is 110 to 160 nm. The laminate according to any one of claims 1 to 6, further comprising an alignment film that is aligned in one direction and adjacent to the patterned optically anisotropic layer. The laminate according to claim 7, wherein the alignment film is a rubbing alignment film that is rubbed in one direction. The laminate according to any one of claims 1 to 8, wherein the patterned optically anisotropic layer is a layer formed from a composition mainly composed of a discotic liquid crystal having a polymerizable group. The laminate according to claim 9, wherein the discotic liquid crystal is fixed in a vertically aligned state. The laminate according to any one of claims 1 to 10, further comprising a second film, wherein the polarizer is disposed between the first and second films. The main component of the first film or the second film is selected from at least one of cellulose acylate, cyclic olefin, acrylic resin, polyethylene terephthalate resin, and polycarbonate resin. The laminate according to item. It is an optical film for 3D display apparatuses, The laminated body of any one of Claims 1-12. The laminate according to any one of claims 1 to 12, which is used as a shutter member. The laminate according to claim 14, wherein a single plate transmittance T ₁ (λ)% at a wavelength λnm satisfies the following formulas (1) and (2).
(1) 55% ≧ T (430) ≧ 38%
(2) 60% ≧ T (590) ≧ 42.5% The laminate according to claim 14 or 15, wherein the single plate transmittance T ₁ (λ)% satisfies the following formula (3).
(3) 1.0 ≧ T (430) / T (590) ≧ 0.9 The laminate according to any one of claims 14 to 16, wherein an orthogonal transmittance T ₂ (λ)% at a wavelength λnm satisfies the following formula (4).
(4) T ₂ (430)> 0.02%

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