TW201923394A - Method for manufacturing polarizing film, and polarizing film - Google Patents

Abstract

The method for manufacturing a polarizing film according to the present invention has: a patterned liquid repellent layer formation step for forming a patterned liquid repellent layer on at least one side of a substrate layer and obtaining a substrate layer provided with a patterned liquid repellent layer; a patterned alignment layer formation step for obtaining a substrate layer provided with a patterned alignment layer, having a patterned alignment layer formed by applying an alignment-layer-forming composition to a surface on the patterned liquid repellent layer side of the substrate layer provided with the patterned liquid repellent layer; and a patterned alignment layer formation step for forming a patterned alignment layer by applying a polarizing-layer-forming composition including a liquid crystal compound and a dichroic dye to the surface on the patterned alignment layer side of the substrate layer provided with the patterned alignment layer. The patterned liquid repellent layer exhibits liquid repellency with respect to the alignment-layer-forming composition and the polarizing-layer-forming composition.

Description

Manufacturing method of polarizing film and polarizing film

The present invention relates to a method for manufacturing a polarizing film and a polarizing film, and more particularly to a method for manufacturing a polarizing film having a layer containing a liquid crystal compound and a dichroic pigment and a polarizing film.

Compared with liquid crystal display devices, organic EL (Electroluminescence) display devices using organic light-emitting diodes (OLEDs) can not only reduce weight or thickness, but also achieve a wide range of viewing angles and faster response. Speed, high contrast and other high image quality, so it is used in various fields such as smart phones or TVs, digital cameras. It is known that in organic EL display devices, a circular polarizing plate or the like is used to improve the anti-reflection performance in order to suppress the decrease in visibility caused by the reflection of external light.

The polarizing film used in such a circular polarizing plate is disclosed in Japanese Patent Laid-Open Publication No. 2015-206852 (Patent Document 1) and Japanese Patent Laid-Open Publication No. 2015-212823 (Patent Document 2). A patterned polarizing film of a patterned liquid crystal hardened film is laminated.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-206852
[Patent Document 2] Japanese Patent Laid-Open No. 2015-212823

[Problems to be solved by the invention]

An object of the present invention is to provide a novel method for manufacturing a polarizing film and a polarizing film having at least two regions where the visual sensitivity correction polarizations are different from each other.
[Technical means to solve the problem]

The present invention provides a method for producing a polarizing film and a polarizing film described below.
[1] A method for manufacturing a polarizing film, including the following steps:
The patterned liquid-repellent layer forming step is to form a patterned liquid-repellent layer on at least one side of the base material layer to obtain a base material layer with a patterned liquid-repellent layer;
The patterned alignment layer forming step is to obtain a base material layer with a patterned alignment layer. The base material layer with the patterned alignment layer has the patterned dial on the base layer with the patterned liquid-repellent layer. A patterned alignment layer formed by applying the composition for forming an alignment layer on the surface of the liquid layer side; and a patterned polarizing layer forming step, because of the patterned alignment layer side of the substrate layer with the patterned alignment layer A polarizing layer-forming composition containing a liquid crystal compound and a dichroic dye is applied on the surface to form a patterned polarizing layer;
The patterned liquid-repellent layer exhibits liquid-repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer.
[2] The method for manufacturing a polarizing film according to [1], wherein the step of forming the patterned liquid-repellent layer includes the following steps:
The substrate layer coating step is obtained by attaching at least one side of the substrate layer with a protective layer for covering the substrate layer and an exposed area for exposing the substrate layer. Base layer of protective layer;
The step of forming a liquid-repellent layer is to apply a liquid-repellent agent to the surface of the protective layer side of the base layer with the protective layer, so as to obtain the base layer with the liquid-repellent layer on which the liquid-repellent layer is formed; and In the layer removing step, the protective layer is peeled off from the base material layer with the liquid-repellent layer, and a part of the liquid-repellent layer is removed to form the patterned liquid-repellent layer.
[3] The method for manufacturing a polarizing film according to [2], wherein the planar shape of the exposed area is circular, oval, oblong, or polygonal,
When the exposed area is circular, the diameter is 5 cm or less.
In the case where the above-mentioned exposed area is oval or oblong, the long diameter is 5 cm or less,
In the case where the exposed area is polygonal, the diameter of the imaginary circle drawn in the manner of the polygon inscribed above is 5 cm or less.
[4] The method for producing a polarizing film according to any one of [1] to [3], wherein the step of forming the patterned liquid-repellent layer is performed by applying a liquid-repellent agent dropwise on at least one side of the substrate layer. The above-mentioned patterned liquid-repellent layer is formed.
[5] The method for producing a polarizing film according to any one of [1] to [4], wherein the composition for forming an alignment layer contains a photo-alignment polymer,
The patterned alignment layer forming step is performed by applying polarized light to a coating layer for a patterned alignment layer formed by applying the composition for forming an alignment layer to form the patterned alignment layer.
[6] The method for producing a polarizing film according to any one of [1] to [5], wherein the liquid crystal compound is a polymerizable liquid crystal compound,
The patterned polarizing layer forming step is to irradiate the coating layer for patterned polarizing layer formed by applying the composition for forming a polarizing layer with active energy rays to form the patterned polarizing layer.
[7] The method for producing a polarizing film according to any one of [1] to [6], wherein the patterned polarizing layer shows a Blegg peak in an X-ray diffraction measurement.
[8] The method for producing a polarizing film according to any one of [1] to [7], wherein the length of the polarizing film is 10 m or more.
[9] The method for producing a polarizing film according to any one of [1] to [8], wherein the substrate layer has a 1/4 wavelength plate function.
[10] A method for manufacturing a circular polarizing plate having a retardation lamination step, a polarizing film manufactured by a method for manufacturing a polarizing film according to any one of [1] to [8], and 4-wavelength plate with phase difference layering.
[11] The method for manufacturing a circular polarizing plate according to [10], wherein the polarizing film is a long polarizing film having a length of 10 m or more,
The phase difference layer is a long phase difference layer with a length of 10 m or more.
The step of laminating the phase difference is to form a long laminated body by laminating the long polarizing film and the long phase difference,
Furthermore, it has a cutting step of cutting the said long laminated body into a single piece.
[12] A polarizing film, which has a polarized area on the substrate layer and a low-polarized area with a correction sensitivity lower than the visual sensitivity of the polarized area,
The above-mentioned polarization region contains a liquid crystal compound and a dichroic pigment, and the visual sensitivity correction polarization degree is 90% or more.
The low-polarization region has a liquid-repellent layer.
[13] The polarizing film according to [12], wherein the visual sensitivity correction polarization degree of the low polarization region is 10% or less.
[14] The polarizing film according to [12] or [13], wherein the visual sensitivity correction monomer transmittance of the above-mentioned polarized region is more than 35%,
The visual sensitivity correction unit transmittance of the low-polarized light region is 80% or more.
[Effect of the invention]

According to the present invention, it is possible to provide a method for manufacturing a polarizing film having at least two regions with different polarized degrees of visual sensitivity correction.

Hereinafter, a method for manufacturing a polarizing film and a preferred embodiment of the polarizing film of the present invention will be described with reference to the drawings. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made without departing from the scope of the present invention.

[First embodiment (manufacturing method of polarizing film and polarizing film)]
The manufacturing method of the polarizing film of the present invention has the following steps:
A patterned liquid-repellent layer forming step, that is, forming a patterned liquid-repellent layer on at least one side of the base material layer to obtain a base material layer with a patterned liquid-repellent layer;
The patterned alignment layer forming step is to obtain a patterned alignment layer having a patterned alignment layer formed by applying a composition for forming an alignment layer on the surface of the patterned liquid repellent layer side of the base material layer with the liquid repellent layer. Layered substrate layer; and a patterned polarizing layer forming step, that is, a layer for forming a polarizing layer containing a liquid crystal compound and a dichroic pigment is coated on the surface of the patterned alignment layer side of the substrate layer with the patterned alignment layer The composition forms a patterned polarizing layer. The patterned liquid-repellent layer exhibits liquid-repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer.

Examples of the method for forming the patterned liquid-repellent layer in the step of forming the patterned liquid-repellent layer include a method of forming a patterned liquid-repellent layer using a protective layer, and forming a patterned liquid-repellent layer by dropwise application of a liquid-repellent agent. Method. Hereinafter, each method will be described in detail.

<First Production Method of Polarizing Film>
FIG. 1 is a schematic plan view showing an example of a polarizing film of the present invention. 2 (a) to (e) are schematic cross-sectional views showing the layer structure obtained in each step of the manufacturing steps of the first manufacturing method of the polarizing film shown in FIG. FIG. 2 (e) is a sectional view taken along the line XX of FIG. 1. FIG. The patterning liquid-repellent layer forming step in the first manufacturing method of the polarizing film 2 has the following steps:
The base material layer coating step is that, since at least one side of the base material layer 13 has a covering area 37a for covering the base material layer 13 and a protective layer 37 for exposing the area 37b for exposing the base material layer 13, A substrate layer 81 with a protective layer is obtained (FIG. 2 (a));
The liquid-repellent layer forming step is to apply a liquid-repellent agent to the surface of the protective layer 37 side of the base-material layer 81 with the protective layer, so as to obtain the base-material layer 82 with the liquid-repellent layer 47 ( FIG. 2 (b)); and the protective layer removing step, that is, by peeling off the protective layer from the base material layer 82 with the liquid-repellent layer attached, and removing a part of the liquid-repellent layer 47 to form a patterned liquid-repellent layer 47b (FIG. 2 (c)).

The first manufacturing method of the polarizing film 2 has the following steps: a patterned alignment layer forming step, that is, obtaining a substrate layer 83 with a patterned liquid-repellent layer obtained by going through the patterned liquid-repellent layer forming step described above ( The patterned liquid-repellent layer 47b on the side of the patterned liquid-repellent layer 47b in FIG. 2 is coated with the composition for forming an alignment layer. The patterned alignment layer 22 has a substrate layer 84 with a patterned alignment layer (FIG. 2 (d)). ); And the step of forming a patterned polarizing layer, that is, the composition for forming a polarizing layer containing a liquid crystal compound and a dichroic pigment is coated on the surface of the patterned alignment layer 22 side of the base material layer 84 with the patterned alignment layer To form a patterned polarizing layer 21. Thereby, a polarizing film 2 having a patterned polarizing layer as shown in FIG. 1 and FIG. 2 (e) can be manufactured, for example.

(Polarizing film)
An example of a polarizing film obtained by the above-mentioned manufacturing method will be described. The polarizing film 2 shown in FIG. 1 is a film having a function of light absorption anisotropy, and has a patterned polarizing layer 21 on a substrate layer 13. The patterned polarizing layer 21 has a polarization region 21 a and a low polarization region 21 b having a visual sensitivity-corrected polarization degree (Py) lower than that of the polarization region 21 a. The polarized region 21 a contains a liquid crystal compound and a dichroic pigment, and the visual sensitivity correction polarization (Py) is 90% or more. The low-polarization region 21b preferably has a patterned liquid-repellent layer (liquid-repellent layer) 47b, and does not contain a liquid crystal compound and a dichroic dye.

The polarizing film 2 is one having a patterned polarizing layer 21 on the base material layer 13, and may further include a patterning alignment layer 22 and other layers. Details of the patterned alignment layer 22 are described below. Examples of the other layer include a surface protection layer provided on the surface of the patterned polarizing layer 21 on the side opposite to the base material layer 13 for the purpose of protecting the surface of the patterned polarizing layer 21. In the case where the release base material layer 13 is used, a surface protective layer may be provided on a surface of the patterned polarizing layer 21 on the side of the release base material layer 13. The surface protective layer may have a single-layer structure or a multilayer structure. When the surface protective layer has a multilayer structure, each layer may be formed of the same material or may be formed of materials different from each other.

Furthermore, in the polarizing film 2 shown in FIG. 2 (e), an example in which an alignment layer and a patterned polarizing layer 21 are provided on one side of the base material layer 13 is disclosed, but it may be provided on both sides of the base material layer 13. It has an alignment layer and a patterned polarizing layer. The structures of the patterned polarizing layers provided on both sides of the substrate layer 13 may be the same as each other or different from each other.

The polarizing film 2 may be a long polarizing film having a length of 10 m or more. In this case, the polarizing film 2 may be a rolled body wound into a roll shape. The polarizing film can be continuously rolled out from the wound body, and steps such as a step of laminating with a retardation described below, a step of cutting into a single sheet, and the like can be performed. There is no particular limitation on the length of the long polarizing film to be a roll, as long as it is 10 m or more, and it may be, for example, 10,000 m or less.

The polarized region 21 a is formed on the base material layer 13 and contains a liquid crystal compound and a dichroic dye. An alignment layer 22 a may be provided between the polarized region 21 a and the substrate layer 13. The visual sensitivity correction polarization (Py) of the polarized region 21a is preferably 90% or more, more preferably 92% or more, still more preferably 95% or more, and usually 100% or less. In addition, the visual sensitivity correction unit transmittance (Ty) of the polarized region 21a is, for example, preferably 35% or more, more preferably 40% or more, still more preferably 44% or more, and usually less than 50%.

The low-polarization region 21 b is preferably one having a liquid-repellent layer (patterned liquid-repellent layer) 47 b formed on the substrate layer 13 and not having an alignment layer or a polarizing layer. The visual sensitivity correction polarization (Py) of the low-polarization region 21b may be, for example, 10% or less, preferably 5% or less, more preferably 1% or less, or 0%. The visual sensitivity correction unit transmittance (Ty) of the low-polarization region 21b may be, for example, 80% or more, preferably 85% or more, more preferably 88% or more, and usually 98% or less.

The visual sensitivity-corrected polarization (Py) and the visual sensitivity-corrected monomer transmittance (Ty) in this specification can be calculated based on the polarized light and the monomer transmittance measured using a spectrophotometer. For example, the spectrophotometer can be used for a device provided with a folder with a polarizing element, and the two-beam method can be used to measure the transmission axis direction (alignment vertical direction) in the range of 380 nm to 780 nm as the wavelength of visible light. Transmittance (T ₁ ) and transmittance (T ₂ ) in the direction of the absorption axis (aligned in the same direction). The degree of polarization and monomer transmittance in the visible light range are calculated using the following formulae (Equation 1) and (Equation 2) at each wavelength, and the degree of polarization and monomer transmittance are calculated according to JIS Z 8701's 2-degree field of view (C light source). ) To perform visual sensitivity correction, thereby calculating the visual sensitivity correction unit transmittance (Ty) and visual sensitivity correction polarization (Py).

Polarization [%] = {(T ₁ -T ₂ ) / (T ₁ + T ₂ )} × 100 (Equation 1)
Cell transmittance [%] = (T ₁ + T ₂ ) / 2 (Equation 2)

The occupied area of the polarized region 21 a and the occupied area of the low-polarized region 21 b may be appropriately selected according to the characteristics required of the polarizing film 2. The ratio of the total occupied area of the polarized region 21a and the low-polarized region 21b to the surface area of the polarizing film 2 is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. The occupied area of the polarized region 21a is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more of the total area of the occupied area of the polarized region 21a and the occupied area of the low-polarized region 21b. For example, as shown in FIG. 1, the occupied area of the low-polarization region 21 b is smaller than the occupied area of the polarized region 21 a and the polarized region 21 a is provided so as to surround the low-polarized region 21 b. In the polarizing film 2 shown in FIG. 1, a polarizing region 21 a is provided so as to surround a circular low-polarizing region 21 b, but a plurality of low-polarizing regions 21 b may be independently provided.

The shape of the polarized region 21a and the shape of the low-polarized region 21b are not particularly limited. For example, as shown in FIG. 1, when the polarized region 21a is provided so as to surround the low-polarized region 21b, the plan shape of the low-polarized region 21b can be formed as Circles; ovals; oblongs; triangles, squares, rectangles, rhombuses, and other polygons; text shapes; combinations of these and other arbitrary shapes.

The plan view shape of the low-polarization region 21b is preferably circular, elliptical, oblong, or polygonal. When the low polarization region 21b is circular, its diameter is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less. When the low polarization region 21b is oval or oblong, its long axis is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less. In the case where the low-polarization region 21b is a polygon, the diameter of an imaginary circle drawn in the polygon inwardly is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less. The low-polarization region 21b having the above-mentioned shape can be preferably used as a region corresponding to a lens position of a camera provided on a smart phone or a tablet. At this time, by setting the low polarization region 21b to a region where the visual sensitivity correction polarization (Py) is 10% or less and the visual sensitivity correction unit transmittance (Ty) is 80% or more, the coloring of the low polarization region 21b can be reduced. , To obtain excellent transparency, so can improve the performance of the camera.

Furthermore, the polarized region 21 a and the low-polarized region 21 b may be provided so that their respective planar shapes are linear, band-shaped, or wavy. In this case, a plurality of polarized regions 21 a and low-polarized regions 21 b may be alternately provided. In this case, the widths of the polarized region 21a and the low-polarized region 21b are independent, preferably 1 μm to 10 mm, more preferably 1 μm to 1 mm, and even more preferably 1 μm to 100 μm.

Furthermore, in the case where the polarizing film is a long polarizing film, the long polarizing film is usually cut to a specific size according to the use of the polarizing film, etc., so it is preferably a specific position of the polarizing film after cutting In the method of forming the polarized region 21a or the low-polarized region 21b, the arrangement of the polarized region or the low-polarized region of the long polarizing film is set. For example, when the polarizing film after cutting is the polarizing film 2 shown in FIG. 1, it is preferable to set a plurality of low-polarization regions 21b at specific intervals in the longitudinal direction and / or the width direction of the long polarizing film. .

The thickness of the polarizing region 21a of the patterned polarizing layer 21 is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 5 μm or less, and even more preferably 3 μm or less. The thickness of the patterned liquid-repellent layer 47b is usually 1 to 200 nm, and preferably 1 to 20 nm. The thickness of the polarized region 21a and the thickness of the patterned liquid-repellent layer 47b can be measured by an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

Next, each step of the manufacturing method of the polarizing film 2 is demonstrated based on FIG.2 (a)-(e).
(Substrate layer coating step)
In the base material layer coating step, as shown in FIG. 2 (a), at least one side of the base material layer 13 has a coating area 37 a for covering the base material layer 13 and a base layer 13 for exposing the base material layer 13. The protective layer 37 of the region 37b is exposed. Thereby, the base material layer 81 with a protective layer can be obtained.

The exposed area 37 b of the protective layer 37 may be, for example, an opening of the protective layer 37. When the coating region 37 a is coated with the following liquid-repellent agent on the base material layer 81 with the protective layer, the liquid-repellent agent can be prevented from being applied to the base material layer 13. On the other hand, in the exposed area 37 b of the protective layer 37, a liquid-repellent agent can be applied on the base material layer 13.

As described below, the patterned liquid-repellent layer 47b is formed on the base material layer 13 by the liquid-repellent agent applied in the exposed area 37b. As described below, it is difficult to form an alignment layer or a polarizing layer on the patterned liquid-repellent layer 47b. Therefore, the exposed region 37 b is preferably formed corresponding to the low-polarization region 21 b of the polarizing film 2. For example, when manufacturing the polarizing film 2 shown in FIGS. 1 and 2 (e), it is preferable to determine the shape of the polarizing film 2 according to the shape of the low-polarization region 21b. For example, if the top-view shape of the low-polarization region 21b is circular; elliptical; oblong; polygons such as triangles, squares, rectangles, and rhombuses; line-shaped; band-shaped; It can be formed.

For example, when the exposed area 37b is circular, the diameter is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less. When the exposed area 37b is oval or oblong, its long axis is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less. In the case where the exposed area 37b is polygonal, the diameter of the imaginary circle drawn in the polygonal inscribed manner is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 2 cm or less.

In addition, the liquid-repellent layer 47 is formed on the coating region 37a in the coating region 37a of the protective layer 37. Therefore, it is preferable to form the liquid-repellent layer 47 corresponding to the region on the base material layer 13 where the liquid-repellent layer 47 is not formed. It is difficult to form an alignment layer or a polarizing layer on the patterned liquid-repellent layer 47b. Therefore, for example, when manufacturing the polarizing film 2 shown in FIGS. 1 and 2 (e), it is preferable to determine the shape according to the shape of the polarizing region 21a. shape.

(Base material layer)
The substrate layer 13 can be used to support the patterned alignment layer 22 or the patterned polarizing layer 21 when manufacturing the polarizing film 2, and can also be used to support the patterned polarizing layer 21 of the polarizing film 2.

The substrate layer 13 may be a glass substrate or a resin substrate, and is preferably a resin substrate. In addition, in terms of the ability to continuously manufacture the polarizing film 2, the base material layer 13 is more preferably a roll-up of a long resin base material wound into a roll shape. The resin substrate is preferably a substrate having a light-transmitting property capable of transmitting visible light. Here, the term "light-transmitting property" refers to a visual sensitivity correction monomer transmittance of light in a wavelength range of 380 to 780 nm, which is 80% or more.

The thickness of the base material layer 13 is preferably thin in terms of practically operable quality, but if it is too thin, the strength tends to decrease and the workability tends to deteriorate. The thickness of the substrate layer 13 is generally 5 μm to 300 μm, and preferably 20 μm to 200 μm. In addition, the base material layer 13 may be provided in a peelable manner. For example, the patterned polarizing layer 21 of the polarizing film 2 may be bonded to a member constituting a display device or a retardation layer described below, and then may be peeled from the polarizing film 2. Thereby, a further thinning effect of the polarizing film 2 can be obtained.

Examples of the resin constituting the resin substrate include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid Esters; polyacrylates; cellulose esters such as triethyl cellulose, diethyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polyfluorene; polyetherfluorene; polyetherketone ; Polyphenylene sulfide and polyphenylene ether.

Examples of commercially available cellulose ester resin substrates include: "Fujitac Film" (manufactured by Fujifilm Corporation); "KC8UX2M", "KC8UY", and "KC4UY" (above, manufactured by Konica Minolta Opto Co., Ltd.) Wait.

Examples of commercially available cyclic olefin resins include "Topas" (registered trademark) (manufactured by Ticona (Germany)), "ARTON" (registered trademark) (manufactured by JSR Corporation), and "ZEONOR" (registered trademark) ), "ZEONEX" (registered trademark) (above, made by Japan Zeon Corporation) and "APEL" (registered trademark) (made by Mitsui Chemicals Co., Ltd.). Such a cyclic olefin-based resin can be formed into a resin substrate by a known method such as a solvent casting method and a melt extrusion method. It is also possible to use a resin substrate of a commercially available cyclic olefin-based resin. Examples of commercially available resin substrates for cyclic olefin resins include "S-SINA" (registered trademark), "SCA40" (registered trademark) (above, manufactured by Sekisui Chemical Industry Co., Ltd.), and "ZEONOR FILM" (Registered trademark) (manufactured by Optronics Corporation) and "ARTON FILM" (registered trademark) (manufactured by JSR Corporation).

The base material layer 13 may have a single-layer structure or a multilayer structure of two or more layers. When the base material layer 13 has a multilayer structure, each layer may be formed of the same material or may be formed of materials different from each other.

Moreover, the base material layer 13 may have a 1/4 wavelength plate function. By making the base material layer 13 have a 1/4 wavelength plate function, and by combining the base material layer 13 and the patterned polarizing layer 21, a polarizing film having the function of a circular polarizing plate can be obtained. Thereby, a circular polarizing plate can be obtained even if the retardation layer having a 1/4 wavelength plate function is not bonded to the polarizing film 2 except for the base material layer 13. When the substrate layer 13 has a multilayer structure, a patterned polarizing layer 21 can be laminated by using a layer having a function of a 1/2 wavelength plate and a layer having a function of a 1/4 wavelength plate. On the side of the layer having the function of a 1/2 wavelength plate, a circular polarizing plate is obtained. Alternatively, in the case where the base material layer 13 has a multilayer structure, it is also possible to obtain a circle by using a layer having a function of a quarter-wavelength plate having inverse wavelength dispersion and a layer having a positive C-plate function. Polarizer.

(The protective layer)
The protective layer 37 can be used for a region in which the exposed region 37 b is formed on the sheet-like substrate. The area that becomes the exposed area 37b can be formed by a method of mechanically punching out a specific portion of the sheet-like substrate by punching, cutting, spraying water, etc .; a sheet by laser ablation, chemical dissolution, etc. Method for removing a specific portion of the substrate.

The material of the sheet-like substrate forming the protective layer 37 is not particularly limited as long as it is insoluble in the liquid-repellent agent when the liquid-repellent agent is applied in the liquid-repellent layer forming step described below. As the sheet-like base material for forming the protective layer 37, for example, the same material as that of the base material layer 13 described above can be used. Particularly, it is preferably formed using a resin base material. More preferably, it is used to easily prevent the protective layer 37 from becoming an exposed area. Polyester resins such as polyethylene terephthalate that are deformed in the area (such as the opening) in 37b.

The protective layer 37 preferably has an adhesive layer for bonding to the base material layer 13. In order to peel the protective layer as described below, the adhesive layer is preferably peelable from the base material layer 13. The thickness of the protective layer 37 is usually 20 μm or more, more preferably 30 μm or more, and usually 250 μm or less, and preferably 200 μm or less.

(Liquid-repellent layer forming step)
In the liquid-repellent layer forming step, a liquid-repellent agent is coated on the surface of the protective layer 37 side of the base layer 81 with the protective layer, so as to obtain the base layer 82 with the liquid-repellent layer 47 on which the liquid-repellent layer is formed. (Figure 2 (b)).

(Liquid Repellent)
As the liquid-repellent agent, if the liquid-repellent layer (patterned liquid-repellent layer 47b) formed to apply the liquid-repellent agent exhibits liquid-repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer, it is not particularly limited. limited. The liquid-repellent property in this specification means that when the composition for forming an alignment layer or the composition for forming a polarizing layer is coated on the patterned liquid-repellent layer 47b, the patterned liquid-repellent layer 47b repels these compositions and is not patterned. A coating layer of these compositions is formed on the liquid-repellent layer 47b. The liquid-repellent property of the patterned liquid-repellent layer 47b refers to, for example, a contact angle of 90 ° or more measured by the θ / 2 method with a water droplet volume of 3 μL on the surface of the patterned liquid-repellent layer 47b. The contact angle may be Above 100 °, it can be above 110 °, and usually less than 120 °.

Examples of the liquid-repellent agent include a first organic silicon compound having a fluorine-containing group having a perfluoroalkyl group or a perfluoropolyether group on the free end side and a hydrolyzable group bonded to a silicon atom, and a hydrolyzable silane oligomer. Or a second organic silicon compound in which a fluorinated carbon-containing group and a hydrolyzable group are bonded to a silicon atom.

The carbon number of the perfluoroalkyl group (especially the carbon number of the longest straight chain portion) is preferably 3 or more, more preferably 5 or more, more preferably 7 or more, and the upper limit of the carbon number is not particularly limited. The so-called perfluoropolyether group refers to a group in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether residue are replaced with fluorine atoms, and may also be referred to as a perfluoropolyalkylene ether. Or perfluoropolyalkylene glycol dialkyl ether residues. The number of carbons contained in the longest linear portion of the perfluoropolyether group is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit of the carbon number is not particularly limited, and may be, for example, about 200.

The fluorine-containing group need only have the above-mentioned perfluoroalkyl group or perfluoropolyether group on the free end side. Therefore, an appropriate linking group may exist on the side bonded to the silicon atom, or the above-mentioned perfluoroalkyl group or perfluoroalkyl group may be directly bonded to the silicon atom without the linking group. Examples of the linking group include a hydrocarbon group such as an alkylene group and an aromatic hydrocarbon group, a (poly) alkylene glycol group, or a group in which a part of hydrogen atoms thereof is substituted with F, and such a suitable group. The carbon number of the linking group is, for example, 1 or more and 20 or less, and preferably 2 or more and 10 or less.

Furthermore, a plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoroalkyl or perfluoropolyether groups may also be bonded to one linking group. The number of fluorine-containing groups bonded to the silicon atom may be 1 or more, and may be 2 or 3, preferably 1 or 2, and particularly preferably 1.

The hydrolyzable group has (1) the first organosilicon compounds, or (2) the first organosilicon compound and active hydrogen (such as a hydroxyl group) on the surface of the substrate, or (3) the first Bonding effect between the organic silicon compound and the second organic silicon compound. Examples of such a hydrolyzable group include an alkoxy group (especially an alkoxy group having 1 to 4 carbon atoms), a hydroxyl group, an ethoxy group, an allyl group, a halogen atom (especially a chlorine atom), and the like. Preferred hydrolyzable groups are alkoxy, allyl, and halogen atoms, and particularly preferred are methoxy, ethoxy, allyl, and chlorine atoms.

The number of the hydrolyzable groups bonded to the silicon atom may be 1 or more, and may be 2 or 3, preferably 2 or 3, and particularly preferably 3. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, and the same hydrolyzable groups are preferably bonded to the silicon atom. The total number of the fluorine-containing group and the hydrolyzable group bonded to the silicon atom is usually 4, and may be 2 or 3 (especially 3). In the case of 3 or less, an alkyl group (especially an alkyl group having 1 to 4 carbon atoms), H, NCO, or the like may be bonded to the remaining bond.

The fluorine-containing group of the first organic silicon compound may be linear or may have a side chain. Specific examples of the liquid-repellent agent include a water-repellent and oil-repellent coating composition described in International Publication No. 2016/076245.

The liquid-repellent agent can be applied to the base material layer 81 with a protective layer by a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, a die coating method, or the like. Surface of the protective layer 37 side. When a composition containing a first organosilicon compound and a second organosilicon compound is used as the liquid-repellent agent, a coating layer formed by applying the liquid-repellent agent to the base material layer 81 with a protective layer is formed in the air. The liquid-repellent layer 47 can be formed by standing still and / or heating and drying.

The liquid-repellent agent is applied on the substrate region 13 in the covered region 37 a of the protective layer 37 and in the exposed region 37 b of the protective layer 37. Thereby, as shown in FIG. 2 (b), a liquid-repellent layer 47 with a liquid-repellent layer 47 can be formed on the substrate layer 13 in the covered area 37a of the protective layer 37 and the exposed area 37b of the protective layer 37, respectively. The substrate layer 82.

(Protective layer removal step)
In the protective layer removing step, the protective layer 37 is peeled from the base layer 82 with the liquid-repellent layer obtained in the liquid-repellent layer forming step. Thereby, a base material layer 83 with a patterned liquid-repellent layer having a patterned liquid-repellent layer 47b formed by removing a part of the liquid-repellent layer 47 can be obtained (FIG. 2 (c)). By removing the protective layer 37 from the base material layer 82 with the liquid-repellent layer, the liquid-repellent layer 47 on the covered area 37a is removed together with the protective layer 37, and the part of the exposed area 37b of the protective layer 37 is placed on the base material layer. A liquid-repellent layer 47 remains on 13 to form a patterned liquid-repellent layer 47b. Thereby, as shown in FIG. 2 (c), a base material layer 83 having a patterned liquid-repellent layer 47b and a patterned liquid-repellent layer can be obtained.

(Step of forming patterned alignment layer)
In the patterned alignment layer forming step, the composition for forming an alignment layer is coated on the surface of the patterned liquid-repellent layer 47b side of the base layer 83 with the patterned liquid-repellent layer obtained in the protective layer removal step. Thereby, a base material layer 84 having a patterned alignment layer 22 with a patterned alignment layer 22 can be obtained (FIG. 2 (d)). The patterned alignment layer 22 formed in the patterned alignment layer forming step may have an alignment restricting force for the liquid crystal compound laminated thereon in a desired direction. As the composition for forming an alignment layer, the following alignment polymer composition, a composition for forming a photo-alignment film, a composition containing a resin material for forming a groove alignment film, and the like can be used.

As described above, the patterned liquid-repellent layer 47b exhibits liquid-repellency to the composition for forming an alignment layer. Therefore, in the patterned alignment layer forming step, if the composition for forming an alignment layer is coated on the surface of the patterned liquid repellent layer 47b side of the base material layer 83 with the patterned liquid repellent layer, the patterned liquid repellent On the layer 47b, the composition for forming an alignment layer is repelled, and a coating layer of the composition is not formed. On the other hand, in a region where the patterned liquid-repellent layer 47b is not formed on the base material layer 83 with the patterned liquid-repellent layer, a coating layer of a composition for forming an alignment layer can be formed. Therefore, in the patterned alignment layer forming step, the patterning of the region having the patterned liquid-repellent layer 47b on the substrate layer 13 and the patterning of the alignment layer 22a in the region where the patterned liquid-repellent layer 47b is not formed can be obtained. A substrate layer of the alignment layer 22 with a patterned alignment layer.

The patterned alignment layer 22 facilitates liquid crystal alignment of a liquid crystal compound. The state of the liquid crystal alignment, such as horizontal alignment, vertical alignment, hybrid alignment, and oblique alignment, changes according to the properties of the patterned alignment layer 22 and the liquid crystal compound, and combinations thereof can be arbitrarily selected. For example, if the patterned alignment layer 22 is a material that exhibits horizontal alignment as an alignment limiting force, the liquid crystal compound may form a horizontal alignment or a hybrid alignment. If the patterned alignment layer 22 is a material that exhibits a vertical alignment, the liquid crystal compound may form a vertical alignment. Or tilt alignment. Expressions such as horizontal and vertical indicate the direction of the long axis of the liquid crystal compound aligned when the plane of the polarizing film 2 is used as a reference. For example, the so-called vertical alignment refers to the long axis of the polymerizable liquid crystal having alignment in the vertical direction with respect to the plane of the polarizing film 2. The vertical here means 90 ° ± 20 ° with respect to the plane of the polarizing film 2. The polarizing film 2 preferably has the polarizing characteristics of the plane of the polarizing film 2. Therefore, the patterned alignment layer 22 is preferably formed using a material that exhibits horizontal alignment.

As the alignment limiting force of the patterned alignment layer 22, when the patterned alignment layer 22 is formed of an alignment polymer, it can be arbitrarily adjusted by the surface state or friction conditions, and in the case of the photo-aligned polymer, In this case, it can be arbitrarily adjusted according to polarized light irradiation conditions and the like. In addition, the liquid crystal alignment can be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The thickness of the patterned alignment layer 22 is usually 10 nm to 5000 nm, preferably 10 nm to 1000 nm, and more preferably 30 nm to 300 nm. The patterned alignment layer 22 formed between the substrate layer 13 and the patterned polarized layer 21 is preferably insoluble to a solvent used when forming the patterned polarized layer 21 on the patterned alignment layer 22. Removes heat resistance from heat treatment of solvent or liquid crystal alignment.

Examples of the patterned alignment layer 22 include an alignment film including an alignment polymer, a photo-alignment film, and a groove alignment film. In the case where the base material layer 13 is an unrolled body from which a long resin base material is wound, the patterned alignment layer 22 is preferably an optical alignment in terms of easily controlling its alignment direction. membrane.

Examples of the alignment polymer include polyamines or gelatins having a amine bond in the molecule, polyimide having a iminium bond in the molecule, polyamic acid as a hydrolyzate thereof, polyvinyl alcohol, Alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylates, etc. Among these, polyvinyl alcohol is preferred. These alignment polymers may be used alone or in combination of two or more.

An alignment film containing an alignment polymer can be generally obtained by applying a composition (hereinafter sometimes referred to as an “alignment polymer composition”) in which a alignment polymer is dissolved in a solvent, to a pattern. The base material layer 83 of the liquid-repellent layer is removed, and the solvent is removed, or the alignment polymer composition is applied to the base material layer 13, and the solvent is removed to perform rubbing (friction method).

Examples of the solvent used in the alignment polymer composition include water; alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cyrus, butyl cyrus, or propylene glycol monomethyl ether Solvents; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone , Ketone solvents such as cyclohexanone, methylpentanone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; aromatic hydrocarbon solvents such as toluene or xylene; nitrile solvents such as acetonitrile; tetrahydrofuran or Ether solvents such as dimethoxyethane; chlorine-substituted hydrocarbon solvents such as chloroform or chlorobenzene. These solvents may be used alone or in combination of two or more.

As long as the content of the alignment polymer in the alignment polymer composition is such that the alignment polymer can be completely dissolved in the solvent, it is preferably 0.1 to 20% by mass in terms of solid content conversion relative to the solution. It is preferably 0.1 to 10% by mass.

As the alignment polymer composition, a commercially available alignment film material can be directly used. Examples of commercially available alignment film materials include Sunever (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark) (manufactured by JSR Corporation).

Examples of a method for applying the alignment polymer composition to the base material layer 83 having a patterned liquid-repellent layer include a spin coating method, an extrusion coating method, a gravure coating method, and a die coating method. A well-known method such as a coating method such as a rod coating method or a dressing method or a printing method such as a flexographic method. When the polarizing film 2 is manufactured by a roll-to-roll continuous manufacturing method, the coating method can generally adopt a printing method such as a gravure coating method, a die coating method, or a flexographic method. .

By removing the solvent contained in the alignment polymer composition, a dry film of the alignment polymer is formed. Examples of the method for removing the solvent include a natural drying method, a ventilation drying method, a heating drying method, and a reduced-pressure drying method. Thereafter, the dry coating film may be brought into contact with a rotating friction roller wound with a friction cloth, thereby forming a patterned alignment layer 22.

A photo-alignment film can be generally obtained by applying a pattern containing a composition (hereinafter sometimes referred to as a "photo-alignment film-forming composition") containing a polymer or monomer having a photoreactive group and a solvent. The base material layer 83 of the liquid-repellent layer is formed to form a coating layer for an alignment layer, and the coating layer for the alignment layer is irradiated with polarized light (preferably polarized ultraviolet (ultraviolet)). The light alignment film is more preferable in that the direction of the alignment restriction force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates liquid crystal alignment ability by irradiating light. Specifically, it is a photoresponder that becomes the origin of the alignment ability of a liquid crystal by irradiating light to generate, for example, molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction. Among these photoreactive groups, those having excellent alignment properties are preferably those that cause a dimerization reaction or a photocrosslinking reaction. As the photoreactive group capable of generating the above reaction, it is preferred to have an unsaturated bond, especially a double bond, more preferably a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), a nitrogen-nitrogen double bond (N = N bond), and a carbon-oxygen double bond (C = O bond).

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyalkenyl group, a fluorenyl group, an oxazolyl group, a stilbazonium group, a chalcone group, and a cinnamyl group. From the viewpoint of easily controlling the reactivity or the expression of the alignment limiting force at the time of photo-alignment, a chalcone group or a cinnamyl group is preferred. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base or an aromatic fluorene. Examples of the photoreactive group having an N = N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, diazo, or methylamino, or the like based on azobenzene oxide. Structurer. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, and the like. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a halogenated alkyl group.

As a solvent of the composition for forming a photo-alignment film, it is preferable to dissolve a polymer and monomer having a photoreactive group. Examples of the solvent include solvents listed as a solvent of the above-mentioned alignment polymer composition. .

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately determined according to the type of the polymer or monomer having a photoreactive group or the thickness of the photoalignment film to be manufactured. The adjustment is preferably 0.2% by mass or more, and particularly preferably within a range of 0.3 to 10% by mass. In addition, a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer may be contained within a range that does not significantly impair the characteristics of the photo-alignment film.

Examples of the method for applying the composition for forming a photo-alignment film to the base material layer 83 having a patterned liquid-repellent layer include the same methods as those described above for applying the alignment polymer composition to the patterned liquid-repellent layer. The method of the material layer 83 is the same. Examples of the method for removing the solvent from the applied photo-alignment film-forming composition include the same method as the method for removing the solvent from the alignment polymer composition.

The polarized light irradiation can be performed directly from the dried film on which the solvent is removed from the photo-alignment film-forming composition coated on the substrate layer 83 with the patterned liquid-repellent layer, or the polarized light irradiation through the substrate layer 13 can be performed. The method to dry the film is performed from the base material layer 13 side. The polarized light used for polarized light irradiation is particularly preferably substantially parallel light. The wavelength of the polarized light to be irradiated is preferably a wavelength region in which a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in a range of 250 to 400 nm is particularly preferable. Examples of the light source used in polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF and other ultraviolet lasers, and more preferably high-pressure mercury lamps, ultra-high pressure mercury lamps, or metal halides. light. These lamps are preferred due to the greater luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized light can be irradiated by irradiating light from a light source through an appropriate polarizing element. As this polarizing element, a polarizing filter, a polarizing element such as Glan-Thompson, Glan-Taylor, or a wire grid type polarizing element can be used.

In addition, when rubbing or polarizing light is irradiated, a plurality of regions (patterns) with different directions of liquid crystal alignment may be formed if they are shielded.

The groove alignment film is a film having a concave-convex pattern or a plurality of grooves (grooves) on the surface of the film. When the liquid crystal molecules are placed in a film having a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned in the direction of the grooves.

Examples of the method for obtaining the groove alignment film include a method for forming a concave-convex pattern by exposing the surface of the photosensitive polyimide film with an exposure mask through a slit having a pattern shape, and then developing and rinsing it. ; A method of forming a UV-curable resin layer before hardening on a plate-shaped master having grooves on the surface, and moving the resin layer to a base material for hardening; pressing a roller-shaped master having a plurality of grooves against the formation A method of forming unevenness on a UV-curable resin film before curing on a substrate, and thereafter curing. Specific examples include the methods described in Japanese Patent Laid-Open No. 6-34976 and Japanese Patent Laid-Open No. 2011-242743.

In order to obtain a less disordered alignment, the width of the convex portion of the groove alignment film is preferably 0.05 μm to 5 μm, the width of the concave portion is preferably 0.1 μm to 5 μm, and the depth of the step difference of the unevenness is preferably 2 μm. Hereinafter, it is preferably 0.01 μm to 1 μm.

(Step of forming patterned polarizing layer)
In the patterned polarizing layer forming step, the surface of the patterned alignment layer 22 side of the base layer 84 with the patterned alignment layer obtained in the patterned alignment layer forming step is coated with a liquid crystal compound and a dichroic pigment. The composition for forming a polarizing layer can obtain the polarizing film 2 on which the patterned polarizing layer 21 is formed (FIG. 2 (e)). The composition for forming a polarizing layer is a composition containing a liquid crystal compound and a dichroic dye, and preferably contains a solvent and a polymerization initiator, and may contain a sensitizer, a polymerization inhibitor, a leveling agent, a reactive additive, and the like.

As described above, the patterned liquid-repellent layer 47b exhibits liquid-repellency to the composition for forming a polarizing layer. Therefore, in the patterned polarizing layer forming step, if the composition for forming a polarizing layer is coated on the surface of the patterned liquid-repellent layer 47b side of the base material layer 84 with the patterned alignment layer, the patterned liquid-repellent layer is applied. On 47b, the composition for forming a polarizing layer is repelled, and a coating layer of the composition is not formed. On the other hand, in a region where the patterned liquid-repellent layer 47 b is not formed on the base material layer 84 with the patterned alignment layer, a coating layer of a composition for forming a polarizing layer can be formed. Therefore, in the step of forming the patterned polarizing layer, the patterning of the region having the patterned liquid-repellent layer 47 b on the substrate layer 13 and the patterning of the polarizing region 21 a on the alignment layer 22 a of the patterned alignment layer 22 can be obtained. The polarizing film 2 of the polarizing layer 21.

The polarizing film 2 shown in FIGS. 1 and 2 (e) may be used by further peeling off the base material layer 13. In this case, the alignment layer 22 a may be peeled together with the base material layer 13. For example, peeling of the base material layer 13 may be performed after bonding the patterned polarizing layer 21 of the polarizing film 2 to a member constituting a display device, a retardation layer, or the like.

(Patterned polarizing layer)
The patterned polarizing layer 21 contains a liquid crystal compound and has a region containing a liquid crystal compound and a dichroic dye. In the case where the patterned polarizing layer 21 has the polarization characteristics of the plane of the polarizing film 2, it is preferable that the patterned polarizing layer 21 has a state where the dichroic pigment and the liquid crystal compound are horizontally aligned with respect to the plane of the polarizing film 2. In the case where the patterned polarizing layer 21 has polarizing characteristics in the film thickness direction of the polarizing film 2, it is preferable to have a region in which the dichroic dye and the liquid crystal compound are aligned horizontally with respect to the plane of the polarizing film 2.

For the region where the dichroic pigment and liquid crystal compound in the patterned polarizing layer 21 are horizontally aligned with respect to the two surfaces of the polarizing film, the absorbance A1 (λ) in the horizontal direction of the liquid crystal alignment for light having a wavelength of λ nm and The two-color ratio (= A1 (λ) / A2 (λ)) of the ratio of the absorbance A2 (λ) in the vertical direction of the liquid crystal alignment plane is preferably 7 or more, more preferably 20 or more, and even more preferably 30 or more. The higher the value, the more polarized light characteristics with excellent absorption selectivity. When the patterned polarizing layer 21 is a nematic liquid crystal phase, the above ratio is about 5 to 10, but it varies depending on the type of the dichroic pigment. When the patterned polarizing layer 21 is a nematic liquid crystal phase or a smectic liquid crystal phase, the liquid crystal compound and the liquid crystal compound can be confirmed by, for example, observing the surface with various microscopes or measuring the scattering with a haze meter. The dichroic pigments are not phase separated.

The thickness of the patterned polarizing layer 21 is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 10 μm or less, and even more preferably 5 μm or less. The thickness of the patterned polarizing layer 21 can be measured by an interference film thickness meter, a laser microscope, a stylus film thickness meter, or the like.

(Liquid crystal compound)
As the liquid crystal compound contained in the polarizing layer-forming composition, a known liquid crystal compound can be used. The type of the liquid crystal compound is not particularly limited, and a rod-shaped liquid crystal compound, a disc-shaped liquid crystal compound, and a mixture thereof can be used. The liquid crystal compound may be a polymer liquid crystal compound, a polymerizable liquid crystal compound, or a mixture thereof.

As the liquid crystal compound, a polymerizable liquid crystal compound is preferably used. By using a polymerizable liquid crystal compound, the hue of the polarizing film can be controlled arbitrarily, and the polarizing film can be significantly thinned. Moreover, since a polarizing film can be manufactured without performing an extending | stretching process, it can be set as the non-stretchable polarizing film which does not generate | occur | produce extensional relaxation by a heat | fever.

The polymerizable liquid crystal compound refers to a compound having a polymerizable group and having liquid crystallinity. The polymerizable group refers to a group participating in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by a living radical or an acid generated from a photopolymerization initiator described below. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a propenyloxy group, a methacryloxy group, an ethylene oxide group, Oxetanyl and the like. Among them, acryloxy, methacryloxy, ethyleneoxy, ethylene oxide, and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal. When the patterned polarizing layer 21 of the embodiment is mixed with a dichroic dye, it is preferable to use a thermotropic liquid crystal.

When the polymerizable liquid crystal compound is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound that displays a nematic liquid crystal phase or a thermotropic liquid crystal compound that displays a smectic liquid crystal phase. The liquid crystal state displayed by the polymerizable liquid crystal compound is preferably a smectic phase, and from the viewpoint of high performance, a high-order smectic phase is more preferable. Among them, it is more preferable to form smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, and smectic K phase. The higher-order smectic liquid crystal compound of the smectic L phase is more preferably a higher-order smectic liquid crystal compound that forms the smectic B phase, the smectic F phase, or the smectic I phase. If the patterned polarizing layer 21 formed by the polymerizable liquid crystal compound is such a high-order smectic phase, a region with higher polarization performance can be formed in the patterned polarizing layer 21. In addition, such a region with a higher polarization performance obtains a Bragg wave peak derived from a hexagonal phase or a crystal having a higher order structure in an X-ray diffraction measurement. The Bragg crests are derived from the periodic structure of the molecular alignment, and a film with a periodic interval of 3 to 6 Å can be obtained. In the polarizing film 2 of this embodiment, the patterned polarizing layer 21 contains a polymer in which a polymerizable liquid crystal compound is polymerized in a smectic phase state, so that the patterned polarizing layer 21 can be given higher polarization characteristics, so it is preferable. .

For example, it can be confirmed whether the polymerizable liquid crystal compound shows a nematic liquid crystal phase or a smectic liquid crystal phase by the following method. After the polarizing film-forming composition is coated on the substrate to form a coating film, the solvent contained in the coating film is removed by performing a heat treatment under conditions in which the polymerizable liquid crystal compound does not polymerize. Then, by using texture observation, X-ray diffraction measurement, or differential scanning calorimetry using a polarizing microscope, the liquid crystal expressed by heating a coating film formed on a substrate to an isotropic phase temperature and slowly cooling it Phase check.

Specific examples of such a polymerizable liquid crystal compound include a compound represented by the following formula (A) (hereinafter sometimes referred to as a compound (A)).
U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (A)
[In the formula (A), X ¹ , X ² and X ³ each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the divalent aromatic group or the divalent alicyclic group The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. The carbon atom of the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom; at least one of X ¹ , X ^2, and X ³ may have a substituent. 1,4-phenylene or cyclohexane-1,4-diyl which may have a substituent;
Y ¹ , Y ² , W ¹ and W ² are independently a single bond or a divalent linking group;
V ¹ and V ² are each independently an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group may be substituted with -O-, -S-, or NH-;
U ¹ and U ² each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group].

In the compound (A), at least one of X ¹ , X ² and X ³ is 1,4-phenylene which may have a substituent or cyclohexane-1,4-diyl which may have a substituent. In particular, X ¹ and X ^{3 are} preferably cyclohexane-1,4-diyl which may have a substituent, and the cyclohexane-1,4-diyl is further preferably trans-cyclohexane-1,4 -Two bases. When a structure containing trans-cyclohexane-1,4-diyl group is used, there is a tendency that the smectic liquid crystal property is easily expressed. Examples of the optionally substituted 1,4-phenylene group and cyclohexane-1,4-diyl group which may have a substituent include carbons such as methyl, ethyl, or butyl. A halogen atom such as an alkyl group having a number of 1 to 4, a cyano group, a chlorine atom, or a fluorine atom. It is preferably unsubstituted.

Y ¹ and Y ^{2 are} preferably single bonds, -CH ₂ CH _2- , -CH ₂ O-, -COO-, -OCO-, -N = N-, -CR ^a = CR ^b -,- C≡C- or CR ^a = N-, and R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ¹ and Y ^{2 are more} preferably -CH ₂ CH _2- , -COO-, -OCO-, or a single bond, and in the case where X ¹ , X ² and X ³ do not contain cyclohexane-1,4-diyl. In this case, Y ¹ and Y ² are more preferably different bonding methods. When Y ¹ and Y ² are different bonding methods, there is a tendency that smectic liquid crystal properties are easily expressed.

W ¹ and W ^{2 are} preferably a single bond, -O-, -S-, -COO-, or OCO-, and more preferably a single bond or -O-, which are independent of each other.

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and V ² include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, and butane. Alkane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane Alkane-1,10-diyl, tetradecane-1,14-diyl or eicosane-1,20-diyl, etc. V ¹ and V ^{2 are} preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably straight chain alkanediyl groups having 6 to 12 carbon atoms. By using a linear alkanediyl group having 6 to 12 carbon atoms, crystallinity is improved, and smectic liquid crystallinity tends to be easily expressed.

Examples of the optionally substituted alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group, a halogen atom such as a chlorine atom, a fluorine atom, and the like. The alkanediyl group is preferably unsubstituted, and more preferably It is an unsubstituted and linear alkanediyl.

U ¹ and U ^{2 are} preferably both polymerizable groups, and more preferably both are photopolymerizable groups. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in terms of being able to polymerize at a lower temperature than a thermally polymerizable group, and thereby forming a polymerizable liquid crystal compound in a state with a higher degree of order.

The polymerizable groups represented by U ¹ and U ² may be different from each other, but are preferably the same. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a propenyloxy group, a methacryloxy group, an ethylene oxide group, Oxetanyl and the like. Among them, acryloxy, methacryloxy, ethyleneoxy, ethylene oxide, or oxetanyl is preferred, and methacryloxy or acryloxy is more preferred.

Examples of such a polymerizable liquid crystal compound include the following.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

Among the above-exemplified compounds, it is preferably selected from the group consisting of formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1- 8) At least one of the group consisting of compounds represented by formula (1-13), formula (1-14) and formula (1-15).

The exemplified compound (A) can be used for the patterned polarizing layer 21 alone or in combination. When two or more kinds of polymerizable liquid crystal compounds are combined, it is preferred that at least one kind is a compound (A), and more preferably two or more kinds are a compound (A). By combining two or more polymerizable liquid crystal compounds, liquid crystallinity may be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature. When the two polymerizable liquid crystal compounds are combined, the mixing ratio is usually 1:99 to 50:50, preferably 5:95 to 50:50, and further preferably 10:90 to 50:50.

Compound (A) can be produced, for example, by a known method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156.

The content of the polymerizable liquid crystal compound in the patterned polarizing layer 21 is generally 50 to 99.5 parts by mass, preferably 60 to 99 parts by mass, and more preferably 70 to 100 parts by mass relative to the solid content of the patterned polarizing layer 21. 98 parts by mass, and more preferably 80 to 97 parts by mass. When the content of the polymerizable liquid crystal compound is within the above range, there is a tendency that the alignment property becomes high. Here, the solid component refers to the total amount of components after the solvent is removed from the polarizing layer-forming composition described below.

(Dichroic pigment)
The so-called dichroic pigment refers to a pigment having different properties in the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction. A dichroic pigment is a pigment which is aligned with a liquid crystal compound to exhibit dichroism. The dichroic pigment itself may have polymerizability or liquid crystallinity. As a dichroic pigment, it is preferable to have a characteristic of absorbing visible light, and it is more preferable to have a maximum absorption wavelength ( _λMAX ) in the range of 380 to 680 nm. Examples of such dichroic pigments include acridine pigments, osmium pigments, cyanine pigments, naphthalene pigments, azo pigments, and anthraquinone pigments. Among these, azo pigments are preferred. Examples of the azo pigment include a monoazo pigment, a disazo pigment, a triazo pigment, a tetraazo pigment, and a triazo pigment, and a diazo pigment or a triazo pigment is preferred. The dichroic pigment may be used alone or in combination of two or more. In order to obtain absorption in the entire visible light region, it is preferable to combine three or more dichroic pigments, and it is more preferable to combine three or more azo pigments.

Examples of the azo pigment include a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)")
T ¹ -A ¹ (-N = NA ² ) _p -N = NA ³ -T ² (I)
[In formula (I), A ¹ , A ² and A ³ independently of each other represent a 1,4-phenylene group, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic ring which may have a substituent T ¹ and T ² are independent of each other as an electron withdrawing group or an electron withdrawing group, and are located at a position substantially 180 ° with respect to the azo bond plane; p represents an integer of 0 to 4; when p is 2 or more, Each A ² may be the same as or different from each other; in a range showing absorption in the visible light range, the -N = N- bond may be replaced by -C = C-, -COO-, -NHCO-, or -N = CH- key].

Examples of the substituents arbitrarily possessed by 1,4-phenylene, naphthalene-1,4-diyl, and divalent heterocyclic group among A ¹ , A ² and A ³ include: methyl, ethyl or C1-C4 alkyl groups such as butyl; C1-C4 alkoxy groups such as methoxy, ethoxy, or butoxy; C1-C4 fluorinated alkyl groups such as trifluoromethyl; Cyano group; nitro group; halogen atom such as chlorine atom, fluorine atom; substituted or unsubstituted amine group such as amine group, diethylamine group and pyrrolidinyl group (the so-called substituted amine group means having 1 or 2 An amine group of an alkyl group having 1 to 6 carbon atoms, or an amine group having 2 to 8 carbon atoms bonded to each other to form an alkyldiyl group having 2 to 8 carbon atoms; an unsubstituted amine group refers to -NH ₂ ). Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and a hexyl group. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl or octane-1,8-diyl, etc. In order to include the compound (I) in a high-order liquid crystal structure such as a smectic liquid crystal, A ¹ , A ² and A ^{3 are} preferably independently unsubstituted, hydrogen substituted with methyl or methoxy 1, 4-phenylene or a divalent heterocyclic group, and p is preferably 0 or 1. Among them, in terms of the simplicity and high performance of molecular synthesis, it is more preferable that p is 1 and at least two of the three structures of A ¹ , A ^2, and A ³ are 1,4-phenylene. .

Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. In the case where A ² is a divalent heterocyclic group, a structure having a molecular bonding angle of substantially 180 ° is preferred, and more specifically, benzothiazole and benzo formed by condensing two 5-membered rings are more preferred. Structure of imidazole and benzoxazole.

T ¹ and T ^{2 are} preferably mutually independent structures that are electron-withdrawing or electron-withdrawing groups, and further preferably T ¹ is an electron-withdrawing group and T ² is an electron-withdrawing group, or T ¹ is an electron-withdrawing group And T ² is an electron withdrawing group. Specifically, T ¹ and T ² are each preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, each having 1 or 2 carbon atoms 1 to An amine group of an alkyl group of 6 or an amine group of two substituted alkyl groups to form an alkanediyl group of 2 to 8 carbon atoms or a trifluoromethyl group, in order to be included in a high order such as a smectic liquid crystal In the liquid crystal structure, a structure having a smaller molecular repulsion volume is necessary, so it is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and having 1 or 2 carbon numbers. The amine group of an alkyl group of 1 to 6 or the amine group of 2 to 8 carbon atoms is bonded to each other to form an alkyl group of 2 to 8 carbon atoms.

Examples of such an azo pigment include the following.

[Chemical 5]

[Chemical 6]

[In the formulae (2-1) to (2-6), B ¹ to B ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group , Substituted or unsubstituted amine groups (the definition of substituted and unsubstituted amine groups is as described above), a chlorine atom or a trifluoromethyl group; and from the viewpoint of obtaining higher polarizing performance In other words, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , B ^{19 is} preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom;
n1 ~ n4 each independently represent an integer of 0 ~ 3;
When n1 is 2 or more, a plurality of B ² may be the same or different,
When n2 is 2 or more, a plurality of B ⁶ may be the same or different, respectively.
When n3 is 2 or more, a plurality of B ⁹ may be the same or different,
When n4 is 2 or more, a plurality of B ¹⁴ may be the same or different.]

The anthraquinone pigment is preferably a compound represented by the formula (2-7).

[Chemical 7]

[In formula (2-7), R ¹ to R ⁸ independently of each other represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom;
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

The fluorene dye is preferably a compound represented by the formula (2-8).

[Chemical 8]

[In formula (2-8), R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom;
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

The acridine dye is preferably a compound represented by the formula (2-9).

[Chemical 9]

[In the formula (2-9), R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom;
R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x in formula (2-7), formula (2-8), and formula (2-9) include methyl, ethyl, propyl, and butyl Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolylmethyl group, a xylyl group, a naphthyl group, and the like.

As said cyanine pigment, the compound represented by Formula (2-10) and the compound represented by Formula (2-11) are preferable.

[Chemical 10]

[In the formula (2-10), D ¹ and D ² independently represent the bases represented by any one of the formulas (2-10a) to (2-10d);

[Chemical 11]

n5 represents an integer from 1 to 3]

[Chemical 12]

[In formula (2-11), D ³ and D ^{4 are} independent of each other and represent the base represented by any one of formulas (2-11a) to (2-11h);
[Chemical 13]

n6 represents an integer from 1 to 3]

As the content of the dichroic pigment (the total amount when plural types are contained), from the viewpoint of obtaining good light absorption characteristics, with respect to 100 parts by mass of the polymerizable liquid crystal compound in the patterned polarizing layer 21, Usually, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 15 parts by mass. If the content of the dichroic pigment is less than this range, the light absorption becomes insufficient, and sufficient polarization performance cannot be obtained. If it exceeds this range, the alignment of the liquid crystal molecules may be hindered.

(Solvent)
The composition for forming a polarizing layer may contain a solvent. Generally, the viscosity of a polymerizable liquid crystal compound is high. Therefore, when a polymerizable liquid crystal compound is used as the liquid crystal compound, by using a composition for forming a polarizing layer containing a solvent, application can be facilitated, resulting in easy pattern formation.化 polarizing layer 21. The solvent is preferably one that can completely dissolve the polymerizable liquid crystal compound and the dichroic dye, and more preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.

Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, and ethylene glycol Ester solvents such as alcohol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate or ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone or methyl Ketone solvents such as isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; aromatic hydrocarbon solvents such as toluene or xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran or dimethoxyethane; chloroform or Chlorine-containing solvents such as chlorobenzene; amines such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, etc. Solvents, etc. These solvents may be used alone or in combination of two or more.

The content of the solvent contained in the composition for forming a polarizing layer is preferably 50 to 98% by mass based on the total amount of the composition for forming a polarizing layer. In other words, the content of the solid component in the polarizing layer-forming composition is preferably 2 to 50% by mass. When the content of the solid component is 50% by mass or less, the viscosity of the composition for forming a polarizing layer becomes low, so that the thickness of the patterned polarizing layer 21 becomes substantially uniform, and unevenness in the patterned polarizing layer 21 tends to be difficult to occur. . The content of the solid component can be determined in consideration of the thickness of the patterned polarizing layer 21 to be manufactured.

(Polymerization initiator)
The composition for forming a polarizing layer may contain a polymerization initiator. The polymerization initiator can be used when a polymerizable liquid crystal compound is used as the liquid crystal compound, and is a compound that can initiate a polymerization reaction of the polymerizable liquid crystal compound and the like. As the polymerization initiator, a photopolymerization initiator that generates an active radical by the action of light is preferred from the viewpoint of not depending on the phase state of the thermotropic liquid crystal.

Examples of the polymerization initiator include a benzoin compound, a benzophenone compound, an alkyl phenone compound, a fluorenylphosphine oxide compound, a three compound, a sulfonium salt, or a sulfonium salt.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyldiphenylsulfide. Ether, 3,3 ', 4,4'-tetrakis (third butylcarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkyl phenone compound include diethoxyacetophenone, 2-methyl-2-olinyl-1- (4-methylthiophenyl) propane-1-one, and 2-benzyl 2-dimethylamino-1- (4-olinylphenyl) butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl -2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1- An oligomer of hydroxycyclohexylphenyl ketone or 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, and the like.

Examples of the fluorenylphosphine oxide compounds include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzylfluorenyl) phenylphosphine oxide. .

Examples of the three compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tri, 2,4-bis (trichloromethyl) ) -6- (4-methoxynaphthyl) -1,3,5-tri, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3 , 5-tri, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tri, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tri, 2,4-bis (trichloromethyl) -6- [2- (4 -Diethylamino-2-methylphenyl) vinyl] -1,3,5-tri or 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxy Phenyl) vinyl] -1,3,5-three.

Commercially available polymerization initiators can also be used. Examples of commercially available polymerization initiators include: Irgacure (registered trademark) 907, 184, 651, 819, 250, 369, 379, 127, 754, OXE01, OXE02, or OXE03 (made by Ciba Specialty Chemicals Co., Ltd.); Seikuol (registered trademark) BZ, Z or BEE (made by Seiko Chemical Co., Ltd.); kayacure (registered trademark) BP100 or UVI-6992 (made by Dow Chemical Co., Ltd.); Adeka Optomer SP-152, N-1717, N- 1919, SP-170, Adeka arkls NCI-831, Adeka arkls NCI-930 (manufactured by ADEKA Co., Ltd.); TAZ-A or TAZ-PP (manufactured by Japan Nihon SiberHegner Co., Ltd.); TAZ-104 (Sanwa Chemical Co., Ltd. Co., Ltd.) and so on. One type of polymerization initiator may be used in the polarizing layer-forming composition, or two or more types of polymerization initiators may be mixed and used depending on the light source of light.

The content of the polymerization initiator in the polarizing layer-forming composition can be appropriately adjusted according to the type or amount of the polymerizable liquid crystal compound, and it is usually 0.1 to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. It is preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass. When the content of the polymerization initiator is within the above range, polymerization can be performed without disturbing the orientation of the polymerizable liquid crystal compound.

(Sensitizer)
The composition for forming a polarizing layer may contain a sensitizer. The sensitizer is preferably used when a polymerizable liquid crystal compound is used as the liquid crystal compound, and when a polymerizable liquid crystal compound having a photopolymerizable group is used, the sensitizer is preferably a photosensitizer. Examples of the sensitizer include ketones and 9-oxysulfur Isoketone compounds (e.g. 2,4-diethyl-9-oxosulfur , 2-isopropyl-9-oxysulfur Etc.); anthracene compounds such as anthracene and alkoxy-containing anthracene (such as dibutoxyanthracene, etc.); phenanthrene or rubrene.

When the composition for polarizing layer formation contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound contained in the composition for polarizing layer formation can be further promoted. The used amount of the sensitizer is 100 parts by mass with respect to the content of the polymerizable liquid crystal compound, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass.

(Polymerization inhibitor)
From the viewpoint of stably proceeding the polymerization reaction, the composition for forming a polarizing layer may contain a polymerization inhibitor. The polymerization inhibitor can be preferably used when a polymerizable liquid crystal compound is used as the liquid crystal compound. The polymerization inhibitor can control the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound.

Examples of the polymerization inhibitor include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butylcatechol, etc.), catechol, 2 , 2,6,6-tetramethyl-1-piperidinyloxy radicals and other free radical scavengers; thiophenols; β-naphthylamines or β-naphthols.

When the composition for forming a polarizing layer contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the content of the polymerizable liquid crystal compound is 100 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, It is more preferably 0.5 to 3 parts by mass. When the content of the polymerization inhibitor is within the above range, polymerization can be performed without disturbing the orientation of the polymerizable liquid crystal compound.

(Leveling agent)
The composition for forming a polarizing layer may contain a leveling agent. The leveling agent refers to an additive having the function of adjusting the fluidity of the composition and making the film obtained by coating the composition flatter, and examples thereof include organically modified silicone oil type, polyacrylate type, or Perfluoroalkyl-based leveling agent. Specific examples: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of which are manufactured by Dow Corning Toray (stock)), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all above manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all above manufactured by Momentive Advanced Materials Japan Co., Ltd.) , Fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all of which are manufactured by Sumitomo 3M (stock)), MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483 ( All of the above are manufactured by DIC (stock), Eftop (brand name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are manufactured by Mitsubishi Electronic Materials Corporation), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, S urflon SC-105, KH-40, SA-100 (all of which are manufactured by AGC Seimi Chemical (stock)), trade name E1830, trade name E5844 (made by Daikin Institute of Precision Chemistry (stock)), BM-1000, BM -1100, BYK-352, BYK-353 or BYK-361N (all are trade names: manufactured by BM Chemie) and the like. Among them, a polyacrylate-based leveling agent or a perfluoroalkyl-based leveling agent is preferred.

When the composition for forming a polarizing layer contains a leveling agent, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the liquid crystal compound. . When the content of the leveling agent is within the above range, there is a tendency that the liquid crystal compound is easily aligned horizontally and the resulting patterned polarizing layer becomes smoother. When the content of the leveling agent with respect to the liquid crystal compound exceeds the above range, there is a tendency that unevenness tends to occur in the obtained patterned polarizing layer. The composition for forming a polarizing layer may contain two or more leveling agents.

(Reactive additive)
The polarizing layer-forming composition may contain a reactive additive. The reactive additive is preferably one having a carbon-carbon unsaturated bond and an active hydrogen reactive group in its molecule. The "active hydrogen-reactive group" herein refers to a group that is reactive with a group having active hydrogen, such as a carboxyl group (-COOH), a hydroxyl group (-OH), and an amine group (-NH ₂ ), and its representative example It is a glycidyl group, an oxazoline group, a carbodiimide group, an aziridinyl group, a fluorenimine group, an isocyanate group, a thioisocyanate group, a maleic anhydride group, and the like. The number of carbon-carbon unsaturated bonds or active hydrogen reactive groups possessed by the reactive additive is usually 1 to 20, preferably 1 to 10, respectively.

It is preferred that at least two active hydrogen reactive groups are present in the reactive additive. In this case, the plurality of active hydrogen reactive groups may be the same or different.

The carbon-carbon unsaturated bond possessed by the reactive additive means a carbon-carbon double bond, a carbon-carbon triple bond, or a combination thereof, and a carbon-carbon double bond is preferred. Among these, as the reactive additive, a carbon-carbon unsaturated bond containing a vinyl group and / or a (meth) acrylfluorenyl group is preferable. Furthermore, it is preferable that the active hydrogen reactive group is a reactive additive selected from the group consisting of an epoxy group, a glycidyl group, and an isocyanate group, and it is more preferable that the active hydrogen reactive group has an acryl group and an isocyanate group. Reactive additive.

Specific examples of the reactive additive include compounds having a (meth) acrylfluorenyl group and an epoxy group, such as methacryloxy glycidyl ether or propylene glycol oxyglycidyl ether; oxetane acrylic acid Compounds such as esters or oxetane methacrylates with (meth) acrylfluorenyl groups and oxetanyl groups; lactone acrylates or lactone methacrylates with (meth) acrylfluorene groups and Compounds with lactone groups; Compounds with vinyl and oxazoline groups such as vinyloxazoline or isopropenyloxazoline; isocyanatomethyl acrylate, isocyanatomethyl methacrylate, acrylic acid 2 -An oligomer of a compound having a (meth) acrylfluorenyl group and an isocyanate group, such as ethyl isocyanate or 2-isocyanate ethyl methacrylate. In addition, examples thereof include compounds having a vinyl group or vinylidene group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, and vinyl maleic anhydride. Of these, methacrylic acid oxyglycidyl ether, propylene glycol oxyglycidyl ether, methyl isocyanate acrylate, methyl isocyanate methacrylate, vinyl oxazoline, and acrylic acid 2- Ethyl isocyanate, 2-isocyanate ethyl methacrylate or the above oligomers, particularly preferably methyl isocyanate acrylate, 2-isocyanate ethyl acrylate or the above oligomers Thing.

Specifically, a compound represented by the following formula (Y) is preferable.

[Chemical 14]

[In formula (Y), n represents an integer from 1 to 10, and R ^{1 ′} represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 5 to 20 carbon atoms; each repeating Among the two R ^2's in the unit, one is -NH- and the other is a group represented by> NC (= O) -R ^{3 '} ; R ^3' represents a hydroxyl group or a group having a carbon-carbon unsaturated bond ;
In R ^{3 ′} in formula (Y), at least one R ^{3 ′} is a group having a carbon-carbon unsaturated bond]

Among the reactive additives represented by the formula (Y), a compound represented by the following formula (YY) (hereinafter sometimes referred to as a compound (YY)) is particularly preferred (in addition, n has the same meaning as described above).

[Chemical 15]

Compound (YY) can be used as it is, or it can refine | purify it as needed. Examples of commercially available products include Laromer (registered trademark) LR-9000 (manufactured by BASF).

When the polarizing layer-forming composition contains a reactive additive, the content of the reactive additive is usually 0.01 to 10 parts by mass, and preferably 0.1 to 5 parts by mass based on 100 parts by mass of the liquid crystal compound.

(Coating method of polarizing layer-forming composition)
Examples of a method for applying the composition for forming a polarizing layer include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a capillary (CAP) coating method, a slit coating method, and a micro gravure. Coating method, die coating method, inkjet method, and the like. In addition, a method of coating using a coating machine such as a dip coater, a bar coater, or a spin coater can also be mentioned. Among them, in the case of continuous coating in a roll-to-roll form, a coating method using a microgravure coating method, an inkjet method, a slit coating method, and a die coating method is preferably applied to glass. In the case of a single-piece substrate, a spin coating method having high uniformity is preferred. In the case of coating in a roll-to-roll form, the patterned alignment layer 22 may be formed by applying an alignment film-forming composition or the like on the base material layer 83 with the patterned liquid-repellent layer, and further applying the obtained pattern. A composition for forming a polarizing layer is continuously applied on the chemical alignment layer 22.

When the polarizing layer-forming composition is applied to form the patterned polarizing layer 21, the solvent is removed from the applied polarizing layer-forming composition to form a polarizing layer coating layer. As a method of removing the solvent, the same method as the method of removing the solvent from the self-aligning polymer composition can be used, and examples thereof include a method of natural drying, air-drying, heat-drying, reduced-pressure drying, and combinations thereof. Among them, natural drying or heat drying is preferred. The drying temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 150 ° C, and even more preferably in the range of 50 to 130 ° C. The drying time is preferably 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes.

When the liquid crystal compound contained in the polarizing layer-forming composition is a polymerizable liquid crystal compound, it is preferable to irradiate the coating layer for a polarizing layer formed in the polarizing layer forming step with active energy rays to polymerize the liquid crystal compound. Photopolymerization is performed to form a patterned polarizing layer 21. The active energy ray to be irradiated depends on the type of the polymerizable liquid crystal compound (especially the type of the photopolymerizable functional group of the polymerizable liquid crystal compound) contained in the coating layer for the polarizing layer, and In the case, it is appropriately selected according to the type and amount of the photopolymerization initiator. Specifically, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be mentioned. Among them, in terms of the ease of controlling the progress of the polymerization reaction and the point that a wide range of users in the field can be used as the photopolymerization device, ultraviolet light is preferred, and photopolymerization by ultraviolet light is preferred. Select the type of polymerizable liquid crystal compound.

Examples of light sources of active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten filament lamps, gallium lamps, excimer lasers, and emission wavelength ranges. 380 ~ 440 nm light LED (light-emitting diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

The irradiation intensity of the active energy ray is usually 10 mW / cm ² to 3000 mW / cm ² . The irradiation intensity of the active energy ray is preferably an intensity in a wavelength region effective for activation of the cationic polymerization initiator or the radical polymerization initiator. The irradiation time of the active energy ray is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and still more preferably 0.1 seconds to 1 minute. If the active energy ray is irradiated once or multiple times, the cumulative light amount is 10 mJ / cm ² to 3000 mJ / cm ² , preferably 50 mJ / cm ² to 2,000 mJ / cm ² , more It is preferably 100 mJ / cm ² to 1000 mJ / cm ² . When the cumulative light amount is below this range, the curing of the polymerizable liquid crystal compound may be insufficient, and a good transferability may not be obtained. Conversely, when the cumulative light amount is above the range, there may be a case where the patterned polarizing layer is colored.

(Continuous manufacturing method of polarizing film)
The manufacturing method of the polarizing film 2 is preferably continuously manufactured in a roll-to-roll format. In this case, in the base material layer coating step, the base material layer wound into a roll shape is rolled out and transported, and the second protective layer wound into a roll shape is rolled out and transported, and the base material is rolled. The material layer and the protective layer are laminated to obtain a base material layer with a protective layer. In the liquid-repellent layer forming step, a liquid-repellent agent is applied while continuously transporting the base material layer with the protective layer to obtain the base-material layer with the liquid-repellent layer. In the protective layer removal step, the liquid-repellent layer is transported. The protective layer may be peeled off continuously on one side of the base material layer of the layer. In the patterned alignment layer forming step, the patterned alignment layer may be formed by continuously applying the composition for forming an alignment layer by a coating device while conveying the base material layer with the patterned liquid-repellent layer. In the patterned polarizing layer forming step, the patterned polarizing layer may be formed by continuously applying the composition for forming a polarizing layer by a coating device while conveying the base material layer with the patterned alignment layer. The polarizing film continuously manufactured as described above may have a length of, for example, 10 m or more.

<Second manufacturing method of polarizing film>
The polarizing film 2 can be manufactured by the second manufacturing method described below in addition to the first manufacturing method described above. FIG. 3 is a schematic cross-sectional view showing an example of a step of forming a patterned liquid-repellent layer in the method of manufacturing the polarizing film 2 shown in FIG. 1. Regarding the step of forming the patterned liquid-repellent layer in the second manufacturing method of the polarizing film 2, the protective layer 37 used in the first manufacturing method is not used, and the coating-repellent liquid is dropped on at least one side of the base material layer 13 Agent (FIG. 3), so that the patterned liquid-repellent layer 47b shown in FIG. 2 (c) can be formed.

The second manufacturing method of the polarizing film 2 has the following steps: a patterned alignment layer forming step, that is, obtaining a substrate layer 83 having a patterned liquid-repellent layer obtained after the patterned liquid-repellent layer formation step as described above ( The surface on the patterned liquid-repellent layer 47b side in FIG. 2 (c)) is the same as the first manufacturing method described above.
The patterned alignment layer 22 formed by coating the alignment layer-forming composition with the patterned alignment layer on the base material layer 84 (FIG. 2 (d)); and the patterned polarizing layer forming step, that is, by attaching the pattern The surface of the patterned alignment layer 22 side of the base material layer 84 of the patterned alignment layer is coated with a composition for forming a polarizing layer containing a liquid crystal compound and a dichroic dye to form the patterned polarized layer 21. Thereby, for example, a polarizing film 2 having a patterned polarizing layer as shown in FIGS. 1 and 2 (e) can be manufactured.

As the base material layer 13 and the liquid-repellent agent used in the patterned liquid-repellent layer forming step of the second manufacturing method, the same base material layer as the base material layer 13 and the liquid-repellent agent used in the first manufacturing method can be used. And liquid repellent. As a method of forming a patterned liquid-repellent layer 47b by drip-coating a liquid-repellent agent on at least one side of the base material layer 13, for example, as shown in FIG. 3, a liquid substance is dropped and applied to this portion The area is called the inkjet method. By applying the liquid-repellent agent dropwise on the base material layer 13, a patterned liquid-repellent layer 47b can be formed on the base material layer 13, thereby obtaining a base material layer 83 with a patterned liquid-repellent layer (FIG. 2 (c)) )

The patterning alignment layer forming step and the patterning polarizing layer forming step in the second manufacturing method are the same as the patterning alignment layer forming step and the patterning polarizing layer forming step in the first manufacturing method described above.

Regarding the second manufacturing method, similarly to the first manufacturing method, the polarizing film 2 may be continuously manufactured in a roll-to-roll format, for example. In this case, in the step of forming the patterned liquid-repellent layer, the substrate layer wound into a roll shape is rolled out and transported, and the liquid-repellent agent is added dropwise to form a patterned liquid-repellent layer on the substrate layer. It is sufficient to obtain a substrate layer with a patterned liquid-repellent layer. In the patterned alignment layer forming step, the patterned alignment layer may be formed by continuously applying the composition for forming an alignment layer by a coating device while conveying the base material layer with the patterned liquid-repellent layer. In the patterned polarizing layer forming step, the patterned polarizing layer may be formed by continuously applying the composition for forming a polarizing layer by a coating device while conveying the base material layer with the patterned alignment layer. The polarizing film continuously manufactured as described above may have a length of, for example, 10 m or more.

[Second Embodiment (Circular Polarizing Plate and Manufacturing Method)]
(Circular polarizer)
4 (a) to 4 (c) are schematic cross-sectional views each showing an example of a circular polarizing plate of the present invention. The polarizing film 2 shown in FIG. 2 (e) can be formed into a circular polarizing plate 5a, 5b as shown in FIGS. 4 (a) and (b) by stacking the retardation layer 15 having a 1/4 wavelength plate function. The retardation layer 15 may be laminated on the patterned polarizing layer 21 side of the polarizing film 2 (FIG. 4 (a)), or may be laminated on the substrate layer 13 side (FIG. 4 (b)). Moreover, the circularly polarizing plate 5a shown in FIG. 4 (a) may be used as the circularly polarizing plate 5c (FIG. 4 (c)), and the pattern may be patterned. The alignment layer 22 is peeled together with the base material layer 13.

The circularly polarizing plate may be formed by laminating a polarizing film 2 and a phase difference of a multilayer structure. In this case, as the retardation layer having a multilayer structure, a retardation layer having a layer having a function of a 1/2 wavelength plate and a layer having a function of a 1/4 wavelength plate can be used. The layer side having the function of a 1/2 wavelength plate and the polarizing film 2 are laminated to form a circular polarizing plate. Alternatively, a circularly polarizing plate can be obtained by using a retardation layer laminated with a 1/4 wavelength plate function having inverse wavelength dispersion and a layer having a positive C plate function as a retardation layer of a multilayer structure.

In addition, a circular polarizing plate can be produced by using a function as a retardation layer as the base material layer 13 of the polarizing film 2 and further laminating the retardation layer. In this case, the function of the base layer 13 and the retardation layer as a retardation layer may be selected according to the laminated position of the base layer 13 and the retardation layer in the circular polarizing plate.

The polarizing film and the retardation layer may be laminated via an adhesive layer using a known adhesive or adhesive.

(Manufacturing method of circular polarizing plate)
The circular polarizing plate can be manufactured by laminating a polarizing film and a retardation layer. In the case where the polarizing film is a continuous polarizing film with a length of 10 m or more, it is preferable to use a long retardation layer with a length of 10 m or more as the above-mentioned retardation layer, and continuously carry both of them on one side and an area of layer length The long polarizing film and the long retardation layer form a long laminated body. At this time, it is preferable to apply an adhesive or an adhesive to at least one of the long polarizing film and the long retardation layer to laminate the two.

In order to mount a polarizing film on a display device of a specific size, etc., the method for manufacturing a circular polarizing plate may have a step of cutting a long laminated body obtained by laminating a long polarizing film and a long retardation layer into a single piece of a specific size. In the cutting step, the long laminated body is preferably cut in at least one of a length direction and a width direction of the long laminated body. In this case, it is preferable to determine the cutting position in the long laminated body by arranging the low-polarized light region of the cut single piece at a specific position.
[Example]

The present invention will be specifically described based on examples. However, the present invention is not limited by these examples.
Unless otherwise specified, "%" and "part" in Examples and Comparative Examples are mass% and mass parts.

[Visual sensitivity correction polarization (Py) and visual sensitivity correction transmittance (Ty)]
(Production of evaluation samples)
A composition for forming an alignment layer and a composition for forming a polarizing layer used in each of Examples, Comparative Examples, and Reference Examples were prepared. In addition, a substrate obtained by cutting out a film of 40 mm × 40 mm in the same film as that used as the substrate layer in each of Examples, Comparative Examples, and Reference Examples was prepared as a substrate layer for evaluation. Using these, a sample for evaluation was obtained in the same procedure as in the production of the polarizing film of each of the examples, comparative examples, and reference examples except that the protective layer was not used.

(Polarity (Py) and Transmittance (Ty))
For the evaluation sample, the visual sensitivity correction unit transmittance (Ty) and the visual sensitivity correction polarization (Py) were calculated in the following order. A spectrophotometer (UV-3150, manufactured by Shimadzu Corporation) equipped with a folder with a polarizing element is used to measure the transmittance in the direction of the transmission axis in the range of 380 nm to 780 nm by the dual beam method (T ₁ ) and transmittance (T ₂ ) in the absorption axis direction. The folder is provided with a sieve on the reference side to cut off the light amount by 50%. Use the following (Equation 1) and (Equation 2) to calculate the transmittance and polarization at each wavelength, and then perform visual sensitivity correction in accordance with JIS Z 8701's 2-degree field of view (C light source) to calculate the visual sensitivity corrected transmittance (Ty ) And visual sensitivity correction polarization (Py).
Polarization [%] = {(T ₁ -T ₂ ) / (T ₁ + T ₂ )} × 100 (Equation 1)
Cell transmittance [%] = (T ₁ + T ₂ ) / 2 (Equation 2)

[Example 1]
(Manufacture of liquid repellent)
The first organosilicon compound (S1) (molecular weight of about 8000) represented by the following formula (a) was synthesized by the methods described in Synthesis Examples 1 and 2 of Japanese Patent Laid-Open No. 2014-15609. In formula (a), n is 43 and m is an integer from 1 to 6.
[Chemical 16]

The compound (hereinafter, compound (a)) represented by the above formula (a) as the first organic silicon compound (S1) and FAS9E (C ₄ F ₉ -C ₂ H ₄ ) as the second organic silicon compound (S2) are mixed. -Si- (OC ₂ H ₅ ) ₃ , boiling point 241 ° C, manufactured by Tokyo Chemical Industry Co., Ltd., and NOVEC 7200 (C ₄ F ₉ OC ₂ H ₅ , manufactured by 3M) as a solvent, and stirred at room temperature for a specific time to Obtain a liquid repellent. Among 100 parts of this liquid repellent, the ratio of the first organic silicon compound (S1) was 0.03 part, and the ratio of the second organic silicon compound (S2) was 0.07 part.

(Manufacture of alignment layer forming composition)
The following components were mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour, thereby obtaining a composition for forming an alignment layer as a composition for forming a photo-alignment film.
・ 2 parts of polymer with photoreactive group shown below
[Chemical 17]

・ Solvent: 98 parts of o-xylene

(Production of composition for forming polarizing layer)
The following components were mixed, and it stirred at 80 degreeC for 1 hour, and obtained the composition for polarizing layer formation. As the dichroic pigment, an azo pigment described in Examples of Japanese Patent Laid-Open No. 2013-101328 is used.
・ 75 parts of polymerizable liquid crystal compound represented by formula (1-6)
[Chemical 18]

・ 25 parts of polymerizable liquid crystal compound represented by formula (1-7)
[Chemical 19]

・ 2.8 parts of dichroic pigment (1) shown below
[Chemical 20]

・ 2.8 parts of dichroic pigment (2) shown below
[Chemical 21]

・ 2.8 parts of dichroic pigment (3) shown below
[Chemical 22]

・ 6 parts of polymerization initiator shown below
2-dimethylamino-2-benzyl-1- (4-olinylphenyl) butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals)
・ 1.2 parts of polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)
・ 250 parts of cyclopentanone

(Manufacture of polarizing film)
A triethylammonium cellulose film was cut out by 20 × 20 mm, and the surface was subjected to corona treatment (AGF-B10, manufactured by Kasuga Electric Corporation). AY-638 manufactured by Fujimori Industry Co., Ltd., which is a protective layer for openings formed by punching with a hole puncher on a substrate layer (including a thickness of 15 μm on a polyester film with a thickness of 38 μm Adhesive layer), the liquid-repellent agent was applied and dried at 120 ° C for 10 minutes to form a liquid-repellent layer. Then, the protective layer is peeled off to obtain a base material layer with a patterned liquid-repellent layer formed with a patterned liquid-repellent layer. The alignment layer-forming composition was coated on the surface of the obtained base material layer with the patterned liquid-repellent layer on the side where the patterned liquid-repellent layer was formed, and then dried in a drying oven set at 120 ° C for 1 minute to obtain the alignment layer. With a coating layer. A polarized UV irradiation device (SPOT CURE SP-7; manufactured by Oxtail Electric Co., Ltd.) was used to irradiate the coating layer for an alignment layer with a cumulative light amount of 50 mJ / cm ² (based on 313 nm) to 0 relative to the film edge. Polarized UV in the direction of ° to form a patterned alignment layer. The polarizing layer-forming composition was applied on the obtained patterned alignment layer using a bar coater, and then dried in a drying oven set at 110 ° C. for 1 minute. Thereafter, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Oxtail Electric Co., Ltd.) was used to irradiate ultraviolet rays (under a nitrogen atmosphere, wavelength: 365 nm, cumulative light quantity at wavelength 365 nm: 1000 mJ / cm ² ), thereby forming a liquid crystal. A patterned polarizing layer formed by aligning a compound and a dichroic pigment to obtain a polarizing film.

The appearance of the obtained polarizing film was visually observed, and as a result, it was clearly confirmed that a circular region (a low polarization region) in which a polarizing layer does not exist. In addition, according to the above procedure, the visual sensitivity-corrected transmittance (Ty) and the visual sensitivity-corrected polarization (Py) of the polarized region of the polarizing film are calculated. The results are shown in Table 1.

[Example 2]
A polarizing film was obtained in the same manner as in Example 1 except that a liquid-repellent agent was partially applied on the base material layer by using a dropper instead of laminating to form a protective layer with an opening formed by a hole opening machine. The appearance of the obtained polarizing film was visually observed, and as a result, it was clearly confirmed that a circular region (a low polarization region) in which a polarizing layer does not exist. In addition, according to the above procedure, the visual sensitivity-corrected transmittance (Ty) and the visual sensitivity-corrected polarization (Py) of the polarized region of the polarizing film are calculated. The results are shown in Table 1.

[Comparative example]
A polarizing film was obtained in the same manner as in Example 1 except that a liquid-repellent agent was not used and a liquid-repellent layer was not formed. The appearance of the obtained polarizing film was visually observed. As a result, it was impossible to confirm a region where no polarizing layer was present, and it was found that a polarizing film having a polarized region and a low-polarized region was not obtained. In addition, an evaluation sample was prepared according to the above procedure, and the visual sensitivity-corrected transmittance (Ty) and the visual sensitivity-corrected polarization (Py) were calculated. The results are shown in Table 1.

In addition, the values of the visual sensitivity-corrected transmittance (Ty) and the visual sensitivity-corrected polarization (Py) measured in each of the examples, comparative examples, and reference examples shown in Table 1 are the visual sensitivity-corrected transmission including the substrate layer. The value of the correction rate (Ty) and the visual sensitivity correction polarization (Py), the visual sensitivity correction transmittance (Ty) of the base material layer alone is 92%, and the visual sensitivity correction polarization (Py) value of the base material layer It is 0%. Therefore, when the substrate layer is removed in each of the examples, comparative examples, and reference examples shown in Table 1, it is considered that the value of the visual sensitivity correction transmittance (Ty) is greater than the value shown in Table 1, and the visual sensitivity is The value of the corrected polarization (Py) is the same as that shown in Table 1.

[Table 1]

2‧‧‧ polarizing film

5a ~ 5c‧‧‧circular polarizer

13‧‧‧ substrate layer

15‧‧‧ retardation layer

21‧‧‧ patterned polarizing layer

21a‧‧‧Polarized area

21b‧‧‧Low polarized light area

22‧‧‧ patterned alignment layer

22a‧‧‧Alignment layer

37‧‧‧ protective layer

37a‧‧‧ Covered Area

37b‧‧‧ exposed area

47‧‧‧Liquid layer

47b‧‧‧Patterned liquid repellent layer (liquid repellent layer)

81‧‧‧ base layer with protective layer

82‧‧‧ Substrate layer with liquid-repellent layer

83‧‧‧ Substrate layer with patterned liquid-repellent layer

84‧‧‧ Substrate layer with patterned alignment layer

FIG. 1 is a schematic plan view showing an example of a polarizing film of the present invention.

2 (a) to (e) are schematic cross-sectional views showing an example of a layer structure obtained in each step of the manufacturing steps of the polarizing film of the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of a step of forming a patterned liquid-repellent layer in the method for manufacturing a polarizing film of the present invention.

4 (a) to 4 (c) are schematic cross-sectional views each showing an example of a circular polarizing plate of the present invention.

Claims (14)

A method for manufacturing a polarizing film includes the following steps: The patterned liquid-repellent layer forming step is to form a patterned liquid-repellent layer on at least one side of the base material layer to obtain a base material layer with a patterned liquid-repellent layer; The patterned alignment layer forming step is to obtain a base material layer with a patterned alignment layer. The base material layer with the patterned alignment layer has the patterned dial on the base layer with the patterned liquid-repellent layer. A patterned alignment layer formed by applying a composition for forming an alignment layer on the surface on the liquid layer side; and The patterned polarizing layer forming step is to form a pattern by coating a polarizing layer-forming composition containing a liquid crystal compound and a dichroic dye on the surface of the patterned alignment layer side of the substrate layer with the patterned alignment layer. Polarizing layer The patterned liquid-repellent layer exhibits liquid-repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer. For example, the method for manufacturing a polarizing film according to claim 1, wherein the step of forming the patterned liquid-repellent layer includes the following steps: The substrate layer coating step is obtained by attaching at least one side of the substrate layer with a protective layer for covering the substrate layer and an exposed area for exposing the substrate layer. Base layer of protective layer; The step of forming a liquid-repellent layer is to apply a liquid-repellent agent to the surface of the protective layer side of the substrate layer with a protective layer to obtain a substrate layer with a liquid-repellent layer and a substrate with a liquid-repellent layer; and The protective layer removing step is to form the patterned liquid-repellent layer by peeling off the protective layer from the base material layer with the liquid-repellent layer and removing a part of the liquid-repellent layer. For example, the method for manufacturing a polarizing film according to claim 2, wherein the plan view shape of the exposed area is a circle, an oval, an oval, or a polygon, When the exposed area is circular, the diameter is 5 cm or less. In the case where the above-mentioned exposed area is oval or oblong, the long diameter is 5 cm or less, In the case where the exposed area is polygonal, the diameter of the imaginary circle drawn in the manner of the polygon inscribed above is 5 cm or less. The method for manufacturing a polarizing film according to any one of claims 1 to 3, wherein the step of forming the patterned liquid-repellent layer is the step of adding a liquid-repellent agent on at least one side of the substrate layer to form the patterned light-repellent agent. Liquid layer. The method for producing a polarizing film according to any one of claims 1 to 4, wherein the composition for forming an alignment layer contains a photo-alignment polymer, The patterned alignment layer forming step is performed by applying polarized light to a coating layer for a patterned alignment layer formed by applying the composition for forming an alignment layer to form the patterned alignment layer. The method for manufacturing a polarizing film according to any one of claims 1 to 5, wherein the liquid crystal compound is a polymerizable liquid crystal compound, The patterned polarizing layer forming step is to irradiate the coating layer for patterned polarizing layer formed by applying the composition for forming a polarizing layer with active energy rays to form the patterned polarizing layer. The method of manufacturing a polarizing film according to any one of claims 1 to 6, wherein the patterned polarizing layer shows a Blegg peak in an X-ray diffraction measurement. The method for manufacturing a polarizing film according to any one of claims 1 to 7, wherein the length of the polarizing film is 10 m or more. The method for manufacturing a polarizing film according to any one of claims 1 to 8, wherein the substrate layer has a 1/4 wavelength plate function. A method for manufacturing a circular polarizing plate includes a step of laminating a retardation layer, and a polarizing film manufactured by the method for manufacturing a polarizing film according to any one of claims 1 to 8 and Phase difference layered. For example, the method for manufacturing a circular polarizing plate according to claim 10, wherein the polarizing film is a long polarizing film with a length of 10 m or more, The phase difference layer is a long phase difference layer with a length of 10 m or more. The step of laminating the phase difference is to form a long laminated body by laminating the long polarizing film and the long phase difference, It further includes a cutting step of cutting the long laminated body into a single piece. A polarizing film comprising a polarizing region and a low-polarizing region having a corrected polarization degree lower than the visual sensitivity of the polarizing region, The above-mentioned polarization region contains a liquid crystal compound and a dichroic pigment, and the visual sensitivity correction polarization degree is 90% or more. The low-polarization region has a liquid-repellent layer. For example, the polarizing film of claim 12, wherein the visual sensitivity correction polarization degree of the above-mentioned low polarization region is 10% or less. For example, the polarizing film of claim 12 or 13, wherein the visual sensitivity correction unit transmittance of the above-mentioned polarized region is more than 35%, The visual sensitivity correction unit transmittance of the low-polarized light region is 80% or more.