TWI821206B - Manufacturing method of polarizing film and polarizing film - Google Patents

Abstract

The manufacturing method of the polarizing film of the present invention includes the following steps: a patterned liquid-repellent layer forming step, which 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 step of forming the patterned alignment layer is to obtain a base material layer with a patterned alignment layer. The base material layer with the patterned alignment layer has a patterned liquid repellent layer on the base material layer with a patterned liquid repellent layer. The patterned alignment layer is formed by coating the composition for forming the alignment layer on the side; and the step of forming the patterned polarizing layer is by surface coating the patterned alignment layer on the side of the base material layer with the patterned alignment layer. A composition for forming a polarizing layer containing a liquid crystal compound and a dichroic dye forms a patterned polarizing layer. The patterned liquid-repellent layer exhibits liquid-repellent properties to the composition for forming an alignment layer and the composition for forming a polarizing layer.

Description

Manufacturing method of polarizing film and polarizing film

The present invention relates to a manufacturing method of a polarizing film and a polarizing film, and in particular to a manufacturing method and a polarizing film of a polarizing film having a layer containing a liquid crystal compound and a dichroic pigment.

Organic EL (Electroluminescence) display devices using organic light-emitting diodes (OLED) can not only be lighter or thinner than liquid crystal display devices, but can also achieve a wide range of viewing angles and faster response. Because of its high image quality such as speed and high contrast, it is used in various fields such as smartphones, TVs, and digital cameras. It is known that in organic EL display devices, circularly polarizing plates and the like are used to improve anti-reflection performance in order to suppress a decrease in visibility caused by reflection of external light.

As a polarizing film used in such a circularly polarizing plate, Japanese Patent Laid-Open No. 2015-206852 (Patent Document 1) and Japanese Patent Laid-Open No. 2015-212823 (Patent Document 2) disclose that the polarizing film is on a base material. A patterned polarizing film laminated with a patterned liquid crystal cured film.

[Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-206852

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

The 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 with different visual sensitivity correction polarization degrees.

The present invention provides a method for manufacturing a polarizing film and a polarizing film shown below.

[1] A method for manufacturing a polarizing film, which includes the following steps: forming a patterned liquid-repellent layer on at least one side of the base material layer to obtain a base with a patterned liquid-repellent layer. material layer; the step of forming the patterned alignment layer is to obtain a base material layer with a patterned alignment layer, and the base material layer with the patterned alignment layer has the above mentioned base material layer with the patterned liquid repellent layer. The patterned alignment layer formed by coating the composition for forming the alignment layer on the surface of the patterned liquid-repellent layer; and the step of forming the patterned polarizing layer is due to the above-mentioned patterning of the base material layer with the patterned alignment layer. The surface of the alignment layer side is coated with a polarizing layer forming composition containing a liquid crystal compound and a dichroic pigment to form a patterned polarizing layer; the patterned liquid repellent layer is complementary to the alignment layer forming composition and the polarizing layer forming combination. The material shows liquid repellency.

[2] The manufacturing method of a polarizing film according to [1], wherein the step of forming the patterned liquid-repellent layer includes the following steps: the step of covering the base material layer is performed by having at least one side of the base material layer having a lateral build-up layer. Cover the covered area of the above-mentioned base material layer and the protective layer for exposing the above-mentioned exposed area of the base material layer to obtain a base material layer with a protective layer; the step of forming the liquid repellent layer is based on the above-mentioned base with a protective layer. The surface of the protective layer side of the material layer is coated with a liquid-repellent agent, thereby obtaining a base material layer with a liquid-repellent layer and a liquid-repellent layer; and the protective layer removal step is by removing the liquid-repellent layer from the above-mentioned liquid-repellent layer. The base material layer peels off the protective layer and removes part of the liquid-repellent layer to form the patterned liquid-repellent layer.

[3] The manufacturing method of the polarizing film according to [2], wherein the top view shape of the above-mentioned exposed area is circular, elliptical, oblong or polygonal, and when the above-mentioned exposed area is circular, the diameter is 5 cm or less , when the above-mentioned exposed area is oval or oval, the major diameter is 5cm or less, when the above-mentioned exposed area is polygonal, the diameter of an imaginary circle drawn by inscribing the above-mentioned polygon is 5cm. the following.

[4] The method for manufacturing a polarizing film according to any one of [1] to [3], wherein the step of forming the patterned liquid-repellent layer is performed by dropwise applying a liquid-repellent agent on at least one side of the base layer. The above patterned liquid repellent layer is formed.

[5] The method for manufacturing a polarizing film according to any one of [1] to [4], wherein the alignment layer forming composition contains a photo-alignment polymer, and the patterned alignment layer forming step is to apply the alignment layer The coating layer for the patterned alignment layer formed from the layer forming composition is irradiated with polarized light to form the patterned alignment layer.

[6] The method for manufacturing a polarizing film according to any one of [1] to [5], wherein the liquid crystal compound is a polymerizable liquid crystal compound, and the patterned polarizing layer forming step is to apply the polarizing layer forming composition. The formed patterned polarizing layer is irradiated with active energy rays using the coating layer to form the above patterned polarized light. layer.

[7] The method for manufacturing a polarizing film according to any one of [1] to [6], wherein the patterned polarizing layer exhibits a Bragg wave peak in X-ray diffraction measurement.

[8] The method for manufacturing 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 manufacturing a polarizing film according to any one of [1] to [8], wherein the base material layer functions as a quarter wave plate.

[10] A method for manufacturing a circularly polarizing plate, which has a retardation layer lamination step, and is made by combining a polarizing film manufactured by the method for manufacturing a polarizing film according to any one of [1] to [8] and a method having 1/ The phase difference layer of the 4-wavelength plate function.

[11] The manufacturing method of a circularly polarizing plate according to [10], wherein the above-mentioned polarizing film is a long polarizing film with a length of more than 10 m, the above-mentioned phase difference layer is a long strip of phase difference layer with a length of more than 10 m, and the above-mentioned phase difference layer The laminating step is to form a long laminated body by laminating the long polarizing film and the long retardation layer, and further includes a cutting step of cutting the long laminated body into individual pieces.

[12] A polarizing film having a polarizing area on a base material layer and a low polarizing area having a corrected polarization degree with a visual sensitivity lower than that of the polarizing area, the polarizing area containing a liquid crystal compound and a dichroic pigment, and having a visual sensitivity The corrected polarization degree is more than 90%, and the above-mentioned low polarization area has a liquid-repellent layer.

[13] The polarizing film of [12], wherein the visual sensitivity corrected polarization degree of the low polarization area is 10% or less.

[14] The polarizing film of [12] or [13], wherein the transmittance of the sensitivity correction unit in the polarized area is 35% or more, and the transmittance of the sensitivity correction unit in the low polarization area is 80% or more.

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

2:Polarizing film

5a~5c: Circular polarizing plate

13:Substrate layer

15: Phase difference layer

21:Patterned polarizing layer

21a:Polarized area

21b: Low polarization area

22: Patterned alignment layer

22a: Alignment layer

37:Protective layer

37a: Covered area

37b:Exposed area

47: Liquid repellent layer

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

81: Base material layer with protective layer

82: Base material layer with liquid repellent layer

83: Base material layer with patterned liquid repellent layer

84:Substrate layer with patterned alignment layer

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

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

Hereinafter, the manufacturing method of the polarizing film of the present invention and the preferred embodiment of the polarizing film will be described with reference to the drawings. In addition, the scope of the present invention is not limited to the embodiment described here, and various changes can be made within the scope that does not impair the gist of the present invention.

[First Embodiment (Production method of polarizing film and polarizing film)]

The manufacturing method of the polarizing film of the present invention has the following steps: The step of forming a patterned liquid-repellent layer 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 step of forming a patterned alignment layer is to obtain a patterned liquid-repellent layer with attached The patterned alignment layer formed by coating the alignment layer forming composition on the patterned liquid repellent layer side of the base layer having the liquid repellent layer; the patterned alignment layer attached to the base material layer; and the formation of the patterned polarizing layer The step is to form a patterned polarizing layer by coating a polarizing layer forming composition containing a liquid crystal compound and a dichroic pigment on the patterned alignment layer side surface of the base material layer with the patterned alignment layer. The patterned liquid-repellent layer exhibits liquid-repellent properties to the composition for forming an alignment layer and the composition for forming a polarizing layer.

Examples of methods for forming the patterned liquid repellent layer in the above patterned liquid repellent layer forming step include a method of forming a patterned liquid repellent layer using a protective layer, and a method of dropwise applying a liquid repellent agent to form a patterned liquid repellent layer. method. Each method is described in detail below.

<First manufacturing method of polarizing film>

FIG. 1 is a schematic plan view showing an example of the 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. 1 . Figure 2(e) is a cross-sectional view along line X-X of Figure 1. The patterned liquid-repellent layer formation step in the first manufacturing method of the polarizing film 2 includes the following steps: a base material layer coating step, that is, having a coating for covering the base material layer 13 by side-laminating at least one side of the base material layer 13 The protective layer 37 in the area 37a and the exposed area 37b for exposing the base material layer 13 is obtained to obtain the base material layer 81 with a protective layer (Fig. 2(a)); the liquid repellent layer forming step is to obtain the base material layer 81 with a protective layer Topcoat on the protective layer 37 side of the base material layer 81 cloth the liquid repellent agent, thereby obtaining the base material layer 82 with the liquid repellent layer formed with the liquid repellent layer 47 (Fig. 2(b)); and the protective layer removal step, that is, by removing the liquid repellent layer from the base material The protective layer of layer 82 is peeled off, and a portion of the liquid repellent layer 47 is removed to form the 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 base material layer 83 with a patterned liquid repellent layer obtained through the above-mentioned patterned liquid repellent layer forming step ( The base material layer 84 with the patterned alignment layer of the patterned alignment layer 22 formed by coating the alignment layer forming composition on the surface of the patterned liquid repellent layer 47b side of Figure 2(c) (Figure 2(d) ); and a patterned polarizing layer forming step, that is, by coating a polarizing layer forming composition containing a liquid crystal compound and a dichroic pigment on the patterned alignment layer 22 side of the base material layer 84 with the patterned alignment layer. , to form the patterned polarizing layer 21. Thereby, the polarizing film 2 having a patterned polarizing layer as shown in FIG. 1 and FIG. 2(e) can be manufactured.

(Polarizing film)

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

The polarizing film 2 has a patterned polarizing layer 21 on the base material layer 13, and may further have a patterned polarizing layer 21. Alignment layer 22, other layers, etc. Details of the patterned alignment layer 22 are described below. Examples of other layers include a surface protective layer provided on the surface of the patterned polarizing layer 21 opposite to the base material layer 13 for the purpose of protecting the surface of the patterned polarizing layer 21 . In addition, when the base material layer 13 is peeled off for use, a surface protective layer can be provided on the surface of the patterned polarizing layer 21 on the side of the peeling base material layer 13 . The surface protective layer may have a single-layer structure or a multi-layer structure. When the surface protective layer has a multi-layer structure, each layer may be formed of the same material or may be formed of different materials.

Furthermore, the polarizing film 2 shown in FIG. 2(e) discloses an example in which the alignment layer and the patterned polarizing layer 21 are provided on one side of the base material layer 13, but it can also 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 base material layer 13 may be the same as each other or may be different from each other.

The polarizing film 2 may be a strip-shaped polarizing film with a length of 10 m or more. In this case, the polarizing film 2 may be a roll wound into a drum shape. The polarizing film can be continuously rolled out from the roll, and steps such as the step of laminating the phase difference layer described below and the step of cutting into individual pieces can be performed. The length of the elongated polarizing film formed into a roll is not particularly limited as long as it is 10 m or more, and may be, for example, 10,000 m or less.

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

The low polarization region 21b preferably has a liquid repellent layer (patterned liquid repellent layer) 47b formed on the base material layer 13 and does not have an alignment layer or a polarizing layer. The visual sensitivity corrected polarization degree (Py) of the low polarization area 21b may be, for example, 10% or less, preferably 5% or less, more preferably 1% or less, or 0%. In addition, the sensitivity correction single unit transmittance (Ty) of the low polarization region 21b can 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 visual sensitivity corrected single transmittance (Ty) in this specification can be calculated based on the polarization and single transmittance measured using a spectrophotometer. For example, a spectrophotometer equipped with a folder with a polarizing element can be used to measure the transmittance in the transmission axis direction (alignment vertical direction) within the wavelength range of 380 nm to 780 nm of visible light by the double-beam method. (T ₁ ) and the transmittance (T ₂ ) in the absorption axis direction (aligned in the same direction). The degree of polarization and single transmittance in the visible light range are calculated using the following formulas (Formula 1) and (Formula 2). The degree of polarization and single transmittance at each wavelength are calculated based on the 2-degree field of view of JIS Z 8701 (C light source). ) to perform visual sensitivity correction, whereby the visual sensitivity corrected single transmittance (Ty) and visual sensitivity corrected polarization (Py) can be calculated.

Polarization degree [%]={(T ₁ -T ₂ )/(T ₁ +T ₂ )}×100% (Formula 1)

Monomer transmittance [%]=(T ₁ +T ₂ )/2 (Formula 2)

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

The shape of the polarizing region 21a and the shape of the low polarizing region 21b are not particularly limited. For example, as shown in FIG. 1, when the polarizing region 21a is arranged to surround the low polarizing region 21b, the top view shape of the low polarizing 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 area 21b is circular, its diameter is preferably 5 cm or less, more preferably 3 cm or less, and further preferably 2 cm or less. When the low polarization area 21b is oval or oblong, its major axis is preferably 5 cm or less, more preferably 3 cm or less, and further preferably 2 cm or less. When the low polarization area 21 b is a polygon, the diameter of an imaginary circle drawn incising the polygon is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less. The low polarization area 21b of the above shape can be preferably used as an area corresponding to the lens position of a camera installed on a smartphone, tablet, etc. At this time, by setting the low polarization area 21b to an area where the visual sensitivity corrected polarization degree (Py) is 10% or less and the visual sensitivity corrected single unit transmittance (Ty) is 80% or more, the coloring of the low polarization area 21b can be reduced. , obtain excellent transparency, thus improving the performance of the camera able.

Furthermore, the polarizing region 21a and the low polarizing region 21b may be provided so that their plan view shapes become linear, strip-like, wavy, or the like. In this case, a plurality of polarizing regions 21a and low polarizing regions 21b may be provided alternately. In this case, the widths of the polarizing region 21a and the low polarizing region 21b are independent, preferably 1 μm~10 mm, more preferably 1 μm~1 mm, and even more preferably 1 μm~100 μm.

Furthermore, when the polarizing film is a strip-shaped polarizing film, the strip-shaped polarizing film is usually cut into a specific size according to the use of the polarizing film, etc., so it is preferably positioned at a specific position of the cut polarizing film. The polarizing area 21a or the low polarizing area 21b is formed by setting the arrangement of the polarizing area or the low polarizing area of the long polarizing film. For example, when the polarizing film after cutting is the polarizing film 2 shown in FIG. 1 , it is preferable to provide a plurality of low polarization regions 21 b at specific intervals in the length direction and/or 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, and is preferably 5 μm or less, more preferably 3 μm or less. In addition, the thickness of the patterned liquid repellent layer 47b is usually 1~200nm, preferably 1~20nm. The thickness of the polarizing 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 explained based on FIGS. 2(a) to (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 region 37a for covering the base material layer 13 and a region for exposing the base material layer 13. The protective layer 37 in the area 37b is exposed. Thereby, the base material layer 81 with the protective layer can be obtained.

The exposed area 37b of the protective layer 37 may be, for example, an opening of the protective layer 37. The coated region 37a can suppress the coating of the liquid repellent agent on the base material layer 13 when the liquid repellent agent described below is applied to the base material layer 81 with the protective layer. On the other hand, in the exposed area 37b of the protective layer 37, a liquid repellent agent may be coated on the base material layer 13.

As described below, the patterned liquid repellent layer 47b is formed on the base material layer 13 by applying the liquid repellent agent in the exposed area 37b. On the patterned liquid-repellent layer 47b, it is difficult to form an alignment layer or a polarizing layer as described below. Therefore, the exposed area 37b is preferably formed corresponding to the low polarization area 21b 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 according to the shape of the low polarization region 21 b. For example, if the top view shape of the low polarization area 21b is a circle; an ellipse; an oval; a triangle, a square, a rectangle, a rhombus and other polygons; a line; a strip; or a wave, then the exposed area 37b corresponds to these shapes. And 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 further preferably 2 cm or less. When the exposed area 37b is oval or oblong, its major axis is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less. When the exposed area 37b is polygonal, the diameter of an imaginary circle drawn by inscribing the polygon is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less.

In addition, in the covered area 37a of the protective layer 37, the liquid repellent layer 47 is formed on the covered area 37a, so it is preferably formed corresponding to the area 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 better to determine the orientation layer according to the shape of the polarizing area 21a. shape.

(Substrate layer)

The base material 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 base material layer 13 can be a glass base material or a resin base material, preferably a resin base material. In addition, from the viewpoint that the polarizing film 2 can be continuously produced, the base material layer 13 is more preferably rolled out from a long resin base material rolled into a roll shape. The resin base material is preferably a base material having translucency that allows visible light to pass through. Here, the so-called light transmittance refers to a sensitivity-corrected single-unit transmittance of 80% or more for light in the wavelength range of 380 to 780 nm.

The thickness of the base material layer 13 is preferably thin in terms of quality that can be practically handled. However, if it is too thin, the strength will decrease and the workability will tend to deteriorate. The thickness of the base material layer 13 is usually 5 μm ~ 300 μm, preferably 20 μm ~ 200 μm. In addition, the base material layer 13 can be provided in a peelable manner. For example, the patterned polarizing layer 21 of the polarizing film 2 can be peeled off from the polarizing film 2 after being bonded to a member constituting the display device or a retardation layer described below. Thereby, a further thinning effect of the polarizing film 2 can be obtained.

烯系聚合物等環狀烯烴系樹脂；聚乙烯醇；聚對苯二甲酸乙二酯；聚甲基丙烯酸酯；聚丙烯酸酯；三乙醯纖維素、二乙醯纖維素及乙酸丙酸纖維素等纖維素酯；聚萘二甲酸乙二酯；聚碳酸酯；聚碸；聚醚碸；聚醚酮；聚苯硫醚及聚苯醚等。 Examples of the resin constituting the resin base material include polyolefins such as polyethylene and polypropylene;

Cyclic olefin resins such as olefinic polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; triacetyl cellulose, diacetyl cellulose and acetate propionate fiber Cellulose esters such as cellulose; polyethylene naphthalate; polycarbonate; polyester; polyether ketone; polyetherketone; polyphenylene sulfide and polyphenylene ether, etc.

Examples of commercially available resin base materials for cellulose esters include: "Fujitac Film" (manufactured by Fuji Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (the above, manufactured by Konica Minolta Opto Co., Ltd.) wait.

Examples of commercially available cyclic olefin-based resins include "Topas" (registered trademark) (manufactured by Ticona Co., Ltd.), "ARTON" (registered trademark) (manufactured by JSR Co., Ltd.), "ZEONOR" (registered trademark) ), "ZEONEX" (registered trademark) (the above, manufactured by Japan ZEON Co., Ltd.) and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). This cyclic olefin-based resin can be formed into a film by known methods such as solvent casting and melt extrusion to produce a resin base material. A commercially available resin base material of cyclic olefin-based resin can also be used. Examples of commercially available resin base materials for cyclic olefin-based resins include "S-SINA" (registered trademark), "SCA40" (registered trademark) (the above, manufactured by Sekisui Chemical Industry Co., Ltd.), and "ZEONOR FILM" (registered trademark) (manufactured by Optronics Co., Ltd.) and "ARTON FILM" (registered trademark) (manufactured by JSR Co., Ltd.).

The base material layer 13 may have a one-layer structure or a multi-layer structure of two or more layers. When the base material layer 13 has a multi-layer structure, each layer may be formed of the same material or may be formed of different materials. become.

In addition, the base material layer 13 may have a quarter wave plate function. By allowing the base material layer 13 to function as a quarter wave plate, 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, even if the retardation layer having the function of a 1/4 wavelength plate is not bonded to the polarizing film 2 except for the base material layer 13, a circularly polarizing plate can be obtained. In addition, when the base material layer 13 has a multilayer structure, the patterned polarizing layer 21 can be laminated by using a layer having a 1/2 wavelength plate function and a layer having a 1/4 wavelength plate function. On the side of the layer having the function of a 1/2 wavelength plate, a circularly polarizing plate is obtained. Alternatively, when the base material layer 13 has a multilayer structure, a layer formed by laminating a layer having a 1/4 wavelength plate function with reverse wavelength dispersion and a layer having a positive C plate function can also be used to obtain a round shape. Polarizing plate.

(protective layer)

As the protective layer 37, a sheet-like base material in which a region serving as the exposed region 37b is formed can be used. The area that becomes the exposed area 37b can be formed by the following methods: mechanical punching of a specific part of the sheet-like base material by drilling, cutting, water injection, etc.; or by laser ablation, chemical dissolution, etc. Methods for removing specific parts of the base material, etc.

The sheet-like base material for 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. The sheet-like base material for forming the protective layer 37 can be formed using, for example, the same material as the above-mentioned base material layer 13 . In particular, it is preferably formed using a resin base material, and more preferably a sheet-like base material that can easily prevent the protective layer 37 from being exposed. Polyester resin such as polyethylene terephthalate that is deformed in the area 37b (such as the opening).

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

(Liquid-repellent layer formation step)

In the step of forming the liquid-repellent layer, a liquid-repellent agent is applied to the surface of the protective layer-attached base material layer 81 on the protective layer 37 side, thereby obtaining a liquid-repellent layer-attached base material layer 82 on which the liquid-repellent layer 47 is formed. (Figure 2(b)).

(liquid repellent)

The liquid repellent agent is not particularly limited as long as the liquid repellent layer (patterned liquid repellent layer 47b) formed by applying the liquid repellent agent shows liquid repellency to the alignment layer forming composition and the polarizing layer forming composition. limited. The liquid repellency in this specification means that when an alignment layer forming composition or a polarizing layer forming composition is coated on the patterned liquid repellent layer 47b, the patterned liquid repellent layer 47b repels these compositions and does not facilitate patterning. A coating layer of these compositions is formed on the liquid repellent layer 47b. For example, the liquid repellency of the patterned liquid repellent layer 47b means that the contact angle measured by the θ/2 method with a water droplet amount of 3 μL on the surface of the patterned liquid repellent layer 47b is 90° or more, and the contact angle may be 100 ° or above, can be above 110°, usually less than 120°.

The liquid repellent may include, for example, a first organosilicon compound in which 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, or a hydrolyzable silane oligomer It is a second organosilicon compound in which a fluorocarbon-containing group and a hydrolyzable group are bonded to the silicon atom.

The carbon number of the perfluoroalkyl group (especially the carbon number of the longest linear part) is, for example, 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 the polyalkylene ether group or polyalkylene glycol dialkyl ether residue are replaced by fluorine atoms. It can also be called perfluoropolyalkylene ether. or perfluoropolyalkylene glycol dialkyl ether residues. The number of carbon atoms contained in the longest linear part of the perfluoropolyether group is preferably 5 or more, more preferably 10 or more, and more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, but may be about 200, for example.

The fluorine-containing group only needs to have the above-mentioned perfluoroalkyl group or perfluoropolyether group on the free end side. Therefore, an appropriate linking group may be present 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 such linking group. Examples of the linking group include hydrocarbon groups such as alkylene groups and aromatic hydrocarbon groups, (poly)alkylene glycol groups, groups in which a part of the hydrogen atoms are substituted with F, and these appropriately linked groups. The carbon number of the connecting group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

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

The hydrolyzable group utilizes hydrolysis and dehydration condensation reactions to cause (1) the first organosilicon compounds to interact with each other, or (2) the first organosilicon compound and active hydrogen (hydroxyl group, etc.) on the surface of the substrate, or (3) the first The role of bonding between the organosilicon compound and the second organosilicon compound. Examples of such a hydrolyzable group include Examples: alkoxy groups (especially alkoxy groups with 1 to 4 carbon atoms), hydroxyl groups, acetyloxy groups, allyl groups, halogen atoms (especially chlorine atoms), etc. Preferred hydrolyzable groups are alkoxy groups, allyl groups and halogen atoms, and particularly preferred ones are methoxy groups, ethoxy groups, allyl groups and chlorine atoms.

The number of hydrolyzable groups bonded to the silicon atom only needs to 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 the silicon atom, different hydrolyzable groups may be bonded to the silicon atom, and preferably the same hydrolyzable group is bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to silicon atoms is usually 4, and may be 2 or 3 (especially 3). In the case of 3 or less, for example, alkyl groups (especially alkyl groups with 1 to 4 carbon atoms), H, NCO, etc. can be bonded to the remaining bonds.

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

The liquid repellent agent can be coated on the base material layer 81 with the protective layer by dip coating, roll coating, rod coating, spin coating, spray coating, die coating, etc. The surface of the protective layer 37 side. When a composition containing a first organosilicon compound and a second organosilicon compound is used as a liquid repellent agent, the coating layer formed by coating the liquid repellent agent on the base material layer 81 with a protective layer is exposed to the air. The liquid-repellent layer 47 can be formed by allowing it to stand and/or heat and dry.

The liquid repellent agent is coated on the coated area 37a of the protective layer 37 and on the base material layer 13 in the exposed area 37b of the protective layer 37. Thereby, as shown in FIG. 2(b), the coating layers respectively on the protective layer 37 can be obtained. The base material layer 82 with the liquid repellent layer 47 is formed on the base material layer 13 in the covering area 37a and the exposed area 37b of the protective layer 37.

(Protective layer removal step)

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

(Patterned alignment layer formation step)

In the patterned alignment layer forming step, the alignment layer forming composition is coated on the patterned liquid repellent layer 47b side of the base material layer 83 with the patterned liquid repellent layer obtained in the protective layer removal step. Thereby, the patterned alignment layer-attached base material layer 84 having the 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 restriction force that aligns the liquid crystal compound stacked 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 trench alignment film, etc. can be used.

As described above, the patterned liquid repellent layer 47b exhibits liquid repellency to the alignment layer forming composition. Therefore, in the step of forming the patterned alignment layer, if the pattern of the base material layer 83 with the patterned liquid repellent layer is If the alignment layer forming composition is coated on the surface of the patterned liquid repellent layer 47b, the alignment layer forming composition will be repelled on the patterned liquid repellent layer 47b, and no coating layer of the composition will be formed. On the other hand, in the area of the base material layer 83 with the patterned liquid repellent layer where the patterned liquid repellent layer 47b is not formed, a coating layer of the alignment layer forming composition can be formed. Therefore, in the step of forming the patterned alignment layer, it is possible to obtain a pattern in which the alignment layer 22a is formed on the base material layer 13 in a region where the patterned liquid repellent layer 47b is formed, and in a region where the patterned liquid repellent layer 47b is not formed. The alignment layer 22 is a base material layer with a patterned alignment layer.

The patterned alignment layer 22 facilitates liquid crystal alignment of the liquid crystal compound. The states of liquid crystal alignment such as horizontal alignment, vertical alignment, mixed alignment, and tilt alignment vary according to the properties of the patterned alignment layer 22 and the liquid crystal compound, and their combinations can be selected arbitrarily. For example, if the patterned alignment layer 22 is a material that exhibits horizontal alignment as an alignment restriction force, the liquid crystal compound can form a horizontal alignment or a mixed alignment. If the patterned alignment layer 22 is a material that exhibits vertical alignment, the liquid crystal compound can form a vertical alignment. or tilted alignment. Expressions such as horizontal and vertical represent the direction of the long axis of the aligned liquid crystal compound when the plane of the polarizing film 2 is used as the reference. For example, the so-called vertical alignment refers to the long axis of the polymerizable liquid crystal that is aligned in the vertical direction relative to the plane of the polarizing film 2 . The vertical here refers to 90°±20° relative 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 , so the patterned alignment layer 22 is preferably formed using a material that exhibits horizontal alignment.

As the alignment restricting 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 surface conditions or friction conditions. When the patterned alignment layer 22 is formed of a photo-alignment polymer, can be arbitrarily adjusted by polarized light irradiation conditions, etc. Also, also Liquid crystal alignment can be controlled by selecting physical properties such as surface tension or liquid crystallinity of the polymerizable liquid crystal compound.

The thickness of the patterned alignment layer 22 is usually 10nm~5000nm, preferably 10nm~1000nm, and more preferably 30nm~300nm. In addition, the patterned alignment layer 22 formed between the base material layer 13 and the patterned polarizing layer 21 is preferably insoluble in the solvent used when forming the patterned polarizing layer 21 on the patterned alignment layer 22, and has the ability to Heat resistance to heat treatment for solvent removal or liquid crystal alignment.

Examples of the patterned alignment layer 22 include an alignment film containing an alignment polymer, a photo alignment film, a groove alignment film, and the like. When the base material layer 13 is rolled out from a roll wound with a long resin base material, the patterned alignment layer 22 is preferably photo-aligned in terms of easily controlling its alignment direction. membrane.

唑、聚伸乙基亞胺、聚苯乙烯、聚乙烯吡咯啶酮、聚丙烯酸或聚丙烯酸酯類等。其中，較佳為聚乙烯醇。該等配向性聚合物可單獨使用，亦可組合兩種以上使用。 Examples of the alignment polymer include polyamide or gelatin having a amide bond in the molecule, polyamide imine having an amide imine bond in the molecule, polyamide acid and polyvinyl alcohol as hydrolysates thereof, Alkyl modified polyvinyl alcohol, polyacrylamide, poly

Azole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate, etc. Among them, 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 generally be obtained by applying a composition in which the alignment polymer is dissolved in a solvent (hereinafter sometimes referred to as the "alignment polymer composition") on a patterned surface. The base material layer 83 of the liquid repellent layer is removed, or the alignment polymer composition is It is applied to the base material layer 13, the solvent is removed, and rubbed (rubbing method).

Examples of solvents used in the alignment polymer composition include water; alcohols such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl siluso, butyl siluso, 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 , cyclohexanone, methylpentanone or methyl isobutyl ketone and other ketone solvents; 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, etc. These solvents can be used alone or in combination of two or more.

The content of the aligning polymer in the aligning polymer composition only needs to be within a range that allows the aligning polymer to be completely dissolved in the solvent. It is preferably 0.1 to 20 mass % in terms of solid content relative to the solution, and more preferably Preferably, it is 0.1~10% by mass.

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

Examples of methods for applying the alignment polymer composition to the base material layer 83 with the patterned liquid repellent layer include spin coating, extrusion coating, gravure coating, and die coating. , coating methods such as bar coating method or dressing method, or printing methods such as flexographic method, etc. are known methods. In the case where the polarizing film 2 is manufactured by a roll-to-roll (Roll-to-Roll) continuous manufacturing method, the coating method Generally, printing methods such as gravure coating, die nozzle coating or flexographic printing can be used.

By removing the solvent contained in the alignment polymer composition, a dry coating of the alignment polymer is formed. Examples of solvent removal methods include natural drying, ventilation drying, heating drying, and reduced pressure drying. Thereafter, the dry coating can be brought into contact with a rotating friction roller wrapped with rubbing cloth, thereby forming the patterned alignment layer 22 .

A photo-alignment film can usually be obtained by the following method: applying a composition containing a polymer or monomer with a photoreactive group and a solvent (hereinafter sometimes referred to as a "photo-alignment film-forming composition") with a pattern The base material layer 83 of the liquid repellent layer is melted to form a coating layer for the alignment layer, and the coating layer for the alignment layer is irradiated with polarized light (preferably polarized UV (ultraviolet, ultraviolet)). A photo-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 irradiated polarized light.

The so-called photoreactive group refers to a group that generates liquid crystal alignment ability by irradiating light. Specifically, it is a photoreaction that is the origin of the alignment ability of liquid crystal, such as alignment induction of molecules or isomerization reaction, dimerization reaction, photo-crosslinking reaction or photodecomposition reaction caused by irradiation of light. Among the photoreactive groups, those that cause a dimerization reaction or a photocrosslinking reaction are preferred in terms of excellent alignment properties. As a photoreactive group that can produce the above reaction, it is preferable that it has an unsaturated bond, especially a double bond, and more preferably it has a carbon-carbon double bond (C=C bond) and a carbon-nitrogen double bond. At least one of the groups consisting of (C=N bond), nitrogen-nitrogen double bond (N=N bond) and 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 stilbene group, a stilbazolyl group, a stilbazonium group, a chalcone group or a cinnamyl group. From the viewpoint of easy control of reactivity or expression of alignment restriction force during photoalignment, a chalcone group or a cinnamyl group is preferred. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of the photoreactive group having an N=N bond include: azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, disazo group or formazan group, or 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 substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonate or halogenated alkyl groups.

The solvent of the composition for forming a photo-alignment film is preferably one that dissolves a polymer and a monomer having a photoreactive group. Examples of the solvent include the solvents listed as solvents for 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 the photoreactive group or the thickness of the photoalignment film to be produced. The adjustment is preferably 0.2% by mass or more, and particularly preferably within the range of 0.3 to 10% by mass. In addition, polymer materials such as polyvinyl alcohol or polyimide or photosensitizers may be contained within a range that does not significantly damage the characteristics of the photo-alignment film.

As a method of applying the composition for forming a photo-alignment film to the base material layer 83 provided with the patterned liquid-repellent layer, the above-mentioned method of applying the alignment polymer composition to the base layer 83 provided with the patterned liquid-repellent layer can be used. The method for the base material layer 83 is the same. An example of a method for removing the solvent from the coated photo-alignment film-forming composition is the same method as the method for removing the solvent from the alignment polymer composition.

The polarized light irradiation can be carried out directly by removing the solvent from the dry film after removing the composition for forming a photo-alignment film on the base material layer 83 with the patterned liquid repellent layer, or it can also be irradiated with polarized light through the base material layer 13 The process of drying the film is carried out from the base material layer 13 side. In addition, the polarized light used for polarized light irradiation is preferably substantially parallel light. The wavelength of the polarized light irradiated is preferably in the wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) with a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of light sources 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 halide lamps. lamp. These lamps are preferred because the luminous intensity of ultraviolet light with a wavelength of 313 nm is greater. Polarized light can be irradiated by passing light from a light source through an appropriate polarizing element. As the polarizing element, a polarizing filter, a polarizing filter such as Glan-Thompson and Glan-Taylor, or a wire grid type polarizing element can be used.

Furthermore, if shielding is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) with different directions of liquid crystal alignment can be formed.

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

An example of a method for obtaining a trench alignment film is to expose the surface of a photosensitive polyimide film through an exposure mask that has a patterned slit, and then develop and rinse it to form a concavo-convex pattern. ; A method of forming a pre-hardened UV curable resin layer on a plate-shaped mother disk with grooves on the surface, and then moving the resin layer to the base material to harden it; pressing a drum-shaped mother disk with a plurality of grooves against the formed Methods such as forming unevenness on the UV curable resin film before curing on the base material and then curing it. Specific examples include methods described in Japanese Patent Application Laid-Open No. 6-34976 and Japanese Patent Application Laid-Open No. 2011-242743.

In order to obtain an alignment with less alignment disorder, the width of the convex portion of the trench alignment film is preferably 0.05 μm ~ 5 μm, the width of the concave portion is preferably 0.1 μm ~ 5 μm, and the depth of the step difference between the concavities and convexities is preferably less than 2 μm. Preferably, it is 0.01μm~1μm or less.

(Patterned polarizing layer formation step)

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

As described above, the patterned liquid repellent layer 47b shows liquid repellency to the polarizing layer forming composition. Therefore, in the step of forming the patterned polarizing layer, if the pattern of the base material layer 84 with the patterned alignment layer is If the polarizing layer forming composition is coated on the surface of the patterned liquid repellent layer 47b, the polarizing layer forming composition will be repelled on the patterned liquid repellent layer 47b, and a coating layer of the composition will not be formed. On the other hand, in the area of the base material layer 84 with the patterned alignment layer where the patterned liquid repellent layer 47b is not formed, a coating layer of the polarizing layer forming composition can be formed. Therefore, in the step of forming the patterned polarizing layer, it is possible to obtain a pattern in which the patterned liquid repellent layer 47b is formed on the base material layer 13 and the polarizing region 21a is formed on the alignment layer 22a of the patterned alignment layer 22. Polarizing film 2 of polarizing layer 21 .

The polarizing film 2 shown in FIG. 1 and FIG. 2(e) can also be used after peeling off the base material layer 13 . In this case, the alignment layer 22a and the base material layer 13 can also be peeled off together. For example, the base material layer 13 may be peeled off after the patterned polarizing layer 21 of the polarizing film 2 is bonded to a member constituting the display device, a phase difference 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. When the patterned polarizing layer 21 has the polarizing characteristics of the plane of the polarizing film 2, it is preferable to have a region in which the dichroic pigment and the liquid crystal compound are aligned horizontally with respect to the plane of the polarizing film 2. In addition, when 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 pigment and the liquid crystal compound are aligned horizontally with respect to the plane of the polarizing film 2.

For the area in the patterned polarizing layer 21 where the dichroic pigment and the liquid crystal compound are horizontally aligned with respect to the polarizing film 2 surface, as the absorbance A1(λ) in the horizontal direction of the liquid crystal alignment for light with wavelength λ nm and The dichromatic ratio of the absorbance A2(λ) in the vertical direction within the liquid crystal alignment plane (=A1(λ)/A2(λ)) is preferably 7 or more, more preferably 20 or more, and still more preferably 30 or more. The higher the value, the more polarizing properties it has with excellent absorption selectivity. When the patterned polarizing layer 21 is in the nematic liquid crystal phase, the above ratio is about 5 to 10, but it varies depending on the type of dichroic dye. Furthermore, when the patterned polarizing layer 21 is in the nematic liquid crystal phase and the smectic liquid crystal phase, it can be confirmed by, for example, surface observation using various microscopes or scattering degree measurement using a haze meter. Dichroic pigments do not phase separate.

The thickness of the patterned polarizing layer 21 is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 10 μm or less, 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 or a stylus film thickness meter.

(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 liquid crystal compound is not particularly limited, and rod-shaped liquid crystal compounds, disk-shaped liquid crystal compounds, and mixtures thereof can be used. Moreover, 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 arbitrarily controlled, and the polarizing film can be made significantly thinner. Furthermore, since the polarizing film can be produced without stretching treatment, it can be produced as a non-stretchable polarizing film that does not undergo stretching and relaxation due to heat.

The polymerizable liquid crystal compound refers to a compound that has a polymerizable group and has liquid crystallinity. The polymerizable group refers to a group that participates in the polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in the polymerization reaction by active radicals or acids generated from the photopolymerization initiator described below. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, and oxirane. Oxetanyl etc. Among them, an acryloxy group, a methacryloxy group, an vinyloxy group, an oxirane group and an oxetanyl group are preferred, and an acryloxy group is more preferred. The liquid crystallinity may be thermotropic liquid crystal or lyotropic liquid crystal. When mixed with dichroic pigments like the patterned polarizing layer 21 in this embodiment, thermotropic liquid crystal is preferably used.

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

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

Specific examples of such polymerizable liquid crystal compounds include compounds represented by the following formula (A) (hereinafter sometimes referred to as compound (A)), etc.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (A)

[In 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 divalent alicyclic hydrocarbon group The hydrogen atoms contained in the hydrocarbon group can be substituted with halogen atoms, alkyl groups with 1 to 4 carbon atoms, fluoroalkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, cyano groups or nitro groups to form 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; wherein, at least one of X ¹ , X ² and X ³ may have a substituent. 1,4-phenylene group or cyclohexane-1,4-diyl group which may have a substituent; Y ¹ , Y ² , W ¹ and W ² are independently single bonds or divalent linking groups; V ¹ and V ² are independently an alkyldiyl group having 1 to 20 carbon atoms that may have a substituent, and -CH ₂ - constituting the alkanediyl group may be substituted with -O-, -S- or NH-; U ¹ and U ² independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group].

In the compound (A), at least one of X ¹ , X ² and X ³ is an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group. In particular, X ^{1 and} -Di base. In the case of a structure containing trans-cyclohexane-1,4-diyl, smectic liquid crystallinity tends to be easily expressed. Moreover, as the substituent that the 1,4-phenylene group which may have a substituent and the cyclohexane-1,4-diyl which may have a substituent optionally have, there may be mentioned carbon atoms such as methyl, ethyl or butyl. Halogen atoms such as alkyl groups from 1 to 4, cyano groups, chlorine atoms or fluorine atoms. Preferably unsubstituted.

Y ¹ and Y ² are preferably mutually independent single bonds, -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCO-, -N=N-, -CR ^a =CR ^b -, - C≡C- or CR ^a =N-, R ^a and R ^b independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Y ¹ and Y ² are more preferably -CH ₂ CH ₂ -, -COO-, -OCO- or a single bond, when X ¹ , X ² and X ³ all do not contain cyclohexane-1,4-diyl When , it is better that Y ¹ and Y ² have different bonding methods. When Y ¹ and Y ² have different bonding methods, there is a tendency for smectic liquid crystallinity to be easily expressed.

W ¹ and W ² are preferably mutually independent single bonds, -O-, -S-, -COO- or OCO-, more preferably mutually independent single bonds or -O-.

Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V ¹ and V ² include: methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, 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 an alkanediyl group having 2 to 12 carbon atoms, and more preferably a linear alkanediyl group having 6 to 12 carbon atoms. By using a linear alkanediyl group having 6 to 12 carbon atoms, the crystallinity is improved and smectic liquid crystallinity tends to be easily expressed.

Examples of optional substituents for the optionally substituted alkylenediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom such as a chlorine atom or a fluorine atom. The alkylenediyl group is preferably unsubstituted, more preferably It is an unsubstituted and straight-chain alkanediyl group.

It is preferable that U ¹ and U ² are both polymerizable groups, and it is more preferable that they are both photopolymerizable groups. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions than a thermally polymerizable group and can therefore form a polymeric liquid crystal compound in a state of higher 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 vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, and oxirane. Oxetanyl etc. Among them, an acryloxy group, a methacryloyloxy group, an vinyloxy group, an oxirane group or an oxetanyl group is preferred, and a methacryloyloxy group or an acryloyloxy group is more preferred.

Examples of such polymerizable liquid crystal compounds include the following.

[Chemical 1]

[Chemicalization 2]

[Chemical 4]

Among the above-mentioned compounds illustrated, it is preferable to be selected from 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 compounds (A) can be used for the patterned polarizing layer 21 alone or in combination. Moreover, when two or more polymerizable liquid crystal compounds are combined, it is preferable that at least one type is compound (A), and it is more preferable that two or more types are 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. The mixing ratio when combining two polymerizable liquid crystal compounds 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 by a known method described in, for example, 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 usually 50 to 99.5 parts by mass, preferably 60 to 99 parts by mass, and more preferably 70 to 100 parts by mass of 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, the alignment tends to be high. Here, the solid content refers to the total amount of components after removing the solvent from the polarizing layer forming composition described below.

(Dichroic pigment)

色素、花青色素、萘色素、偶氮色素或蒽醌色素等，其中較佳為偶氮色素。作為偶氮色素，可列舉：單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素或茋偶氮色素等，較佳為雙偶氮色素或三偶氮色素。二色性色素可單獨使用，亦可組合兩種以上使用，為於可見光全部區域獲得吸收，較佳為組合三種以上之二色性色素，更佳為組合三種以上之偶氮色素。 The so-called dichroic pigments refer to pigments whose absorbance in the long axis direction and the absorbance in the short axis direction of the molecule have different properties. A dichroic pigment is a pigment that is aligned with a liquid crystal compound to exhibit dichroism. The dichroic pigment itself may have polymerizability or liquid crystallinity. As the dichroic pigment, it is preferable that it has the characteristic of absorbing visible light, and it is more preferable that it has an absorption maximum wavelength (λ _MAX ) in the range of 380 to 680 nm. Examples of such dichroic dyes include acridine dyes,

Pigments, cyanine pigments, naphthalene pigments, azo pigments or anthraquinone pigments, etc., among which azo pigments are preferred. Examples of azo dyes include monoazo dyes, disazo dyes, trisazo dyes, tetrasazo dyes, and stilbeneazo dyes. Preferably, they are disazo dyes or trisazo dyes. Dichroic pigments can be used alone or in combination of two or more. In order to obtain absorption in the entire range of visible light, a combination of three or more dichroic pigments is preferred, and a combination of three or more azo pigments is more preferred.

Examples of the azo dye include compounds represented by formula (I) (hereinafter may also be 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 represent an optionally substituted 1,4-phenylene group, a naphthalene-1,4-diyl group, or an optionally substituted divalent heterocycle. Bases, T ¹ and T ² are independently electron-withdrawing or electron-pushing groups, located at a position of substantially 180° relative to the azo bond plane; p represents an integer from 0 to 4; when p is 2 or more, Each A ² can be the same as each other or different; within the range of absorption in the visible light range, the -N=N- bond can be replaced by -C=C-, -COO-, -NHCO- or -N=CH- key].

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

唑及苯并

唑去除2個氫原子後之基。於A²為2 價之雜環基之情形時，較佳為分子鍵結角度實質成為180°之結構，具體而言，更佳為2個5員環縮合而成之苯并噻唑、苯并咪唑、苯并

唑結構。 Examples of the divalent heterocyclic group include: quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole,

Azoles and benzo

Azole is the base after removing 2 hydrogen atoms. When A ² is a divalent heterocyclic group, a structure in which the molecular bonding angle is substantially 180° is preferred. Specifically, benzothiazole or benzothiazole, which is formed by the condensation of two 5-membered rings, is more preferred. imidazole, benzo

Azole structure.

It is preferable that T ¹ and T ² are independently electron-withdrawing groups or electron-donating groups and have different structures. Furthermore, it is more preferable that T ¹ is an electron-withdrawing group and T ² is an electron-donating group, or T ¹ is an electron-donating group. base and T ² is an electron-withdrawing base. Specifically, T ¹ and T ² are preferably independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, or having 1 or 2 carbon atoms of 1 to 4 carbon atoms. The amine group of an alkyl group of 6, or two substituted alkyl groups bonded to each other to form the amine group of an alkyldiyl group having 2 to 8 carbon atoms, or a trifluoromethyl group, among which, in order to be included in high order such as smectic liquid crystals In the liquid crystal structure, it must be a structure with a smaller exclusion volume of molecules, so it is preferably an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, or one with 1 or 2 carbon atoms. The amine group of an alkyl group with 1 to 6 carbon atoms, or the amine group of an alkyldiyl group with 2 to 8 carbon atoms bonded with two substituted alkyl groups.

Examples of such azo dyes include the following.

[Chemistry 5]

[In formulas (2-1) ~ (2-6), B ¹ ~ B ²⁰ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, and a nitro group , substituted or unsubstituted amine groups (substituted amine groups and unsubstituted amine groups are defined as above), chlorine atoms or trifluoromethyl groups; and, from the perspective of obtaining higher polarizing properties In other words, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , and B ¹⁹ are preferably hydrogen atoms or methyl groups, and more preferably hydrogen atoms; n1 ~ n4 independently represent integers from 0 to 3; n1 is When n2 is 2 or more, the plural B ² may be the same or different. When n2 is 2 or more, the plural B ⁶ may be the same or different. When n3 is 2 or more, the plural B 6 may be the same or different. B ⁹ can be the same or different respectively. When n4 is 2 or more, the plural B ¹⁴ can be the same or different respectively]

As the anthraquinone dye, a compound represented by formula (2-7) is preferred.

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

色素，較佳為式(2-8)所表示之化合物。 As above

The pigment is preferably a compound represented by formula (2-8).

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

As the acridine dye, a compound represented by formula (2-9) is preferred.

[In formula (2-9), R ¹⁶ ~ R ²³ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom; R ^x represents a carbon number of 1 ~4 alkyl group or aryl group with 6~12 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, butyl group, pentyl group or hexyl group, etc. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, toluyl group, xylyl group or naphthyl group.

As the cyanine pigment, a compound represented by formula (2-10) and a compound represented by formula (2-11) are preferred.

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

n5 represents an integer from 1 to 3]

[Chemical 12]

[In formula (2-11), D ³ and D ⁴ independently represent the base represented by any one of formula (2-11a) ~ formula (2-11h);

n6 represents an integer from 1 to 3]

As the content of the dichroic dye (the total amount when a plurality of species are contained), from the viewpoint of obtaining good light absorption characteristics, relative 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 further preferably 3 to 15 parts by mass. If the content of the dichroic dye is less than this range, light absorption becomes insufficient and sufficient polarizing performance cannot be obtained. If it is more than this range, alignment of liquid crystal molecules may be hindered.

(solvent)

The polarizing layer forming composition 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 polarizing layer forming composition containing a solvent, coating can be facilitated, resulting in easy pattern formation. polarizing layer 21. As the solvent, one that can completely dissolve the polymerizable liquid crystal compound and the dichroic dye is preferred, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferred.

Examples of solvents 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, 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; dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone and other amide systems Solvents, etc. These solvents can be used alone or in combination of two or more.

The content of the solvent contained in the polarizing layer forming composition is preferably 50 to 98 mass % relative to the total amount of the polarizing layer forming composition. In other words, the content of the solid component in the polarizing layer forming composition is preferably 2 to 50% by mass. If the content of the solid component is 50% by mass or less, the viscosity of the polarizing layer forming composition becomes low, so the thickness of the patterned polarizing layer 21 becomes substantially uniform, and unevenness tends to be less likely to occur in the patterned polarizing layer 21 . . In addition, the content of the solid component can be determined taking into account the thickness of the patterned polarizing layer 21 to be produced.

(polymerization initiator)

The polarizing layer forming composition 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 start the polymerization reaction of the polymerizable liquid crystal compound or the like. As the polymerization initiator, from the viewpoint of being independent of the phase state of the thermotropic liquid crystal, a photopolymerization initiator that generates active radicals by the action of light is preferred.

化合物、錪鹽或鋶鹽等。 Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, and trisulfide compounds.

Compounds, iodonium salts or strontium salts, etc.

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

Examples of the benzophenone compound include benzophenone, methyl o-phenylbenzoate, 4-phenylbenzophenone, and 4-benzyl-4'-methyldiphenylsulfide. Ether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc.

啉基-1-(4-甲硫基苯基)丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1,2-二苯基-2,2-二甲氧基乙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮或2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮之低聚物 等。 Examples of alkylphenone compounds include: diethoxyacetophenone, 2-methyl-2-

Phinyl-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Phinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane- 1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone or 2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one oligomer, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyldiphenylphosphine oxide), and the like. .

化合物，例如可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三

或2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 as three

Examples of compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 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-dimethoxyphenyl)vinyl]-1,3,5-tri

wait.

A commercially available polymerization initiator can also be used. Commercially available polymerization initiators include: Irgacure (registered trademark) 907, 184, 651, 819, 250, 369, 379, 127, 754, OXE01, OXE02 or OXE03 (manufactured by Ciba Specialty Chemicals Co., Ltd.); Seikuol (registered trademark) BZ, Z or BEE (manufactured by Seiko Chemical Co., Ltd.); kayacure (registered trademark) BP100 or UVI-6992 (manufactured 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 Nihon SiberHegner Co., Ltd., Japan); TAZ-104 (Sanwa Chemical Co., Ltd. Co., Ltd.), etc. The polymerization initiator in the polarizing layer forming composition may be used alone, or two or more types of polymerization initiators may be mixed and used depending on the light source.

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. It is usually 0.1 to 30 parts by mass relative to 100 parts by mass of the content of the polymerizable liquid crystal compound. Preferably, it is 0.5~10 parts by mass, and more preferably, it is 0.5~8 parts by mass. If the content of the polymerization initiator is within the above range, polymerization can be performed without disturbing the alignment of the polymerizable liquid crystal compound.

(sensitizer)

酮及9-氧硫

等

酮化合物(例如2,4-二乙基-9-氧硫

、2-異丙基-9-氧硫

等)；蒽及含烷氧基之蒽(例如二丁氧基蒽等)等蒽化合物；啡噻

或紅螢烯等。 The polarizing layer forming composition may contain a sensitizer. The sensitizer is preferably used when a polymerizable liquid crystal compound is used as the liquid crystal compound. When a polymerizable liquid crystal compound having a photopolymerizable group is used, the sensitizer is preferably a photosensitizer. Examples of sensitizers include:

Ketones and 9-oxosulfide

wait

Ketone compounds (such as 2,4-diethyl-9-oxosulfide

, 2-isopropyl-9-oxosulfide

etc.); anthracene compounds such as anthracene and alkoxy-containing anthracene (such as dibutoxyanthracene, etc.); thiophene

Or rubrene, etc.

When the polarizing layer forming composition contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound contained in the polarizing layer forming composition can be further accelerated. The usage amount of the sensitizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and further preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

(polymerization inhibitor)

From the viewpoint of stably advancing the polymerization reaction, the polarizing layer forming composition may contain a polymerization inhibitor. The polymerization inhibitor can be used when a polymerizable liquid crystal compound is used as the liquid crystal compound. It is preferably used when the polymerization inhibitor is used to control the progress of the polymerization reaction of the polymerizable liquid crystal compound.

Examples of the polymerization inhibitor include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (such as butyl catechol, etc.), pyrogallol, 2 , 2,6,6-tetramethyl-1-piperidinyloxy radical and other free radical scavengers; thiophenols; β-naphthylamines or β-naphthols, etc.

When the polarizing layer forming composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. More preferably, it is 0.5~3 parts by mass. If the content of the polymerization inhibitor is within the above range, polymerization can proceed without disturbing the alignment of the polymerizable liquid crystal compound.

(leveling agent)

The polarizing layer forming composition may contain a leveling agent. The so-called leveling agent refers to an additive that has the function of adjusting the fluidity of the composition and making the film obtained by coating the composition flatter. Examples include: organically modified polysiloxane oil type, polyacrylate type or Perfluoroalkyl leveling agent. Specific examples include: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Dow Corning Toray (Co., Ltd.)), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all of the above are manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of the above are manufactured by Momentive Advanced Materials Japan Co., Ltd.) , fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all manufactured by Sumitomo 3M Co., Ltd.), 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 manufactured by DIC Corporation), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all manufactured by Mitsubishi Materials Electronics Corporation), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.), BM-1000, BM- 1100, BYK-352, BYK-353 or BYK-361N (all trade names: manufactured by BM Chemie Co., Ltd.), etc. Among them, polyacrylate leveling agents or perfluoroalkyl leveling agents are preferred.

When the polarizing layer forming composition 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 based on 100 parts by mass of the liquid crystal compound. . If the content of the leveling agent is within the above range, the liquid crystal compound will be easily aligned horizontally, and the resulting patterned polarizing layer will tend to become smoother. If the content of the leveling agent relative to the liquid crystal compound exceeds the above range, unevenness tends to easily occur in the resulting patterned polarizing layer. Furthermore, the polarizing layer forming composition may contain two or more leveling agents.

(reactive additive)

唑啉基、碳二醯亞胺基、氮丙啶基、醯亞胺基、異氰酸基、硫代異氰酸基、順丁烯二酸酐基等。反應性添加劑所具有之碳-碳不飽和鍵或活性氫反應性基之個數通常分別為1~20個，較佳為分別為1~10個。 The polarizing layer forming composition may contain a reactive additive. As a reactive additive, one having a carbon-carbon unsaturated bond and an active hydrogen reactive group in its molecule is preferred. In addition, the "active hydrogen reactive group" here refers to a group that is reactive toward a group having active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), an amine group (-NH ₂ ), etc. Typical examples are is glycidyl,

Zozoline group, carbodiimide group, aziridinyl group, acyl imide group, isocyanate group, thioisocyanate group, maleic anhydride group, etc. 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 there are at least two active hydrogen reactive groups in the reactive additive. In this case, the plurality of active hydrogen reactive groups may be the same or different.

The so-called carbon-carbon unsaturated bonds possessed by the reactive additive refer to carbon-carbon double bonds, carbon-carbon triple bonds or combinations thereof, preferably carbon-carbon double bonds. Among them, the reactive additive preferably contains a carbon-carbon unsaturated bond as a vinyl group and/or a (meth)acrylyl group. Furthermore, it is preferable that the active hydrogen reactive group is at least one reactive additive selected from the group consisting of an epoxy group, a glycidyl group and an isocyanate group, and more preferably a reactive additive having an acryl group and an isocyanate group. reactive additives.

唑啉或異丙烯基

唑啉等具有乙烯基與

唑啉基之化合物；丙烯酸異氰酸基甲酯、甲基丙烯酸異氰酸基甲酯、丙烯酸2-異氰酸基乙酯或甲基丙烯酸2-異氰酸基乙酯等具有(甲基)丙烯醯基與 異氰酸基之化合物之低聚物等。又，可列舉：甲基丙烯酸酐、丙烯酸酐、順丁烯二酸酐或乙烯基順丁烯二酸酐等具有乙烯基或伸乙烯基與酸酐之化合物等。其中，較佳為甲基丙烯醯氧基縮水甘油醚、丙烯醯氧基縮水甘油醚、丙烯酸異氰酸基甲酯、甲基丙烯酸異氰酸基甲酯、乙烯基

唑啉、丙烯酸2-異氰酸基乙酯、甲基丙烯酸2-異氰酸基乙酯或上述之低聚物，尤佳為丙烯酸異氰酸基甲酯、丙烯酸2-異氰酸基乙酯或上述之低聚物。 Specific examples of the reactive additive include compounds having a (meth)acrylyl group and an epoxy group such as methacryloxyglycidyl ether or acryloxyglycidyl ether; oxetane acrylic acid Compounds with (meth)acrylyl and oxetanyl groups such as ester or oxetane methacrylate; compounds with (meth)acrylyl and oxetane groups such as lactone acrylate or lactone methacrylate Lactone-based compound; vinyl

oxazoline or isopropenyl

Zozoline, etc. have vinyl groups and

Zozoline-based compounds; isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate or 2-isocyanatoethyl methacrylate, etc. have (methyl ) Oligomers of acrylic and isocyanate compounds, etc. Furthermore, compounds having a vinyl group or an vinyl vinyl group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride, or vinyl maleic anhydride, may be cited. Among them, preferred are methacryloyloxyglycidyl ether, acryloyloxyglycidyl ether, isocyanatomethyl acrylate, isocyanatomethylmethacrylate, and vinyl.

Zozoline, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate or oligomers of the above, especially isocyanatomethyl acrylate, 2-isocyanatoethyl acrylate Esters or oligomers of the above.

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

[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 repeat Of the two R ^2's in the unit, one is -NH- and the other is the group represented by >NC(=O)-R ^3' ; R ^3' represents a hydroxyl group or a group with a carbon-carbon unsaturated bond ; Among R ^3' in formula (Y), at least one R ^3' is a group with a carbon-carbon unsaturated bond]

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

[Chemical 15]

Compound (YY) can be used as it is on the market, or if necessary, it can be purified and used. Examples of commercially available products include Laromer (registered trademark) LR-9000 (manufactured by BASF Corporation).

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, 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 methods for applying the polarizing layer forming composition include extrusion coating, direct gravure coating, reverse gravure coating, capillary (CAP) coating, slit coating, and microgravure coating. Coating method, die nozzle coating method, inkjet method, etc. Furthermore, a method of coating using a coater such as a dip coater, a rod coater, a spin coater, etc. may also be mentioned. Among them, in the case of continuous coating in a roll-to-roll form, a coating method using microgravure coating, inkjet coating, slit coating, or die coating is preferred when coating on glass. In the case of a single substrate, the spin coating method with higher uniformity is preferred. In the case of coating in a roll-to-roll manner, the alignment film forming composition or the like can also be coated on the base material layer 83 with the patterned liquid repellent layer to form the patterned alignment layer 22, and then the resulting pattern can be The polarizing layer forming composition is continuously coated 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 for removing the solvent, the same method as the method for removing the solvent from the alignment polymer composition can be used. Examples thereof include: natural drying, ventilated drying, heating drying, reduced pressure drying, and methods combining these. Among them, natural drying or heated 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 further 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 polarizing layer formed in the polarizing layer forming step with active energy rays so that the polymerizable liquid crystal compound Photopolymerization is performed to form the patterned polarizing layer 21 . As the active energy ray for irradiation, depending on the type of the polymerizable liquid crystal compound contained in the coating layer for the polarizing layer (especially the type of photopolymerizable functional group the polymerizable liquid crystal compound has), the photopolymerization initiator should be used in the coating layer. In this case, it is appropriately selected depending on the type of photopolymerization initiator and the amount thereof. Specifically, one or more types 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 cited. Among them, in terms of being easy to control the progress of the polymerization reaction and being usable as a photopolymerization device widely used in this field, ultraviolet light is preferable, and it is preferable that it is photopolymerized by ultraviolet light. 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 380~440nm light LED (Light-emitting diode (light emitting diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

The irradiation intensity of active energy rays is usually 10mW/cm ² ~3000mW/cm ² . The irradiation intensity of the active energy ray is preferably the intensity in the wavelength region effective for activating the cationic polymerization initiator or the radical polymerization initiator. The irradiation time of active energy rays is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and further preferably 0.1 seconds to 1 minute. If the irradiation intensity of such active energy rays is irradiated once or multiple times, the cumulative light amount is 10mJ/cm ² ~3000mJ/cm ² , preferably 50mJ/cm ² ~2,000mJ/cm ² , and more preferably 100mJ. /cm ² ~1000mJ/cm ² . When the integrated light intensity is below this range, the curing of the polymerizable liquid crystal compound may become insufficient, and good transferability may not be obtained. On the contrary, when the accumulated light amount is above this range, the patterned polarizing layer may be colored.

(Method for continuously manufacturing polarizing film)

The manufacturing method of the polarizing film 2 is preferably continuous manufacturing in a roll-to-roll format. In this case, in the base material layer coating step, the base material layer rolled into a roll is rolled out and conveyed, and the second protective layer rolled into a roll is conveyed while being rolled out, so that the base material layer is rolled out and conveyed. The material layer and the protective layer are laminated to obtain a base material layer with a protective layer. In the step of forming the liquid-repellent layer, the liquid-repellent agent is applied while continuously conveying the base material layer with the protective layer to obtain a base material layer with the liquid-repellent layer. In the step of removing the protective layer, the base material layer with the liquid-repellent layer is continuously conveyed while Just peel off the protective layer continuously from the base material layer. In the step of forming the patterned alignment layer, the patterned alignment layer is formed by continuously applying the composition for forming the alignment layer using a coating device while conveying the base material layer with the patterned liquid repellent layer. In the step of forming the patterned polarizing layer, the base material layer with the patterned alignment layer is transported while It suffices to continuously apply the composition for forming a polarizing layer on one side using a coating device to form a patterned polarizing layer. The polarizing film continuously produced as described above may have a length of 10 m or more, for example.

<Second manufacturing method of polarizing film>

In addition to the above-mentioned first manufacturing method, the polarizing film 2 can also be manufactured by the second manufacturing method shown below. 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 formation step of 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, but liquid-repellent coating is dropwise applied to at least one side of the base layer 13. agent (Fig. 3), thereby forming the patterned liquid-repellent layer 47b shown in Fig. 2(c).

The second manufacturing method of the polarizing film 2 has the following steps: a patterned alignment layer forming step, that is, obtaining a base material layer 83 with a patterned liquid repellent layer obtained through the above-mentioned patterned liquid repellent layer forming step ( The surface on the side of the patterned liquid repellent layer 47b in Figure 2(c) is the same as the first manufacturing method described above. The patterned alignment layer 22 formed by applying the alignment layer forming composition is attached with the patterned alignment layer. The base material layer 84 (Fig. 2(d)); and the step of forming the patterned polarizing layer, that is, by coating the surface of the patterned alignment layer 22 side of the base material layer 84 with the patterned alignment layer containing a liquid crystal compound and two The polarizing layer forming composition of the color pigment is used to form the patterned polarizing layer 21. By this, for example, the polarizing film 2 with the patterned polarizing layer as shown in FIG. 1 and FIG. 2(e) can be manufactured.

The base material layer 13 and the liquid repellent layer used in the patterned liquid repellent layer formation step of the second manufacturing method The same base material layer and liquid repellent agent as the base material layer 13 and the liquid repellent agent used in the first manufacturing method can be used as the agent. As a method for forming the patterned liquid repellent layer 47b by dropwise applying a liquid repellent agent on at least one side of the base layer 13, for example, as shown in FIG. 3, a liquid substance is dropped and applied to this part. The so-called inkjet method in the area. By dropwise coating the liquid repellent agent 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 patterned alignment layer forming steps and the patterned polarizing layer forming steps of the second manufacturing method are the same as the patterned alignment layer forming steps and the patterned polarizing layer forming steps of the first manufacturing method.

Regarding the second manufacturing method, similarly to the first manufacturing method, the polarizing film 2 can also be continuously manufactured in a roll-to-roll system, for example. In this case, in the step of forming the patterned liquid-repellent layer, the base material layer rolled into a drum shape is rolled out and transported, and the liquid-repellent agent is dropped and applied to form a patterned liquid-repellent layer on the base material layer. Just obtain the base material layer with the patterned liquid repellent layer. In the step of forming the patterned alignment layer, the patterned alignment layer is formed by continuously applying the composition for forming the alignment layer using 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 can be formed by continuously applying the polarizing layer forming composition using a coating device while conveying the base material layer with the patterned alignment layer. The polarizing film continuously produced as described above may have a length of 10 m or more, for example.

[Second embodiment (circular polarizing plate and manufacturing method thereof)] (circular polarizing plate)

4(a) to (c) are schematic cross-sectional views respectively showing an example of the circularly polarizing plate of the present invention. The polarizing film 2 shown in Fig. 2(e) can become the circularly polarizing plates 5a and 5b shown in Figs. 4(a) and (b) by laminating the retardation layer 15 having the function of a quarter wave plate. The phase difference 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 base material layer 13 side (Fig. 4(b)). In addition, what is obtained by peeling off the base material layer 13 from the circular polarizing plate 5a shown in FIG. 4(a) may also be used as the circular polarizing plate 5c (FIG. 4(c)). In this case, the patterned The alignment layer 22 and the base material layer 13 are peeled off together.

In addition, the circularly polarizing plate may be formed by laminating the polarizing film 2 and a retardation layer of a multilayer structure. In this case, as the retardation layer of the multilayer structure, a retardation layer in which a layer having a function of a 1/2 wavelength plate and a layer having a function of a 1/4 wavelength plate are laminated can be used. By combining the retardation layer of the multilayer structure The layer side with the function of a 1/2 wavelength plate is laminated with the polarizing film 2, and can be made into a circular polarizing plate. Alternatively, a circularly polarizing plate can also be obtained by using a retardation layer in which a layer having the function of a quarter-wavelength plate with reverse wavelength dispersion and a layer having the function of a positive C plate are laminated as a retardation layer of a multilayer structure.

Moreover, what has the function as a retardation layer can be used as the base material layer 13 of the polarizing film 2, and a retardation layer can be further laminated|stacked to make a circularly polarizing plate. In this case, the functions of the base material layer 13 and the retardation layer as the retardation layer can be selected according to the stacking positions of the base material layer 13 and the retardation layer in the circular polarizing plate.

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

(Manufacturing method of circularly polarizing plate)

Circularly polarizing plates can be manufactured by laminating polarizing films and retardation layers. When the polarizing film is a long polarizing film with a length of 10m or more that is continuously produced, it is preferable to use a long retardation layer with a length of 10m or more as the above-mentioned retardation layer, and layer the long polarizing film in one area while continuously conveying the two. The film and the elongated retardation layer form a elongated laminate. At this time, it is preferable to apply an adhesive or an adhesive on at least one of the long polarizing film and the long retardation layer and laminate the two.

In order to install the polarizing film on a display device of a specific size, etc., the manufacturing method of the circularly polarizing plate may include the step of cutting the long laminated body obtained by laminating the long polarizing film and the long retardation layer into individual pieces of a specific size. In the cutting step, it is preferable to cut the long laminated body in at least one direction of the longitudinal direction and the 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 polarization area in the cut single piece at a specific position.

[Example]

The present invention will be further described in detail based on examples. However, the present invention is not limited by these examples.

Unless otherwise specified, "%" and "parts" in the examples and comparative examples are mass % and mass parts.

[Visual sensitivity corrected polarization (Py) and visual sensitivity corrected transmittance (Ty)] (Preparation of samples for evaluation)

An alignment layer forming composition and a polarizing layer forming composition used in each of the Examples, Comparative Examples and Reference Examples were prepared. In addition, the same film as that used as the base material layer in each of the Examples, Comparative Examples and Reference Examples was cut into 40 mm×40 mm pieces and prepared as the base material layer of the evaluation sample. make Using these, except not using a protective layer, the same procedure as the production of the polarizing film of each Example, Comparative Example, and Reference Example was performed to obtain a sample for evaluation.

(Visual sensitivity corrected polarization (Py) and visual sensitivity corrected transmittance (Ty))

Regarding the evaluation sample, the visual sensitivity corrected single transmittance (Ty) and the visual sensitivity corrected polarization degree (Py) were calculated according to the following procedures. Using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) equipped with a folding device with a polarizing element, the transmittance (T ₁ ) and the transmittance in the absorption axis direction (T ₂ ). The folder is provided with a screen on the reference side that cuts off 50% of the light amount. Using the following (Equation 1) and (Equation 2), calculate the transmittance and polarization degree at each wavelength, and then correct the visual sensitivity according to the 2-degree field of view (C light source) of JIS Z 8701 to calculate the visual sensitivity corrected transmittance (Ty ) and visual sensitivity correction polarization (Py).

Polarization degree [%]={(T ₁ -T ₂ )/(T ₁ +T ₂ )}×100% (Formula 1)

Monomer transmittance [%]=(T ₁ +T ₂ )/2 (Formula 2)

[Example 1] (Manufacture of liquid repellent)

The first organosilicon compound (S1) (molecular weight approximately 8000) represented by the following formula (a) was synthesized by the method described in Synthesis Examples 1 and 2 of Japanese Patent Application Laid-Open No. 2014-15609. In formula (a), n is 43, and m is an integer from 1 to 6.

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

(Production of alignment layer forming composition)

The following components were mixed, and the resulting mixture was stirred at 80° C. for 1 hour, thereby obtaining an alignment layer forming composition as a photo alignment film forming composition.

‧2 parts of the polymer with photoreactive groups shown below

‧Solvent: 98 parts of o-xylene

(Production of polarizing layer forming composition)

The following components were mixed and stirred at 80° C. for 1 hour to obtain a polarizing layer forming composition. As the dichroic dye, the azo dye described in the Examples of Japanese Patent Application Laid-Open No. 2013-101328 was used.

‧75 parts of polymerizable liquid crystal compound represented by formula (1-6)

‧25 parts of polymerizable liquid crystal compound represented by formula (1-7)

‧2.8 parts of dichroic pigment (1) shown below

‧2.8 parts of dichroic pigment (2) shown below

‧2.8 parts of dichroic pigment (3) shown below

‧6 parts of the polymerization initiator shown below

啉基苯基)丁烷-1-酮(Irgacure 369；Ciba Specialty Chemicals公司製造) 2-Dimethylamino-2-benzyl-1-(4-

Linylphenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals)

‧1.2 parts of the leveling agent shown below

Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

‧250 parts of the solvent shown below

cyclopentanone

(Manufacturing of polarizing film)

The triacetyl cellulose film was cut into 20×20 mm pieces, and the surface was subjected to corona treatment (AGF-B10, manufactured by Kasuga Electric Co., Ltd.). AY-638 manufactured by Fujimori Industrial Co., Ltd. (a polyester film with a thickness of 38 μm including an adhesive layer of 15 μm on a polyester film with a thickness of 38 μm) was bonded to the base material layer as a protective layer for forming openings by drilling holes with a hole drilling machine. agent layer), apply the liquid repellent agent and dry 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 and a patterned liquid repellent layer. After coating the alignment layer forming composition on the side of the patterned liquid-repellent layer-formed base material layer with the patterned liquid-repellent layer, dry it in a drying oven set at 120°C for 1 minute to obtain an alignment layer. Use coating layer. Using a polarized UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), with a cumulative light intensity of 50mJ/cm ² (based on 313nm), the coating layer of the alignment layer was irradiated in a direction of 0° relative to the film edge. Polarized UV forms a patterned alignment layer. After using a rod coater to coat the polarizing layer forming composition on the obtained patterned alignment layer, it was dried in a drying oven set at 110° C. for 1 minute. Then, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) is used to irradiate ultraviolet light (under nitrogen environment, wavelength: 365nm, cumulative light intensity at wavelength 365nm: 1000mJ/cm ² ), thereby forming a liquid crystal compound and two A patterned polarizing layer formed by aligning color pigments to obtain a polarizing film.

When the appearance of the obtained polarizing film was visually observed, it was clearly confirmed that there was no circular area (low polarization area) in the polarizing layer. Furthermore, according to the above procedure, calculate the viewing angle of the polarizing area of the polarizing film. Sensitivity corrected transmittance (Ty) and visual sensitivity corrected polarization (Py). 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 dropper was used to partially apply the liquid-repellent agent on the base layer instead of laminating the protective layer that was drilled by a hole drilling machine to form an opening. When the appearance of the obtained polarizing film was visually observed, it was clearly confirmed that there was no circular area (low polarization area) in the polarizing layer. Furthermore, based on the above procedure, the visual sensitivity corrected transmittance (Ty) and the visual sensitivity corrected polarization degree (Py) of the polarizing area of the polarizing film were 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 not possible to confirm a region without a polarizing layer, indicating that a polarizing film having a polarizing region and a low polarizing region was not obtained. Furthermore, an evaluation sample was produced according to the above procedure, and its visual sensitivity corrected transmittance (Ty) and visual sensitivity corrected polarization degree (Py) were calculated. The results are shown in Table 1.

Furthermore, the values of the sensitivity-corrected transmittance (Ty) and the sensitivity-corrected polarization (Py) measured in each of the Examples, Comparative Examples and Reference Examples shown in Table 1 include the sensitivity-corrected transmittance of the base material layer. The value of the sensitivity (Ty) and the value of the visual sensitivity corrected polarization (Py). The visual sensitivity corrected transmittance (Ty) of the base material layer alone is 92%, and the value of the visual sensitivity corrected polarization (Py) of the base material layer. is 0%, so when the base material 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 corrected transmittance (Ty) is greater than the value shown in Table 1, and the visual sensitivity The values of corrected polarization (Py) are the same as those shown in Table 1.

2:Polarizing film

13:Substrate layer

21:Patterned polarizing layer

21a:Polarized area

22: Patterned alignment layer

22a:Alignment layer

37:Protective layer

37a: Covered area

37b:Exposed area

47: Liquid repellent layer

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

81: Base material layer with protective layer

82: Base material layer with liquid repellent layer

83: Base material layer with patterned liquid repellent layer

84:Substrate layer with patterned alignment layer

Claims (12)

A method for manufacturing a polarizing film, which includes the following steps: a patterned liquid-repellent layer forming step, which 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 step of forming the patterned alignment layer is to obtain a base material layer with a patterned alignment layer. The base material layer with the patterned alignment layer has the above-mentioned patterned repellent layer on the above-mentioned base material layer with a patterned liquid-repellent layer. The patterned alignment layer formed by coating the composition for forming the alignment layer on the liquid layer side; and the step of forming the patterned polarizing layer is performed by the above-mentioned patterned alignment layer side of the base material layer with the patterned alignment layer A polarizing layer-forming composition containing a liquid crystal compound and a dichroic pigment is coated on the surface to form a patterned polarizing layer; the patterned liquid-repellent layer exhibits repellency to the alignment layer-forming composition and the polarizing layer-forming composition. liquid, and the above-mentioned patterned liquid-repellent layer formation step includes the following steps: the base material layer coating step is because at least one side of the above-mentioned base material layer has a coating area for covering the above-mentioned base material layer and a step for applying The protective layer in the exposed area of the above-mentioned base material layer is exposed to obtain a base material layer with a protective layer; the step of forming the liquid repellent layer is to apply liquid repellent on the surface of the above-mentioned protective layer side of the above-mentioned base material layer with a protective layer. liquid to obtain a base material layer with a liquid repellent layer formed with a liquid repellent layer; and the protective layer removal step is to remove the above repellent layer by peeling off the protective layer from the base material layer with the liquid repellent layer. A part of the liquid layer thereby forms the above-mentioned patterned liquid-repellent layer. The method for manufacturing a polarizing film according to claim 1, wherein the above-mentioned exposed area has a circular shape when viewed from above. Shape, ellipse, oblong or polygon, when the above-mentioned exposed area is circular, the diameter is 5cm or less, when the above-mentioned exposed area is oval or oblong, the major diameter is 5cm or less, when When the above-mentioned exposed area is a polygon, the diameter of an imaginary circle drawn by inscribing the polygon shall be 5 cm or less. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the step of forming the patterned liquid-repellent layer is to drop-coat a liquid-repellent agent on at least one side of the base layer to form the patterned liquid-repellent layer. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the alignment layer forming composition contains a photo-alignment polymer, and the patterned alignment layer forming step is a pattern formed by applying the alignment layer forming composition. The coating layer for the alignment layer is irradiated with polarized light to form the patterned alignment layer. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the liquid crystal compound is a polymerizable liquid crystal compound, and the patterned polarizing layer forming step is a coating of the patterned polarizing layer formed by applying the polarizing layer forming composition. The cloth layer is irradiated with active energy rays to form the patterned polarizing layer. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the patterned polarizing layer exhibits a Bragg wave peak in X-ray diffraction measurement. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the length of the polarizing film is more than 10 m. The method for manufacturing a polarizing film according to claim 1 or 2, wherein the base material layer has a 1/4 wavelength plate function. A method of manufacturing a circularly polarizing plate, which includes a phase difference layer lamination step, and is a method of combining a polarizing film manufactured by the method of manufacturing a polarizing film according to any one of claims 1 to 7 and a polarizing film having a 1/4 wavelength plate function. Phase difference layer stacking. The manufacturing method of a circularly polarizing plate according to claim 9, wherein the above-mentioned polarizing film is a long polarizing film with a length of more than 10 m, the above-mentioned phase difference layer is a long phase difference layer with a length of more than 10 m, and the step of laminating the above-mentioned phase difference layer is The elongated laminated body is formed by laminating the elongated polarizing film and the elongated retardation layer, and further includes a cutting step of cutting the elongated laminated body into individual pieces. A polarizing film having a polarizing area on a base material layer and a low polarizing area having a visual sensitivity correction polarization lower than that of the polarizing area, the polarizing area containing a liquid crystal compound and a dichroic pigment, and the visual sensitivity correcting polarization. It is more than 90%. The above-mentioned low polarization area has a liquid-repellent layer and does not contain liquid crystal compounds and dichroic colors. The element, the visual sensitivity corrected polarization degree is 0%, the contact angle of the above-mentioned liquid-repellent layer measured by the θ/2 method with a water droplet volume of 3 μL is more than 90°, and the thickness of the above-mentioned liquid-repellent layer is 1~200nm. The polarizing film of claim 11, wherein the transmittance of the sensitivity correction unit in the polarized area is more than 35%, and the transmittance of the sensitivity correction unit in the low polarization area is more than 80%.