WO2019082746A1 - 偏光フィルムの製造方法及び偏光フィルム - Google Patents

偏光フィルムの製造方法及び偏光フィルム

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Publication number
WO2019082746A1
WO2019082746A1 PCT/JP2018/038526 JP2018038526W WO2019082746A1 WO 2019082746 A1 WO2019082746 A1 WO 2019082746A1 JP 2018038526 W JP2018038526 W JP 2018038526W WO 2019082746 A1 WO2019082746 A1 WO 2019082746A1
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WO
WIPO (PCT)
Prior art keywords
layer
patterned
group
polarizing
polarizing film
Prior art date
Application number
PCT/JP2018/038526
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
伸行 幡中
耕太 村野
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020207012636A priority Critical patent/KR20200080246A/ko
Priority to CN201880069758.7A priority patent/CN111279233B/zh
Priority to JP2019551035A priority patent/JP7272957B2/ja
Publication of WO2019082746A1 publication Critical patent/WO2019082746A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

Definitions

  • the present invention relates to a method for producing a polarizing film and a polarizing film, and more particularly to a method for producing a polarizing film having a layer containing a liquid crystal compound and a dichroic dye, and a polarizing film.
  • An organic EL display device using an organic light emitting diode can not only be reduced in weight and thickness as compared with a liquid crystal display device, but also has high image quality such as wide viewing angle, fast response speed, and high contrast. Because it can be realized, it is used in various fields such as smartphones, televisions, digital cameras, and the like. In the organic EL display device, it is known to improve the antireflection performance by using a circularly polarizing plate or the like in order to suppress a decrease in visibility due to the reflection of external light.
  • An object of the present invention is to provide a method of producing a novel polarizing film and a polarizing film having at least two regions having different degrees of visibility correction polarization.
  • the present invention provides a method for producing a polarizing film shown below and a polarizing film.
  • a patterned polarizing layer is formed by applying a composition for forming a polarizing layer containing a liquid crystal compound and a dichroic dye on the surface on the patterned alignment layer side of the substrate layer with a patterned alignment layer.
  • the patterned liquid repellent layer forming step A substrate layer with a protective layer is formed by laminating a protective layer having a coated region for coating the substrate layer and an exposed region for exposing the substrate layer on at least one side of the substrate layer.
  • the exposed area is a circle, an ellipse, an oval or a polygon in a plan view shape, When the exposed area is circular, the diameter is 5 cm or less.
  • the major axis is 5 cm or less.
  • region is a polygon
  • the manufacturing method of the polarizing film as described in [2] whose diameter of the virtual circle drawn so that the said polygon may be inscribed is 5 cm or less.
  • the manufacturing method of the polarizing film as described in-.
  • the composition for forming an alignment layer contains a photoalignable polymer
  • the patterned alignment layer forming step forms a patterned alignment layer by irradiating polarized light on the coating layer for a patterned alignment layer formed by applying the composition for forming an alignment layer
  • the liquid crystal compound is a polymerizable liquid crystal compound
  • the patterned polarizing layer is formed by performing active energy ray irradiation on the coating layer for a patterned polarizing layer formed by applying the composition for forming a polarizing layer.
  • the manufacturing method of the polarizing film in any one of 1]-[5].
  • the polarizing film is a long polarizing film having a length of 10 m or more
  • the retardation layer is a long retardation layer having a length of 10 m or more
  • an elongated laminate is formed by laminating the elongated polarizing film and the elongated retardation layer.
  • a polarizing film comprising a polarization region and a low polarization region having a visibility correction polarization degree lower than that of the polarization region on a substrate layer,
  • the polarization region contains a liquid crystal compound and a dichroic dye, and has a visibility correction polarization degree of 90% or more.
  • the polarizing film, wherein the low polarization region has a liquid repellent layer.
  • the polarizing film according to [12], wherein the low polarization region has a visibility correction polarization degree of 10% or less.
  • the polarization region has a visibility correction single transmittance of 35% or more,
  • FIG. 1 It is a schematic plan view which shows an example of the polarizing film of this invention.
  • FIG. 1 (A) to (e) are schematic cross-sectional views showing an example of the layer structure obtained in each step of the process for producing a polarizing film of the present invention. It is a schematic sectional drawing which shows an example of the patterning liquid repellent layer formation process in the manufacturing method of the polarizing film of this invention.
  • (A) to (c) are each a schematic cross-sectional view showing an example of the circularly polarizing plate of the present invention.
  • the method for producing a polarizing film of the present invention is A patterned liquid repellent layer forming step of forming a patterned liquid repellent layer on at least one side of the substrate layer to obtain a substrate layer with a patterned liquid repellent layer; Liquid-Repellent Layer-Coated Substrate Layer A patterned alignment-layer-provided substrate layer having a patterned alignment layer formed by coating the composition for forming an alignment layer on the patterned liquid-repellent layer side is patterned An alignment layer forming step, The patterned polarizing layer which forms a patterning polarizing layer by coating the composition for polarizing layer formation containing a liquid crystal compound and a dichroic dye on the surface at the side of the patterning alignment layer of a base material layer with a patterning alignment layer. And a forming step. The patterned liquid repellent layer exhibits liquid repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer
  • a method of forming a patterned liquid repellent layer in the above-mentioned patterned liquid repellent layer forming step a method of forming a patterned liquid repellent layer using a protective layer, and a patterned liquid repellent layer by drop application of a liquid repellent agent. And methods for forming Each method will be described in detail below.
  • FIG. 1 is a schematic plan view showing an example of the polarizing film of the present invention.
  • 2 (a) to 2 (e) are schematic cross-sectional views showing the layer structure obtained in each step of the manufacturing process of the first method of manufacturing a polarizing film shown in FIG.
  • FIG. 2 (e) is a cross-sectional view taken along the line XX in FIG.
  • the patterned liquid repellent layer forming step in the first manufacturing method of the polarizing film 2 is A protective layer-attached group is formed by laminating a protective layer 37 having a coated area 37a for coating the base layer 13 and an exposed area 37b for exposing the base layer 13 on at least one side of the base layer 13.
  • a base layer coating step of obtaining the material layer 81 (FIG. 2 (a)); A liquid repellent layer is applied to the surface on the protective layer 37 side of the protective layer-provided base layer 81 to obtain a liquid-repellent layer-provided base layer 82 (FIG. 2B) on which the liquid repellent layer 47 is formed.
  • the 1st manufacturing method of the polarizing film 2 is a patterned liquid repellent layer of the base material layer 83 with a patterned liquid repellent layer (FIG.2 (c)) obtained through the above-mentioned patterned liquid repellent layer formation process.
  • Patterned alignment layer formation to obtain a substrate with patterned alignment layer 84 (FIG.
  • a polarizing film 2 having a patterned polarizing layer shown in FIG. 1 and FIG. 2 (e) can be manufactured.
  • the polarizing film 2 shown in FIG. 1 is a film having a function of light absorption anisotropy, and has a patterned polarizing layer 21 on the base layer 13.
  • the patterned polarization layer 21 has a polarization area 21 a and a low polarization area 21 b having a visibility correction polarization degree (Py) lower than that of the polarization area 21 a.
  • the polarization region 21a contains a liquid crystal compound and a dichroic dye, and has a visibility correction polarization degree (Py) of 90% or more.
  • the low polarization region 21 b preferably includes a patterned liquid repellent layer (liquid repellent layer) 47 b and does not contain a liquid crystal compound and a dichroic dye.
  • the polarizing film 2 has the patterned polarizing layer 21 on the base layer 13, but may further have the patterned alignment layer 22, other layers, and the like. Details of the patterned alignment layer 22 will be described later.
  • a surface protective layer provided for the purpose of protecting the surface of the patterned polarizing layer 21 or the like may be mentioned on the surface of the patterned polarizing layer 21 opposite to the substrate layer 13. it can.
  • the surface protective layer may have a single layer structure or a multilayer structure. When the surface protective layer has a multilayer structure, each layer may be formed of the same material, or may be formed of different materials.
  • the alignment layer and the patterned polarizing layer 21 are provided on one side of the base layer 13 is shown. It may have an optical polarization layer.
  • the structures of the patterned polarizing layers provided on both sides of the substrate layer 13 may be identical to one another or may be different from one another.
  • the polarizing film 2 may be a long polarizing film having a length of 10 m or more.
  • the polarizing film 2 can be a wound body wound in a roll.
  • the polarizing film can be continuously drawn out from the wound body and laminated with a retardation layer to be described later, or can be cut into pieces.
  • the length of the elongate polarizing film used as a winding body will not be specifically limited if it is 10 m or more, For example, it can be 10000 m or less.
  • the polarization area 21 a is formed on the base material layer 13 and contains a liquid crystal compound and a dichroic dye.
  • An alignment layer 22 a may be provided between the polarization region 21 a and the base material layer 13.
  • the polarization region 21a preferably has a visibility correction polarization degree (Py) of 90% or more, more preferably 92% or more, still more preferably 95% or more, and usually 100% or less.
  • the low polarization region 21 b preferably has a liquid repellent layer (patterned liquid repellent layer) 47 b formed on the base material layer 13 and does not have an alignment layer or a polarizing layer.
  • the low polarization region 21b can have a visibility correction polarization degree (Py) of, for example, 10% or less, preferably 5% or less, more preferably 1% or less, and 0%. It is also good.
  • the visibility correction single 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%. It is below.
  • the visibility correction polarization degree (Py) and the visibility correction single transmittance (Ty) in the present specification can be calculated based on the degree of polarization and the single transmittance measured using a spectrophotometer.
  • the transmittance of the transmittance of the transmission axis direction in the wavelength range of 380 nm ⁇ 780 nm is visible light (alignment vertical) (T 1) and the absorption axis direction (oriented the same direction) to (T 2)
  • the spectrophotometer It can measure by a double beam method using the apparatus which set the folder with a polarizer.
  • the degree of polarization and single transmittance at each wavelength are calculated using the following formulas (Formula 1) and (Formula 2) By performing the visibility correction with the light source), it is possible to calculate the visibility correction single transmittance (Ty) and the visibility correction polarization degree (Py).
  • the occupied area of the polarization area 21 a and the occupied area of the low polarization area 21 b may be appropriately selected according to the characteristics required for the polarizing film 2.
  • the ratio of the total occupied area of the polarization region 21a and the low polarization region 21b to the surface area of the polarizing film 2 is preferably 90% or more, more preferably 95% or more, and 99% or more More preferable.
  • the occupied area of the polarization area 21a is preferably 50% or more, more preferably 70% or more, with respect to the total area of the occupied area of the polarization area 21a and the occupied area of the low polarization area 21b. More preferably, it is 80% or more. For example, as shown in FIG.
  • the polarization area 21a may be provided so that the area occupied by the low polarization area 21b is smaller than the area occupied by the polarization area 21a and the low polarization area 21b is surrounded.
  • the polarization area 21a is provided so as to surround one circular low polarization area 21b, but a plurality of low polarization areas 21b may be provided independently.
  • the shape of the polarization area 21a and the shape of the low polarization area 21b are not particularly limited.
  • the low polarization area 21b has a plan view
  • the shape may be any shape such as a circle, an oval, an oval, a polygon such as a triangle, a square, a rectangle, a rhombus, a letter shape, and a combination thereof.
  • the low polarization region 21 b preferably has a circular, elliptical, oval, or polygonal shape in a plan view.
  • its diameter is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less.
  • the major axis is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less.
  • the diameter of the virtual circle drawn so as to be inscribed in this polygon is preferably 5 cm or less, more preferably 3 cm or less, and 2 cm or less Is more preferred.
  • the low polarization area 21b having the above-described shape can be suitably used as an area corresponding to the lens position of a camera provided in a smartphone, a tablet or the like. At this time, coloring the low polarization region 21b by setting the low polarization region 21b as a region having a visibility correction polarization degree (Py) of 10% or less and a visibility correction single transmittance (Ty) of 80% or more.
  • the camera performance can be improved because the transparency of the camera can be reduced.
  • the polarization area 21a and the low polarization area 21b may be provided such that the shape in plan view is linear, band-like, wave-like or the like.
  • a plurality of polarization regions 21a and low polarization regions 21b may be alternately provided.
  • the widths of the polarization area 21a and the low polarization area 21b are preferably independently 1 ⁇ m to 10 mm, more preferably 1 ⁇ m to 1 mm, and still more preferably 1 ⁇ m to 100 ⁇ m.
  • the long polarizing film is usually cut into a predetermined size according to the application of the polarizing film, etc. It is preferable to set the arrangement of the polarization area and the low polarization area in the long polarizing film so that the polarization area 21a and the low polarization area 21b are formed.
  • the polarizing film after cutting is the polarizing film 2 shown in FIG. 1, a plurality of low polarization regions 21b are provided at predetermined intervals in the longitudinal direction and / or width direction of the long polarizing film. Is preferred.
  • the thickness of the polarizing region 21a of the patterned polarizing layer 21 is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less .
  • the thickness of the patterned liquid repellent layer 47b is usually 1 to 200 nm, preferably 1 to 20 nm.
  • the thickness of the polarization region 21a and the thickness of the patterned liquid repellent layer 47b can be measured by an interference film thickness meter, a laser microscope, a stylus film thickness meter, or the like.
  • Base layer coating step In the base material layer coating step, as shown in FIG. 2A, exposure for exposing the base material layer 13 and a coated region 37a for coating the base material layer 13 on at least one side of the base material layer 13 And a protective layer 37 having a region 37b is stacked. Thereby, the base layer 81 with a protective layer can be obtained.
  • the exposed region 37 b of the protective layer 37 can be, for example, an opening of the protective layer 37.
  • the coated region 37 a can suppress the coating of the liquid repellent agent on the base material layer 13 when the liquid repellent agent described later is coated on the protective layer-provided base layer 81.
  • the liquid repellent agent can be coated on the base layer 13.
  • a patterned liquid repellent layer 47 b is formed on the base material layer 13 by the liquid repellent agent applied to the exposed area 37 b.
  • the exposed area 37 b is preferably formed to correspond to the low polarization area 21 b of the polarizing film 2.
  • the shape is preferable to determine the shape according to the shape of the low polarization area
  • the plan view shape of the low polarization area 21b is circular; oval; oval; polygonal such as triangular, square, rectangular, rhombus, etc .; linear; It may be formed corresponding to the shape.
  • the exposed area 37b when the exposed area 37b is circular, its diameter is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less.
  • the major axis is preferably 5 cm or less, more preferably 3 cm or less, and still more preferably 2 cm or less.
  • the diameter of a virtual circle drawn so as to be inscribed in the polygon is preferably 5 cm or less, more preferably 3 cm or less, and 2 cm or less. More preferable.
  • liquid repellent layer 47 is formed on the covered area 37a in the covered area 37a of the protective layer 37, it is preferable to form the liquid repellent layer 47 corresponding to the area on the base material layer 13 where the liquid repellent layer 47 is not formed. . Since it is difficult to form an alignment layer or a polarizing layer on the patterned liquid repellent layer 47b, for example, when manufacturing the polarizing film 2 shown in FIG. 1 and FIG. 2 (e), according to the shape of the polarizing region 21a. It is preferable to determine the shape.
  • the base material layer 13 can be used to support the patterned alignment layer 22 or the patterned polarizing layer 21 when producing the polarizing film 2, and also supports the patterned polarizing layer 21 of the polarizing film 2. Can be used to
  • the base material layer 13 may be a glass base material or a resin base material, but is preferably a resin base material. Moreover, from the point which can manufacture the polarizing film 2 continuously, it is more preferable that the base material layer 13 unrolls the elongate resin base material wound by roll shape.
  • the resin substrate is preferably a light-transmissive substrate capable of transmitting visible light.
  • the term “transparency” means that the transmittance of a single visible sensitivity correction is 80% or more for light in a wavelength range of 380 to 780 nm.
  • the thickness of the base material layer 13 is preferably thin in that it is a mass that can be practically handled, but if it is too thin, the strength tends to decrease and the processability tends to be poor.
  • the thickness of the base layer 13 is usually 5 ⁇ m to 300 ⁇ m, preferably 20 ⁇ m to 200 ⁇ m.
  • the base material layer 13 may be provided so that peeling is possible, for example, after bonding the patterning polarizing layer 21 of the polarizing film 2 to the member which makes a display apparatus, the phase difference layer mentioned later, etc. It may be one that can be peeled off from the film 2. Thereby, the further film thinning effect of the polarizing film 2 is acquired.
  • the resin constituting the resin base examples include polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; Cellulose esters such as cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyethersulfone; polyether ketone; polyphenylene sulfide and polyphenylene oxide;
  • polyolefins such as polyethylene and polypropylene
  • cyclic olefin resins such as norbornene polymers
  • polyvinyl alcohol polyethylene terephthalate
  • polymethacrylic acid esters polyacrylic acid esters
  • Cellulose esters such as cellulose and cellulose acetate propionate
  • polyethylene naphthalate polycarbonate
  • Examples of commercially available resin base materials of cellulose ester include “Fujitack film” (manufactured by Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (all manufactured by Konica Minolta Opto Co., Ltd.), etc. .
  • cyclic olefin resins examples include “Topas” (registered trademark) (manufactured by Ticona, Germany), “Arton” (registered trademark) (manufactured by JSR Corporation), “ZEONOR” (registered trademark), Examples include “ZEONEX” (registered trademark) (manufactured by Nippon Zeon Co., Ltd.) and "APEL” (registered trademark) (manufactured by Mitsui Chemicals, Inc.).
  • Such a cyclic olefin resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to make a resin substrate.
  • the resin base material of cyclic olefin resin marketed can also be used.
  • resin base materials of commercially available cyclic olefin-based resins "ESSINA” (registered trademark), "SCA 40” (registered trademark) (above, manufactured by Sekisui Chemical Co., Ltd.), "Zeonor Film” (registered trademark) (OPTES share) And “Arton Film” (registered trademark) (manufactured by JSR Corporation).
  • the base material layer 13 may have a single layer structure or a multilayer structure of two or more layers. When the base material layer 13 is a multilayer structure, each layer may be formed of the same material, or may be formed of different materials.
  • the base material layer 13 may have a 1 ⁇ 4 wavelength plate function.
  • a combination of the base material layer 13 and the patterned polarizing layer 21 can provide a polarizing film having the function of a circularly polarizing plate. Thereby, a circularly-polarizing plate can be obtained even if it does not bond the retardation film which has a 1 ⁇ 4 wavelength plate function separately from the base material layer 13 to the polarizing film 2.
  • the patterned polarizing layer 21 may be halved using a laminate of a layer having a half wave plate function and a layer having a quarter wave plate function.
  • a circularly polarizing plate can be obtained by laminating on the layer side having the wavelength plate function.
  • a circularly polarizing plate can also be used by using a layer in which a layer having inverse wavelength dispersive 1/4 wavelength plate function and a layer having positive C plate function are laminated. You can get
  • the protective layer 37 what formed the area
  • a predetermined portion of the sheet-like substrate is mechanically removed by punching, cutting plotter, water jet or the like, or a predetermined portion of the sheet-like substrate is removed by laser ablation, chemical dissolution or the like. It can be formed by a method or the like.
  • the sheet-like base material 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 later.
  • a sheet-like base material which forms protection layer 37 it can be formed using the same material as base material layer 13 mentioned above, for example, and it is preferred to form using resin base material especially, and protection layer 37 It is more preferable to use a polyester resin such as polyethylene terephthalate that easily suppresses deformation of a region (for example, an opening) to be the exposed region 37b.
  • the protective layer 37 preferably has an adhesive layer for bonding to the base layer 13.
  • the protective layer is peeled off as described later, so the adhesive layer is preferably peelable with respect to the base layer 13.
  • the thickness of the protective layer 37 is usually 20 ⁇ m or more, preferably 30 ⁇ m or more, and usually 250 ⁇ m or less, preferably 200 ⁇ m or less.
  • a liquid repellent agent is applied to the surface on the protective layer 37 side of the protective layer provided base material layer 81 to obtain a liquid repellent layer provided base material layer 82 having a liquid repellent layer 47 formed (FIG. 2 (b).
  • a liquid repellent layer (patterned liquid repellent layer 47b) formed by applying a liquid repellent agent exhibits liquid repellency to the composition for forming an alignment layer and the composition for forming a polarizing layer.
  • the liquid repellent layer 47b repels these compositions. It means that a coating layer of these compositions is not formed on the patterned liquid repellent layer 47b.
  • the liquid repellency of the patterned liquid repellent layer 47b is, for example, one having a contact angle of 90 ° or more measured by the ⁇ / 2 method with a water droplet volume of 3 ⁇ L on the surface of the patterned liquid repellent layer 47b. It may be 100 ° or more, 110 ° or more, and generally less than 120 °.
  • liquid repellent 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 are bonded to a silicon atom, hydrolysis Or a second organosilicon compound in which a fluorocarbon-containing group and a hydrolyzable group are bonded to a silicon atom.
  • the carbon number of the perfluoroalkyl group (in particular, the carbon number of the longest linear portion) 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 particularly limited. I will not.
  • the perfluoropolyether group is a group in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether residue are substituted by a fluorine atom, a perfluoropolyalkylene ether group, or a perfluoropolyalkylene glycol dialkyl It can also be said that it is an ether residue.
  • the number of carbon atoms contained in the longest linear portion of the perfluoropolyether group is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more.
  • the upper limit of the carbon number is not particularly limited, and may be, for example, about 200.
  • the fluorine-containing group may have the above perfluoroalkyl group or perfluoropolyether group on the free end side. Therefore, a suitable linking group may be present on the side to be bound to a silicon atom, and the perfluoroalkyl group or the perfluoroalkyl group may be directly bound to a silicon atom without the linking group.
  • the linking group is, for example, a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) alkylene glycol group, or a group in which a part of these hydrogen atoms is substituted with F, and these are suitably linked And the like.
  • the carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.
  • a plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoroalkyl groups or perfluoropolyether groups may be bonded to one linking group.
  • the number of fluorine-containing groups bonded to a silicon atom may be one or more, and may be two or three, preferably one or two, and particularly preferably one.
  • the hydrolyzable group is either (1) the first organosilicon compounds, or (2) the first organosilicon compound and the active hydrogen (such as hydroxyl group) on the surface of the substrate, through hydrolysis and dehydration condensation reactions. Or (3) has an effect of bonding the first organosilicon compound and the second organosilicon compound.
  • a hydrolyzable group include an alkoxy group (in particular, an alkoxy group having 1 to 4 carbon atoms), a hydroxy group, an acetoxy group, an allyl group and a halogen atom (in particular, a chlorine atom).
  • Preferred hydrolyzable groups are an alkoxy group, an allyl group and a halogen atom, and in particular a methoxy group, an ethoxy group, an allyl group and a chlorine atom are preferred.
  • the number of hydrolyzable groups bonded to a silicon atom may be one or more, and may be two or three, preferably two or three, and particularly preferably three. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group may be bonded to the silicon atom preferable.
  • the total number of fluorine-containing groups and hydrolyzable groups bonded to silicon atoms is usually 4, but may be 2 or 3 (especially 3). In the case of 3 or less, for example, an alkyl group (in particular, an alkyl group having 1 to 4 carbon atoms), H, NCO or the like can be bonded to the remaining bond.
  • the fluorine-containing group of the first organosilicon compound may be linear or have a side chain.
  • the liquid repellent agent the water and oil repellent coating composition described in WO 2016/076245 can be mentioned.
  • the liquid repellent agent can be applied to the surface on the protective layer 37 side of the protective layer-provided base layer 81 by dip coating, roll coating, bar coating, spin coating, spray coating, die coating, etc. .
  • the coating layer formed by applying the liquid repellent agent to the protective layer-provided substrate layer 81 is subjected to air
  • the liquid repellent layer 47 can be formed by standing in the inside and / or drying by heating.
  • the liquid repellent agent is applied on the covering area 37 a of the protective layer 37 and on the base layer 13 in the exposed area 37 b of the protective layer 37.
  • the liquid repellent layer 47 is formed on the covering area 37a of the protective layer 37 and on the base layer 13 in the exposed area 37b of the protective layer 37.
  • the layered substrate layer 82 can be obtained.
  • the protective layer removing step the protective layer 37 is peeled off from the liquid repellent layer-provided base layer 82 obtained in the liquid repellent layer forming step.
  • the base material layer 83 with a patterned liquid repellent layer which has the patterned liquid repellent layer 47b formed by removing a part of the liquid repellent layer 47 can be obtained (FIG. 2 (c)).
  • the protective layer 37 is peeled off from the liquid repellent layer-provided base layer 82 obtained in the liquid repellent layer forming step.
  • the base material layer 83 with a patterned liquid repellent layer which has the patterned liquid repellent layer 47b formed by removing a part of the liquid repellent layer 47 can be obtained (FIG. 2 (c)).
  • the protective layer 37 By peeling the protective layer 37 from the liquid repellent layer-attached base layer 82, the liquid repellent layer 47 on the coated area 37a is removed together with the protective layer 37, and the base layer 13 is removed in the exposed area 37b of the protective layer 37.
  • the composition for forming an alignment layer is applied to the surface on the patterned liquid repellent layer 47 b side of the substrate layer 83 with a patterned liquid repellent layer obtained in the protective layer removing step.
  • the base material layer 84 with a patterning alignment layer which has the patterning alignment layer 22 can be obtained (FIG. 2 (d)).
  • the patterned alignment layer 22 formed in the patterned alignment layer forming step can have an alignment regulating force to align the liquid crystal compound laminated thereon in a desired direction.
  • an alignment polymer composition described later a composition for forming a photo alignment film, a composition containing a resin material for forming a glue alignment film, and the like can be used.
  • the patterned liquid repellent layer 47 b exhibits liquid repellency to the composition for forming an alignment layer. Therefore, when the composition for forming an alignment layer is applied to the surface on the side of the patterned liquid repellent layer 47b of the substrate layer 83 with a patterned liquid repellent layer in the step of forming a patterned alignment layer, the patterned liquid repellent layer 47b is formed. In this case, the composition for forming an alignment layer is repelled and a coated layer of this composition is not formed.
  • the coating layer of the composition for formation of alignment layers can be formed in the area
  • the alignment layer 22a is formed on the base material layer 13 in the region where the patterned liquid repellent layer 47b is formed and in the region where the patterned liquid repellent layer 47b is not formed.
  • a patterned alignment layer-provided substrate layer having a patterned alignment layer 22 can be obtained.
  • the patterned alignment layer 22 facilitates liquid crystal alignment of the liquid crystal compound.
  • the state of liquid crystal alignment such as horizontal alignment, vertical alignment, hybrid alignment, and tilt alignment changes depending on the properties of the patterned alignment layer 22 and the liquid crystal compound, and the combination thereof can be arbitrarily selected.
  • the patterned alignment layer 22 is a material that expresses horizontal alignment as alignment control force
  • the liquid crystal compound can form horizontal alignment or hybrid alignment
  • the patterned alignment layer 22 is a material that expresses vertical alignment. If so, the liquid crystal compound can form vertical alignment or tilt alignment.
  • the expression of horizontal, vertical, etc. represents the direction of the major axis of the aligned liquid crystal compound based on the plane of the polarizing film 2.
  • the vertical alignment is to have the long axis of the aligned polymerizable liquid crystal in the direction perpendicular to the plane of the polarizing film 2.
  • perpendicular as used herein means 90 ° ⁇ 20 ° with respect to the plane of the polarizing film 2. Since it is preferable that the polarizing film 2 has the polarization
  • the alignment control force of the patterned alignment layer 22 can be arbitrarily adjusted depending on the surface state and the rubbing conditions when the patterned alignment layer 22 is formed of an alignment polymer, and is formed of a photo alignment polymer If it is set, it can be adjusted arbitrarily according to the polarized light irradiation condition and the like.
  • the liquid crystal alignment can also be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.
  • the thickness of the patterned alignment layer 22 is usually 10 nm to 5000 nm, preferably 10 nm to 1000 nm, and more preferably 30 nm to 300 nm.
  • the patterned alignment layer 22 formed between the base material layer 13 and the patterned polarizing layer 21 is insoluble in the solvent used when forming the patterned polarizing layer 21 on the patterned alignment layer 22.
  • the patterned alignment layer 22 examples include an alignment film made of an alignment polymer, a photo alignment film, a groove alignment film, and the like.
  • the patterned alignment layer 22 is a photo alignment film from the viewpoint that the alignment direction can be easily controlled. Is preferred.
  • orientation polymers include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, Examples thereof include polyethylene imine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid, and polyacrylic acid esters. Among them, polyvinyl alcohol is preferred. These orientable polymers may be used alone or in combination of two or more.
  • an alignment film made of an alignment polymer a composition obtained by dissolving the alignment polymer in a solvent (hereinafter sometimes referred to as “alignment polymer composition”) is usually used as the substrate layer 83 with a patterned liquid repellent layer. It can be obtained by applying, removing the solvent, or applying the orienting polymer composition to the substrate layer 13, removing the solvent and rubbing (rubbing method).
  • solvent used for the orientable polymer composition examples include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve or propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl Ester solvents such as ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone or methyl isobutyl ketone; fats such as pentane, hexane or heptane Group hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene or xylene; nitrile solvents such as acetonitrile; Rofuran or
  • the content of the orienting polymer in the orientating polymer composition may be in the range in which the orienting polymer can be completely dissolved in the solvent, but is preferably 0.1 to 20% by mass in terms of solid content with respect to the solution. 0.1 to 10% by mass is more preferable.
  • a commercially available alignment film material may be used as it is as an alignment polymer composition.
  • Examples of commercially available alignment film materials include Sun Ever (registered trademark) (manufactured by Nissan Chemical Industries, Ltd.) or Optomer (registered trademark) (manufactured by JSR Corporation).
  • coating methods such as spin coating method, extrusion method, gravure coating method, die coating method, bar coating method or applicator method And publicly known methods such as printing methods such as flexo method.
  • a printing method such as a gravure coating method, a die coating method or a flexo method can be adopted as the coating method.
  • a dry film of the orientable polymer is formed.
  • a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method and the like can be mentioned.
  • the dried coating can then be contacted with a rotating rubbing roll wrapped with a rubbing cloth to form the patterned alignment layer 22.
  • the photoalignment film usually has a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter sometimes referred to as a "photoalignment film-forming composition") with a patterned liquid repellent layer-containing group. It can be obtained by irradiating polarized light (preferably, polarized UV) to the coating layer for alignment layer formed by coating on the material layer 83.
  • polarized light preferably, polarized UV
  • the photo alignment film is more preferable in that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • the photoreactive group refers to a group that generates liquid crystal alignment ability by irradiating light. Specifically, it generates a light reaction that is the source of liquid crystal alignment ability, such as alignment induction or isomerization reaction of molecules generated by light irradiation, dimerization reaction, photocrosslinking reaction, or photolysis reaction. is there.
  • a light reaction that is the source of liquid crystal alignment ability, such as alignment induction or isomerization reaction of molecules generated by light irradiation, dimerization reaction, photocrosslinking reaction, or photolysis reaction. is there.
  • the photoreactive groups those capable of causing a dimerization reaction or a photocrosslinking reaction are preferable in that they are excellent in orientation.
  • These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group or a halogenated alkyl group.
  • a solvent of the composition for forming a photo alignment film those capable of dissolving a polymer having a photo reactive group and a monomer are preferable.
  • the solvent for example, the solvents mentioned as the solvent of the alignment polymer composition described above, etc. Can be mentioned.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film is appropriately adjusted depending on the type of the polymer or monomer having a photoreactive group and the thickness of the photoalignment film to be produced. Although it is possible, 0.2 mass% or more is preferable, and a range of 0.3 to 10 mass% is particularly preferable.
  • a polymer material such as polyvinyl alcohol or polyimide and a photosensitizer may be contained within the range that the characteristics of the photo alignment film are not significantly impaired.
  • a method for applying the composition for forming a photoalignment film to the patterned liquid repellent layer-carrying substrate layer 83 a method for applying the above-mentioned alignment polymer composition to the patterned liquid repellent layer-bearing substrate layer 83 and Similar methods can be mentioned.
  • a method of removing a solvent from the composition for photo-alignment film formation applied the same method as the method of removing a solvent from alignment polymer composition is mentioned, for example.
  • the polarized light irradiation may be performed directly on the dried film from which the solvent has been removed from the composition for forming a photo alignment film coated on the patterned liquid repellent layer-coated substrate layer 83, and the substrate layer 13 was transmitted. You may carry out from the base material layer 13 side so that polarized light may be irradiated to a dry film.
  • polarized light used for polarized light irradiation is substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy.
  • UV (ultraviolet light) having a wavelength of 250 to 400 nm is particularly preferable.
  • light sources used for polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet light lasers such as KrF and ArF, etc., and high pressure mercury lamps, ultra high pressure mercury lamps or metal halide lamps are more preferable. . These lamps are preferable because the emission intensity of ultraviolet light with a wavelength of 313 nm is large.
  • Polarized light can be illuminated by illuminating the light from the light source through a suitable polarizer.
  • a polarizing filter, a polarizing prism such as Glan-Thomson, Glan-Taylor, or a wire grid type polarizer can be used.
  • a plurality of regions (patterns) having different liquid crystal alignment directions can also be formed by performing masking when performing rubbing or polarized light irradiation.
  • the groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the film surface.
  • a method of forming a concavo-convex pattern by performing development and rinsing after exposure through an exposure mask having slits of a pattern shape on the surface of a photosensitive polyimide film, a plate having grooves on the surface Method of forming a layer of a UV curable resin before curing on a sheet-like master, transferring the resin layer to a substrate and then curing, a plurality of films of the UV curable resin before curing formed on a substrate, The roll-shaped original disc which has a groove
  • the methods described in JP-A-6-34976 and JP-A-2011-242743 can be mentioned.
  • the width of the convex portion of the glue alignment film is preferably 0.05 ⁇ m to 5 ⁇ m, and the width of the concave portion is preferably 0.1 ⁇ m to 5 ⁇ m.
  • the depth is preferably 2 ⁇ m or less, and more preferably 0.01 ⁇ m to 1 ⁇ m or less.
  • a polarizing layer containing a liquid crystal compound and a dichroic dye is formed on the surface on the patterned alignment layer 22 side of the patterned alignment layer-provided base layer 84 obtained in the patterned alignment layer forming step.
  • the composition for a polarizing film the polarizing film 2 in which the patterning polarizing layer 21 was formed is obtained (FIG.2 (e)).
  • the composition for forming a polarizing layer is a composition containing a liquid crystal compound and a dichroic dye, and preferably contains a solvent and a polymerization initiator, and a sensitizer, a polymerization inhibitor, a leveling agent, a reactive additive, etc. May be included.
  • the patterned liquid repellent layer 47 b exhibits liquid repellency to the composition for forming a polarizing layer. Therefore, when the composition for forming a polarizing layer is applied to the surface on the side of the patterned liquid repellent layer 47b of the base material layer 84 with a patterned alignment layer in the step of forming a patterned polarizing layer, on the patterned liquid repellent layer 47b The composition for forming a polarizing layer is repelled and a coated layer of this composition is not formed.
  • the coating layer of the composition for forming a polarizing layer can be formed in a region where the patterned liquid repellent layer 47b of the patterned alignment layer-provided base material layer 84 is not formed.
  • a patterned area is formed on the base layer 13 where the patterned liquid repellent layer 47 b is formed and the polarized area 21 a is formed on the alignment layer 22 a of the patterned alignment layer 22.
  • a polarizing film 2 having the polarizing layer 21 can be obtained.
  • the polarizing film 2 shown in FIG. 1 and FIG. 2 (e) can also be used by peeling off the base material layer 13.
  • the alignment layer 22 a may be peeled off together with the base layer 13.
  • peeling of the base material layer 13 can also be performed after bonding the patterned polarizing layer 21 of the polarizing film 2 to the member, retardation layer, etc. which make a display apparatus.
  • the patterned polarizing layer 21 contains a liquid crystal compound and has a region containing the liquid crystal compound and a dichroic dye.
  • the patterned polarizing layer 21 has the polarization characteristic of the plane of the polarizing film 2, it is preferable to have a region in which the dichroic dye and the liquid crystal compound are horizontally aligned with respect to the plane of the polarizing film 2.
  • the patterned polarizing layer 21 has polarization characteristics in the film thickness direction of the polarizing film 2, it is preferable to have a region in which the dichroic dye and the liquid crystal compound are horizontally aligned with the plane of the polarizing film 2.
  • the above ratio is about 5 to 10.
  • the fact that the liquid crystal compound and the dichroic dye are not phase separated means, for example, surface observation with various microscopes or scattering degree measurement with a haze meter. It can confirm by.
  • the thickness of the patterned polarizing layer 21 is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the thickness of the patterned polarizing layer 21 can be measured by an interference film thickness meter, a laser microscope, a stylus film thickness meter, or the like.
  • liquid crystal compound A well-known liquid crystal compound can be used as a liquid crystal compound contained in the composition for polarizing layer formation.
  • the type of liquid crystal compound is not particularly limited, and rod-like liquid crystal compounds, discotic liquid crystal compounds, and mixtures thereof can be used.
  • the liquid crystal compound may be a polymer liquid crystal compound, a polymerizable liquid crystal compound, or a mixture of these.
  • a polymerizable liquid crystal compound As the liquid crystal compound, it is preferable to use a polymerizable liquid crystal compound as the liquid crystal compound.
  • the hue of the polarizing film can be arbitrarily controlled, and the thickness of the polarizing film can be significantly reduced.
  • a polarizing film can be manufactured without performing an extending
  • the polymerizable liquid crystal compound refers to a compound having a polymerizable group and having liquid crystallinity.
  • the polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group.
  • the photopolymerizable group means a group capable of participating in the polymerization reaction by active radicals or acids generated from a photopolymerization initiator described later.
  • Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like.
  • the liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, it is preferable to use a thermotropic liquid crystal when it is mixed with a dichroic dye as in the patterned polarizing layer 21 of the present embodiment.
  • the polymerizable liquid crystal compound when it is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound exhibiting a nematic liquid crystal phase or a thermotropic liquid crystal compound exhibiting a smectic liquid crystal phase.
  • the liquid crystal state of the polymerizable liquid crystal compound is preferably a smectic phase, and more preferably a higher smectic phase from the viewpoint of enhancing the performance.
  • higher-order smectic liquid crystal compounds forming 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, a smectic K phase or a smectic L phase
  • More preferred are higher order smectic liquid crystal compounds which form smectic B phase, smectic F phase or smectic I phase.
  • the patterned polarizing layer 21 formed by the polymerizable liquid crystal compound is a high-order smectic phase of these, it is possible to form a region with higher polarization performance in the patterned polarizing layer 21.
  • regions with high polarization performance as described above are those in which Bragg peaks derived from higher order structures such as hexatic phase and crystal phase are obtained in X-ray diffraction measurement.
  • the Bragg peak is a peak derived from the periodic structure of molecular orientation, and a film having a periodic spacing of 3 to 6 ⁇ can be obtained.
  • the patterned polarizing layer 21 preferably contains a polymer obtained by polymerizing the polymerizable liquid crystal compound in the smectic phase, so that the patterned polarizing layer 21 can be imparted with higher polarization characteristics, which is preferable. .
  • the polymerizable liquid crystal compound exhibits a nematic liquid crystal phase or a smectic liquid crystal phase can be confirmed, for example, as follows. After the composition for forming a polarizing film is applied to a substrate to form a coated film, the solvent contained in the coated film is removed by heat treatment under the condition that the polymerizable liquid crystal compound is not polymerized. Subsequently, the coating film formed on the substrate is heated to an isotropic phase temperature, and the liquid crystal phase developed by gradually cooling is inspected by texture observation with a polarizing microscope, X-ray diffraction measurement or differential scanning calorimetry Do.
  • X 1 , X 2 and X 3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and here, the divalent aromatic group Or a hydrogen atom contained in a divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group Or a nitro group may be substituted, and a carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted by an oxygen atom, a sulfur atom or a nitrogen atom .
  • X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent It is.
  • Y 1 , Y 2 , W 1 and W 2 are each independently a single bond or a divalent linking group.
  • V 1 and V 2 each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH 2- constituting the alkanediyl group is -O-,- It may be replaced by S- or NH-.
  • U 1 and U 2 independently of one another represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • compound (A) and the like can be mentioned.
  • X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent, or cyclohexane which may have a substituent It is a 1,4-diyl group.
  • X 1 and X 3 are preferably a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-. More preferably, it is a 1,4-diyl group.
  • smectic liquid crystallinity tends to be easily developed.
  • substituents which the 1,4-phenylene group which may have a substituent and the cyclohexane-1,4-diyl group which may have a substituent optionally have, a methyl group, ethyl
  • substituents include alkyl groups having 1 to 4 carbon atoms such as a group or a butyl group, halogen atoms such as a cyano group, a chlorine atom or a fluorine atom. Preferably it is unsubstituted.
  • Y 1 and Y 2 are more preferably —CH 2 CH 2 —, —COO—, —OCO— or a single bond
  • X 1 , X 2 and X 3 all contain a cyclohexane-1,4-diyl group. If not, it is more preferred that Y 1 and Y 2 be different bonding systems. In the case where Y 1 and Y 2 are bonding systems different from each other, smectic liquid crystallinity tends to be easily exhibited.
  • W 1 and W 2 are preferably, independently of one another, a single bond, —O—, —S—, —COO— or OCO—, and more preferably, independently of each other, be a single bond or —O—.
  • C 1-20 alkanediyl group represented by V 1 and V 2 a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4 -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane There may be mentioned -1,14-diyl or icosane-1,20-diyl and the like.
  • V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably linear alkanediyl groups having 6 to 12 carbon atoms.
  • the crystallinity is improved, and smectic liquid crystallinity tends to be easily exhibited.
  • Examples of the substituent optionally possessed by the optionally substituted alkanediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom such as a chlorine atom or a fluorine atom, and the alkanediyl group is It is preferably unsubstituted, and more preferably an unsubstituted and linear alkanediyl group.
  • Both U 1 and U 2 are preferably polymerizable groups, and both are more preferably photopolymerizable groups.
  • a polymerizable liquid crystal compound having a photopolymerizable group can be polymerized under a lower temperature condition than a thermally polymerizable group, and is thus advantageous in that a polymer of the polymerizable liquid crystal compound can be formed in a highly ordered state.
  • the polymerizable groups represented by U 1 and U 2 may be different from each other, but are preferably the same.
  • the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group or an oxetanyl group is preferable, and a methacryloyloxy group or an acryloyloxy group is more preferable.
  • Examples of such a polymerizable liquid crystal compound include the following.
  • the exemplified compounds (A) can be used for the patterned polarizing layer 21 alone or in combination.
  • two or more polymerizable liquid crystal compounds it is preferable that at least one be a compound (A), and it is more preferable that two or more be a compound (A).
  • the mixing ratio when combining two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, and 10:90 to 50:50. Is more preferred.
  • the compound (A) is described, for example, in Lub et al. Recl. Trav. Chim. It can manufacture by the well-known method as described in Pays-Bas, 115, 321-328 (1996) or patent 4719156 grade
  • 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 with respect to 100 parts by mass of the solid content of the patterned polarizing layer 21. It is more preferably 70 to 98 parts by mass, and still more preferably 80 to 97 parts by mass. If the content of the polymerizable liquid crystal compound is in the above range, the orientation tends to be high.
  • solid content means the thing of the total amount of the component except the solvent from the composition for polarizing layer formation mentioned later.
  • the dichroic dye is a dye having a property in which the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction are different.
  • the dichroic dye is a dye that is oriented with the liquid crystal compound to exhibit dichroism, and the dichroic dye itself may have polymerizability or liquid crystallinity.
  • the dichroic dye preferably has a property of absorbing visible light, and more preferably one having an absorption maximum wavelength ( ⁇ MAX ) in the range of 380 to 680 nm.
  • a dichroic dye for example, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye and the like can be mentioned, and among them, an azo dye is preferable.
  • the azo dye include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, stilbene azo dyes and the like, with preference given to bisazo dyes or trisazo dyes.
  • the dichroic dyes may be used alone or in combination of two or more types, but in order to obtain absorption in the entire visible light range, it is preferable to combine three or more types of dichroic dyes, It is more preferable to combine a kind or more of azo dyes.
  • a 1 , A 2 and A 3 are each independently a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group, or a substituent
  • T 1 and T 2 independently of each other are an electron withdrawing group or an electron emitting group, and the position is substantially 180 ° with respect to the azo bonding surface.
  • Have to. p represents an integer of 0 to 4; When p is 2 or more, each A 2 may be the same or different.
  • a compound represented by hereinafter sometimes referred to as "compound (I)").
  • the 1,4-phenylene group, the naphthalene-1,4-diyl group and the divalent heterocyclic group in A 1 , A 2 and A 3 optionally have, such as methyl group, ethyl group or butyl group
  • unsubstituted amino group is -NH 2.
  • Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group and a hexyl group.
  • Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group. And hexane-1,6-diyl group, heptane-1,7-diyl group, and octane-1,8-diyl group.
  • a 1 , A 2 and A 3 are each independently unsubstituted, and hydrogen is substituted with a methyl group or a methoxy group
  • a 1,4-phenylene group or a divalent heterocyclic group is preferable, and p is preferably 0 or 1.
  • p is 1 and at least two of the three structures of A 1 , A 2 and A 3 are 1,4-phenylene groups, in that they have both simplicity of molecular synthesis and high performance. More preferable.
  • divalent heterocyclic group examples include quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and a group in which two hydrogen atoms are removed from benzoxazole.
  • a 2 is a divalent heterocyclic group, a structure having a molecular bonding angle of substantially 180 ° is preferable, and specifically, benzothiazole, benzimidazole, benzoxazole in which two 5-membered rings are condensed. The structure is more preferred.
  • T 1 and T 2 are, independently of each other, an electron withdrawing group or an electron emitting group, which are preferably different from each other, and T 1 is an electron withdrawing group and T 2 is an electron emitting group, or More preferably, T 1 is an electron-emitting group and T 2 is an electron-withdrawing group.
  • T 1 and T 2 independently represent 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 an alkyl group having 1 to 6 carbon atoms.
  • an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group An amino group having one or two alkyl groups having 1 to 6 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms is preferable.
  • azo dyes examples include the following.
  • B 1 to B 20 independently of each other represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, It represents a nitro group, a substituted or unsubstituted amino group (as defined for the substituted amino group and the unsubstituted amino group as described above), a chlorine atom or a trifluoromethyl group.
  • B 2 , B 6 , B 9 , B 14 , B 18 and B 19 are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • n1 to n4 each independently represent an integer of 0 to 3.
  • a plurality of B 2 may be identical to or different from each other
  • a plurality of B 6 may be identical to or different from each other
  • a plurality of B 9 may be identical to or different from each other
  • the plurality of B 14 may be identical to or different from each other.
  • anthraquinone dye a compound represented by Formula (2-7) is preferable.
  • R 1 to 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 an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the oxazine dye is preferably a compound represented by the formula (2-8).
  • R 9 to 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 an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the acridine dye is preferably a compound represented by formula (2-9).
  • R 16 to 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 an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms represented by Rx in formulas (2-7), (2-8) and (2-9) include a methyl group, an ethyl group, a propyl group and a butyl group And a pentyl group or a hexyl group.
  • Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group or a naphthyl group.
  • the cyanine dye is preferably a compound represented by Formula (2-10) and a compound represented by Formula (2-11).
  • D 1 and D 2 independently represent a group represented by any one of Formula (2-10a) to Formula (2-10d).
  • n5 represents an integer of 1 to 3;
  • D 3 and D 4 each independently represent a group represented by any one of the formulas (2-11 a) to (2-11 h).
  • n6 represents an integer of 1 to 3;
  • the content of the dichroic dye (the total amount thereof in the case of containing plural kinds) is usually 0 with respect to 100 parts by mass of the polymerizable liquid crystal compound in the patterned polarizing layer 21.
  • the amount is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 3 to 15 parts by mass.
  • the content of the dichroic dye is less than this range, light absorption is insufficient, sufficient polarization performance can not be obtained, and when it is more than this range, the alignment of liquid crystal molecules may be inhibited.
  • the composition for forming a polarizing layer may contain a solvent.
  • a solvent since the polymerizable liquid crystal compound has a high viscosity, when a polymerizable liquid crystal compound is used as the liquid crystal compound, coating is facilitated by using a composition for forming a polarizing layer containing a solvent, and as a result, the patterned polarizing layer 21 is formed. It becomes easy to form.
  • the solvent is preferably one that can completely dissolve the polymerizable liquid crystal compound and the dichroic dye, and is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound.
  • 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 methyl ether acetate, ⁇ -butyrolactone Or ester solvents such as propylene glycol methyl ether acetate or ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone or methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane or heptane; toluene Or an aromatic hydrocarbon solvent such as xylene, a nitrile solvent such as acetonitrile; Ether solvents such as dimethoxyethane
  • the content of the solvent contained in the composition for forming a polarizing layer is preferably 50 to 98% by mass with respect to the total amount of the composition for forming a polarizing layer.
  • the content of solid content in the composition for forming a polarizing layer is preferably 2 to 50% by mass.
  • the viscosity of the composition for forming a polarizing layer is lowered, so that the thickness of the patterned polarizing layer 21 becomes substantially uniform, and unevenness occurs in the patterned polarizing layer 21. It tends to be difficult to occur.
  • the solid content can be determined in consideration of the thickness of the patterned polarizing layer 21 to be produced.
  • the composition for forming a polarizing layer may contain a polymerization initiator.
  • the polymerization initiator can be used when a polymerizable liquid crystal compound is used as the liquid crystal compound, and is a compound capable of initiating a polymerization reaction of the polymerizable liquid crystal compound or the like.
  • the polymerization initiator is preferably a photopolymerization initiator that generates active radicals by the action of light from the viewpoint of being independent of the phase state of the thermotropic liquid crystal.
  • polymerization initiator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acyl phosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) And benzophenone and 2,4,6-trimethylbenzophenone.
  • alkylphenone compounds examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) 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-hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-propane On-oligomer etc. are mentioned.
  • acyl phosphine oxide compound examples include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide or bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide.
  • triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine or 2,4
  • polymerization initiators include Irgacure (registered trademark) 907, 184, 651, 819, 250, 369, 379, 127, 754, OXE01, OXE02, or OXE03 (manufactured by Ciba Specialty Chemicals Inc.) Seikol (registered trademark) BZ, Z, or BEE (manufactured by SEIKO CHEMICAL CO., LTD.); Kayacure (registered trademark) BP 100, or UVI-6992 (manufactured by Dow Chemical Co.); Adeka Optomer SP-152, N-1717, N-1919, SP-170, Adeka Arkles NCI-831, Adeka Arkles NCI-930 (manufactured by ADEKA Co., Ltd.); TAZ-A, or TAZ-PP (manufactured by Nihon Shiber Hegner Co., Ltd.); TAZ-A, or TAZ-PP (manufactured by Nihon Shiber
  • the content of the polymerization initiator in the composition for forming a polarizing layer can be appropriately adjusted according to the type of the polymerizable liquid crystal compound and the amount thereof, but the content is usually 0. 1 parts by mass relative to 100 parts by mass of the content of the polymerizable liquid crystal compound.
  • the amount is 1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass.
  • the composition for forming a polarizing layer may contain a sensitizer.
  • the sensitizer can be suitably used when a polymerizable liquid crystal compound is used as a liquid crystal compound, and when a polymerizable liquid crystal compound having a photopolymerizable group is used, the sensitizer is a photosensitizer. It is preferably an agent.
  • sensitizers include xanthone compounds such as xanthone and thioxanthone (eg, 2,4-diethylthioxanthone, 2-isopropylthioxanthone etc.); anthracene compounds such as anthracene and alkoxy group-containing anthracene (eg dibutoxyanthracene etc) And phenothiazine or rubrene and the like.
  • the composition for forming a polarizing layer contains a sensitizer
  • the polymerization reaction of the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer can be further promoted.
  • the amount of the sensitizer used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Parts are more preferred.
  • the composition for forming a polarizing layer may contain a polymerization inhibitor from the viewpoint of stably advancing the polymerization reaction.
  • the polymerization inhibitor can be suitably used when a polymerizable liquid crystal compound is used as the liquid crystal compound, and the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled by the polymerization inhibitor.
  • polymerization inhibitor examples include radical scavenging such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butyl catechol etc.), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical etc. Agents; thiophenols; ⁇ -naphthylamines or ⁇ -naphthols.
  • the content of the polymerization inhibitor is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of the content of the polymerizable liquid crystal compound.
  • the amount is 0.5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass.
  • the composition for forming a polarizing layer may contain a leveling agent.
  • the leveling agent is an additive having a function of adjusting the flowability of the composition and making the film obtained by applying the composition more flat, and is, for example, an organic modified silicone oil type, polyacrylate type or perfluoro type. An alkyl type leveling agent is mentioned.
  • DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.)
  • KP 321, KP 323, KP 324, KP 326, KP 340, KP341, X22-161A, KF6001 (all from Shin-Etsu Chemical Co., Ltd.)
  • TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4446, TSF-4446, TSF4452, TSF4460 (all, Momentive Performance Materials Japan Ltd.
  • Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (above, Sumitomo 3M Co., Ltd., Megafuck (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all available from DIC Corporation), F-Top (trade names) EF301, EF303, EF351, EF 352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S-393, S-101, S-105, KH -40, SA-100 (all available from AGC Seimi Chemical Co., Ltd.), under the trade names E1830 and E5844 (manufactured by Daikin Fine Chemical Laboratories), BM-1000, BM-1100, BYK-352, BY -353 or BYK-361N
  • the composition for forming a polarizing layer contains a leveling agent, it is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, still more preferably 0.1 based on 100 parts by mass of the liquid crystal compound. ⁇ 3 parts by mass.
  • the content of the leveling agent is in the above range, it is easy to horizontally align the liquid crystal compound, and the resulting patterned polarizing layer tends to be smoother.
  • the composition for polarizing layer formation may contain 2 or more types of leveling agents.
  • the composition for forming a polarizing layer may contain a reactive additive.
  • the reactive additive is preferably one having a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule.
  • active hydrogen reactive group refers to a group having reactivity with a group having active hydrogen such as carboxyl group (-COOH), hydroxyl group (-OH), amino group (-NH 2 ) and the like.
  • glycidyl group, oxazoline group, carbodiimide group, aziridine group, imide group, isocyanate group, thioisocyanate group, maleic anhydride group and the like are representative examples.
  • the number of carbon-carbon unsaturated bonds or active hydrogen reactive groups contained in the reactive additive is usually 1 to 20, and preferably 1 to 10.
  • the active hydrogen reactive groups are preferably present, and in this case, the active hydrogen reactive groups may be the same or different.
  • the carbon-carbon unsaturated bond possessed by the reactive additive may be a carbon-carbon double bond, a carbon-carbon triple bond, or a combination thereof, but is preferably a carbon-carbon double bond.
  • the reactive additive contains a carbon-carbon unsaturated bond as a vinyl group and / or a (meth) acrylic group.
  • a reactive additive in which the active hydrogen reactive group is at least one selected from the group consisting of an epoxy group, a glycidyl group and an isocyanate group is preferable, and a reactive additive having an acrylic group and an isocyanate group is more preferable. .
  • the reactive additive include compounds having a (meth) acrylic group and an epoxy group such as methacryloxy glycidyl ether and acryloxy glycidyl ether; (meth) acrylic groups and oxetane such as oxetane acrylate and oxetane methacrylate A compound having a group; a compound having a (meth) acrylic group and a lactone group such as lactone acrylate and lactone methacrylate; a compound having a vinyl group and an oxazoline group such as vinyl oxazoline and isopropenyl oxazoline; isocyanato methyl acrylate And oligomers of compounds having a (meth) acrylic group and an isocyanate group, such as isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate or 2-isocyanatoethyl methacrylate.
  • an epoxy group such as methacryloxy glycidyl
  • compounds having a vinyl group or vinylene group and an acid anhydride such as methacrylic anhydride, acrylic anhydride, maleic anhydride or vinyl maleic anhydride, may be mentioned.
  • methacryloxy glycidyl ether, acryloxy glycidyl ether, isocyanato methyl acrylate, isocyanato methyl methacrylate, vinyl oxazoline, 2-isocyanato ethyl acrylate, 2-isocyanato ethyl methacrylate or the above-mentioned oligomers are preferable, isocyanato methyl acrylate, Particularly preferred is 2-isocyanatoethyl acrylate or the above mentioned oligomers.
  • a compound represented by the following formula (Y) is preferable.
  • n represents an integer of 1 to 10
  • R 1 ′ represents a divalent aliphatic or alicyclic hydrocarbon group having 2 to 20 carbon atoms, or 2 Represents a substituted aromatic hydrocarbon group.
  • R 3 ' represents a group having a hydroxyl group or a carbon-carbon unsaturated bond. 'Of at least one R 3' formula (Y) in R 3 is a carbon - is a group having a carbon unsaturated bond.
  • a compound represented by the following formula (YY) (hereinafter sometimes referred to as a compound (YY)) is particularly preferable (where n is the same as above). Is the meaning).
  • the content of the reactive additive is usually 0.01 to 10 parts by mass, preferably 0.1 to 100 parts by mass of the liquid crystal compound. 5 parts by mass.
  • Coating method of composition for forming a polarizing layer As a method of applying the composition for forming a polarizing layer, extrusion coating method, direct gravure coating method, reverse gravure coating method, CAP coating method, slit coating method, microgravure method, die coating method, ink jet method, etc. may be mentioned. . Moreover, the method etc. of coating using coaters, such as a dip coater, a bar coater, a spin coater, etc. are mentioned. Among them, the coating method by microgravure method, ink jet method, slit coating method, die coating method is preferable in the case of continuous coating in the Roll to Roll format, and in the case of coating on a sheet substrate such as glass A highly uniform spin coating method is preferred.
  • a patterned alignment layer 22 is formed by applying a composition for forming an alignment film or the like on the substrate layer 83 with a patterned liquid repellent layer, and the patterned alignment layer obtained.
  • the composition for forming a polarizing layer can also be coated continuously on 22.
  • a solvent is removed from the composition for polarizing layer formation coated, and the coating layer for polarizing layers is formed.
  • the method of removing the solvent the same method as the method of removing the solvent from the oriented polymer composition can be used, and for example, natural drying, air drying, heat drying, reduced pressure drying and a combination thereof are mentioned. Be Among these, natural drying or heat drying is preferred.
  • the drying temperature is preferably in the range of 0 to 200 ° C., more preferably in the range of 20 to 150 ° C., and still more preferably in the range of 50 to 130 ° C.
  • the drying time is preferably 10 seconds to 10 minutes, more preferably 30 seconds to 5 minutes.
  • the coating layer for a polarizing layer formed in the step for forming a polarizing layer is irradiated with active energy rays to photopolymerize the polymerizable liquid crystal compound.
  • the patterned polarizing layer 21 is formed.
  • the type of the polymerizable liquid crystal compound particularly, the type of the photopolymerizable functional group possessed by the polymerizable liquid crystal compound
  • the photopolymerization initiator contained as the active energy ray to be irradiated It is suitably selected according to the kind of photoinitiator and those quantities.
  • one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, ⁇ -rays, ⁇ -rays, and ⁇ -rays can be mentioned.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and in that it can be used widely as an apparatus for photopolymerization, polymerization is possible so that it can be photopolymerized by ultraviolet light. It is preferable to select the type of the liquid crystal compound.
  • a light source of active energy ray for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, wavelength range 380
  • Examples thereof include an LED light source emitting ⁇ 440 nm, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp and the like.
  • Irradiation intensity of the active energy rays are usually, 10mW / cm 2 ⁇ 3000mW / cm 2.
  • the irradiation intensity of the active energy ray is preferably an intensity in a wavelength range effective for activating the cationic polymerization initiator or the radical polymerization initiator.
  • the irradiation time of the active energy ray is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, still more preferably 0. 1 second to 1 minute.
  • the cumulative amount of light is, 10mJ / cm 2 ⁇ 3000mJ / cm 2, preferably 50mJ / cm 2 ⁇ 2,000mJ / cm 2, more preferably It can be 100 mJ / cm 2 to 1000 mJ / cm 2 .
  • the integrated light amount is less than this range, the curing of the polymerizable liquid crystal compound may be insufficient, and good transferability may not be obtained.
  • the patterned polarizing layer may be colored.
  • the manufacturing method of the polarizing film 2 can preferably be continuously manufactured by a Roll to Roll type
  • the base layer coating step the base layer wound in a roll is conveyed while being unwound, and the second protective layer wound in a roll is conveyed while being unwound,
  • the layer and the protective layer may be laminated to obtain a substrate layer with a protective layer.
  • the liquid repellent layer forming step the liquid repellent agent is applied while continuously conveying the protective layer-attached base layer to obtain a liquid repellent layer-attached base layer, and in the protective layer removing step, the liquid repellent layer attached substrate
  • the protective layer may be peeled off continuously while transporting the layer.
  • the patterned alignment layer may be formed by continuously applying the composition for forming an alignment layer by a coating device while transporting the substrate layer with a patterned liquid repellent layer.
  • the patterned polarizing layer may be formed by continuously applying the composition for forming a polarizing layer with a coating device while transporting the substrate layer with a patterned alignment layer.
  • the polarizing film manufactured continuously as mentioned above can have a length of 10 m or more, for example.
  • FIG. 3 is a schematic sectional drawing which shows an example of the patterning liquid-repellent layer formation process in the manufacturing method of the polarizing film 2 shown in FIG.
  • the liquid repellent agent is dropped and applied to at least one side of the substrate layer 13 without using the protective layer 37 used in the first manufacturing method.
  • the patterned liquid repellent layer 47b shown in FIG. 2C can be formed.
  • the second manufacturing method of the polarizing film 2 is a patterned liquid repellent layer of the substrate layer 83 with a patterned liquid repellent layer (FIG. 2 (c)) obtained through the above-described patterned liquid repellent layer forming step.
  • a patterned alignment layer forming step of obtaining a substrate with patterned alignment layer 84 (FIG.
  • a polarizing film 2 having a patterned polarizing layer shown in FIG. 1 and FIG. 2 (e) can be manufactured.
  • the base layer 13 and the liquid repellent agent used in the patterned liquid repellent layer forming step of the second manufacturing method are the same as the base layer 13 and the liquid repellent agent used in the first manufacturing method, and the liquid repellent agent. Can be used.
  • coat can be mentioned.
  • a liquid repellent agent is dropped and applied onto the substrate layer 13 to form a patterned liquid repellent layer 47 b on the substrate layer 13, whereby a substrate layer 83 with a patterned liquid repellent layer can be obtained (FIG. c))
  • the patterned alignment layer forming step and the patterned polarizing layer forming step of the second manufacturing method are the same as the patterned alignment layer forming step and the patterned polarizing layer forming step of the first manufacturing method.
  • the polarizing film 2 can be continuously produced, for example, by the Roll to Roll method.
  • the base material layer wound in a roll in the patterned liquid repellent layer forming step is transported while being unwound, and a liquid repellent agent is dropped and applied to form a patterned liquid repellent layer on the base material layer, What is necessary is just to obtain the base material layer with a patterned liquid repelling layer.
  • the patterned alignment layer may be formed by continuously applying the composition for forming an alignment layer by a coating device while transporting the substrate layer with a patterned liquid repellent layer.
  • the patterned polarizing layer may be formed by continuously applying the composition for forming a polarizing layer with a coating device while transporting the substrate layer with a patterned alignment layer.
  • the polarizing film manufactured continuously as mentioned above can have a length of 10 m or more, for example.
  • FIG. 4 (a) to 4 (c) are each a schematic cross-sectional view showing an example of the circularly polarizing plate of the present invention.
  • the polarizing film 2 shown in FIG. 2 (e) is made to be circularly polarizing plates 5a and 5b shown in FIGS. 4 (a) and 4 (b) by laminating a retardation layer 15 having a quarter wave plate function.
  • the retardation layer 15 may be laminated on the side of the patterned polarizing layer 21 of the polarizing film 2 (FIG. 4 (a)) or may be laminated on the side of the base material layer 13 (FIG. 4 (b)).
  • FIG.4 (c) what peeled the base material layer 13 from the circularly-polarizing plate 5a shown to Fig.4 (a) can also be used as a circularly-polarizing plate 5c (FIG.4 (c)), In this case, a pattern is carried out with the base material layer 13.
  • the alignment layer 22 may also be peeled off.
  • the circularly polarizing plate may be one in which the polarizing film 2 and the retardation layer having a multilayer structure are laminated.
  • a retardation layer of the multilayer structure a retardation layer in which a layer having a half wave plate function and a layer having a quarter wave plate function can be laminated can be used.
  • a circularly polarizing plate can also be obtained by using a retardation layer in which a layer having a function of a quarter wavelength plate with reverse wavelength dispersion and a layer having a positive C plate function are laminated as a retardation layer having a multilayer structure. be able to.
  • the base material layer 13 of the polarizing film 2 one having a function as a retardation layer may be used, and a retardation layer may be further laminated to form a circularly polarizing plate.
  • the function as the retardation layer of the base material layer 13 and the retardation layer may be selected according to the lamination position of the base material layer 13 and the retardation layer in the circularly polarizing plate.
  • the polarizing film and the retardation layer can be laminated via an adhesive layer using a known pressure-sensitive adhesive or adhesive.
  • the circularly polarizing plate can be manufactured by laminating a polarizing film and a retardation layer.
  • the polarizing film is a long polarizing film having a length of 10 m or more continuously produced
  • the long retardation layer having a length of 10 m or more is used as the retardation layer, and the both are continuously conveyed.
  • the manufacturing method of a circularly polarizing plate is a sheet of a predetermined size in order to attach the polarizing film to a display device of a predetermined size, etc., by attaching a long laminate obtained by laminating a long polarizing film and a long retardation layer to a display of a predetermined size. It may have a process of cutting into In the cutting step, the long laminate is preferably cut in at least one of the length direction and the width direction of the long laminate. In this case, it is preferable to determine the cutting position in the long laminate so that the low polarization area is disposed at a predetermined position in the cut sheet.
  • the luminosity correction single transmittance (Ty) and the luminosity correction polarization degree (Py) were calculated in the following procedure.
  • the apparatus was used to measure by the double beam method.
  • a mesh was provided to cut the light amount by 50% on the reference side.
  • the transmittance and polarization degree at each wavelength are calculated using the following (Equation 1) and (Equation 2), and the visibility is corrected with a 2-degree field of view (C light source) of JIS Z 8701, and the visibility correction transmittance (Ty) and the visibility correction polarization degree (Py) were calculated.
  • Degree of polarization [%] ⁇ (T 1 ⁇ T 2 ) / (T 1 + T 2 ) ⁇ ⁇ 100
  • Single transmittance [%] (T 1 + T 2 ) / 2 (equation 2)
  • Example 1 (Production of liquid repellent) A first organosilicon compound (S1) (having a molecular weight of about 8000) represented by the following formula (a) was synthesized by the methods described in Synthesis Examples 1 and 2 of JP-A-2014-15609. In the formula (a), n is 43 and m is an integer of 1 to 6.
  • the compound represented by the above formula (a) as the first organosilicon compound (S1) (hereinafter referred to as compound (a)), FAS9E (C 4 F 9 -C 2 H 4 ) as the second organosilicon compound (S2) -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 , 3M company) as a solvent and mixed, and stirring at room temperature for a predetermined time
  • the liquid repellent was obtained.
  • the ratio of the first organosilicon compound (S1) is 0.03 parts
  • the ratio of the second organosilicon compound (S2) is 0.07 parts.
  • composition for Forming Alignment Layer (Production of Composition for Forming Alignment Layer) The following components were mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming an alignment layer which is a composition for forming a photo alignment film.
  • ⁇ 2 parts of polymer having photoreactive group shown below Solvent: 98 parts of o-xylene
  • composition for forming polarizing layer (Production of composition for forming polarizing layer) The following components were mixed and stirred at 80 ° C. for 1 hour to obtain a composition for forming a polarizing layer.
  • the dichroic dye the azo dye described in the example of JP-A-2013-101328 was used.
  • AY-638 Flujimori Kogyo Co., Ltd. made of AY-638 (A polyester film with a thickness of 38 ⁇ m and a pressure-sensitive adhesive layer with a thickness of 15 ⁇ m are formed as a protective layer in which an opening is formed by forming a hole) Liquid is applied and dried at 120.degree. C. for 10 minutes to form a liquid repellent layer.
  • the protective layer was peeled off to obtain a patterned liquid repellent layer-formed substrate layer on which a patterned liquid repellent layer was formed.
  • the composition for forming an alignment layer is applied to the surface of the obtained substrate layer with a patterned liquid repellent layer on which the patterned liquid repellent layer is formed, the composition is set at 120 ° C. in a drying oven set at 120 ° C. It dried in the drying oven for 1 minute, and obtained the coating layer for alignment layers.
  • the liquid crystal is irradiated with ultraviolet light (in nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: 1000 mJ / cm 2 ) using a high pressure mercury lamp (UNIQUEUR VB-15201BY-A, manufactured by USHIO INC.)
  • a patterned polarizing layer in which the compound and the dichroic dye were oriented was formed to obtain a polarizing film.
  • Example 2 Example 1 except that a liquid repellent agent is partially applied drop-wise on the base material layer using a dropper instead of bonding the protective layer in which the opening portion is formed by forming a hole with a punching punch.
  • a polarizing film was obtained in the same manner as in. When the external appearance of the obtained polarizing film was observed visually, the circular area
  • Comparative Example A polarizing film was obtained in the same manner as Example 1, except that the liquid repellent was not used and the liquid repellent layer was not formed. When the appearance of the obtained polarizing film was visually observed, it was found that the region where the polarizing layer was not present could not be confirmed, and that a polarizing film having a polarizing region and a low polarizing region was not obtained. Moreover, the sample for evaluation was produced in the above-mentioned procedure, and the visual sensitivity correction
  • the values of the visibility correction transmittance (Ty) and the visibility correction polarization degree (Py) measured in each example, comparative example and reference example shown in Table 1 are the visibility correction transmittance of the base material layer ( Ty) and the visibility correction polarization degree (Py) value, the visibility correction transmittance (Ty) of the base material layer alone is 92%, and the visibility correction polarization degree of the base material layer (Ty) Since the value of Py) is 0%, when the base material layer is removed in each of the examples, comparative examples and reference examples shown in Table 1, the value of the visibility correction transmittance (Ty) is the value shown in Table 1 The value of the degree of visibility correction polarization (Py) is considered to be the same as the value shown in Table 1.
  • Polarizing film 5a to 5c circularly polarizing plate, 13 base layer, 15 retardation layer, 21 patterned polarizing layer, 21a polarized area, 21b low polarized area, 22 patterned alignment layer, 22a alignment layer, 37 protective layer, 37a coated area, 37b exposed area, 47 liquid repellent layer, 47b patterned liquid repellent layer (liquid repellent layer), 81 base layer with protective layer, 82 base layer with liquid repellent layer, 83 group with patterned liquid repellent layer Material layer, 84 A substrate layer with a patterned alignment layer.

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PCT/JP2018/038526 2017-10-27 2018-10-16 偏光フィルムの製造方法及び偏光フィルム WO2019082746A1 (ja)

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