WO2020218104A1 - Composition pour former un film durci à cristaux liquides et son utilisation - Google Patents

Composition pour former un film durci à cristaux liquides et son utilisation Download PDF

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WO2020218104A1
WO2020218104A1 PCT/JP2020/016520 JP2020016520W WO2020218104A1 WO 2020218104 A1 WO2020218104 A1 WO 2020218104A1 JP 2020016520 W JP2020016520 W JP 2020016520W WO 2020218104 A1 WO2020218104 A1 WO 2020218104A1
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liquid crystal
cured film
group
crystal cured
film
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PCT/JP2020/016520
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English (en)
Japanese (ja)
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辰昌 葛西
伸行 幡中
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住友化学株式会社
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Priority to CN202080040736.5A priority Critical patent/CN113906322A/zh
Priority to KR1020217038358A priority patent/KR20220003574A/ko
Publication of WO2020218104A1 publication Critical patent/WO2020218104A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • 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
    • G02B5/3016—Polarising elements involving passive liquid crystal 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a composition for forming a liquid crystal cured film, a liquid crystal cured film, an elliptical polarizing plate, and an organic EL display device.
  • An elliptical polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated.
  • a polarizing plate and a retardation plate are laminated.
  • a so-called ⁇ / 4 plate is used as the retardation plate.
  • a retardation plate exhibiting inverse wavelength dispersibility is suitable in that it exhibits equivalent retardation performance in a wide wavelength range of visible light.
  • a retardation plate exhibiting reverse wavelength dispersibility a retardation plate made of a horizontally oriented liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility in a horizontally oriented state is known. ..
  • liquid crystal cured films such as horizontally oriented cured films and vertically oriented liquid crystal cured films are generally liquid crystal cured by producing a composition containing a polymerizable liquid crystal compound, applying the composition to a substrate, an alignment film, or the like and curing the composition.
  • a film is formed, but the liquid crystal cured film to be formed is generally a thin film of 5 ⁇ m or less, and there has been a problem that the appearance of the product is significantly deteriorated due to uneven film thickness.
  • an additive is added to a composition containing a polymerizable liquid crystal compound, there is a problem that the orientation of the polymerizable liquid crystal compound is deteriorated depending on the additive.
  • the present invention has been carried out in view of the above circumstances, and is to provide a composition for producing a liquid crystal cured film having less uneven film thickness.
  • the present inventors have completed the present invention as a result of diligent studies to solve the above problems. That is, the present invention provides the following preferred embodiments.
  • [1] Containing at least one silicon-based or fluorine-based leveling agent, at least one acrylic leveling agent, and at least one polymerizable liquid crystal compound.
  • [3] The composition for forming a liquid crystal cured film according to any one of [1] and [2], which further contains a dichroic dye.
  • the liquid crystal cured film according to [12] which further satisfies the following formula (S3). -150 nm ⁇ RthC (550) ⁇ -30 nm ...
  • RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm.
  • RthC (450) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 450 nm
  • RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm.
  • An elliptical polarizing plate including a horizontally oriented retardation film and a polarizing film.
  • An elliptical polarizing plate in which at least one of the horizontally oriented retardation film and the polarizing film is the liquid crystal cured film according to any one of [6] to [11].
  • An elliptical polarizing plate including a horizontally oriented retardation film, a vertically oriented liquid crystal cured film, and a polarizing film.
  • An elliptical polarizing plate in which at least one of a horizontally oriented retardation film, a vertically oriented liquid crystal cured film, and a polarizing film is the liquid crystal cured film according to any one of [6] to [14].
  • An organic EL display device including the elliptical polarizing plate according to any one of [15] to [17].
  • the total amount of the two types of leveling agents is 3.0% by mass or less with respect to the total amount of the polymerizable liquid crystal compound. It is blended in the polymerizable liquid crystal composition in a blending amount.
  • These two types of leveling agents work differently in the liquid crystal composition. Since silicon-based or fluorine-based leveling agents have low surface free energy, they tend to segregate on the surface layer of the liquid crystal composition, and by reducing the surface tension of the composition, they are effective in flattening the surface layer of the coating film.
  • the acrylic leveling agent has the effect of equalizing the local unevenness of the liquid physical properties in the film of the liquid crystal composition, and by including the combination of both in a specific blending amount, a liquid crystal cured film having less uneven film thickness can be obtained. Can be provided.
  • Leveling agent> At least one silicon-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are used, and the total amount of the leveling agent is the total amount of the polymerizable liquid crystal compound. It is characterized in that it is blended in a polymerizable liquid crystal composition in an amount of 0% by mass or less.
  • Examples of the silicon-based leveling agent include leveling agents having a polyorganosiloxane skeleton.
  • Examples of the group bonded to the silicon atom (silicon atom forming the siloxane bond) in the polyorganosiloxane include a hydrocarbon group and the like. Among them, an alkyl group and an aryl group having 1 to 10 carbon atoms are preferable, a methyl group and a phenyl group are more preferable, and a methyl group is further preferable.
  • the group bonded to the silicon atom may be only one type or two or more types.
  • the number of repetitions (degree of polymerization) of the siloxane unit is not particularly limited, but is preferably 2 to 10000, more preferably 3 to 5000, and even more preferably 5 to 1000.
  • silicon-based leveling agent for example, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-.
  • a radically polymerizable group such as a
  • the content of the silicon-based leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 2 parts by mass, more preferably 0.01 part by mass or more, based on 100 parts by mass of the polymerizable liquid crystal compound. It is 1.5 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass.
  • the fluorine-based leveling agent is not particularly limited, and examples thereof include leveling agents having a fluoroaliphatic hydrocarbon skeleton.
  • the fluoroaliphatic hydrocarbon skeleton is not particularly limited, and has, for example, the number of carbon atoms of fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, fluorohexane and the like. Examples thereof include 1 to 10 fluoroalkanes.
  • the fluoroaliphatic hydrocarbon skeleton may be a perfluoroaliphatic hydrocarbon skeleton in which at least a part of hydrogen atoms are substituted with fluorine atoms, but all hydrogen atoms are substituted with fluorine atoms.
  • the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton which is a repeating unit via an ether bond.
  • the fluoroaliphatic hydrocarbon group as the repeating unit is not particularly limited, and examples thereof include fluoroC1-4alkylene groups such as fluoromethylene, fluoroethylene, fluoropropylene, and fluoroisopropylene.
  • the above-mentioned fluoroaliphatic hydrocarbon group may be only one kind or two or more kinds.
  • the number of repetitions (degree of polymerization) of the fluoroalkylene ether unit is not particularly limited, but is preferably 10 to 10000, more preferably 30 to 5000, and further preferably 50 to 1000.
  • fluorine-based leveling agent a commercially available product can be used, for example, "Megafuck (registered trademark) R-08", “R-30”, “R-90”, “F-410”. , “F-411”, “F-443”, “F-445”, “F-470”, “F-471”, “F-477”, “F-479” , “F-482", “F-483", "F-281”, “F-253", “F-251", “F-114", "F-510", Same as “F-551”, Same as “F-552", Same as “F-553", Same as “F-554”, Same as “F-555”, Same as "F-556", Same as “F-557”, Same as above “F-558", "F-559”, “F-560”, “F-561”, “F-562”, “F-563”, “F-565”, “F-565" F-568 “,” F-569 “,” F-570 “,” F-572 “,” F-574 “,” F-575 “,” F-576
  • the content of the fluorine-based leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 2 parts by mass, more preferably 0.01 part by mass or more, based on 100 parts by mass of the polymerizable liquid crystal compound. It is 1.5 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass.
  • Acrylic leveling agents are produced, for example, by copolymerizing a monomer having a (meth) acryloyl group.
  • the acrylic leveling agent has a hydrophilic group such as a (meth) acrylate having a hydroxyl group and a (meth) acrylate having an alkylene oxide typified by ethylene oxide and propylene oxide as a monomer having a (meth) acryloyl group. It can be produced by copolymerizing a monomer.
  • acrylic leveling agents may be used, for example, "BYK-350”, “BYK-352”, “BYK-353”, “BYK-354”, “BYK-355”, “BYK-356”. ",” BYK-358N “,” BYK-361N “,” BYK-380 “,” BYK-381 “,” BYK-392 “,” BYK-394 “,” BYK-3441 "(Big Chemie Japan Co., Ltd.) Company).
  • the content of the acrylic leveling agent in the polymerizable liquid crystal composition is preferably 0.001 part by mass to 3 parts by mass, and more preferably 0.01 part by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is about 2 parts by mass, more preferably 0.1 part by mass to 1.5 parts by mass.
  • the acrylic leveling agent tends to deteriorate the orientation of the liquid crystal cured film because segregation in the film thickness direction is unlikely to occur in the liquid crystal cured film.
  • the molecular weight (weight average molecular weight) of the acrylic leveling agent is preferably 100 to 100,000, more preferably 500 to 50,000. , More preferably 500 to 10000, and particularly preferably 500 to 5000.
  • At least one silicon-based or fluorine-based leveling agent and at least one acrylic-based leveling agent are used, and the total amount of the leveling agent is 3.0% by weight or less based on the total amount of the polymerizable liquid crystal compound. It is preferable to mix in an amount.
  • the silicon-based or fluorine-based leveling agent since the action of the silicon-based or fluorine-based leveling agent in the polymerizable liquid crystal composition and the action of the acrylic-based leveling agent in the polymerizable liquid crystal composition are different, it is recommended to combine both leveling agents. preferable.
  • the silicon-based or fluorine-based leveling agent a silicon-based leveling agent is preferable.
  • the total amount of the leveling agent is preferably 0.001 to 3% by mass, more preferably 0.01 to 2.5% by mass. If the amount of the leveling agent added is smaller than the above range, the effect of adding the leveling agent tends to be difficult to be exhibited.
  • the weight ratio of the silicon-based or fluorine-based leveling agent to the acrylic-based leveling agent is 0.01 to 30, more preferably 0.05 to 10, in terms of the weight ratio of the silicon-based or fluorine-based leveling agent / acrylic-based leveling agent. is there. Even if the amount of either leveling agent is increased, the balance of action is lost and uneven film thickness occurs.
  • polymerizable liquid crystal compound examples include a polymerizable liquid crystal compound exhibiting positive wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility, and only one of the polymerizable liquid crystal compounds can be used. However, both types of polymerizable liquid crystal compounds can be mixed and used.
  • a vertically oriented liquid crystal cured film when the vertically oriented liquid crystal cured film is applied to a display device, it is polymerizable that exhibits inverse wavelength dispersibility from the viewpoint of having a large effect of improving the oblique reflection hue at the time of black display. It preferably contains a liquid crystal compound.
  • a polymerizable liquid crystal when used for a horizontally oriented liquid crystal cured film, when the horizontally oriented liquid crystal cured film is applied to a display device, a polymerizable liquid crystal exhibiting reverse wavelength dispersibility from the viewpoint of improving the frontal reflection hue at the time of black display. It preferably contains a compound.
  • the polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility is preferably a compound having the following characteristics (A) to (D).
  • A A compound capable of forming a nematic phase or a smectic phase.
  • B The polymerizable liquid crystal compound has ⁇ electrons in the long axis direction (a).
  • C It has ⁇ electrons in the direction [intersection direction (b)] that intersects the major axis direction (a).
  • D A polymerizable liquid crystal compound defined by the following formula (i), where the total number of ⁇ electrons existing in the major axis direction (a) is N ( ⁇ a) and the total molecular weight existing in the major axis direction is N (Aa).
  • the polymerizable liquid crystal compound having ⁇ electrons on the major axis and in the intersecting direction with respect to the major axis has, for example, a T-shaped structure.
  • the major axis direction (a) and the number of ⁇ electrons N are defined as follows.
  • the major axis direction (a) is, for example, the rod-shaped major axis direction of a compound having a rod-like structure.
  • the number of ⁇ electrons N ( ⁇ a) existing in the long axis direction (a) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the number of ⁇ electrons N ( ⁇ a) existing in the major axis direction (a) is the total number of ⁇ electrons on the major axis and ⁇ electrons conjugated thereto, for example, existing in the major axis direction (a).
  • the polymerizable liquid crystal compound satisfying the above has a mesogen structure in the major axis direction.
  • the liquid crystal phase (nematic phase, smectic phase) is expressed by this mesogen structure.
  • the polymerizable liquid crystal compound satisfying the above (A) to (D) can be applied on a substrate or an alignment film and heated to a phase transition temperature or higher to form a nematic phase or a smectic phase.
  • the polymerizable liquid crystal compounds are usually oriented so that the major axis directions are parallel to each other, and this major axis direction is the orientation direction of the nematic phase. It becomes.
  • a polymer film composed of a polymer oriented in the long axis direction (a) can be formed. ..
  • This polymer film absorbs ultraviolet rays by ⁇ electrons in the long axis direction (a) and ⁇ electrons in the crossing direction (b).
  • the absorption maximum wavelength of ultraviolet rays absorbed by ⁇ electrons in the crossing direction (b) is defined as ⁇ bmax.
  • ⁇ bmax is usually 300 nm to 400 nm.
  • the density of ⁇ electrons satisfies the above equation (iii), and since the ⁇ electron density in the crossing direction (b) is larger than the ⁇ electron density in the major axis direction (a), the oscillating surface in the crossing direction (b).
  • the absorption of linearly polarized ultraviolet rays (wavelength is ⁇ bmax) having a vibration plane in the long axis direction (a) is larger than the absorption of linearly polarized ultraviolet rays (wavelength is ⁇ bmax) having a vibration plane.
  • the ratio (the ratio of the absorbance in the crossing direction (b) of the linearly polarized ultraviolet rays / the absorbance in the major axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, usually 30 or less, for example, 10 or less. Is.
  • the polymerizable liquid crystal compound having the above characteristics often exhibits reverse wavelength dispersibility.
  • a compound represented by the following formula (X) can be mentioned.
  • the polymerizable liquid crystal compound represented by the following formula (X) may be referred to as a polymerizable liquid crystal compound having a T-shaped structure.
  • Ar represents a divalent group having an aromatic group which may have a substituent.
  • the aromatic group referred to here refers to a ring structure having [4n + 2] ⁇ electrons according to Hückel's law, and is exemplified by (Ar-1) to (Ar-23) described later, for example.
  • Such Ar groups may have two or more such Ar groups via a divalent linking group.
  • n represents an integer.
  • the aromatic group contains at least one or more of a nitrogen atom, an oxygen atom and a sulfur atom.
  • the divalent group Ar may contain one aromatic group or two or more aromatic groups. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When two or more aromatic groups are contained in the divalent group Ar, the two or more aromatic groups are single-bonded to each other or bonded to each other by a divalent bonding group such as -CO-O- or -O-. You may be.
  • G 1 and G 2 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, respectively.
  • the hydrogen atom contained in the divalent aromatic group or the 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, and carbon.
  • the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an alkoxy group, a cyano group or a nitro group of the number 1 to 4, and the carbon atom constitutes an oxygen atom or a sulfur atom. Alternatively, it may be substituted with a nitrogen atom.
  • L 1 , L 2 , B 1 and B 2 are independently single-bonded or divalent linking groups, respectively.
  • E 1 and E 2 each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ⁇ k + l.
  • B 1 and B 2 G 1 and G 2 may be the same as or different from each other.
  • Each of E 1 and E 2 independently represents an alkanediyl group having 1 to 17 carbon atoms, and an alkanediyl group having 4 to 12 carbon atoms is more preferable.
  • P 1 and P 2 independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • G 1 and G 2 are each independently substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, preferably a 1,4-phenylenediyl group.
  • a 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group.
  • at least one of a plurality of G 1 and G 2 present is preferably a divalent alicyclic hydrocarbon group, and at least one of G 1 and G 2 bonded to L 1 or L 2 is present. More preferably, it is a divalent alicyclic hydrocarbon group.
  • L 1 and L 2 are independent of each other, preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a1 OR a2- , -R a3 COOR a4- , -R a5.
  • R a1 to R a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms
  • R c and R d represent an alkyl group or a hydrogen atom having 1 to 4 carbon atoms.
  • L 1 and L 2 are each independently more preferably a single bond, -OR a2-1 -, - CH 2 -, - CH 2 CH 2 -, - COOR a4-1 -, or OCOR a6-1 - a ..
  • R a2-1 , R a4-1 , and R a6-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2- .
  • L 1 and L 2 are independent, more preferably single bonds, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- , or OCO-, respectively.
  • B 1 and B 2 are independent of each other, preferably single bond, alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R a9 OR a10- , -R a11 COOR a12- , -R a13.
  • OCOR a14- or R a15 OC OOR a16- .
  • R a9 to R a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms.
  • B 1 and B 2 are independently, more preferably single-bonded, -OR a10-1- , -CH 2- , -CH 2 CH 2- , -COOR a12-1- , or OCOR a14-1-. ..
  • R a10-1 , R a12-1 , and R a14-1 independently represent either single bond, -CH 2- , or -CH 2 CH 2- .
  • B 1 and B 2 are independent, more preferably single-bonded, -O-, -CH 2 CH 2- , -COO-, -COOCH 2 CH 2- , -OCO-, or OCOCH 2 CH 2-. ..
  • the polymerizable group represented by P 1 or P 2 includes an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxylanyl group. , And an oxetanyl group and the like.
  • an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxylanyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.
  • Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring and a naphthalene ring are preferable.
  • aromatic heterocycle examples include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrrolin ring, an imidazole ring, and a pyrazole ring.
  • a thiazole ring it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole group.
  • Ar contains a nitrogen atom, the nitrogen atom preferably has ⁇ electrons.
  • the total number N ⁇ of ⁇ electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and particularly. It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.
  • Examples of the aromatic group represented by Ar include the following groups.
  • Z 0 , Z 1 and Z 2 are independently hydrogen atoms, halogen atoms, and alkyl having 1 to 12 carbon atoms.
  • Z 0 , Z 1 and Z 2 may contain a
  • Q 1 and Q 2 each independently, -CR 2 'R 3' - , - S -, - NH -, - NR 2 '-, - CO- or O- to represent, R 2' and R 3 ' Independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • J 1 and J 2 independently represent a carbon atom or a nitrogen atom.
  • Y 1 , Y 2 and Y 3 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.
  • W 1 and W 2 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
  • Examples of the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group, and a phenyl group.
  • a naphthyl group is preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic group has 4 to 20 carbon atoms containing at least one heteroatom such as a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group or a benzothiazolyl group, an oxygen atom and a sulfur atom.
  • a nitrogen atom such as a frill group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group or a benzothiazolyl group, an oxygen atom and a sulfur atom.
  • a fryl group, a thienyl group, a pyridinyl group, a thiazolyl group and a benzothiazolyl group are preferable.
  • Y 1 , Y 2 and Y 3 may be independently substituted polycyclic aromatic hydrocarbon groups or polycyclic aromatic heterocyclic groups, respectively.
  • the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
  • the polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 12 carbon atoms, cyano groups, nitro groups, and alkoxy groups having 1 to 12 carbon atoms, respectively.
  • 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group
  • Z 1 and Z 2 are further preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.
  • Z 0 , Z 1 and Z 2 may contain a polymerizable group.
  • Q 1 and Q 2 -NH -, - S -, - NR 2 '-, - O- are preferable, R 2' is preferably a hydrogen atom. Of these, -S-, -O-, and -NH- are particularly preferable.
  • the formulas (Ar-1) to (Ar-23) are preferable from the viewpoint of molecular stability.
  • Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is attached and Z 0 .
  • the aromatic heterocyclic group include those described above as the aromatic heterocycle that Ar may have.
  • a pyrrole ring, an imidazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and an indol examples thereof include a ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring.
  • This aromatic heterocyclic group may have a substituent.
  • Y 1 may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted as described above, together with the nitrogen atom to which the Y 1 is bonded and Z 0 .
  • a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.
  • polymerizable liquid crystal compound (Y) a compound containing a group represented by the following formula (Y) (hereinafter, also referred to as “polymerizable liquid crystal compound (Y)”) is used. May be good.
  • the polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersibility.
  • the polymerizable liquid crystal compound may be used alone or in combination of two or more.
  • P11 represents a polymerizable group.
  • A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
  • the hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro. It may be substituted with a group, and the hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
  • B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 16- , -NR 16- CO-, -CO-,- Represents CS- or single bond.
  • R 16 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • E11 represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted. May be substituted with a halogen atom. Further, -CH 2- constituting the alkanediyl group may be replaced with -O- or -CO-. ]
  • the carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably in the range of 5 or 6. preferable.
  • A11 a cyclohexane-1,4-diyl group and a 1,4-phenylene group are preferable.
  • a linear alkanediyl group having 1 to 12 carbon atoms is preferable.
  • -CH 2- constituting the alkanediyl group may be replaced with -O-.
  • B11 -O-, -S-, -CO-O-, and -O-CO- are preferable, and -CO-O- is more preferable.
  • the polymerizable group represented by P11 a radically polymerizable group or a cationically polymerizable group is preferable in that it has high polymerization reactivity, particularly photopolymerization reactivity, and it is easy to handle and the liquid crystal compound itself is easy to produce. Therefore, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15). [In formulas (P-11) to (P-15), R 17 to R 21 each independently represent an alkyl group or a hydrogen atom having 1 to 6 carbon atoms. ]
  • P11 is preferably a group represented by the formulas (P-14) to (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group. It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a metaacryloyloxy group.
  • Examples of the polymerizable liquid crystal compound (Y) include compounds represented by the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V) or the formula (VI).
  • P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 I) P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11
  • II P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12
  • III P11-B11-E11-B12-A11-B13-A12-B14-A13-F11
  • P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 V) P11-B11-E11-B12-
  • F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, and a sulfo group.
  • (-SO 3 H) carboxyl group, an alkoxycarbonyl group or a halogen atom having 1 to 10 carbon atoms, -CH 2 constituting the alkyl group and alkoxy group - is also have I replace the -O- Good.
  • polymerizable liquid crystal compound (Y) "3.8.6 network (completely crosslinked type)" of the liquid crystal handbook (edited by the liquid crystal handbook editorial committee, published by Maruzen Co., Ltd. on October 30, 2000).
  • polymerizable liquid crystal compound (Y) examples include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to formulas (III-1) to. (III-26), formulas (IV-1) to formulas (IV-26), formulas (V-1) to formulas (V-2) and formulas (VI-1) to formulas (VI-6). Examples include compounds. In the following formula, k1 and k2 independently represent integers of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or availability.
  • a polymerizable liquid crystal compound exhibiting smectic liquid crystal property in that a horizontally oriented liquid crystal cured film or a vertically oriented liquid crystal cured film having a high degree of orientation order can be formed.
  • the polymerizable liquid crystal compound has a higher smectic phase from the viewpoint of achieving a higher degree of orientation order. (Higher-order smectic liquid crystal state) is more preferable.
  • the higher-order smectic phase includes smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase and smectic L phase.
  • the liquid crystal property may be a thermotropic liquid crystal or a liotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible.
  • the polymerizable liquid crystal compound exhibiting smectic liquid crystal property may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.
  • the polymerizable liquid crystal compound exhibiting smectic liquid crystal property is a liquid crystal compound having at least one polymerizable group, and may be a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of the liquid crystal cured film.
  • the polymerizable group include (meth) acryloyloxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, oxylanyl group, oxetanyl group and the like. It is preferable to contain a (meth) acryloyloxy group because it is easy to use, the heat resistance of the cured liquid crystal film is easily improved, and the adhesion between the cured liquid crystal film and the base material is easily adjusted.
  • Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystal property include a compound represented by the following formula (Z) (hereinafter, may be referred to as “polymerizable liquid crystal compound (Z)”).
  • Z polymerizable liquid crystal compound
  • X 1z and X 2z independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, where the divalent aromatic group or 2
  • the hydrogen atom contained in the valent 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, a cyano group or a nitro group.
  • X 1z and X 2z are 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
  • Y 1z is a single bond or divalent linking group.
  • nz is 1 to 3, and when nz is 2 or more, a plurality of X1z may be the same as each other or may be different from each other.
  • X 2z may be the same as or different from any or all of the plurality of X 1z . Further, when nz is 2 or more, a plurality of Y 1z may be the same as each other or may be different from each other. From the viewpoint of liquid crystallinity, nz is preferably 2 or more.
  • U 1z represents a hydrogen atom or a (meth) acryloyloxy group.
  • U 2z represents a polymerizable group.
  • W 1z and W 2z are single-bonded or divalent linking groups independently of each other.
  • V 1z and V 2z represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent independently of each other, and -CH 2- constituting the alkanediyl group is -O-, It may be replaced with -CO-, -S- or NH-. ]
  • X 1z and X 2z are independent of each other and preferably have a 1,4-phenylene group which may have a substituent or a substituent. It is a good cyclohexane-1,4-diyl group, and at least one of X 1z and X 2z has a 1,4-phenylene group which may have a substituent, or a substituent. It is also a good cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group.
  • the substituents arbitrarily contained in the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent include a methyl group and an ethyl. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group and a butyl group, a cyano group and a halogen atom such as a chlorine atom and a fluorine atom. It is preferably unsubstituted.
  • the polymerizable liquid crystal compound (Z) has the formula (Z1): in the formula (Z). - (X 1z -Y 1z -) nz -X 2z - (Z1) [In the formula, X 1z , Y 1z , X 2z and nz have the same meanings as described above. ] Part indicated by [hereinafter, referred to as a partial structure (Z1). ] Has an asymmetrical structure, which is preferable in that smectic liquid crystallinity is easily exhibited.
  • the partial structure (Z1) is asymmetrical structure polymerizable liquid crystal compound (Z), for example, nz is 1, and one X 1z and X 2z are different structures from each other polymerizable liquid crystal compound (Z) is Can be mentioned. Further, nz is 2, a two Y 1z compounds have the same structure each other, the two X 1z is same structure, one X 2z is different structure from these two X 1z the polymerizable liquid crystal compound (Z), X 1z that binds to W 1z of the two X 1z is, the other of X 1z and X 2z are different structures, the other of X 1z and X 2z mutually the same structure Also mentioned is the polymerizable liquid crystal compound (Z).
  • nz is 3 and three Y 1z have the same structure as each other, and any one of the three X 1z and one X 2z has a structure different from all the other three.
  • the sex liquid crystal compound (Z) can be mentioned.
  • R az and R bz independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Y 1z is, -CH 2 CH 2 -, - more preferably COO- or a single bond, when a plurality of Y 1z is present, Y 1z that binds X 2z is, -CH 2 CH 2 - or CH It is more preferably 2 O ⁇ .
  • X 1z and X 2z all have the same structure, it is preferable that two or more Y 1z having different bonding methods exist.
  • the structure is asymmetrical, so that smectic liquid crystallinity tends to be easily exhibited.
  • U 2z is the above-mentioned polymerizable group.
  • U 1z is a hydrogen atom or a polymerizable group.
  • the polymerizable group is a (meth) acryloyloxy group because it is easy to manufacture, the heat resistance of the cured liquid crystal film is easily improved, and the adhesion between the cured liquid crystal film and the substrate is easy to adjust. preferable.
  • the polymerizable group may be in a polymerized state or a non-polymerized state, but is preferably in a non-polymerized state.
  • the alkanediyl groups represented by V 1z and V 2z include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-. 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decan-1,10-diyl group, tetradecane-1,14-diyl group Examples include groups and icosan-1,20-diyl groups.
  • V 1z and V 2z are preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.
  • alkanediyl group examples include a cyano group and a halogen atom.
  • the alkanediyl group is preferably unsubstituted and is an unsubstituted linear alkanediyl group. Is more preferable.
  • W 1z and W 2z are preferably single-bonded, -O-, -S-, -COO- or OCOO- independently of each other, and more preferably single-bonded or O-.
  • the polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure in its molecular structure, and specifically, is a polymerizable liquid crystal compound having the following partial structures (Aa) to (Ai). More preferably. It is more preferable to have the partial structure of (A), (Ab) or (Ac) from the viewpoint of easily exhibiting higher-order smectic liquid crystal property. In the following (Aa) to (Ai), * represents a bond (single bond).
  • polymerizable liquid crystal compound (Z) examples include compounds represented by formulas (A-1) to (A-25).
  • the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group
  • the cyclohexane-1,4-diyl group is preferably a trans form.
  • the polymerizable liquid crystal compound (Z) one type may be used alone, or two or more types may be used in combination.
  • the polymerizable liquid crystal compound (Z) is described in, for example, Lub and the like, Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.
  • the polymerizable liquid crystal compound forming the liquid crystal cured film is preferably a polymerizable liquid crystal compound having a maximum absorption wavelength between the wavelengths of 300 and 400 nm.
  • the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage.
  • the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if ultraviolet light is exposed during storage, the reaction active species are generated from the photopolymerization initiator and the polymerizable liquid crystal compound by the reactive liquid compound is generated. The progress of polymerization reaction and gelation can be effectively suppressed.
  • the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer.
  • the solvent is a solvent capable of dissolving a polymerizable liquid crystal compound, and examples thereof include tetrahydrofuran and chloroform.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 70 to 99.5 parts by mass, based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass.
  • the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.
  • the solid content of the polymerizable liquid crystal composition means all the components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents.
  • the polymerizable liquid crystal composition used for forming the liquid crystal cured film contains a polymerizable liquid crystal compound, a silicon-based or fluorine-based leveling agent, and an acrylic-based leveling agent. Further, it may contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, a photosensitizer, and a dichroic dye. As each of these components, only one kind may be used, or two or more kinds may be used in combination.
  • the polymerizable liquid crystal composition can be obtained by stirring the above components at a predetermined temperature or the like.
  • the polymerizable liquid crystal composition for forming a liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, it is preferable to contain a solvent.
  • a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable.
  • the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and alcohols such as propylene glycol monomethyl ether.
  • Solvents Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone.
  • Ketone solvent aliphatic hydrocarbon solvent such as pentane, hexane and heptane; alicyclic hydrocarbon solvent such as ethylcyclohexane; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; tetrahydrofuran and dimethoxyethane and the like Ether solvent; chlorine-containing solvent such as chloroform and chlorobenzene; amide-based solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. Be done.
  • solvents can be used alone or in combination of two or more.
  • alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.
  • the content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass.
  • the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, so that the thickness of the film becomes substantially uniform, and unevenness tends to be less likely to occur.
  • the solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.
  • the polymerization initiator is a compound that can generate a reactive species by the contribution of heat or light and initiate a polymerization reaction such as a polymerizable liquid crystal compound.
  • the reactive active species include active species such as radicals or cations or anions.
  • a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.
  • photopolymerization initiator examples include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, oxime compounds, triazine compounds, iodonium salts and sulfonium salts.
  • Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, BASF Japan Co., Ltd.) (Made), Sakeol BZ, Sakeol Z, Sakeol BEE (manufactured by Seiko Kagaku Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), ADEKA PUTMER SP- 152, ADEKA OPTMER SP-170, ADEKA OPTMER N-1717, ADEKA PTMER N-1919, ADEKA ARCLUDS NCI-831
  • the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and above all, the ⁇ -acetophenone type.
  • a polymerization initiator and an oxime-based photopolymerization initiator are preferable.
  • Examples of the ⁇ -acetophenone-based polymerization initiator include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl.
  • Examples thereof include butane-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butane-1-one, and more preferably 2-methyl-2-morpholino-.
  • Examples thereof include 1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one.
  • Examples of commercially available ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Kagaku Co., Ltd.).
  • Oxime-based photopolymerization initiators generate radicals such as phenyl radicals and methyl radicals when irradiated with light.
  • the polymerization of the polymerizable liquid crystal compound proceeds preferably by this radical, and among them, the oxime-based photopolymerization initiator that generates a methyl radical is preferable in that the polymerization reaction initiation efficiency is high. Further, from the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet rays having a wavelength of 350 nm or more.
  • Oxime-based photopolymerization initiators include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.
  • oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), ADEKA PUTMER N-1919, and ADEKA ARCULDS NCI-831. (The above is manufactured by ADEKA CORPORATION) and the like.
  • the content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Is. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation of the polymerizable liquid crystal compound is not easily disturbed.
  • the antioxidant may be a primary antioxidant selected from phenol-based antioxidants, amine-based antioxidants, quinone-based antioxidants, and nitroso-based antioxidants, as well as phosphorus-based antioxidants and sulfur. It may be a secondary antioxidant selected from the system antioxidants.
  • the content of the antioxidant is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass.
  • Antioxidants can be used alone or in combination of two or more.
  • the photopolymerization initiator can be made highly sensitive.
  • the photosensitizer include xanthones such as xanthones and thioxanthones; anthracenes having substituents such as anthracene and alkyl ethers; phenothiazines; rubrenes.
  • the photosensitizer can be used alone or in combination of two or more.
  • the content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.
  • the polymerizable liquid crystal composition of the present invention may contain a dichroic dye.
  • the dichroic dye means a dye having a property that the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different.
  • the dichroic dye that can be used in the present invention is not particularly limited as long as it has the above-mentioned properties, and may be a dye or a pigment. Further, two or more kinds of dyes or pigments may be used in combination, or dyes and pigments may be used in combination.
  • the dichroic dye When such a dichroic dye is contained in the horizontally oriented liquid crystal cured film or the vertically oriented liquid crystal cured film, the dichroic dye can be oriented together with the polymerizable liquid crystal compound and exhibit absorption anisotropy.
  • the degree of orientation order is high as represented by the smectic liquid crystal phase, the absorption anisotropy derived from the dichroic dye contained tends to be remarkably improved.
  • the dichroic dye preferably has a maximum absorption wavelength ( ⁇ MAX ) in the range of 300 to 700 nm.
  • dichroic pigments include acridine pigments, oxazine pigments, cyanine pigments, naphthalene pigments, azo pigments and anthraquinone pigments.
  • the azo dye examples include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye, and the like, and a bisazo dye and a trisazo dye are preferable, and for example, a compound represented by the formula (I) (hereinafter, "compound").
  • compound a compound represented by the formula (I) (hereinafter, "compound”).
  • compound a compound represented by the formula (I) (hereinafter, "compound”).
  • compound a compound represented by the formula (I) (hereinafter, "compound”).
  • compound a bisazo dye and a trisazo dye
  • K 1 (-N N-K 2 )
  • p -N N-K 3 (I)
  • K 1 and K 3 may independently have a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent. Represents a good mono
  • K 2 is a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocycle which may have a substituent.
  • p represents an integer of 1 to 4.
  • the plurality of K 2s may be the same or different from each other.
  • Examples of the monovalent heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole, and benzoxazole.
  • Examples of the divalent heterocyclic group include a group obtained by removing two hydrogen atoms from the heterocyclic compound.
  • Phenyl group in K 1 and K 3, a naphthyl group and a monovalent heterocyclic group, and p- phenylene group in K 2, as a naphthalene-1,4-diyl group and a divalent substituent heterocyclic group has optionally Is an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; an alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; Nitro group; Halogen atom; Substituent or unsubstituted amino group such as amino group, diethylamino group, pyrrolidino group (Substituent amino group is an amino group having one or two alkyl groups having 1 to 6 carbon atoms, or two It means an amino group in which substituted alkyl groups are bonded to each other to form an alcandi
  • B 1 to B 30 are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, and a substituted or unsubstituted amino group (substituted amino group). And the definition of an unsubstituted amino group is as described above), representing a chlorine atom or a trifluoromethyl group.
  • n1 to n4 represent integers of 0 to 3 independently of each other.
  • n1 is 2 or more, a plurality of B 2 may be the same or different from each other, If n2 is 2 or more, plural B 6 may be the same or different from each other, If n3 is 2 or more, plural B 9 may be the same or different from each other, When n4 is 2 or more, the plurality of B 14s may be the same or different from each other. ]
  • 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.
  • 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.
  • 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.
  • the alkyl group having 1 to 6 carbon atoms of Rx includes a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. And a hexyl group and the like, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xsilyl group and a naphthyl group.
  • a compound represented by the formula (I-12) and a compound represented by the formula (I-13) are preferable.
  • D 1 and D 2 represent groups represented by any of the formulas (I-12a) to (I-12d) independently of each other.
  • n5 represents an integer of 1 to 3.
  • D 3 and D 4 represent groups represented by any of the formulas (I-13a) to (1-13h) independently of each other.
  • n6 represents an integer of 1 to 3.
  • the vertically oriented liquid crystal cured film contains at least one azo dye as the dichroic dye from the viewpoint of orientation.
  • the weight average molecular weight of the dichroic dye is usually 300 to 2000, preferably 400 to 1000.
  • the content of the dichroic dye in the polymerizable liquid crystal composition forming the liquid crystal cured film can be appropriately determined depending on the type of the dichroic dye used and the like, but it is based on 100 parts by mass of the polymerizable liquid crystal compound. It is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass. When the content of the dichroic dye is within the above range, the orientation of the polymerizable liquid crystal compound is not easily disturbed, and a liquid crystal cured film having a high degree of orientation order can be obtained.
  • the vertically oriented liquid crystal curing film is a liquid crystal curing in which the polymerizable liquid crystal composition is applied onto a base material or an alignment film and the polymerizable liquid crystal compound is cured in a state of being oriented perpendicular to the base material or the alignment film. It is a membrane.
  • RthC (450) / RthC (550) ⁇ 1.0 ... (S4) [In the formula (S4), RthC (450) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 450 nm, and RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm)]
  • the vertically oriented liquid crystal cured film When the horizontally oriented liquid crystal cured film satisfies the formula (S4), the vertically oriented liquid crystal cured film has a so-called inverse value in which the phase difference value in the thickness direction at a short wavelength is smaller than the phase difference value in the thickness direction at a long wavelength. Shows wavelength dispersibility.
  • RthC (450) / RthC (550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.95 or less, more preferably 0.92 or less.
  • the retardation value in the thickness direction can be adjusted by the thickness dC of the vertically oriented liquid crystal cured film.
  • the film thickness dC may be adjusted.
  • the vertically oriented liquid crystal cured film satisfies the following formula (S3). -150 nm ⁇ RthC (550) ⁇ -30 nm ... (S3) [In the formula (S3), RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm]
  • RthC (550) indicates the phase difference value in the thickness direction of the liquid crystal cured film at a wavelength of 550 nm]
  • a more preferable range of the thickness direction retardation RthC (550) of the vertically oriented liquid crystal cured film is ⁇ 110 nm ⁇ RthC (550) ⁇ ⁇ 45 nm.
  • the vertically oriented liquid crystal cured film is, for example, A step of forming a coating film of a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film, A step of drying the coating film to form a dry coating film, and It can be produced by a method including a step of irradiating a dry coating film with active energy rays to form a vertically oriented liquid crystal cured film.
  • the coating film of the polymerizable liquid crystal composition is formed, for example, by applying the polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film onto a substrate, an alignment film, or a horizontally oriented liquid crystal cured film described later. Can be done.
  • the base material include a glass base material and a film base material, and a resin film base material is preferable from the viewpoint of processability.
  • Resins constituting the film substrate include, for example, polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohols; polyethylene terephthalates; polymethacrylic acid esters; polyacrylic acid esters; triacetylcellulose, Examples include diacetyl cellulose, and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; polyphenylene sulfide and plastics such as polyphenylene oxide.
  • Such a resin can be formed into a film by a known means such as a solvent casting method and a melt extrusion method to form a base material.
  • the surface of the base material may have a protective layer formed of an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like. Surface treatment such as plasma treatment may be applied.
  • a commercially available product may be used as the base material.
  • Commercially available cellulose ester base materials include, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M”, “KC8UY”, and “KC4UY”. Examples include the cellulose ester base material of.
  • Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as “Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)".
  • Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui such as "Apel” (registered trademark) Cyclic olefin resin manufactured by Chemical Co., Ltd. can be mentioned.
  • a commercially available cyclic olefin resin base material can also be used.
  • As commercially available cyclic olefin resin base materials cyclic olefin resin base materials manufactured by Sekisui Chemical Industry Co., Ltd.
  • the thickness of the base material is usually 5 to 300 ⁇ m, preferably 10 to 150 ⁇ m.
  • Examples of the method for applying the polymerizable liquid crystal composition to a substrate or the like include a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method and other coating methods, and a flexography method and other printing methods. And the like.
  • a dry coating film is formed by removing the solvent by drying or the like.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • the heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material of the base material or the like forming the coating film, but the liquid crystal is used to make a phase transition of the polymerizable liquid crystal compound to the liquid crystal layer state.
  • the temperature is equal to or higher than the phase transition temperature.
  • the liquid crystal phase transition temperature (smetic phase transition) of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition can be heated to a temperature of about (temperature or nematic phase transition temperature) or higher.
  • the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like.
  • the phase transition temperature is a polymerization in which all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed at the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured by using a mixture of sex liquid crystal compounds in the same manner as when one kind of polymerizable liquid crystal compound is used. It is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.
  • the heating time can be appropriately determined depending on the heating temperature, the type of the polymerizable liquid crystal compound used, the type of the solvent, its boiling point and its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 0.5 minutes. 5 minutes.
  • the solvent may be removed from the coating film at the same time as heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, or separately, but it is preferable to remove the solvent at the same time from the viewpoint of improving productivity.
  • the solvent in the coating film Before heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, the solvent in the coating film is appropriately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize.
  • a pre-drying step may be provided for removal.
  • drying method in the pre-drying step examples include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the drying temperature (heating temperature) in the drying step is the type of polymerizable liquid crystal compound used and the solvent. It can be appropriately determined according to the type of the above, its boiling point, its amount and the like.
  • a vertically oriented liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertically oriented state of the polymerizable liquid crystal compound.
  • the polymerization method include a thermal polymerization method and a photopolymerization method, but the photopolymerization method is preferable from the viewpoint of easily controlling the polymerization reaction.
  • the light irradiated to the dry coating film includes the type of photopolymerization initiator contained in the dry coating film and the type of polymerizable liquid crystal compound (particularly, the type of polymerizable group contained in the polymerizable liquid crystal compound). And appropriately selected according to the amount.
  • ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use a photopolymerization apparatus widely used in the art, so that photopolymerization can be performed by ultraviolet light. It is preferable to select the type of the polymerizable liquid crystal compound or the photopolymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means.
  • a vertically oriented liquid crystal cured film can be appropriately formed even if a base material having a relatively low heat resistance is used. It is also possible to promote the polymerization reaction by raising the polymerization temperature within a range in which defects due to heat during light irradiation (deformation due to heat of the base material, etc.) do not occur.
  • a patterned cured film can also be obtained by masking or developing during photopolymerization.
  • Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range.
  • Examples thereof include an LED light source that emits 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.
  • the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
  • the ultraviolet irradiation intensity is preferably the intensity in the wavelength region effective for activating the photopolymerization initiator.
  • the time for irradiating light 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 seconds to 1 minute. is there.
  • the integrated light intensity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , and more preferably 100 to 1,000 mJ / cm. It is 2 .
  • the thickness of the vertically oriented liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 3 ⁇ m, more preferably 0.2 to 2 ⁇ m.
  • the vertically oriented liquid crystal cured film has a positive wavelength dispersibility, 0.2 to 1 ⁇ m is more preferable, and when the vertically oriented liquid crystal cured film has a reverse wavelength dispersibility, 0.4 to 2 ⁇ m is further preferable.
  • the vertically oriented liquid crystal cured film has a reverse wavelength dispersibility, the light absorption in the diagonal direction increases for the same dye concentration as compared with the case where the vertically oriented liquid crystal cured film has a positive wavelength dispersibility. preferable.
  • the vertically oriented liquid crystal cured film may contain a dichroic dye.
  • the higher the alignment order of the liquid crystal the better the absorption selectivity derived from the dichroic dye.
  • the above-mentioned smectic phase particularly the higher-order smectic phase It is preferable to use the polymerizable liquid crystal compound shown, and it is preferable to polymerize while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase, to form a vertically oriented liquid crystal cured film containing a dichroic dye.
  • the x-axis means an arbitrary direction in the plane of the vertically oriented liquid crystal cured film
  • the y-axis means the direction perpendicular to the x-axis in the film surface
  • the z-axis means the thickness direction of the vertically oriented liquid crystal cured film.
  • the absorbance in the present specification indicates the absorbance when measured in a state excluding the influence of interfacial reflection at the time of measurement.
  • the absorbance at a wavelength where absorption of the compound can be ignored at a long wavelength such as 800 nm is set to 0, and in that state, the wavelength of the region where absorption of the compound exists is set to 0.
  • Methods such as measuring the absorbance can be mentioned.
  • the above AxC can be measured by incident linearly polarized light vibrating in the x-axis direction from the z-axis direction toward the film surface of the liquid crystal cured film.
  • the above formula (11) means that the absorbance in the front direction in the plane of the vertically oriented liquid crystal cured film is 0.001 or more and 0.3 or less, and the smaller the value of AxC, the more the plane of the obtained liquid crystal cured film. It can be said that the dichroic dyes are accurately oriented in the vertical direction.
  • the AxC value exceeds 0.3 the vertically oriented liquid crystal cured film is strongly colored in the front direction, so that the front hue tends to be inferior when applied to a display device in combination with a horizontally oriented retardation film. Therefore, the value of AxC is preferably 0.1 or less, more preferably 0.05 or less.
  • the lower limit of the value of AxC is usually 0.001 or more, preferably 0.003 or more, and more preferably 0.005 or more.
  • the rotation of the film is performed by rotating the film in the state where Ax is measured by 60 ° in the incident direction of linear polarization with the y-axis as the rotation axis.
  • AxC and AyC are usually approximately equal values.
  • AxC and AyC are different, they have dichroism in the plane, and in this case, the front hue of the vertically oriented liquid crystal cured film tends to be heavily colored.
  • the vertical liquid crystal alignment film has excellent polarization performance (absorption anisotropy), whereby light from the front direction is effectively emitted. It can transmit light and effectively absorb light from an oblique direction.
  • the coating film of the polymerizable liquid crystal composition is formed on the alignment film.
  • the alignment film has an orientation-regulating force that orients the polymerizable liquid crystal compound in a desired direction.
  • an alignment film having an orientation regulating force for orienting a polymerizable liquid crystal compound in the horizontal direction may be referred to as a horizontal alignment film
  • an alignment film having an orientation restricting force for orienting a polymerizable liquid crystal compound in the vertical direction may be referred to as a vertical alignment film.
  • the orientation regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when the alignment film is formed of a photoalignable polymer, it is arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible to do.
  • the alignment film preferably has solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described later.
  • the alignment film include an alignment film containing an orientation polymer, a photoalignment film, a grub alignment film having an uneven pattern or a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like, and the accuracy of the orientation angle and A photoalignment film is preferable from the viewpoint of quality.
  • the oriented polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and poly. Examples thereof include oxazol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable.
  • the oriented polymer can be used alone or in combination of two or more.
  • the alignment film containing the orientation polymer is usually obtained by applying a composition in which the orientation polymer is dissolved in a solvent (hereinafter, may be referred to as "orientation polymer composition") to a substrate to remove the solvent, or. It is obtained by applying an oriented polymer composition to a substrate, removing a solvent, and rubbing (rubbing method).
  • the solvent include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition.
  • the concentration of the oriented polymer in the oriented polymer composition may be within the range in which the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, and is 0. .1 to 10% is more preferable.
  • a commercially available alignment film material may be used as it is as the orientation polymer composition.
  • Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).
  • Examples of the method of applying the oriented polymer composition to the base material include the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the base material.
  • Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • a rubbing treatment can be performed as needed to impart orientation regulating force to the alignment film (rubbing method).
  • a method of imparting orientation-regulating force by the rubbing method a rubbing cloth is wrapped around a rotating rubbing roll, and an orientation polymer composition is applied to the substrate and annealed to form the surface of the substrate. Examples thereof include a method of contacting a film of an oriented polymer. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed on the alignment film.
  • the photoalignment film is usually formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming a photoalignment film”) to a substrate, removing the solvent, and then polarizing the film. It is obtained by irradiating (preferably polarized UV).
  • composition for forming a photoalignment film preferably polarized UV.
  • the photoalignment film is also advantageous in that the direction of the orientation regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • a photoreactive group is a group that produces liquid crystal alignment ability when irradiated with light.
  • Specific examples thereof include groups involved in photoreactions that are the origin of liquid crystal orientation ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction generated by light irradiation. Of these, groups involved in the dimerization reaction or photocrosslinking reaction are preferable because they are excellent in orientation.
  • a photoreactive group involved in a photodimerization reaction is preferable, and a photoalignment film having a relatively small amount of polarized light required for photoalignment and excellent thermal stability and stability over time can be easily obtained.
  • a cinnamoyl group and a chalcone group are preferable.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group such that the terminal portion of the side chain of the polymer has a cinnamic acid structure is particularly preferable.
  • a photoalignment-inducing layer By applying the composition for forming a photoalignment film on a base material, a photoalignment-inducing layer can be formed on the base material.
  • the solvent contained in the composition include the same solvents as those exemplified above as the solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group. can do.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the target photoalignment film, but the composition for forming a photoalignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass with respect to the mass of.
  • the composition for forming a photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer as long as the characteristics of the photoalignment film are not significantly impaired.
  • Examples of the method of applying the composition for forming a photoalignment film to the base material include the same method as the method of applying the orientation polymer composition to the base material.
  • Examples of the method for removing the solvent from the applied composition for forming a photoalignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • the polarized light is transmitted from the base material side. It may be in the form of being irradiated. Further, it is particularly preferable that the polarized light 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. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the 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, and high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halides. Lamps are more preferred. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because they have a high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer.
  • a polarizing element a polarizing filter, a polarizing prism such as a Gran Thomson or a Granter, or a wire grid type polarizing element can be used.
  • the groove alignment film is a film having an uneven pattern or a plurality of grooves on the surface of the film.
  • the polymerizable liquid crystal compound is applied to a film having a plurality of linear grubs arranged at equal intervals, the liquid crystal molecules are oriented in the direction along the groove.
  • a method of forming a concavo-convex pattern by developing and rinsing after exposure through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, or a plate having a groove on the surface A method of forming a layer of UV-curable resin before curing on a shaped master, transferring the formed resin layer to a substrate and then curing, and a film of UV-curable resin before curing formed on the substrate. Examples thereof include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
  • Examples of the material exhibiting the orientation-regulating force for orienting the polymerizable liquid crystal compound in the direction perpendicular to the plane of the coating film include fluoropolymers such as perfluoroalkyl and silane compounds, and their condensation reactions, in addition to the above-mentioned orientation polymers. You may use the polysiloxane compound obtained by the above.
  • the constituent elements include Si element and C element from the viewpoint that the surface tension can be easily lowered and the adhesion to the layer adjacent to the alignment film can be easily improved.
  • the compound is preferable, and the silane compound can be preferably used.
  • the silane compound a nonionic silane compound described later, a silane-containing ionic compound as exemplified in the section of ionic compound, and the like can be used, and by using these silane compounds, the vertical orientation regulating force can be used. Can be enhanced.
  • These silane compounds may be used alone, in combination of two or more, or mixed with other materials.
  • silane compound is a nonionic silane compound
  • a silane compound having an alkyl group at the molecular terminal is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable from the viewpoint of easily increasing the vertical orientation restricting force. ..
  • the thickness of the alignment film is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and further preferably. Is in the range of 10 to 300 nm, particularly preferably 50 to 250 nm.
  • the coating film of the polymerizable liquid crystal composition does not require an alignment film and can be formed directly on the substrate.
  • the polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film usually contains an orientation accelerator.
  • the orientation accelerator means a material that promotes the liquid crystal orientation of the polymerizable liquid crystal compound in a desired direction. Examples of the orientation promoter that promotes the vertical orientation of the polymerizable liquid crystal compound include an ionic compound composed of non-metal atoms and a non-ionic silane compound.
  • the polymerizable liquid crystal composition forming the vertically oriented liquid crystal cured film preferably contains at least one of an ionic compound composed of non-metal atoms and a non-ionic silane compound, and an ionic compound composed of non-metal atoms and It is more preferable to contain both nonionic silane compounds.
  • the dry coating film formed from the vertically oriented liquid crystal cured film forming composition on the substrate contains an ionic compound composed of non-metal atoms
  • the dry coating film formed from the vertically oriented liquid crystal cured film forming composition on the substrate the dry coating film is formed.
  • the electrostatic interaction exerts a force to regulate the vertical orientation of the polymerizable liquid crystal compound, and the polymerizable liquid crystal compound tends to be oriented perpendicular to the surface of the substrate in the dry coating film.
  • the liquid crystal cured film can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.
  • Examples of ionic compounds composed of non-metal atoms include onium salts (more specifically, quaternary ammonium salts in which nitrogen atoms have a positive charge, tertiary sulfonium salts, and phosphorus atoms have a positive charge. Quaternary phosphonium salt, etc.).
  • onium salts more specifically, quaternary ammonium salts in which nitrogen atoms have a positive charge, tertiary sulfonium salts, and phosphorus atoms have a positive charge. Quaternary phosphonium salt, etc.).
  • a quaternary onium salt is preferable from the viewpoint of further improving the vertical orientation of the polymerizable liquid crystal compound, and a quaternary phosphonium salt or a quaternary from the viewpoint of improving availability and mass productivity.
  • Ammonium salts are more preferred.
  • the onium salt may have two or more quaternary onium salt moieties in the molecule,
  • the molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical orientation of the polymerizable liquid crystal compound while ensuring the coatability of the polymerizable composition.
  • the molecular weight of the ionic compound is more preferably 5000 or less, still more preferably 3000 or less.
  • Examples of the cation component of the ionic compound include an inorganic cation and an organic cation. Of these, organic cations are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur.
  • Examples of the organic cation include imidazolium cation, pyridinium cation, ammonium cation, sulfonium cation, phosphonium cation and the like.
  • Ionic compounds generally have a counter anion.
  • the anion component that becomes the counter ion of the cation component include an inorganic anion and an organic anion. Of these, organic anions are preferable because orientation defects of the polymerizable liquid crystal compound are unlikely to occur. It should be noted that the cation and the anion do not necessarily have to have a one-to-one correspondence.
  • anion component examples include the following. Chloride anion [Cl -], Bromide anion [Br -], Iodide anion [I -], Tetrachloroaluminate anion [AlCl 4 -], Hepta-chloro-di-aluminate anion [Al 2 Cl 7 -], Tetrafluoroborate anion [BF 4 -], Hexafluorophosphate anion [PF 6 -], Perchlorate anions [ClO 4 -], Nitrate anions [NO 3 -], Acetate anion [CH 3 COO -], Trifluoroacetate anion [CF 3 COO -], Fluorosulfonate anion [FSO 3 -], Methanesulfonate anion [CH 3 SO 3 -], Trifluoromethanesulfonate anion [CF 3 SO 3 -], p- toluenesulfonate anion [p-CH 3 C 6 H 4 SO 3
  • ionic compound can be appropriately selected from the combination of the above-mentioned cation component and anion component.
  • compound which is a combination of a cation component and an anion component include the following.
  • the ionic compound has a Si element and / or an F element in the molecular structure of the cation site.
  • the ionic compound is likely to segregate on the surface of the vertically oriented liquid crystal cured film.
  • the following ionic compounds (i) to (iii) are preferable as the ionic compounds in which all the constituent elements are non-metal elements.
  • a method for improving the vertical orientation of the polymerizable liquid crystal compound for example, a method of treating the surface of the substrate with a surfactant having an alkyl group having a long chain length to some extent is known (for example, "Liquid Crystal Handbook"). See Chapter 2 Liquid Crystal Orientation and Physical Properties (published by Maruzen Co., Ltd.).
  • the method of improving the vertical orientation of a liquid crystal compound by using such a surfactant can also be applied to an ionic compound. That is, the vertical orientation of the polymerizable liquid crystal compound can be effectively improved by treating the surface of the substrate with an ionic compound having an alkyl group having a long chain length to some extent.
  • the ionic compound satisfies the following formula (8). 5 ⁇ M ⁇ 16 (8)
  • M is represented by the following formula (9).
  • M (Among the substituents directly bonded to the positively charged atom, the number of covalent bonds from the positively charged atom to the end of the molecular chain of the substituent having the largest number of covalent bonds to the end of the molecular chain ) ⁇ (Number of atoms with a positive charge) (9)
  • the ionic compound satisfies the above (8), the vertical orientation of the polymerizable liquid crystal compound can be effectively improved.
  • the substituents having two or more positively charged atoms are counted from the positively charged atoms considered as the base point.
  • the number of covalent bonds to the closest atom having a positive charge is defined as "the number of covalent bonds from the atom having a positive charge to the end of the molecular chain" described in the definition of M above.
  • the number of covalent bonds to the positively charged atom via the ring structure, or to the end of the substituent bonded to the ring structure is defined as "the number of covalent bonds from an atom having a positive charge to the end of the molecular chain" described in the definition of M above.
  • the content thereof is usually 0.01 to 5% by mass with respect to the solid content of the polymerizable liquid crystal composition. It is preferably 0.05 to 4% by mass, more preferably 0.1 to 3% by mass.
  • the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.
  • the nonionic silane compound lowers the surface tension of the polymerizable liquid crystal composition, and the vertically oriented liquid crystal cured film is placed on the substrate.
  • the nonionic silane compound is present on the surface of the dry coating film on the opposite side to the base material, which enhances the vertical orientation restricting force for the polymerizable liquid crystal compound and is dry-coated.
  • the polymerizable liquid crystal compound tends to be oriented in the direction perpendicular to the surface of the substrate. As a result, the liquid crystal cured film can be formed while maintaining the vertically oriented state of the polymerizable liquid crystal compound.
  • the nonionic silane compound is a compound that is nonionic and contains a Si element.
  • Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic-inorganic silane compounds such as silicone oligomers, silces siloxane and alkoxysilanes (more specifically). , Silane coupling agent, etc.), silane-containing compound described in the section of leveling agent, and the like.
  • the nonionic silane compound may be a silicone monomer type or a silicone oligomer (polymer) type.
  • silicone oligomer is shown in the form of a (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Propyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Mercaptomethyl group-containing copolymers such as ethoxysilane copo
  • the silane coupling agent is selected from the group consisting of a vinyl group, an epoxy group, a styryl group, a methacryl group, an acrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, an isocyanate group, a carboxy group, and a hydroxy group at the end. It is a compound containing a Si element having a functional group such as at least one thereof and at least one alkoxysilyl group or silanol group.
  • the mechanical strength of the vertically oriented liquid crystal cured film can be improved, the surface of the vertically oriented liquid crystal cured film can be modified, and the vertically oriented liquid crystal cured film and an adjacent layer (for example, a base material) can be used. It is possible to impart a peculiar effect such as improvement of adhesion.
  • the silane coupling agent is a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). Further, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group.
  • the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical orientation of the polymerizable liquid crystal compound is more likely to be improved, and the vertical orientation promoting effect can be remarkably obtained.
  • the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group and a hydroxy group.
  • the polar group may appropriately have a substituent or a protecting group in order to control the reactivity of the silane coupling agent.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-.
  • silane coupling agents examples include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, and KBM-403. , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as -9103, KBM-573, KBM-575, KBM-9569, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007. Can be mentioned.
  • the content thereof is usually 0.01% by mass to 5% by mass with respect to the solid content of the polymerizable liquid crystal composition. It is preferably 0.05% by mass to 4% by mass, and further preferably 0.1% by mass to 3% by mass.
  • the content of the nonionic silane compound is within the above range, the vertical orientation of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.
  • the electrostatic interaction derived from the ionic compound and the surface tension lowering effect derived from the nonionic silane compound make it easier to promote the vertical orientation of the polymerizable liquid crystal compound.
  • the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is more accurately vertically oriented.
  • the horizontally oriented liquid crystal cured film in the present invention is a polymerized liquid crystal compound in which the above-mentioned polymerizable liquid crystal composition is coated on a base material or an oriented film, and the base sphere is in the plane of the oriented film. Shows a liquid crystal cured film cured in an oriented state.
  • the horizontally oriented liquid crystal cured film When the horizontally oriented liquid crystal cured film satisfies the formula (S2), the horizontally oriented liquid crystal cured film has a so-called inverse wavelength dispersion in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength. Show sex.
  • the ReA (450) / ReA (550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0, because the effect of improving the reflected hue in the front direction can be further enhanced. It is 95 or less, more preferably 0.92 or less.
  • the horizontally oriented liquid crystal cured film satisfies the following formula (S1). 100 nm ⁇ ReA (550) ⁇ 180 nm (S1) [In equation (S1), ReA ( ⁇ ) has the same meaning as above]
  • the in-plane phase difference ReA (550) of the horizontally oriented liquid crystal cured film is within the range of the formula (S1), the effect of improving the specular hue at the time of black display when applied to an organic EL display device (suppressing coloring). The effect of causing) becomes remarkable.
  • a more preferable range of the in-plane retardation value is 120 nm ⁇ ReA ⁇ 170 nm, and a more preferable range is 130 nm ⁇ ReA (550) ⁇ 150 nm.
  • polymerizable liquid crystal compounds can be used in the field of horizontally oriented liquid crystal cured film.
  • a polymerizable liquid crystal compound exhibiting so-called reverse wavelength dispersibility is preferable, and as such a polymerizable liquid crystal compound, for example, a polymerizable liquid crystal compound represented by the above formula (X) can be preferably used.
  • the polymerizable liquid crystal compound may be used alone or in combination of two or more.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used for forming the horizontally oriented liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. , It is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and further preferably 90 to 95 parts by mass.
  • the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.
  • the polymerizable liquid crystal composition used for forming the horizontally oriented liquid crystal cured film further contains additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound.
  • additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound.
  • these components include the same components as those exemplified above as components that can be used in the vertically oriented liquid crystal cured film, and each of these components may use only one type or a combination of two or more types. ..
  • the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature. ..
  • the horizontally oriented liquid crystal cured film is, for example, A step of applying a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film onto a base material or an oriented film to obtain a coating film. A step of drying the coating film to form a dry coating film, and It can be produced by a method including a step of irradiating a dry coating film with active energy rays to form a horizontally oriented liquid crystal cured film.
  • the coating film of the polymerizable liquid crystal composition can be formed, for example, by applying the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film on a substrate or an alignment film.
  • the base material that can be used here the same base material as those exemplified above can be used as the base material that can be used for producing the vertically oriented liquid crystal cured film.
  • the alignment film can be appropriately selected from materials having a horizontal orientation regulating force that orients the polymerizable liquid crystal compound in the horizontal direction with respect to the coating film plane.
  • the orientation-regulating force can be arbitrarily adjusted according to the type of alignment layer, surface condition, rubbing conditions, etc., and when formed from a photo-alignable polymer, it can be arbitrarily adjusted according to polarization irradiation conditions, etc. It is possible. Examples of such a material include the above-mentioned oriented polymer as an oriented film that can be used for producing a vertically oriented liquid crystal cured film.
  • the horizontal alignment film can be obtained by applying a composition containing such a material and a solvent, for example, the solvent exemplified in the vertically oriented liquid crystal cured film, to a substrate, removing the solvent, and then heating the coating film or the like. It can.
  • a photoalignment film it is preferable to use a photoalignment film from the viewpoint of quality.
  • a dry coating film is formed by removing the solvent by drying or the like.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method. From the viewpoint of productivity, heat drying is preferable, and the heating temperature in that case is preferably equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound while the solvent can be removed. Examples of the procedure and conditions in such a step are the same as those that can be adopted in the method for producing a vertically oriented liquid crystal cured film.
  • the obtained dry coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.), and the polymerizable liquid crystal compound remains oriented horizontally with respect to the plane of the coating film.
  • active energy rays more specifically, ultraviolet rays, etc.
  • the polymerizable liquid crystal compound remains oriented horizontally with respect to the plane of the coating film.
  • the polymerization method include the same methods that can be adopted in the method for producing a vertically oriented liquid crystal cured film.
  • a film having a polarizing function may be referred to as a polarizing film.
  • the higher the alignment order of the liquid crystal the better the absorption selectivity derived from the dichroic dye. Therefore, the above-mentioned smectic phase, particularly the higher-order smectic phase, is used.
  • the polymerizable liquid crystal compound shown above it is preferable to form a polarizing film by polymerizing while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase.
  • the polarizing film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase is obtained from the conventional host guest type polarizing film, that is, the liquid crystal state of the nematic phase due to the action of the dichroic dye.
  • the polarizing performance is high as compared with the polarizing film.
  • the strength is excellent as compared with the one coated only with the dichroic dye or the lyotropic liquid crystal.
  • a polarizing film with a high degree of orientation order can obtain a Bragg peak derived from a higher-order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
  • the Bragg peak means a peak derived from the plane periodic structure of molecular orientation. Therefore, in the polarizing film formed from the polymerizable liquid crystal composition of the present invention, it is preferable that the polymerizable liquid crystal compound or a polymer thereof is oriented so that the polarizing film shows a Bragg peak in X-ray diffraction measurement. It is more preferable that the molecules of the polymerizable liquid crystal compound are oriented in the direction of absorbing light in a "horizontal orientation".
  • a polarizing film having a molecular orientation plane period interval of 3.0 to 6.0 ⁇ is preferable.
  • a high degree of orientation order such as showing the Bragg peak can be realized by controlling the type of the polymerizable liquid crystal compound used, the type and amount of the antioxidant, the type and amount of the dichroic dye, and the like.
  • the thickness of the horizontally oriented liquid crystal cured film can be appropriately selected, and is preferably 0.1 to 5 ⁇ m, more preferably 0.3 to 4 ⁇ m, and further preferably 0.4 to 3 ⁇ m.
  • the present invention includes an elliptical polarizing plate including the liquid crystal cured film of the present invention.
  • the elliptical polarizing plate is a laminate including at least a retardation film and a polarizing film.
  • the polarizing film is a film having a polarizing function.
  • the dye having absorption anisotropy include a dichroic dye.
  • a film containing a stretched film having a dye having absorption anisotropy adsorbed as a polarizer is usually obtained by uniaxially stretching a polyvinyl alcohol-based resin film and dyeing the polyvinyl alcohol-based resin film with a bicolor dye.
  • the polyvinyl alcohol-based resin is obtained by saponifying the polyvinyl acetate-based resin.
  • the polyvinyl acetate-based resin in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
  • examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • the degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
  • the degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.
  • a film formed of such a polyvinyl alcohol-based resin is used as a raw film for a polarizing film.
  • the method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
  • the film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 ⁇ m.
  • the uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing.
  • the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages.
  • rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch.
  • the uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent.
  • the draw ratio is usually about 3 to 8 times.
  • the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.
  • iodine or a dichroic organic dye is used as the dichroic dye.
  • the dichroic organic dye include C.I. I.
  • examples thereof include a dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as trisazo and tetrakisazo.
  • the polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.
  • iodine When iodine is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually adopted.
  • the iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water.
  • the content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water.
  • the temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C.
  • the immersion time (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.
  • a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted.
  • the content of the dichroic organic dye in this aqueous solution is usually about 1 ⁇ 10 -4 to 10 parts by mass, preferably 1 ⁇ 10 -3 to 1 part by mass, more preferably 1 ⁇ 10 -3 to 1 part by mass, per 100 parts by mass of water. Is 1 ⁇ 10 -3 to 1 ⁇ 10 -2 parts by mass.
  • This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid.
  • the temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C.
  • the immersion time (staining time) in this aqueous solution is usually about 10 to 1,800 seconds.
  • the boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution.
  • the content of boric acid in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water.
  • this boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in that case is usually 0.1 to 100 parts by mass per 100 parts by mass of water. It is about 15 parts by mass, preferably 5 to 12 parts by mass.
  • the immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds.
  • the temperature of the boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., and more preferably 60 to 80 ° C.
  • the polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water.
  • the water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water.
  • the temperature of water in the washing treatment is usually about 5 to 40 ° C.
  • the immersion time is usually about 1 to 120 seconds.
  • the drying process can be performed using, for example, a hot air dryer or a far-infrared heater.
  • the temperature of the drying treatment is usually about 30 to 100 ° C, preferably 50 to 80 ° C.
  • the drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds.
  • the moisture content of the polarizer is reduced to a practical level.
  • the water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by weight, the polarizer loses its flexibility and the polarizer may be damaged or broken after its drying. Further, if the water content exceeds 20% by mass, the thermal stability of the polarizer may deteriorate.
  • the thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on the polyvinyl alcohol-based resin film is preferably 5 to 40 ⁇ m.
  • Examples of the film coated with the dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystal properties, a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. Can be mentioned.
  • the film preferably has a protective film on one or both sides thereof.
  • Examples of the protective film include the same resin films as those exemplified above as the base material that can be used for producing the horizontally oriented liquid crystal cured film.
  • the film coated with the dye having absorption anisotropy is thin, but if it is too thin, the strength is lowered and the processability tends to be inferior.
  • the thickness of the film is usually 20 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 0.5 to 3 ⁇ m.
  • film coated with the dye having absorption anisotropy include the films described in JP2012-33249A.
  • a polarizing film can be obtained by laminating a transparent protective film on at least one surface of the polarizing element thus obtained via an adhesive.
  • a transparent protective film a transparent film similar to the resin film exemplified above can be preferably used as a base material that can be used for producing a horizontally oriented liquid crystal cured film.
  • the elliptical polarizing plate of the present invention is configured to include the liquid crystal cured film of the present invention.
  • the present invention is made by laminating the liquid crystal cured film of the present invention with a polarizing film or the like via an adhesive layer or the like. Elliptical polarizing plate can be obtained.
  • the slow axis (optical axis) of the horizontally oriented retardation film constituting the laminate and the absorption axis of the polarizing film it is preferable to stack the films so that the forming angle is 45 ⁇ 5 °.
  • the elliptical polarizing plate of the present invention may have a configuration provided by a conventional general elliptical polarizing plate, or a polarizing film and a retardation film. Such a configuration is used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, a polarizing film or a retardation film from scratches and stains. Protective film and the like.
  • the laminate and elliptical polarizing plate of the present invention can be used in various display devices.
  • the display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source.
  • the display devices include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), and a surface electric field emission display device).
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, a projection type liquid crystal display device, and the like. These display devices may be display devices that display two-dimensional images or three-dimensional display devices that display three-dimensional images.
  • the elliptical polarizing plate of the present invention has an effect.
  • the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device.
  • These display devices can be used. It is excellent in frontal reflection hue and oblique reflection hue at the time of black display, and is also excellent at frontal hue and oblique hue at the time of white display, and can exhibit good image display characteristics.
  • Example 1 [Preparation of liquid crystal compounds]
  • the liquid crystal compound A was produced according to the method described in JP-A-2010-31223. Further, the liquid crystal compound B was produced according to the method described in JP-A-2009-173893. The molecular structures of the liquid crystal compound A and the liquid crystal compound B are shown below, respectively.
  • Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture.
  • Ionic compound A When the molecular weight of the acrylic leveling agent "BYK-361N” was measured by GPC (manufactured by Tosoh Corporation, HLC-8220GPC, solvent tetrahydrofuran, detector: RI), the number average molecular weight was 4800.
  • Corona treatment is performed on a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd., a composition for forming a vertically oriented liquid crystal cured film is applied using a bar coater, and the film is heated at 120 ° C. for 60 seconds.
  • High-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) is used to irradiate ultraviolet rays from the surface coated with the composition for forming a horizontally oriented liquid crystal cured film (in a nitrogen atmosphere, integrated light intensity at a wavelength of 365 nm: By 500 mJ / cm 2 ), a vertically oriented liquid crystal cured film was formed.
  • the film thickness of the obtained vertically oriented liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 1.2 ⁇ m.
  • a polyvinyl alcohol film having an average degree of polymerization of about 2,400, a saponification degree of 99.9 mol% or more and a thickness of 75 ⁇ m is immersed in pure water at 30 ° C., and then the weight ratio of iodine / potassium iodide / water is 0. It was immersed in an aqueous solution of 02/2/100 at 30 ° C. for iodine staining (iodine staining step).
  • the polyvinyl alcohol film that had undergone the iodine dyeing step was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform boric acid treatment (boric acid treatment step). ).
  • the polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8 ° C. and then dried at 65 ° C. to obtain a polarizer (thickness 27 ⁇ m after stretching) in which iodine was adsorbed and oriented on the polyvinyl alcohol. .. At this time, stretching was performed in the iodine dyeing step and the boric acid treatment step.
  • the total draw ratio in such stretching was 5.3 times.
  • the obtained polarizer and a saponified triacetyl cellulose film (KC4UYTAC 40 ⁇ m manufactured by Konica Minolta) were bonded to each other with a nip roll via an aqueous adhesive. While maintaining the tension of the obtained laminate at 430 N / m, it was dried at 60 ° C. for 2 minutes to obtain a polarizing film having a triacetyl cellulose film as a protective film on one side.
  • the water-based adhesive is 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kuraray Poval KL318 manufactured by Kuraray), and a water-soluble polyamide epoxy resin (Aqueous solution of Sumire's resin 650 solid content concentration 30% manufactured by Sumika Chemtex). Prepared by adding 1.5 parts.
  • the obtained polarizing film was confirmed for unevenness and evaluated for orientation.
  • the measurement was carried out with a spectrophotometer (V7100, manufactured by JASCO Corporation) using the polarizer surface of the polarizing plate obtained above as an incident surface.
  • the obtained luminosity factor correction single transmittance was 42.1%
  • the luminosity factor correction polarization degree was 99.996%
  • the single hue a was ⁇ 1.1
  • the single hue b was 3.7.
  • the vertically oriented liquid crystal cured film was bonded to a glass having a thickness of 5 ⁇ 5 cm ⁇ 0.7 mm via a pressure-sensitive adhesive (25 ⁇ m) manufactured by Lintec Corporation.
  • the obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a visual field of 480 ⁇ m ⁇ 320 ⁇ m was counted.
  • BX-51 manufactured by Olympus Corporation
  • Examples 2 to 5 As shown in Table 1, the leveling agents to be added when preparing the composition for forming a vertically oriented liquid crystal cured film are "BYK-361N" (acrylic leveling agent) and “BYK-UV3500” (silicon type) manufactured by BYK-chemie. A vertically oriented liquid crystal cured film was produced in the same manner as in Example 1 except that the leveling agent), DIC's "F-556” (fluorine-based leveling agent) was changed, and the amount of addition was changed. The measurement of Rth, unevenness and orientation were confirmed. The results are shown in Table 1.
  • the leveling agents to be added when preparing the composition for forming a vertically oriented liquid crystal cured film are "BYK-361N" (acrylic leveling agent) and “BYK-UV3500” (silicon type) manufactured by BYK-chemie.
  • a vertically oriented liquid crystal cured film was produced in the same manner as in Example 1 except that the leveling agent), DIC's
  • a horizontal alignment film is obtained by mixing 5 parts (weight average molecular weight: 30,000) of a photo-oriented material having the following structure and 95 parts of cyclopentanone (solvent) as components, and stirring the obtained mixture at 80 ° C. for 1 hour. A composition for forming was obtained.
  • composition for forming horizontally oriented liquid crystal cured film Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.1 part by mass of the leveling agent "BYK-361N" (manufactured by BYK-Chemie) and 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC). With 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (“Irgacure® 369 (Irg369)” manufactured by BASF Japan Ltd.) as a photopolymerization initiator was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The composition for forming a horizontally oriented liquid crystal cured film was obtained by stirring at 80 ° C. for 1 hour.
  • a 1 mg / 50 mL tetrahydrofuran solution of liquid crystal compound A was prepared, a measurement sample was placed in a measurement cell having an optical path length of 1 cm, and the measurement sample was an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation).
  • UV-2450 ultraviolet-visible spectrophotometer
  • the maximum absorption wavelength ⁇ max in the wavelength range of 300 to 400 nm was 350 nm.
  • a composition for forming a horizontally oriented film was coated on a cycloolefin film (ZF-14-50) manufactured by Nippon Zeon Co., Ltd. with a bar coater, dried at 80 ° C. for 1 minute, and a polarized UV irradiation device (SPOT CURE SP-9) was applied.
  • SPOT CURE SP-9 polarized UV irradiation device
  • polarized UV exposure was carried out at an integrated light intensity of 100 mJ / cm 2 at a wavelength of 313 nm to obtain a horizontally aligned film.
  • the film thickness of the obtained horizontal alignment film was measured with an ellipsometer and found to be 200 nm.
  • a composition for forming a horizontally oriented liquid crystal cured film is applied onto the horizontally aligned film using a bar coater, and after heating at 120 ° C. for 60 seconds, a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) ) Was irradiated from the surface coated with the composition for forming a horizontally oriented liquid crystal cured film (integrated light amount at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm 2 ) to form a horizontally oriented liquid crystal cured film. .. After confirming that there was no phase difference in the COP film, Re (450) and Re (550) were measured using KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd. The results are shown in Table 1.
  • the horizontally oriented liquid crystal cured film was bonded to glass having a thickness of 5 ⁇ 5 cm ⁇ 0.7 mm via a pressure-sensitive adhesive (25 ⁇ m) manufactured by Lintec Corporation.
  • the obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a visual field of 480 ⁇ m ⁇ 320 ⁇ m was counted.
  • BX-51 manufactured by Olympus Corporation
  • a horizontal alignment film is obtained by mixing 5 parts (weight average molecular weight: 30,000) of a photo-oriented material having the following structure and 95 parts of cyclopentanone (solvent) as components, and stirring the obtained mixture at 80 ° C. for 1 hour. A composition for forming was obtained.
  • Polymerizable liquid crystal compound 75 copies 25 parts dichroic dye 1: polyazo dye; compound (1-8) 2.5 parts Compound (1-5) 2.5 parts Compound (1-16) 2.5 parts Polymerization initiator; 2-Dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6-part leveling agent; "BYK-361N” (manufactured by BYK-Chemie) 0.1 parts by mass (acrylic leveling agent) "F-556” (manufactured by DIC Corporation) 0.25 parts by mass (fluorine-based leveling agent) Solvent; 250 parts of o-xylene
  • a composition for forming a horizontal alignment film (composition for forming a polarizing layer) is applied to a corona-treated surface with a bar coater, dried at 80 ° C. for 1 minute, and a polarized UV irradiation device (SPOT CURE SP-7; Ushio Denki).
  • Polarized UV exposure was carried out at an axial angle of 90 ° with an integrated light intensity of 100 mJ / cm 2 using (manufactured by Co., Ltd.).
  • the film thickness of the obtained horizontally oriented layer was measured with an ellipsometer and found to be 150 nm.
  • a composition for forming a horizontally oriented liquid crystal cured film (composition for forming a polarizing layer) is applied using a bar coater, and then dried in a drying oven set at 120 ° C. for 1 minute to obtain a polymerizable liquid crystal compound and dichroism.
  • a dry coating film in which the color dye was oriented was obtained.
  • the dry coating film After the dry coating film is naturally cooled to room temperature, it is irradiated with ultraviolet rays using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.) (in a nitrogen atmosphere, wavelength: 365 nm, integrated light amount at wavelength 365 nm: By polymerizing the polymerizable liquid crystal compound by 1000 mJ / cm 2 ), a horizontally oriented liquid crystal cured film (polarizing film) was prepared.
  • a high-pressure mercury lamp Unicure VB-15201BY-A, manufactured by Ushio Denki Co., Ltd.
  • the degree of polarization and the single transmittance of the obtained horizontally oriented liquid crystal cured film (polarizing film) were measured as follows.
  • the transmittance in the transmission axis direction (T 1 ) and the transmittance in the absorption axis direction (T 2 ) are doubled using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a polarizer set.
  • the measurement was performed by the beam method in a wavelength range of 2 nm step 380 to 680 nm.
  • the horizontally oriented liquid crystal cured film was bonded to glass having a thickness of 5 ⁇ 5 cm ⁇ 0.7 mm via a pressure-sensitive adhesive (25 ⁇ m) manufactured by Lintec Corporation.
  • the obtained sample was observed with a polarizing microscope (“BX-51” manufactured by Olympus Corporation) under the condition of a magnification of 200 times, and the number of orientation defects in a visual field of 480 ⁇ m ⁇ 320 ⁇ m was counted.
  • BX-51 manufactured by Olympus Corporation
  • Ring agent "KBE-9103" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (BASF) as a photopolymerization initiator 6 parts by mass of "Irgacure (registered trademark) 369 (Irg369)") manufactured by Japan Co., Ltd. was added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically oriented liquid crystal cured film.
  • BASF 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one
  • NMP N-methyl-2-pyrrolidone
  • the x-axis means an arbitrary direction in the plane of the vertically oriented liquid crystal cured film
  • the y-axis means the direction perpendicular to the x-axis in the film surface
  • the z-axis means the thickness direction of the vertically oriented liquid crystal cured film
  • AxC represents the absorbance of linearly polarized light oscillating in the x-axis direction
  • AxC (z 60).
  • 60) represents the absorbance of linearly polarized light that vibrates in the x-axis direction when the film is rotated by 60 ° with the y-axis as the rotation axis.
  • UV-2450 ultraviolet-visible spectrophotometer
  • Re in Table 1 represents either the in-plane retardation value of the horizontally oriented film or the in-plane retardation value of the vertically aligned film.
  • unevenness can be improved by using a predetermined leveling agent without impairing the orientation of the liquid crystal cured film.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

La présente invention aborde le problème consistant à fournir une composition pour former un film durci à cristaux liquides, ladite composition étant utilisée pour la production d'un film durci à cristaux liquides ayant peu de variation d'épaisseur de film.　La présente invention concerne une composition pour former un film durci à cristaux liquides, ladite composition contenant au moins un agent de nivellement à base de silicium ou de fluor, au moins un agent de nivellement acrylique, et au moins un composé de cristaux liquides polymérisable, la quantité totale des agents de nivellement étant de 3,0 % en poids ou moins par rapport à la quantité totale des composés de cristaux liquides polymérisables.
PCT/JP2020/016520 2019-04-26 2020-04-15 Composition pour former un film durci à cristaux liquides et son utilisation WO2020218104A1 (fr)

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CN202080040736.5A CN113906322A (zh) 2019-04-26 2020-04-15 液晶固化膜形成用组合物及其用途
KR1020217038358A KR20220003574A (ko) 2019-04-26 2020-04-15 액정 경화막 형성용 조성물 및 그 용도

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CN113296180B (zh) * 2021-05-20 2022-02-01 苏州大学 一种“主-宾”型偏振片及其制备方法

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CN113906322A (zh) 2022-01-07

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