Classifications

• • 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
• • 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
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
• • 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
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/60—Pleochroic dyes
  • C09K19/601—Azoic
• • 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
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • 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
  • G02B5/3083—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
  • G02F1/0009—Materials therefor
  • G02F1/0063—Optical properties, e.g. absorption, reflection or birefringence
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/855—Optical field-shaping means, e.g. lenses
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
  • C09K19/3833—Polymers with mesogenic groups in the side chain
  • C09K19/3842—Polyvinyl derivatives
  • C09K19/3852—Poly(meth)acrylate derivatives
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  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/60—Pleochroic dyes
  • C09K19/603—Anthroquinonic
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  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
  • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
• • 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
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K2019/525—Solvents

Definitions

• the present invention relates to an optical film and an electroluminescence display device.
• LED displays using light emitting diodes which are self-luminous elements, have been developed.
• LEDs light emitting diodes
• a micro LED display in which chip-shaped micro LEDs are mounted has been developed, and has attracted attention in recent years as a display device that can easily achieve both high definition and large size.
• Micro LEDs generally use InGaN/GaN for G light-emitting elements, B light-emitting elements, and GaInP/AlGaInP for R light-emitting elements. Due to the difference in refractive index, the color in the front direction was adjusted to be neutral. In this case, a phenomenon occurs in which the color shifts in the oblique direction, and the brightness derived from G (green) and B (blue) increases (Non-Patent Document 1).
• the present inventors investigated placing a layer having G and B absorbers on the surface of the micro LED, and found that it is possible to neutralize the color in the oblique direction. However, it has been clarified that the front transmittance is greatly reduced.
• an object of the present invention is to provide an optical film and an electroluminescence display device which, when used in a micro LED, can suppress a decrease in transmittance in the front direction and suppress color change in a direction oblique to the front direction.
• an optical film having an anisotropic light absorption layer containing a dichroic dye compound has an optical absorption property in which the anisotropic light absorption layer absorbs light in the normal direction of the film. has an axis, has an orientation degree of 0.7 or more at 530 nm, and the optical film satisfies a specific relationship of transmittance at a specific wavelength in a direction at 45° to the normal direction of the film , when used in a micro LED, it was found that it is possible to suppress the decrease in transmittance in the front and to suppress the color change in the oblique direction with respect to the front, resulting in the present invention. That is, the inventors have found that the above object can be achieved by the following configuration.
• An optical film having a light absorption anisotropic layer containing a dichroic dye compound has an absorption axis in the normal direction of the film and has a degree of orientation at 530 nm of 0.7 or more,
• Tb, Tg and Tr transmittance of the optical film at 460 nm, 530 nm and 630 nm in the direction of 45° to the normal direction of the film
• the light absorption anisotropic layer contains a dichroic dye compound having an absorption peak at 430 nm or more and less than 500 nm and a dichroic dye compound having an absorption peak at 500 nm or more and 560 nm or less, [1] or [ 2].
• [5] The optical film according to any one of [1] to [4], which has a transmittance of 70% or more at 530 nm in the normal direction of the film.
• [6] The optical film according to any one of [1] to [5], which has a transmittance of 75% or more at 630 nm in the normal direction of the film.
• An electroluminescence display device comprising an electroluminescence substrate having electroluminescence light-emitting elements of a plurality of colors, and the optical film according to any one of [1] to [6] laminated on the electroluminescence substrate.
• [8] The electroluminescence display device according to [7], wherein the light emitting element is a light emitting diode.
• an optical film and an electroluminescence display device that can suppress a decrease in transmittance in the front direction and suppress a change in color tone in a direction oblique to the front direction when micro LEDs are used.
• a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
• parallel, orthogonal and normal do not mean parallel, orthogonal and normal in a strict sense, respectively, but a range of ⁇ 5° from parallel, orthogonal and normal respectively. means.
• both the liquid crystalline composition and the liquid crystalline compound conceptually include those that no longer exhibit liquid crystallinity due to curing or the like.
• each component may use the substance applicable to each component individually by 1 type, or may use 2 or more types together.
• the content of the component refers to the total content of the substances used in combination unless otherwise specified.
• (meth)acrylate is a notation representing “acrylate” or “methacrylate”
• (meth)acryl is a notation representing "acryl” or “methacryl”
• (Meth)acryloyl is a notation representing “acryloyl” or “methacryloyl”.
• visible light is light with a wavelength visible to the human eye among electromagnetic waves, and indicates light in the wavelength range of 380 to 780 nm.
• Invisible light is light in the wavelength range below 380 nm and the wavelength range above 780 nm.
• the optical film of the present invention is an optical film having a light absorption anisotropic layer containing a dichroic dye compound.
• the anisotropic light absorption layer of the optical film of the present invention is an anisotropic light absorption layer having an absorption axis in the normal direction of the film and having a degree of orientation at 530 nm of 0.7 or more.
• the absorption axis means the normal direction of the surface of the light absorption anisotropic layer, that is, the normal direction (90° ) to have an absorption axis within a range of ⁇ 5°.
• the absorption axis means the direction of the absorption axis of the dichroic dye compound contained in the light absorption anisotropic layer (molecular long axis direction), and in the present invention, the light absorption anisotropic layer surface
• the transmittance is measured by changing the tilt angle (polar angle) and the tilt direction (azimuth angle) with respect to the normal direction, it can be confirmed as the direction showing the highest transmittance.
• AxoScan OPMF-1 (manufactured by Optoscience) is used to actually measure the Mueller matrix at a wavelength of 550 nm. More specifically, in the measurement, the azimuth angle at which the absorption axis is tilted is first searched, and then the plane (absorption axis In the plane perpendicular to the layer surface), the polar angle, which is the angle with respect to the normal direction of the light absorption anisotropic layer surface, is changed from -70 to 70 ° in increments of 1 °, Mueller matrix with a wavelength of 550 nm is actually measured to derive the transmittance of the light absorption anisotropic layer. As a result, the direction with the highest transmittance is taken as the absorption axis.
• transmittance at 460 nm, 530 nm and 630 nm in a direction 45° to the normal direction of the film refers to values measured and derived as follows.
• AxoScan OPMF-1 manufactured by Optoscience
• the polar angle which is the angle with respect to the normal direction of the optical film, is set to 45°
• the Mueller matrix for each measurement wavelength is actually measured, and the transmittance of the optical film is derived.
• the normal direction that is the reference of the polar angle means the normal direction (90°) in a strict sense.
• the light absorption anisotropic layer has an absorption axis in the normal direction of the film and has a degree of orientation at 530 nm of 0.7 or more
• the optical film is a film method.
• the light absorption anisotropic layer has an absorption axis in the normal direction of the film and the degree of orientation at 530 nm is 0.7 or more, it is possible to suppress a decrease in front transmittance.
• the dichroic dye compound contained in the anisotropic light absorption layer is oriented perpendicular to the surface of the anisotropic light absorption layer, so that the absorption axis of the anisotropic light absorption layer It is considered that this is because the transmittance in the direction along the line is increased.
• the optical film satisfies the relationship of the above-described formulas (1) and (2) for the transmittance of the specific wavelength in the direction at 45° to the film normal direction, the color change in the direction oblique to the front is suppressed. can be suppressed.
• the luminance ratio of red, green, and blue that affects the color change in the oblique direction can be adjusted to neutral color in the front direction. This is probably because the values approximate the luminance ratios of red, green, and blue.
• the transmittances at 460 nm, 530 nm and 630 nm in the direction at 45° to the film normal direction are defined as Tb(45), Tg(45) and Tr(45), respectively.
• Tb(45), Tg(45) and Tr(45) are satisfied, but the following formulas (1-2) and (2- It is preferable to satisfy both the relationships of 2).
• Tb(0) is It is preferably 50% or more, more preferably 70% or more. Also, Tg(0) is preferably 50% or more, more preferably 70% or more. Also, Tr(0) is preferably 75% or more, more preferably 80% or more. As a result, it is possible to further suppress a decrease in the transmittance of the front surface.
• the transmittance of each wavelength in the normal direction of the film is a value calculated by measuring as follows. First, AxoScan OPMF-1 (manufactured by Optoscience) is used to actually measure the Mueller matrix of the optical film at each measurement wavelength.
• the polar angle which is the angle with respect to the normal direction of the optical film, is measured every 5° from ⁇ 70° to 70°. From the average value of Tmax and Tmin of the measurement results, the transmittance (frontal transmittance) at each wavelength is calculated.
• the light absorption anisotropic layer of the optical film of the present invention has absorption in the normal direction of the film.
• a dichroic dye compound for example, an organic dichroic dye
• the orientation of the liquid crystalline compound is used. It is more preferable to orient the dichroic dye compound by An example of such a preferred embodiment is an anisotropic light absorption layer in which at least one kind of dichroic dye compound is oriented perpendicular to the plane.
• the technology for aligning the dichroic dye compound in the desired direction it is possible to refer to the technology for manufacturing a polarizer using a dichroic dye compound and the technology for manufacturing a guest-host liquid crystal cell.
• a method for producing a dichroic polarizing element described in JP-A-11-305036 and JP-A-2002-90526, and a guest-host type liquid crystal described in JP-A-2002-99388 and JP-A-2016-27387 can also be used in manufacturing the light absorption anisotropic layer used in the present invention.
• molecules of a dichroic dye compound can be oriented as desired along with the orientation of the host liquid crystal.
• a dichroic dye compound as a guest and a rod-like liquid crystalline compound as a host liquid crystal are mixed, the host liquid crystal is aligned, and molecules of the dichroic dye compound are mixed along the alignment of the liquid crystal molecules.
• the orientation of the dichroic dye compound can be fixed by proceeding with the polymerization of the host liquid crystal, dichroic dye compound, or optional polymerizable component.
• the light absorption anisotropic layer used in the present invention A polymer film can be made that satisfies the required light absorption properties. Specifically, it can be produced by coating a solution of a dichroic dye compound on the surface of a polymer film and permeating the film.
• the orientation of the dichroic dye compound can be adjusted by the orientation of polymer chains in the polymer film, their properties (chemical and physical properties such as polymer chains or functional groups possessed by them), coating methods, and the like. Details of this method are described in JP-A-2002-90526.
• the optical absorption anisotropic layer of the optical film of the present invention has an orientation degree S of 0.7 or more at 530 nm. 0.9 or more is preferable.
• the degree of orientation measured at a wavelength of ⁇ nm shall conform to the following definition in this specification.
• AxoScan OPMF-1 manufactured by Optoscience Co., Ltd.
• the polar angle which is the angle with respect to the normal direction of the light absorption anisotropic layer, from 0 to 90 ° in increments of 5 °
• each The Mueller matrix is actually measured at a wavelength of 530 nm at a polar angle, and the minimum transmittance (Tmin) is derived.
• Tmin is Tm(0) at the polar angle where Tmin is the highest, and Tmin is Tm(40) in the direction where the polar angle is further increased by 40° from the highest polar angle of Tmin.
• the absorbance is calculated from the obtained Tm(0) and Tm(40) by the following formula, and A(0) and A(40) are calculated.
• A -log(Tm)
• Tm represents transmittance
• A represents absorbance.
• the dichroic dye compound contained in the light absorption anisotropic layer is not particularly limited, and conventionally known dichroic dye compounds can be used, and dichroic azo dye compounds are particularly preferably used.
• the dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used, but the compounds described below are preferably used.
• a dichroic azo dye compound means a dye having different absorbance depending on the direction.
• the dichroic azo dye compound may or may not exhibit liquid crystallinity.
• the dichroic azo dye compound When the dichroic azo dye compound exhibits liquid crystallinity, it may exhibit nematicity or smecticity.
• the temperature range showing the liquid crystal phase is preferably room temperature (approximately 20° C. to 28° C.) to 300° C., and more preferably 50° C. to 200° C. from the viewpoint of handleability and production suitability.
• the light absorption anisotropic layer preferably contains two or more dichroic dye compounds (especially dichroic azo dye compounds).
• the light absorption anisotropic layer preferably contains a dichroic dye compound having an absorption peak at a wavelength of 430 nm or more and 560 nm or less. At least one dichroic dye compound having an absorption peak at a wavelength of less than (e.g., a second dichroic azo dye compound described later) and at least one having an absorption peak at a wavelength of 500 nm or more and 560 nm or less It is more preferable to contain a dichroic dye compound (for example, a first dichroic azo dye compound to be described later). Specifically, it is particularly preferable to contain at least a dichroic azo dye compound represented by formula (5) described later and a dichroic azo dye compound represented by formula (6) described later. .
• the light absorption anisotropic layer preferably does not have a dichroic dye compound having an absorption peak at a wavelength of 600 nm or more and 700 nm or less. It is more preferable not to have a dichroic dye compound having absorption at the following wavelengths.
• the dichroic azo dye compound preferably has a crosslinkable group from the viewpoint of better pressure resistance.
• the crosslinkable group include a (meth)acryloyl group, an epoxy group, an oxetanyl group, a styryl group, etc. Among them, a (meth)acryloyl group is preferred.
• the first dichroic azo dye compound is preferably a compound having a chromophore that is the nucleus of the dichroic azo dye compound and a side chain that binds to the terminal of the chromophore.
• the chromophore include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups and the like, and structures having both aromatic hydrocarbon groups and azo groups are preferred. , a bisazo or trisazo structure having an aromatic hydrocarbon group and two or three azo groups is more preferred.
• the side chain is not particularly limited, and includes groups represented by R4, R5 or R6 in formula (5) described below.
• the first dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 500 nm or more and 560 nm or less, and from the viewpoint of color adjustment, the maximum absorption wavelength is in the wavelength range of 510 to 550 nm. and more preferably a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 520 to 540 nm.
• the first dichroic azo dye compound is preferably a compound represented by Formula (5) in terms of further improving the degree of orientation of the polarizer.
• n 1 or 2.
• Ar3, Ar4 and Ar5 are each independently a phenylene group optionally having substituent(s), a naphthylene group optionally having substituent(s) or a heterocyclic group optionally having substituent(s) represents a cyclic group.
• Heterocyclic groups can be either aromatic or non-aromatic. Atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. When the aromatic heterocyclic group has a plurality of non-carbon ring-constituting atoms, these may be the same or different.
• aromatic heterocyclic groups include, for example, pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group), and isoquinolylene.
• R4 is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, alkyloxycarbonyl group, acyloxy group, alkylcarbonate group, alkylamino group, acylamino group, alkylcarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, alkylsulfamoyl group, alkylcarbamoyl group, alkylsulfinyl group, alkylureido group, an alkylphosphoamide group, an alkylimino group, or an alkylsilyl group.
• R4 is a group other than a hydrogen atom
• R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In each group, when a plurality of R1' are present, they may be the same or different.
• R5 and R6 are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxy represents a carbonyl group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamido group; —CH 2 — constituting the alkyl group is —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —C(O) -S-, -S-C(O)-, -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -, -NR2'-, -NR2'-CO-, -CO-NR2'-,
• R2 and R3 are groups other than hydrogen atoms
• R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. In each group, when a plurality of R2' are present, they may be the same or different.
• R5 and R6 may combine with each other to form a ring, or R5 or R6 may combine with Ar2 to form a ring.
• R4 is preferably an electron-withdrawing group
• R5 and R6 are preferably groups with low electron-donating properties.
• specific examples in which R4 is an electron-withdrawing group are the same as those in which R1 is an electron-withdrawing group
• R5 and R6 are groups with low electron-donating properties.
• R2 and R3 are low electron-donating groups, specific examples are the same as the specific examples.
• first dichroic azo dye compound examples include but are not limited thereto.
• the second dichroic azo dye compound is a dichroic azo dye compound other than the first dichroic azo dye compound, specifically, the chemical structure of the first dichroic azo dye compound is different.
• the second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 430 nm or more and less than 500 nm, and from the viewpoint of color adjustment, the maximum absorption wavelength in the wavelength range of 440 to 490 nm. and more preferably a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 450 to 480 nm.
• the second dichroic azo dye compound preferably contains a dichroic azo dye represented by the following formula (6).
• a and B each independently represent a crosslinkable group.
• a and b each independently represent 0 or 1. Both a and b are preferably 0 in terms of excellent orientation at 420 nm.
• Ar 1 represents a (n1+2)-valent aromatic hydrocarbon group or heterocyclic group
• Ar 2 represents a (n2+2)-valent aromatic hydrocarbon group or heterocyclic group
• Ar 3 represents ( represents an n3+2)-valent aromatic hydrocarbon group or heterocyclic group
• R 1 , R 2 and R 3 each independently represent a monovalent substituent.
• n1 ⁇ 2 the plurality of R1 may be the same or different
• n2 ⁇ 2 the plurality of R2 may be the same or different
• n3 ⁇ 2. may be the same or different from each other.
• k represents an integer of 1-4.
• Examples of the crosslinkable groups represented by A and B in formula (6) include polymerizable groups described in paragraphs [0040] to [0050] of JP-A-2010-244038.
• acryloyl group, methacryloyl group, epoxy group, oxetanyl group, and styryl group are preferred from the viewpoint of improving reactivity and synthesis aptitude, and acryloyl group and methacryloyl group are preferred from the viewpoint of further improving solubility. more preferred.
• L2 represents a monovalent substituent
• L2 represents a single bond or a divalent linking group
• the monovalent substituent represented by L 1 and L 2 includes a group introduced to increase the solubility of the dichroic dye compound, or an electron-donating group introduced to adjust the color tone of the dye.
• Groups having electron-withdrawing properties are preferred.
• an alkyl group preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as vinyl group,
• a phosphate amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as a diethyl phosphate amide group and a phenyl phosphate amide group) ),
• a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., for example, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably a silyl group having 3
• R B (OR A ) na — groups, which are groups in which an alkoxy group is substituted with an alkyl group.
• R A represents an alkylene group having 1 to 5 carbon atoms
• R B represents an alkyl group having 1 to 5 carbon atoms
• na is 1 to 10 (preferably 1 to 5, more preferably 1 to 3) represents an integer.
• monovalent substituents represented by L 1 and L 2 include alkyl groups, alkenyl groups, alkoxy groups, and groups in which these groups are further substituted with these groups (for example, R B —(OR A ) na — group) is preferred, and alkyl groups, alkoxy groups, and groups in which these groups are further substituted with these groups (for example, R B —(OR A ) na described above) are preferred.
• - group is more preferred.
• Examples of divalent linking groups represented by L 1 and L 2 include -O-, -S-, -CO-, -COO-, -OCO-, -O-CO-O-, -CO-NR N —, —O—CO—NR N —, —NR N —CO—NR N —, —SO 2 —, —SO—, alkylene groups, cycloalkylene groups and alkenylene groups, and two of these groups
• RN represents a hydrogen atom or an alkyl group. When there are multiple RNs , the multiple RNs may be the same or different.
• the number of atoms in the main chain of at least one of L 1 and L 2 is preferably 3 or more, and preferably 5 or more. More preferably, the number is 7 or more, and particularly preferably 10 or more.
• the upper limit of the number of atoms in the main chain is preferably 20 or less, more preferably 12 or less.
• the number of atoms in the main chain of at least one of L 1 and L 2 is preferably 1 to 5 from the viewpoint of further improving the degree of orientation of the light absorption anisotropic layer.
• the “main chain” in L 1 means the “O” atom that connects L 1 and “A”, It refers to a moiety, and "the number of atoms in the main chain” refers to the number of atoms constituting the moiety.
• the “main chain” in L 2 means the “O” atom that connects L 2 and “B”,
• the number of atoms in the main chain refers to the number of atoms that make up the moiety.
• the “number of atoms in the main chain” does not include the number of branched chain atoms, which will be described later.
• the number of atoms in the main chain in L1 means the number of atoms in L1 that does not contain branched chains.
• the " number of main chain atoms" in L2 refers to the number of atoms in L2 not including branched chains.
• the number of atoms in the main chain of L 1 is 5 (the number of atoms in the dotted frame on the left side of the following formula (D1))
• the main chain of L 2 The number of atoms of is 5 (the number of atoms within the dotted frame on the right side of formula (D1) below).
• the number of atoms in the main chain of L 1 is 7 (the number of atoms in the dotted frame on the left side of the formula (D10) below), and the number of atoms in the main chain of L 2 is The number is 5 (the number of atoms in the dotted frame on the right side of formula (D10) below).
• L 1 and L 2 may have a branched chain.
• the “branched chain” in L 1 means that the “O” atom that connects L 1 in formula (6) and “A” are directly connected. It means a part other than the part necessary for
• the “branched chain” in L 2 means that the “O” atom that connects L 2 in formula (6) and “B” are directly connected It means a part other than the part necessary for
• the “branched chain” in L 1 means the longest atomic chain extending starting from the “O” atom connected to L 1 in formula (6) (that is, the main chain).
• the “branched chain” in L2 means the longest atomic chain extending from the “O” atom connecting L2 in formula (6) (i.e. main chain).
• the number of atoms in the branched chain is preferably 3 or less. When the number of atoms in the branched chain is 3 or less, there is an advantage that the degree of orientation of the light absorption anisotropic layer is further improved.
• the number of branched chain atoms does not include the number of hydrogen atoms.
• Ar 1 is (n1+2)-valent (e.g., trivalent when n1 is 1)
• Ar 2 is (n2+2)-valent (e.g., trivalent when n2 is 1)
• Ar 3 represents an (n3+2)-valent (for example, trivalent when n3 is 1) aromatic hydrocarbon group or heterocyclic group.
• each of Ar 1 to Ar 3 can be rephrased as a divalent aromatic hydrocarbon group or divalent heterocyclic group substituted with n1 to n3 substituents (R 1 to R 3 described later).
• the divalent aromatic hydrocarbon group represented by Ar 1 to Ar 3 may be monocyclic or have a condensed ring structure of two or more rings.
• the ring number of the divalent aromatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1 (that is, a phenylene group) from the viewpoint of further improving the solubility.
• the divalent aromatic hydrocarbon group include a phenylene group, an azulene-diyl group, a naphthylene group, a fluorene-diyl group, anthracene-diyl group and a tetracene-diyl group, which further improve solubility. From this point of view, a phenylene group and a naphthylene group are preferable, and a phenylene group is more preferable.
• Specific examples of the second dichroic dye compound are shown below, but the present invention is not limited to these. In the following specific examples, n represents an integer of 1-10.
• a structure in which the second dye does not have a radically polymerizable group is preferable from the viewpoint of excellent orientation at 460 nm.
• Examples include the following structures.
• the second dichroic azo dye compound is more preferably a dichroic dye compound having a structure represented by the following formula (1-1) in that the degree of orientation at 460 nm is particularly excellent.
• R 1 , R 3 , R 4 , R 5 , n1, n3, L 1 and L 2 are defined respectively as R 1 , R 3 , R 4 and R 5 in formula (3) , n1, n3 , L1 and L2.
• definitions of R 21 and R 22 are independently the same as R 2 in formula (3).
• definitions of n21 and n22 are each independently synonymous with n2 in formula (3). n1+n21+n22+n3 ⁇ 1, and n1+n21+n22+n3 is preferably 1-9, more preferably 1-5.
• the content of the dichroic dye compound is 5 to 30 with respect to the total solid mass of the light absorption anisotropic layer, because it becomes easy to adjust the degree of orientation of the light absorption anisotropic layer to 0.7 or more. % by mass is preferable, 8 to 20% by mass is more preferable, and 10 to 15% by mass is even more preferable.
• the dichroic dye in the light absorption anisotropic layer It is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, based on the total mass of the entire compound.
• the light absorption anisotropic layer preferably contains a liquid crystalline compound.
• a liquid crystalline compound By containing a liquid crystalline compound, it is possible to align the dichroic dye compound with a high degree of alignment while suppressing precipitation of the dichroic dye compound.
• a liquid crystalline compound is a liquid crystalline compound that does not exhibit dichroism.
• the liquid crystalline compound it is possible to use either a low-molecular-weight liquid crystalline compound or a high-molecular-weight liquid crystalline compound, and it is also preferable to use both together.
• the term "low-molecular-weight liquid crystalline compound” refers to a liquid crystalline compound having no repeating unit in its chemical structure.
• polymeric liquid crystalline compound refers to a liquid crystalline compound having a repeating unit in its chemical structure.
• low-molecular-weight liquid crystalline compounds examples include liquid crystalline compounds described in JP-A-2013-228706.
• polymer liquid crystalline compounds examples include thermotropic liquid crystalline polymers described in JP-A-2011-237513.
• the polymer liquid crystalline compound preferably has a repeating unit having a crosslinkable group at the terminal from the viewpoint of excellent strength (in particular, bending resistance) of the light absorption anisotropic film.
• the crosslinkable group examples include polymerizable groups described in paragraphs [0040] to [0050] of JP-A-2010-244038. Among these, acryloyl group, methacryloyl group, epoxy group, oxetanyl group, and styryl group are preferred, and acryloyl group and methacryloyl group are more preferred, from the viewpoint of improving reactivity and synthesis suitability.
• the polymer liquid crystal compound When the light absorption anisotropic layer contains a polymer liquid crystal compound, the polymer liquid crystal compound preferably forms a nematic liquid crystal phase.
• the temperature range showing the nematic liquid crystal phase is preferably room temperature (23° C.) to 450° C., and preferably 50° C. to 400° C. from the viewpoint of handling and production suitability.
• the content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and 200 to 900 parts by mass with respect to 100 parts by mass of the content of the dichroic dye compound in the liquid crystal composition. is more preferred.
• the liquid crystalline compound may be contained individually by 1 type, and may be contained 2 or more types. When two or more kinds of liquid crystalline compounds are contained, the content of the liquid crystalline compounds means the total content of the liquid crystalline compounds.
• the liquid crystalline compound is preferably a polymer liquid crystalline compound containing a repeating unit represented by the following formula (1L) (hereinafter also referred to as "repeating unit (1L)”) because of its superior degree of orientation.
• P1 represents the main chain of the repeating unit
• L1 represents a single bond or a divalent linking group
• SP1 represents a spacer group
• M1 represents a mesogenic group
• T1 represents a terminal group.
• main chain of the repeating unit represented by P1 include groups represented by the following formulas (P1-A) to (P1-D).
• a group represented by the following formula (P1-A) is preferable from the viewpoint of diversity and ease of handling.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. represents an alkoxy group.
• the alkyl group may be a linear or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl group).
• the number of carbon atoms in the alkyl group is preferably 1 to 5.
• the group represented by formula (P1-A) is preferably one unit of the partial structure of poly(meth)acrylic acid ester obtained by polymerization of (meth)acrylic acid ester.
• the group represented by formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group.
• the group represented by formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetane group of a compound having an oxetane group.
• the group represented by formula (P1-D) is preferably a siloxane unit of polysiloxane obtained by condensation polymerization of a compound having at least one of an alkoxysilyl group and a silanol group.
• compounds having at least one of an alkoxysilyl group and a silanol group include compounds having a group represented by the formula SiR 4 (OR 5 ) 2 —.
• R 4 has the same definition as R 4 in (P1-D), and each of a plurality of R 5 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• L1 is a single bond or a divalent linking group.
• the divalent linking group represented by L1 includes -C(O)O-, -OC(O)-, -O-, -S-, -C(O)NR 3 -, and -NR 3 C(O). -, -SO 2 -, and -NR 3 R 4 -.
• R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent W (described later).
• P1 is a group represented by formula (P1-A)
• L1 is preferably a group represented by -C(O)O- for the reason that the degree of orientation is superior.
• P1 is a group represented by formulas (P1-B) to (P1-D)
• L1 is preferably a single bond because the degree of orientation is superior.
• the spacer group represented by SP1 is at least one selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and an alkylene fluoride structure, for reasons such as the ease of exhibiting liquid crystallinity and the availability of raw materials. It preferably contains a seed structure.
• the oxyethylene structure represented by SP1 is preferably a group represented by *-(CH 2 -CH 2 O) n1 -*.
• n1 represents an integer of 1 to 20
• * represents the bonding position with L1 or M1 in the above formula (1L).
• n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3, because the degree of orientation is more excellent.
• the oxypropylene structure represented by SP1 is preferably a group represented by *-(CH(CH 3 )-CH 2 O) n2 --* because of its superior degree of orientation.
• n2 represents an integer of 1 to 3
• * represents the bonding position with L1 or M1.
• the polysiloxane structure represented by SP1 is preferably a group represented by *-(Si(CH 3 ) 2 -O) n3 -* because of its superior degree of orientation.
• n3 represents an integer of 6 to 10 * represents the bonding position with L1 or M1.
• alkylene fluoride structure represented by SP1 is preferably a group represented by *-(CF 2 -CF 2 ) n4 -* because of its superior degree of orientation.
• n4 represents an integer of 6 to 10
• * represents the bonding position with L1 or M1.
• the mesogenic group represented by M1 is a group showing the main skeleton of liquid crystal molecules that contributes to liquid crystal formation.
• Liquid crystal molecules exhibit liquid crystallinity, which is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state.
• the mesogenic group is preferably, for example, a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups.
• the mesogenic group preferably has an aromatic hydrocarbon group, more preferably has 2 to 4 aromatic hydrocarbon groups, and has 3 aromatic hydrocarbon groups for the reason that the degree of orientation is better. is more preferred.
• the mesogenic group As the mesogenic group, the following formula (M1-A) or the following formula (M1-B) is used from the viewpoint of liquid crystal expression, adjustment of liquid crystal phase transition temperature, availability of raw materials and synthesis suitability, and superior degree of orientation.
• a group represented by is preferable, and a group represented by formula (M1-B) is more preferable.
• A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. These groups may be substituted with an alkyl group, a fluorinated alkyl group, an alkoxy group or a substituent W (described later).
• the divalent group represented by A1 is preferably a 4- to 6-membered ring. Also, the divalent group represented by A1 may be monocyclic or condensed. * represents the binding position with SP1 or T1.
• the divalent aromatic hydrocarbon group represented by A1 includes a phenylene group, a naphthylene group, a fluorene-diyl group, an anthracene-diyl group and a tetracene-diyl group.
• a phenylene group or a naphthylene group is preferred, and a phenylene group is more preferred, from the viewpoint of properties and the like.
• the divalent heterocyclic group represented by A1 may be either aromatic or non-aromatic, but from the viewpoint of further improving the degree of orientation, it is preferably a divalent aromatic heterocyclic group.
• Atoms other than carbon constituting the divalent aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom.
• the aromatic heterocyclic group has a plurality of non-carbon ring-constituting atoms, these may be the same or different.
• divalent aromatic heterocyclic groups include, for example, pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group ), isoquinolylene group (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group , thiazolothiazole-diyl group, thienothiophene-diyl group, and thienooxazole-diyl group.
• pyridylene group pyridine-diy
• divalent alicyclic group represented by A1 examples include a cyclopentylene group and a cyclohexylene group.
• a1 represents an integer of 1-10. When a1 is 2 or more, multiple A1s may be the same or different.
• A2 and A3 are each independently a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as those of A1 in formula (M1-A), so description thereof is omitted.
• a2 represents an integer of 1 to 10, and when a2 is 2 or more, multiple A2 may be the same or different, and multiple A3 may be the same or different.
• a plurality of LA1 may be the same or different.
• a2 is preferably an integer of 2 or more, more preferably 2, because the degree of orientation is better.
• LA1 is a divalent linking group.
• each of the plurality of LA1 is independently a single bond or a divalent linking group, and at least one of the plurality of LA1 is a divalent linking group.
• a2 is 2 or more, each of the plurality of LA1 is independently a single bond or a divalent linking group, and at least one of the plurality of LA1 is a divalent linking group.
• a2 is 2, it is preferable that one of the two LA1s is a divalent linking group and the other is a single bond, because the degree of orientation is better.
• M1 include the following structures.
• Ac represents an acetyl group.
• Terminal groups represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, Alkoxycarbonyloxy group having 1 to 10 carbon atoms, alkoxycarbonyl group having 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), acyloxy group having 1 to 10 carbon atoms, acylamino group having 1 to 10 carbon atoms , an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon
• the (meth)acryloyloxy group-containing group includes, for example, -LA (L represents a single bond or a linking group. Specific examples of the linking group are the same as L1 and SP1 described above.
• A is (meth) represents an acryloyloxy group).
• T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably a methoxy group, because the degree of orientation is superior. These terminal groups may be further substituted with these groups or the crosslinkable groups described above.
• the number of atoms in the main chain of T1 is preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 1 to 10, and particularly preferably from 1 to 7, because the degree of orientation is superior. When the number of atoms in the main chain of T1 is 20 or less, the degree of orientation of the polarizer is further improved.
• the "main chain" in T1 means the longest molecular chain that binds to M1, and hydrogen atoms are not counted in the number of atoms in the main chain of T1. For example, when T1 is an n-butyl group, the number of atoms in the main chain is 4, and when T1 is a sec-butyl group, the number of atoms in the main chain is 3.
• the content is preferably 20 to 100% by mass with respect to 100% by mass of all repeating units in the polymer liquid crystalline compound, since the degree of orientation is more excellent.
• the content of each repeating unit contained in the polymer liquid crystalline compound is calculated based on the charged amount (mass) of each monomer used to obtain each repeating unit.
• the repeating unit (1L) may be contained alone or in combination of two or more in the polymer liquid crystalline compound. Among them, it is preferable that two kinds of repeating units (1L) are contained in the polymer liquid crystalline compound for the reason that the degree of orientation is more excellent.
• the terminal group represented by T1 in one (repeating unit A) is an alkoxy group, and in the other (repeating unit B), the orientation degree is more excellent.
• the terminal group represented by T1 is preferably a group other than an alkoxy group.
• the terminal group represented by T1 in the repeating unit B is preferably an alkoxycarbonyl group, a cyano group, or a (meth)acryloyloxy group-containing group for the reason that the degree of orientation is better, and an alkoxycarbonyl group or a cyano more preferably a group.
• the ratio (A/B) between the content of the repeating unit A in the liquid crystalline polymer compound and the content of the repeating unit B in the liquid crystalline polymer compound is 50/50 for the reason that the degree of orientation is more excellent. 95/5 is preferred, 60/40 to 93/7 is more preferred, and 70/30 to 90/10 is even more preferred.
• both the repeating unit (1L) and the polymer liquid crystalline compound may have a repeating unit having no mesogenic group.
• Repeating units having no mesogenic group include repeating units in which M1 in formula (1L) is a single bond.
• the polymer liquid crystalline compound has a repeating unit having no mesogenic group, the degree of orientation is more excellent, and therefore the amount is more than 0% by mass and 30% by mass or less with respect to 100% by mass of all repeating units possessed by the polymer liquid crystalline compound. is preferable, and more than 10% by mass and 20% by mass or less is more preferable.
• the weight-average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, because the degree of orientation is better.
• the Mw of the liquid crystalline polymer compound is within the above range, the liquid crystalline polymer compound can be easily handled.
• the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 10,000 or more, more preferably 10,000 to 300,000.
• the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10,000, more preferably 2,000 or more and less than 10,000.
• the weight average molecular weight and number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method.
• the substituent W in the present specification will be explained.
• the substituent W include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, and cyclohexyl group), alkenyl group (preferably having 2 to 20 carbon atoms) , more preferably an alkenyl group having 2 to 12 carbon atoms, particularly preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an aryl group, a 2-butenyl group, and a 3-pentenyl group), alkynyl a group (preferably an
• heterocyclic groups having heteroatoms such as epoxy groups, oxetanyl groups, imidazolyl groups, pyridyl groups, quinolyl groups, furyl groups, piperidyl groups, morpholino groups, maleimido groups, benzoxazolyl groups, benzimidazolyl groups, and , a benzthiazolyl group, etc.), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as a trimethylsilyl group, and a triphenylsilyl group), a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like.
• a silyl group preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as a trimethylsilyl group, and
• the anisotropic light absorption layer can be produced, for example, using a composition for forming an anisotropic light absorption layer containing the above dichroic dye compound and any liquid crystalline compound.
• the composition for forming a light absorption anisotropic layer may contain components other than the dichroic dye compound and the liquid crystalline compound, such as a solvent, a vertical alignment agent, an interface modifier, a polymerizable component, and a polymerization initiator. (for example, a radical polymerization initiator) and the like.
• the composition for forming an anisotropic light absorption layer preferably contains a solvent.
• solvents include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ethers (eg, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentylmethyl ether, tetrahydropyran, dioxolane, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, trimethylbenzene, etc.), halogenated Carbons (e.g., dichloromethane, trichloromethane, dichloroethan
• solvents may be used singly or in combination of two or more.
• ketones especially cyclopentanone, cyclohexanone
• ethers especially tetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane
• amides especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone) , N-ethylpyrrolidone
• the content of the solvent is preferably 80 to 99% by mass, preferably 83 to 99% by mass, based on the total mass of the composition for forming an anisotropic light absorption layer. 98% by mass is more preferred, and 85 to 96% by mass is even more preferred.
• the content of the solvent means the total content of the solvents.
• the interface improver As the interface improver, the interface improver described in the Examples section to be described later can be used.
• the content of the interface modifier is the same as the dichroic dye compound and the liquid crystalline compound in the composition for forming an anisotropic light absorption layer. 0.001 to 5 parts by mass is preferable for a total of 100 parts by mass.
• Polymerizable components include compounds containing acrylates (eg, acrylate monomers).
• the light absorption anisotropic layer in the present invention contains polyacrylate obtained by polymerizing the compound containing the acrylate.
• the polymerizable component include compounds described in paragraph 0058 of JP-A-2017-122776.
• the content of the polymerizable component is the same as the dichroic dye compound and the liquid crystalline compound in the composition for forming a light absorption anisotropic layer. 3 to 20 parts by mass is preferable for a total of 100 parts by mass.
• Vertical alignment agents include boronic acid compounds and onium salts.
• a compound represented by formula (30) is preferable as the boronic acid compound.
• R1 and R2 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
• R3 represents a substituent containing a (meth)acryl group.
• Specific examples of boronic acid compounds include boronic acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of JP-A-2008-225281. As the boronic acid compound, compounds exemplified below are also preferable.
• ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocyclic ring.
• X represents an anion.
• L1 represents a divalent linking group.
• L2 represents a single bond or a divalent linking group.
• Y1 represents a divalent linking group having a 5- or 6-membered ring as a partial structure.
• Z represents a divalent linking group having 2 to 20 alkylene groups as a partial structure.
• P1 and P2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated bond.
• onium salts include onium salts described in paragraphs 0052 to 0058 of JP-A-2012-208397, onium salts described in paragraphs 0024-0055 of JP-A-2008-026730, JP-A-2002- Onium salts described in JP-A-37777 and onium salts described in paragraphs 0153 to 0171 of JP-A-2020-076920.
• the content of the vertical alignment agent in the light absorption anisotropic layer-forming composition is preferably 0.1 to 400% by mass, more preferably 0.5 to 350% by mass, based on the total mass of the liquid crystalline compound.
• the vertical alignment agents may be used alone or in combination of two or more. When two or more vertical alignment agents are used, the total amount thereof is preferably within the above range.
• Leveling agent suitable for vertical alignment In the case of vertical alignment, the following leveling agents are preferably included.
• the leveling agent is not particularly limited, and is preferably a leveling agent containing fluorine atoms (fluorine-based leveling agent) or a leveling agent containing silicon atoms (silicon-based leveling agent), more preferably a fluorine-based leveling agent.
• fluorine-based leveling agents include fatty acid esters of polyvalent carboxylic acids in which a portion of the fatty acid is substituted with a fluoroalkyl group, and polyacrylates having fluoro substituents.
• the repeating unit derived from the compound represented by formula (40) is used from the viewpoint of promoting the vertical alignment of the dichroic dye compound and the liquid crystalline compound.
• a leveling agent containing is preferred.
• R0 represents a hydrogen atom, a halogen atom, or a methyl group.
• L represents a divalent linking group. L is preferably an alkylene group having 2 to 16 carbon atoms, and any non-adjacent —CH2— in the alkylene group is —O—, —COO—, —CO—, or —CONH— and substituted with good too.
• n represents an integer from 1 to 18;
• the leveling agent having repeating units derived from the compound represented by formula (40) may further contain other repeating units.
• Other repeating units include repeating units derived from the compound represented by formula (41).
• R11 represents a hydrogen atom, a halogen atom, or a methyl group.
• X represents an oxygen atom, a sulfur atom, or -N(R13)-.
• R13 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
• R12 represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic group.
• the number of carbon atoms in the alkyl group is preferably 1-20.
• the alkyl group may be linear, branched, or cyclic. Further, examples of substituents that the alkyl group may have include a poly(alkyleneoxy) group and a polymerizable group. The definition of the polymerizable group is as described above.
• repeating units derived from the compound represented by formula (40) is preferably 10 to 90 mol %, more preferably 15 to 95 mol %, based on the total repeating units contained in the leveling agent.
• repeating units derived from the compound represented by formula (41) is preferably 10 to 90 mol %, more preferably 5 to 85 mol %, based on the total repeating units contained in the leveling agent.
• the leveling agent also includes a leveling agent containing repeating units derived from the compound represented by formula (42) instead of repeating units derived from the compound represented by formula (40) described above.
• R2 represents a hydrogen atom, a halogen atom, or a methyl group.
• L2 represents a divalent linking group.
• n represents an integer from 1 to 18;
• leveling agent examples include compounds exemplified in paragraphs 0046 to 0052 of JP-A-2004-331812 and compounds described in paragraphs 0038-0052 of JP-A-2008-257205.
• the content of the leveling agent in the composition for forming a light absorption anisotropic layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total mass of the liquid crystalline compound.
• a leveling agent may be used independently and may be used in combination of 2 or more type. When two or more leveling agents are used, the total amount thereof is preferably within the above range.
• the composition for forming a light absorption anisotropic layer preferably contains a polymerization initiator.
• the polymerization initiator is not particularly limited, it is preferably a compound having photosensitivity, that is, a photopolymerization initiator.
• Various compounds can be used as the photopolymerization initiator without any particular limitation. Examples of photoinitiators include ⁇ -carbonyl compounds (US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (US Pat. No. 2,448,828), ⁇ -hydrocarbon-substituted aromatic acyloins, compounds (US Pat. No. 2,722,512), polynuclear quinone compounds (US Pat.
• photopolymerization initiators and BASF Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01 and Irgacure- OXE-02 and the like.
• the content of the polymerization initiator is the dichroic dye compound and the polymer liquid crystal 0.01 to 30 parts by mass is preferable, and 0.1 to 15 parts by mass is more preferable, with respect to 100 parts by mass in total with the active compound.
• the content of the polymerization initiator is 0.01 parts by mass or more, the durability of the light absorption anisotropic film is improved. be better.
• a polymerization initiator may be used individually by 1 type, or may use 2 or more types together. When two or more polymerization initiators are included, the total amount is preferably within the above range.
• the method for forming the anisotropic light absorption layer is not particularly limited, and the step of applying the composition for forming the anisotropic light absorption layer to form a coating film (hereinafter also referred to as the “coating film forming step”). and a step of orienting the liquid crystalline component or dichroic dye compound contained in the coating film (hereinafter also referred to as an “orientation step”), in this order.
• the liquid crystalline component is a component containing not only the liquid crystalline compound described above but also a dichroic dye compound having liquid crystallinity when the dichroic dye compound described above has liquid crystallinity.
• the coating film forming step is a step of applying a composition for forming a light absorption anisotropic layer to form a coating film.
• a composition for forming a light absorption anisotropic layer containing the solvent described above, or by using a liquid such as a melt by heating the composition for forming an anisotropic light absorption layer, It becomes easy to apply the composition for forming a light-absorbing anisotropic layer.
• Specific examples of the coating method of the composition for forming a light-absorbing anisotropic layer include roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, and reverse coating. Known methods such as a gravure coating method, a die coating method, a spray method, and an inkjet method can be used.
• the alignment step is a step of orienting the liquid crystalline component contained in the coating film. Thereby, a light absorption anisotropic layer is obtained.
• the orientation step may include drying. Components such as the solvent can be removed from the coating film by the drying treatment.
• the drying treatment may be performed by a method of leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by a method of heating and/or blowing air.
• the liquid crystalline component contained in the composition for forming a light-absorbing anisotropic layer may be oriented by the coating film forming step or drying treatment described above.
• the coating film is dried to remove the solvent from the coating film, thereby obtaining the anisotropic light absorption.
• a coating film (that is, a light absorption anisotropic film) is obtained.
• the transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase is preferably 10 to 250°C, more preferably 25 to 190°C, from the standpoint of production suitability.
• the transition temperature is 10° C. or higher, cooling treatment or the like for lowering the temperature to the temperature range where the liquid crystal phase is exhibited is not required, which is preferable.
• the transition temperature is 250° C. or less, a high temperature is not required even when the isotropic liquid state is converted to an isotropic liquid state at a temperature higher than the temperature range in which the liquid crystal phase is once exhibited, which wastes thermal energy and reduces substrate damage. This is preferable because it can reduce deformation, deterioration, and the like.
• the orientation step preferably includes heat treatment.
• the liquid crystalline component contained in the coating film can be oriented, so that the coating film after heat treatment can be suitably used as a light absorption anisotropic film.
• the heat treatment is preferably from 10 to 250° C., more preferably from 25 to 190° C., from the standpoint of suitability for production.
• the heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
• the orientation step may have a cooling treatment performed after the heat treatment.
• the cooling process is a process of cooling the coated film after heating to about room temperature (20 to 25° C.). Thereby, the orientation of the liquid crystalline component contained in the coating film can be fixed.
• a cooling means is not particularly limited, and a known method can be used. Through the above steps, a light absorption anisotropic film can be obtained. In this embodiment, drying treatment, heat treatment, and the like are mentioned as methods for orienting the liquid crystalline component contained in the coating film.
• the method for forming the anisotropic light absorption layer may include a step of curing the anisotropic light absorption layer (hereinafter also referred to as a “curing step”) after the alignment step.
• the curing step is carried out by heating and/or light irradiation (exposure), for example, when the light absorption anisotropic layer has a crosslinkable group (polymerizable group).
• the curing step is preferably carried out by light irradiation.
• Various light sources such as infrared light, visible light, and ultraviolet light can be used as the light source for curing, but ultraviolet light is preferred.
• ultraviolet rays may be irradiated while being heated during curing, or ultraviolet rays may be irradiated through a filter that transmits only specific wavelengths.
• the heating temperature during exposure is preferably 25 to 140° C., depending on the transition temperature of the liquid crystalline component contained in the liquid crystal film to the liquid crystal phase.
• the exposure may be performed in a nitrogen atmosphere. In the case where the liquid crystal film is cured by radical polymerization, it is preferable to perform the exposure in a nitrogen atmosphere because the inhibition of polymerization by oxygen is reduced.
• the thickness of the light absorption anisotropic layer is not particularly limited, it is preferably 100 to 8000 nm, more preferably 300 to 5000 nm from the viewpoint of flexibility when the laminate of the present invention described later is used in a polarizing element. It is more preferable to have
• the optical film of the invention may have a transparent substrate film.
• the transparent substrate film is preferably arranged on the surface of the anisotropic light absorption layer opposite to the surface provided with the optical film.
• a known transparent resin film, transparent resin plate, transparent resin sheet, or the like can be used, and there is no particular limitation.
• transparent resin films include cellulose acylate films (e.g., cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, and polyethersulfone.
• Polyacrylic resin films polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyether ketone films, (meth)acrylonitrile films and the like can be used.
• cellulose acylate films which are highly transparent, have little optical birefringence, are easy to manufacture, and are generally used as protective films for polarizing plates, are preferred, and cellulose triacetate films are particularly preferred.
• the thickness of the transparent substrate film is usually 20 ⁇ m to 100 ⁇ m.
• the transparent base film is a cellulose ester film and has a thickness of 20 to 70 ⁇ m.
• the optical film of the present invention may have an alignment film between the transparent substrate film and the light absorption anisotropic layer.
• the alignment film may be any layer as long as the dichroic dye compound can be oriented in a desired state on the alignment film.
• a film formed from a polyfunctional acrylate compound or polyvinyl alcohol may be used. Polyvinyl alcohol is particularly preferred.
• the optical film of the present invention preferably has a barrier layer together with the light absorption anisotropic layer.
• the barrier layer is also called a gas blocking layer (oxygen blocking layer), and has a function of protecting the polarizing element of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. have.
• the optical film of the present invention preferably has a refractive index adjusting layer from the viewpoint of suppressing internal reflection caused by the high refractive index of the light absorption anisotropic layer.
• the refractive index adjustment layer is a layer arranged so as to be in contact with the light absorption anisotropic layer, and has an in-plane average refractive index of 1.55 or more and 1.70 or less at a wavelength of 550 nm. It is preferably a refractive index adjustment layer for performing so-called index matching.
• the optical film of the invention preferably has a tint adjustment layer containing at least one dye compound.
• the dye compound contained in the color tone adjusting layer is preferably in a non-oriented state.
• This tint adjustment layer may have only the function of the tint adjustment layer alone, or may have the functions integrated with those of other layers.
• the absorption peak wavelength of the dye compound contained in the color adjustment layer is preferably 500 nm or more and 650 nm or less, more preferably 550 nm or more and 600 nm or less. By setting the absorption of the dye compound within this range, the color of the optical film in the invention can be adjusted to be more neutral.
• Dye compounds contained in the color tone adjusting layer include, for example, azo, methine, anthraquinone, triarylmethane, oxazine, azomethine, phthalocyanine, porphyrin, perylene, pyrrolopyrrole, squarylium and the like.
• Azo, phthalocyanine and anthraquinone are preferred from the viewpoint of excellent properties, and anthraquinone is particularly preferred.
• An example of the method for producing the optical film of the present invention includes a step of coating the composition for forming an alignment film on the transparent base film to form an alignment film, and applying the composition for forming an anisotropic light absorption layer. and a step of coating on an alignment film to orient the dichroic dye compound contained in the coating film to obtain the light absorption anisotropic layer, in this order.
• Each step can be carried out according to a known method and is not particularly limited.
• the electroluminescence (EL) display device of the present invention is an EL display device in which the optical film of the present invention is laminated on an EL substrate having EL light-emitting elements of a plurality of colors. Further, the EL display device of the present invention is preferably a self-luminous display device using inorganic EL light-emitting elements. Further, in the EL display device of the present invention, the light emitting element is preferably a light emitting diode (LED).
• LED light emitting diode
• the EL substrate various known EL substrates used in self-luminous display devices using inorganic EL light-emitting elements or the like can be used.
• the EL substrate has a large number of R light-emitting elements, G light-emitting elements, and B light-emitting elements arranged two-dimensionally, like known EL substrates.
• the EL substrate may be a transparent substrate.
• inorganic EL light emitting elements are arranged on a transparent substrate.
• the light-emitting element is a light-emitting diode (LED)
• the LED has three colors of red, green and blue, and has wavelengths of 460 nm, 530 nm and 630 nm in the normal direction of the electroluminescent display device.
• the luminance is defined as Lb, Lg, and Lr, respectively, it is preferable to satisfy both the relationships of the following formulas (3) and (4).
• luminance at 460 nm, 530 nm and 630 nm in the normal direction of the electroluminescence display device can be measured by a spectroradiometer SR-UL1R manufactured by Topcon Corporation, for example.
• Example 1 ⁇ Formation of Alignment Film>
• the surface of a cellulose acylate film (TAC substrate having a thickness of 40 ⁇ m; TG40, Fuji Film Co., Ltd.) was saponified with an alkaline solution, and the composition for forming an alignment film was applied thereon with a wire bar.
• the support on which the coating film was formed was dried with hot air at 60° C. for 60 seconds and further with hot air at 100° C. for 120 seconds to form an alignment film AL1, and TAC film 1 with an alignment film was obtained.
• the film thickness was 1 ⁇ m.
• the following light absorption anisotropic layer forming composition P1 was continuously applied with a wire bar, heated at 120 ° C. for 60 seconds, and then cooled to room temperature (23 ° C.). did. Then, it was heated at 80° C. for 60 seconds and cooled again to room temperature. Thereafter, an anisotropic light absorption layer P1 was formed on the alignment film 1 by irradiating for 2 seconds under irradiation conditions of an illuminance of 200 mW/cm 2 using an LED lamp (center wavelength of 365 nm). The film thickness of the light absorption anisotropic layer P1 was 3.5 ⁇ m.
• Composition of Composition P1 for Forming Light-Absorbing Anisotropic Layer ⁇ ⁇ 0.63 parts by mass of the following dichroic dye compound D-1 ⁇ 0.85 parts by mass of the following dichroic dye compound D-2 ⁇ 8.63 parts by mass of the following polymer liquid crystalline compound P-1 ⁇ IRGACUREOXE-02 ( BASF Corporation) 0.16 parts by mass, compound E-1 below: 0.13 parts by mass, compound E-2 below: 0.13 parts by mass, surfactant F-1 below: 0.004 parts by mass, cyclopentanone 80. 53 parts by mass benzyl alcohol 8.95 parts by mass ⁇
• composition B1 for forming an oxygen blocking layer A coating liquid having the following composition (composition B1 for forming an oxygen blocking layer) was continuously applied on the formed light absorption anisotropic layer P1 with a wire bar. Then, it was dried with hot air at 100° C. for 2 minutes to form a 0.5 ⁇ m-thick polyvinyl alcohol (PVA) orientation layer (oxygen blocking layer B1) on the light absorption anisotropic layer P1.
• PVA polyvinyl alcohol
• an optical film 1 comprising a cellulose acylate film, an alignment film AL1, an anisotropic light absorption layer P1 and an oxygen blocking layer B1 adjacent to each other in this order was obtained.
• Example 2 An optical film 2 was prepared in the same manner as in Example 1, except that the dichroic dye compound D-2 was changed to the following dichroic dye compound D-3.
• Example 3 An optical film 3 was produced in the same manner as in Example 1, except that the dichroic dye compound D-2 was changed to the following dichroic dye compound D-4.
• Composition of Composition P5 for Forming Light-Absorbing Anisotropic Layer ⁇ - 0.63 parts by mass of the dichroic dye compound D-1 - 0.17 parts by mass of the dichroic dye compound D-3 - 9.31 parts by mass of the polymer liquid crystalline compound P-1 - IRGACUREOXE-02 ( BASF Corporation) 0.16 parts by mass, 0.13 parts by mass of compound E-1, 0.13 parts by mass of compound E-2, 0.004 parts by mass of surfactant F-1, and cyclopentanone 80. 53 parts by mass benzyl alcohol 8.95 parts by mass ⁇
• Example 4 An optical film 6 was produced in the same manner as in Example 1, except that the composition of the light absorption anisotropic layer P1 was changed to the composition of P6 below.
• Composition of Composition P6 for Forming Light-Absorbing Anisotropic Layer ⁇ - 0.80 parts by weight of the following dichroic dye compound D-6 - 9.31 parts by weight of the polymer liquid crystalline compound P-1 - IRGACUREOXE-02 (manufactured by BASF) 0.16 parts by weight -
• Example 5 An optical film 7 was produced in the same manner as in Example 1, except that the composition of the light absorption anisotropic layer P1 was changed to the composition of P7 below.
• Composition of Composition P7 for Forming Light-Absorbing Anisotropic Layer ⁇ - 0.50 parts by mass of the dichroic dye compound D-1 - 0.68 parts by mass of the dichroic dye compound D-2 - 0.30 parts by mass of the dichroic dye compound D-6 -
• the polymer liquid crystal Sexual compound P-1 8.63 parts by weight IRGACUREOXE-02 (manufactured by BASF) 0.16 parts by weight Compound E-1 0.13 parts by weight Above compound E-2 0.13 parts by weight Above surface activity Agent F-1 0.004 parts by mass Cyclopentanone 80.53 parts by mass Benzyl alcohol 8.95 parts by mass ⁇ ⁇
• the brightness in the direction of 45° was the average value of four azimuth angles of the panel up, down, left, and right.
• the optical film obtained above was placed on the upper surface of the fabricated micro LED, and the front surface was again adjusted to be white. After that, the tint was confirmed from the 45° direction and evaluated as follows. A: Neutral with no color shift B: Substantially neutral with some color shift observed C: Color shift observed but not neutral.
• the evaluation results are shown in Table 1 below.
• the ratio in Table 1 below represents the ratio of each dichroic dye compound when the total solid content is 100%.

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