WO2018221360A1 - Dispositif d'affichage à cristaux liquides et son procédé de fabrication - Google Patents

Dispositif d'affichage à cristaux liquides et son procédé de fabrication Download PDF

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Publication number
WO2018221360A1
WO2018221360A1 PCT/JP2018/019915 JP2018019915W WO2018221360A1 WO 2018221360 A1 WO2018221360 A1 WO 2018221360A1 JP 2018019915 W JP2018019915 W JP 2018019915W WO 2018221360 A1 WO2018221360 A1 WO 2018221360A1
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liquid crystal
monomer
group
display device
crystal display
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PCT/JP2018/019915
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English (en)
Japanese (ja)
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真伸 水▲崎▼
康司郎 谷池
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シャープ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G02F1/1343—Electrodes
    • 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
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device

Definitions

  • the present invention relates to a liquid crystal display device and a method for manufacturing the liquid crystal display device. More specifically, the present invention relates to a liquid crystal display device having a photo-alignment film and a manufacturing method thereof.
  • a liquid crystal display device is a display device that uses a liquid crystal composition for display.
  • a typical display method is to irradiate light from a backlight onto a liquid crystal panel in which the liquid crystal composition is sealed between a pair of substrates. The amount of light transmitted through the liquid crystal panel is controlled by applying a voltage to the liquid crystal composition to change the orientation of the liquid crystal material.
  • Such a liquid crystal display device has features such as thinness, light weight, and low power consumption, and thus is used in electronic devices such as smartphones, tablet PCs, and car navigation systems.
  • a horizontal electric field type horizontal control in which the orientation of a liquid crystal material is controlled mainly in a plane parallel to the substrate surface for the purpose of easily obtaining a wide viewing angle characteristic.
  • the orientation mode is attracting attention.
  • Examples of the horizontal electric field type horizontal alignment mode include an in-plane switching (IPS: In-Plane Switching) mode and a fringe electric field switching (FFS: Fringe Field Switching) mode.
  • the alignment of a liquid crystal material in a state where no voltage is applied is generally controlled by an alignment film that has been subjected to an alignment treatment (see, for example, Patent Document 1).
  • the alignment film is formed, for example, by applying an alignment film material such as polyamic acid on a substrate and then baking it.
  • an alignment film material such as polyamic acid
  • a polymer-supported alignment technique Polymer
  • Polymer that polymerizes a polymerizable monomer added in the liquid crystal layer to form a polymer layer for controlling the alignment of the liquid crystal material on the surface of the alignment film.
  • Sustained Alignment has also been studied (see, for example, Non-Patent Document 1).
  • Yohei Nakanishi Yohei Nakanishi
  • three others "the relationship of the phenomenon sticking with the monomer structure of the polymer support alignment liquid crystal display (Relation between Monomer Structure and Image Sticking Phenomenon of Polymer-Sustained-Alignment Liquid Crystal Displays)", Japanese Journal of Applied Physics 2011, Vol. 50, p. 051702-1-051702-5
  • FIG. 7 is an enlarged schematic plan view of a liquid crystal display device according to a reference example, showing a liquid crystal compound and a linear portion of a pixel electrode and / or a common electrode.
  • the pixel electrode with respect to the initial alignment direction 31a of the liquid crystal compound 31 and It is necessary to make the inclination angle (Inclination Angle; IA) ⁇ of the linear portion 27 of the common electrode as small as possible. Therefore, the inclination angle ⁇ is normally set to less than 7 °.
  • the liquid crystal compound 31 rotates greatly from the initial alignment azimuth 31a when the tilt angle ⁇ is small.
  • the anchoring strength (especially the azimuth anchoring strength) of the horizontal photo-alignment film is relatively weak (low orientation regulation force), as shown in FIG.
  • the liquid crystal compound 31 does not return to the initial orientation azimuth 31a, and as a result, burn-in occurs.
  • an alignment film material having an azobenzene group (isomerization type) in the polymer main chain which is a kind of horizontal light alignment film material
  • the image sticking from the AC voltage becomes remarkable. This is presumably because the azimuth anchoring strength is particularly low in an alignment film formed from an alignment film material having an azobenzene group in the polymer main chain (hereinafter also referred to as an azobenzene group-containing photo-alignment film material).
  • the factors are (1) the weight-average molecular weight of the azobenzene group-containing photoalignment film material is relatively small (for example, 20,000 or less), and (2) some azobenzene groups by irradiation with polarized ultraviolet rays are expressed by the following reaction formula: As shown, because of photocleavage, the weight average molecular weight of the polymer is further reduced.
  • the azobenzene group-containing photo-alignment film material is designed to improve the molecular mobility by reducing the weight average molecular weight to some extent in order to align the polymer in one direction by irradiation with polarized ultraviolet rays.
  • the azobenzene group is susceptible to cleavage reaction in addition to isomerization by (polarized) ultraviolet irradiation.
  • polyamic acid and / or polyimide is used as the polymer and the one having a bent molecular structure is used as tetracarboxylic dianhydride, the absorption efficiency of polarized ultraviolet light is improved, so the number of cleavage of the azobenzene group is further increased. Become.
  • the present invention has been made in view of the above situation, and provides a liquid crystal display device capable of suppressing burn-in caused by application of an AC voltage and a method of manufacturing a liquid crystal display device capable of manufacturing such a liquid crystal display device. It is intended to do.
  • One embodiment of the present invention includes a liquid crystal layer containing a liquid crystal material having a positive dielectric anisotropy, a sealant disposed so as to surround the liquid crystal layer in a plan view, and a pair of sandwiching the liquid crystal layer A substrate and a photo-alignment film provided on at least one surface of the pair of substrates, wherein the photo-alignment film contains at least one of polyamic acid and polyimide, and contains the liquid crystal compound in the liquid crystal material.
  • One of the pair of substrates includes a pixel electrode and a common electrode, and at least one of the pixel electrode and the common electrode includes a linear portion,
  • the liquid crystal display device may have an inclination angle of the linear portion with respect to the initial alignment direction of the liquid crystal compound of 7 ° or more in plan view.
  • Another embodiment of the present invention is a preparatory step of preparing a pair of substrates, and an orientation containing at least one polymer of polyamic acid and polyimide and at least one monomer on at least one surface of the pair of substrates.
  • the at least one monomer may be a method for producing a liquid crystal display device that exhibits orientation by causing at least one of an isomerization reaction and a dimerization reaction by irradiation with polarized ultraviolet rays.
  • Patent Document 1 discloses a polyamic acid-based alignment film material having an azobenzene group in the main chain.
  • the inclination angle of the linear portion of the pixel electrode and / or the common electrode with respect to the initial alignment direction of the liquid crystal compound is 7 ° or more.
  • liquid crystal display device and the manufacturing method of the liquid crystal display device of the present invention, it is possible to suppress image sticking caused by application of an AC voltage.
  • FIG. 1 is a schematic cross-sectional view of a liquid crystal display device according to Embodiment 1.
  • FIG. 1 is a schematic plan view of a liquid crystal display device according to Embodiment 1.
  • FIG. 2 is an enlarged schematic plan view of the liquid crystal display device according to Embodiment 1, showing a liquid crystal compound and a linear portion of a pixel electrode and / or a common electrode.
  • FIG. 5 is an enlarged schematic plan view of a liquid crystal display device according to a modification of Embodiment 1, showing a liquid crystal compound and a linear portion of a pixel electrode and / or a common electrode.
  • FIG. 1 is a schematic cross-sectional view of a liquid crystal display device according to Embodiment 1.
  • FIG. 1 is a schematic plan view of a liquid crystal display device according to Embodiment 1.
  • FIG. 2 is an enlarged schematic plan view of the liquid crystal display device according to Embodiment 1, showing a liquid crystal compound and a linear portion of a pixel electrode and
  • FIG. 3 is a schematic diagram illustrating states of a polyimide polymer having an azobenzene group and a polymer of an alignment monomer in a photo-alignment film of the liquid crystal display device according to Embodiment 1. It is the schematic diagram explaining the state of the molecule
  • the “photoreactive monomer” means a monomer containing a photofunctional group.
  • the “photofunctional group” means a functional group capable of causing a photoreaction.
  • observation surface side means a side closer to the screen (display surface) of the liquid crystal display device
  • back side means the screen (display surface) of the liquid crystal display device. Means the farther side.
  • the “initial alignment direction of the liquid crystal compound” means the alignment direction of the liquid crystal compound in a state in which no voltage is applied between the pixel electrode and the common electrode.
  • the “alignment orientation of the liquid crystal compound” means the direction of the long axis (liquid crystal director) of the liquid crystal compound.
  • FIG. 1 is a schematic cross-sectional view of the liquid crystal display device according to the first embodiment.
  • FIG. 2 is a schematic plan view of the liquid crystal display device according to the first embodiment.
  • FIG. 3 is an enlarged schematic plan view of the liquid crystal display device according to Embodiment 1, and shows a liquid crystal compound and a linear portion of a pixel electrode and / or a common electrode.
  • the liquid crystal display device 100 of the present embodiment is an FFS mode that is a kind of horizontal electric field type horizontal alignment mode, and contains a liquid crystal material having positive dielectric anisotropy.
  • the liquid crystal display device 100 further includes a backlight 70 behind one of the pair of substrates 10 and 20.
  • one of the substrates 10 and 20 is arranged between the planar electrode 22, the slit electrode 24 provided with at least one slit 24 s, and the planar electrode 22 and the slit electrode 24.
  • a structure (FFS electrode structure) including the insulating film (interlayer insulating film) 23 is provided, and an oblique electric field (fringe electric field) including a lateral electric field component is formed in the liquid crystal layer 30.
  • the slit electrode 24 upper layer electrode
  • the insulating film 23 and the planar electrode 22 lower layer electrode
  • slit electrode 24 for example, a linear opening surrounded by an electrode around the entire circumference as the slit 24s, or a linear electrode provided with a plurality of comb teeth and disposed between the comb teeth.
  • a comb-shaped slit that forms the slit 24s can be used.
  • one of the slit electrode 24 and the planar electrode 22 functions as the pixel electrode 25 provided corresponding to each pixel, and the other functions as the common electrode 26.
  • one of the slit electrode 24, that is, the pixel electrode 25 and the common electrode 26 includes a plurality of linear portions 27 parallel to each other.
  • the linear portion 27 and the slit 24 s of the slit electrode 24 include the liquid crystal compound 31. They are alternately arranged in the direction orthogonal to the initial orientation direction 31a.
  • Each linear portion 27 is usually composed of one or more straight portions, and when composed of two straight portions, it is composed of three or more straight portions in a V shape as shown in FIG. If it is, it is formed in a zigzag shape.
  • FIG. 4 is an enlarged schematic plan view of a liquid crystal display device according to a modification of the first embodiment, and shows a liquid crystal compound and a linear portion of a pixel electrode and / or a common electrode.
  • each linear portion 27 may be composed of a plurality of linear portions having different inclination angles ⁇ with respect to the initial alignment azimuth 31 a of the liquid crystal compound 31. It is preferable that the smallest of these satisfy the numerical range described later.
  • the photo-alignment film 50 includes at least one polymer of polyamic acid and polyimide (hereinafter also referred to as polyimide polymer), and the liquid crystal compound 31 in the liquid crystal material is oriented in a horizontal direction with respect to the substrates 10 and 20. To be oriented.
  • a photo-alignment film usually has a lower anchoring strength (particularly azimuth angle anchoring strength) than a horizontal alignment film for rubbing treatment. Therefore, as described above, even in the liquid crystal display device 100, the liquid crystal panel (liquid crystal There is concern over the occurrence of burn-in due to the application of an AC voltage to the layer 30 and each pixel).
  • the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment direction 31a of the liquid crystal compound 31 is large, specifically, set to 7 ° or more in plan view. .
  • the amount of change ⁇ d in the azimuth direction of the liquid crystal compound 31 due to the application of the AC voltage is reduced, so that burn-in due to the application of the AC voltage can be reduced.
  • the return of the liquid crystal compound 31 (liquid crystal director) to the initial alignment azimuth 31a at the time of removing the AC voltage becomes faster, a high-speed response is possible.
  • the upper limit of the tilt angle ⁇ is not particularly limited and can be set as appropriate from the viewpoint of reducing the burn-in resulting from the AC voltage application and increasing the response speed.
  • the tilt angle ⁇ is too large, the liquid crystal compound 31 A decrease in transmittance and contrast due to a small change ⁇ d in the azimuth direction may occur (although there are effects of low image sticking and high-speed response). Therefore, from the viewpoint of transmittance and contrast, the inclination angle ⁇ is preferably not too large, and specifically, it is preferably 13 ° or less in plan view.
  • Examples of the pair of substrates 10 and 20 include a combination of an active matrix substrate (TFT substrate) and a color filter (CF) substrate.
  • TFT substrate active matrix substrate
  • CF color filter
  • the active matrix substrate those normally used in the field of liquid crystal display devices can be used.
  • the transparent matrix 21 has a plurality of parallel gate signal lines; a plurality of parallel gate signal lines extending in a direction perpendicular to the gate signal lines and parallel to each other.
  • TFTs thin film transistors
  • a common electrode In the case of the horizontal electric field type horizontal alignment mode, a common electrode; a common electrode 26 that is connected to the common wire and applies a common voltage to a plurality of pixels (or all pixels) is provided.
  • the pixel electrode 25 and the common electrode 26 may be stacked via the insulating film 23.
  • an amorphous silicon, polysilicon, or an oxide semiconductor IGZO indium-gallium-zinc-oxygen
  • VHR voltage holding ratio
  • the color filter substrate those usually used in the field of liquid crystal display devices can be used.
  • the configuration of the color filter substrate include a configuration in which a black matrix formed in a lattice shape, a color filter formed inside a lattice, that is, a pixel, and the like are provided on a transparent substrate.
  • the color filter may include a red color filter, a green color filter, and a blue color filter.
  • the thickness of the blue color filter may be greater than the thickness of the red color filter or the green color filter. By increasing the blue color filter, the liquid crystal layer thickness can be reduced and the cell thickness can be optimized.
  • the pair of substrates 10 and 20 may be one in which both the color filter and the active matrix are formed on one substrate.
  • the sealing material 40 is disposed so as to surround the liquid crystal layer 30 in a plan view.
  • the sealing material 40 may be cured by light such as ultraviolet rays, may be cured by heat, or may be cured by both light and heat. Those that cure by both heat and heat are preferred.
  • Examples of the sealing material 40 include those containing an epoxy resin, a (meth) acrylic resin, and the like.
  • the sealing material 40 may contain a curing agent such as a silane coupling agent, an inorganic filler, an organic filler, and an epoxy curing material.
  • As the sealing material 40 for example, Sekisui Chemical Co., Ltd., Photorec, etc. can be used.
  • variety of the sealing material 40 in planar view is not specifically limited, According to the adhesive strength requested
  • the sealing material 40 before and after curing may contain a (meth) acrylic monomer, a radical polymerization initiator, an epoxy monomer, and an epoxy curing material. These components are contained in the sealing material 40 before curing, and are unreacted components remaining in the sealing material 40 after curing.
  • the liquid crystal layer is formed from the cured sealing material 40. 30 and is adsorbed on the surface of the photo-alignment film 50 to cause a decrease in the azimuth anchoring strength of the photo-alignment film 50.
  • the inclination angle ⁇ is set to 7 ° or more in plan view, even when such an unreacted component remains in the sealing material 40, it is attributed to the unreacted component.
  • the (meth) acrylic monomer and the radical polymerization initiator have higher solubility in the liquid crystal material than the epoxy monomer and the epoxy cured material, and therefore the orientation of the photo-alignment film 50 compared to the epoxy monomer and the epoxy cured material.
  • the possibility of reducing the angle anchoring strength is considered very high.
  • radical polymerization initiator a polymerization initiator that generates radicals upon irradiation with light (preferably ultraviolet rays), that is, a photo radical polymerization initiator is preferable, and a (meth) acrylic monomer contained in the sealant 40 before curing.
  • radical polymerization is performed by radicals generated from a radical polymerization initiator by light irradiation to form a (meth) acrylic resin.
  • the (meth) acrylic monomer may be of low polarity.
  • the (meth) acrylic monomer is not particularly limited, and examples thereof include urethane (meth) acrylate having a urethane bond, and epoxy (meth) acrylate derived from a compound having a glycidyl group and (meth) acrylic acid. . Any of these may be used alone or in combination of two or more.
  • (meth) acryl means acryl or methacryl.
  • the urethane (meth) acrylate is not particularly limited, and examples thereof include derivatives of diisocyanates such as isophorone diisocyanate and reactive compounds that undergo addition reaction with isocyanates such as acrylic acid and hydroxyethyl acrylate. These derivatives may be chain-extended with caprolactone or polyol. Examples of commercially available products include U-122P, U-340P, U-4HA, U-1084A (manufactured by Shin-Nakamura Chemical Co., Ltd.); KRM7595, KRM7610, KRM7619 (manufactured by Daicel UCB) and the like. .
  • the epoxy (meth) acrylate is not particularly limited, and examples thereof include an epoxy (meth) acrylate derived from an epoxy resin such as bisphenol A type epoxy resin or propylene glycol diglycidyl ether, and (meth) acrylic acid. It is done. Examples of commercially available products include EA-1020, EA-6320, EA-5520 (above, Shin-Nakamura Chemical Co., Ltd.); Epoxy ester 70PA, Epoxy ester 3002A (above, Kyoeisha Chemical Co., Ltd.) and the like. .
  • acrylic monomers include, for example, methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, (poly) ethylene glycol dimethacrylate, 1,4-butane Examples thereof include diol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and glycerin dimethacrylate.
  • the radical polymerization initiator is not particularly limited, and examples thereof include compounds represented by the following chemical formula (R-1) or (R-2). Moreover, as a commercial item, IRGACURE 651, IRGACURE189, IRGACURE-OXE01 (above, BASF Japan make) etc. are mentioned, for example. Any of these may be used alone or in combination of two or more.
  • R represents hydrogen or an aliphatic hydrocarbon residue having 4 or less carbon atoms
  • X represents a residue of a bifunctional isocyanate derivative having 13 or less carbon atoms
  • Y represents carbon. This represents an aliphatic hydrocarbon residue having a number of 4 or less or a residue having an atomic ratio of carbon to oxygen constituting the residue of 3 or less.
  • the epoxy monomer means a compound having a reactive epoxy group at both ends, and includes a prepolymer.
  • a prepolymer is a compound (intermediate product) having a repeating structure between two epoxy groups (may be glycidyl groups) at both ends.
  • Many of the epoxy monomers contained in the sealing material 40 before curing are cross-linked by an addition reaction of the epoxy curing material to form an epoxy resin when heated.
  • epoxy resin examples include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a biphenyl novolac epoxy resin, a trisphenol novolac epoxy resin, a dicyclopentadiene novolac epoxy resin, a bisphenol A epoxy resin, and a bisphenol F type.
  • Epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene oxide added bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, resorcinol type Examples include epoxy resins and glycidylamines. Any of these may be used alone or in combination of two or more.
  • those commercially available include, for example, NC-3000S (manufactured by Nippon Kayaku Co., Ltd.) as a phenyl novolac type epoxy resin, and EPPN-501H and EPPN-501H as trisphenol novolak type epoxy resins.
  • the epoxy curing material is not particularly limited, but preferably contains an amine and / or thiol group having excellent low-temperature reactivity in order to cure the sealing material 40 before curing at a curing temperature of 100 to 120 ° C.
  • an epoxy curing material is not particularly limited, but for example, hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], adipic acid dihydrazide; dicyandiamide, guanidine derivatives, 1-cyanoethyl-2 -Phenylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, N , N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl
  • the liquid crystal layer 30 contains a liquid crystal material including at least one liquid crystal compound (liquid crystal molecule) 31.
  • the liquid crystal material is a thermotropic liquid crystal, and preferably a liquid crystal material exhibiting a nematic phase (nematic liquid crystal).
  • the liquid crystal material preferably has a phase transition to an isotropic phase when the temperature rises from a nematic phase and reaches a certain critical temperature (nematic phase-isotropic phase transition point (T NI )) or higher.
  • T NI critical temperature
  • the liquid crystal layer 30 preferably exhibits a nematic phase under the usage environment of the liquid crystal display device (for example, ⁇ 40 ° C. to 90 ° C.).
  • the temperature of the nematic phase-isotropic phase transition point of the liquid crystal material is not particularly limited, but is, for example, 70 to 110 ° C., and preferably 95 ° C. or higher. By setting the temperature to 95 ° C. or higher, the liquid crystal display device 100 can be made suitable for in-vehicle use, marine use, aviation use, and the like.
  • the method for measuring the nematic phase-isotropic phase transition point of the liquid crystal material is, for example, by differential scanning calorimetry (DSC) or by directly observing the temperature dependence by enclosing the liquid crystal material in a capillary. can do.
  • the liquid crystal material and the liquid crystal compound 31 have a positive dielectric anisotropy ( ⁇ ) defined by the following formula. That is, the liquid crystal material and the liquid crystal compound 31 have positive dielectric anisotropy.
  • the liquid crystal material having positive dielectric anisotropy and the liquid crystal compound 31 have characteristics such as high T NI and high-speed response (low rotational viscosity).
  • As the liquid crystal material having positive dielectric anisotropy for example, a material having ⁇ of 1 to 20 can be used.
  • the liquid crystal layer 30 and the liquid crystal material may contain a liquid crystal compound (neutral liquid crystal compound) having no polarity, that is, ⁇ is substantially zero.
  • the neutral liquid crystal compound include a liquid crystal compound having an alkene structure.
  • a liquid crystal material and a liquid crystal compound having positive dielectric anisotropy are also referred to as a positive liquid crystal material and a positive liquid crystal compound, respectively.
  • ⁇ (dielectric constant in the major axis direction)-(dielectric constant in the minor axis direction)
  • the liquid crystal material may have a dielectric anisotropy of 1 or more and less than 3.5 (preferably 1.5 or more and 3 or less, more preferably 1.8 or more and 2.7 or less). .
  • the liquid crystal display device 100 can achieve high-speed response and is suitable for in-vehicle use.
  • a high AC voltage for example, about 6 V
  • the burn-in derived from the AC voltage becomes remarkable. There is concern.
  • the inclination angle ⁇ is set to 7 ° or more in plan view, image sticking due to application of a high AC voltage occurs even when the dielectric anisotropy of the liquid crystal material is small. This can be effectively suppressed.
  • the liquid crystal material may contain a liquid crystal compound having an alkenyl group.
  • the liquid crystal compound having an alkenyl group is preferably a neutral liquid crystal compound.
  • the rotational viscosity of the liquid crystal material is improved, so that the response performance of the liquid crystal material can be improved and the speed can be increased. Accordingly, it is possible to introduce a liquid crystal compound having a liquid crystal phase at a high temperature and having a high viscosity at a low temperature into the liquid crystal material. As a result, the liquid crystal material has a fast response and exhibits a liquid crystal phase in a wide temperature range.
  • a liquid crystal material having a nematic phase-isotropic phase transition point of 95 ° C. or higher can be used.
  • the liquid crystal compound having an alkenyl group may be a compound represented by any of the following chemical formulas (L-1) to (L-4). Any of these may be used alone or in combination of two or more.
  • n are the same or different and are integers of 1 to 6)
  • liquid crystal compound having an alkenyl group examples include a compound represented by the following chemical formula (L-1-1).
  • the photo-alignment film 50 is disposed in contact with the liquid crystal layer 30 and aligns the liquid crystal compound 31 in the liquid crystal material included in the liquid crystal layer 30 in the horizontal direction with respect to the surfaces of the substrates 10 and 20.
  • the alignment of the liquid crystal material in a state where a voltage equal to or higher than the threshold value of the liquid crystal material is not applied to the liquid crystal layer 30 is controlled by the photo-alignment film 50.
  • aligning the liquid crystal compound 31 in the liquid crystal material in the horizontal direction with respect to the substrates 10 and 20 means that the pretilt angle of the liquid crystal material with respect to the substrates 10 and 20 is 10 ° or less.
  • the pretilt angle is more preferably 3 ° or less.
  • the pretilt angle refers to an angle formed by the major axis of the liquid crystal material (liquid crystal compound 31) with respect to the surface of the substrate when the applied voltage to the liquid crystal layer 30 is less than the threshold voltage (including no voltage applied).
  • the surface is 0 ° and the substrate normal is 90 °.
  • the photo-alignment film 50 includes at least one polymer (polyimide polymer) of polyimide and polyamic acid.
  • the polyimide that can be included in the photo-alignment film 50 may be a partially imidized polyamic acid, that is, a partially included polyamic acid structure, or a completely imidized polyamic acid. That is, it may not contain any polyamic acid structure.
  • the photo-alignment film 50 may contain only one type of polyimide polymer, or may contain two or more types of polyimide polymers.
  • the photo-alignment film 50 is subjected to photo-alignment treatment, and the polyimide polymer has a photofunctional group in the main chain.
  • the photofunctional group is irradiated with light (electromagnetic wave, preferably deflected light, more preferably deflected ultraviolet light, particularly preferably linearly polarized ultraviolet light) such as ultraviolet light and visible light, for example, dimerization (dimer formation). It is preferably a functional group capable of causing structural changes such as isomerization, light fleece transition, and decomposition (cleavage) and exhibiting orientation regulating power.
  • the photofunctional group include azobenzene group, chalcone group, cinnamate group, coumarin group, tolan group, stilbene group, and cyclobutane ring.
  • the photo-alignment film 50 By using the photo-alignment film 50, the liquid crystal display device 100 can have high contrast.
  • the polyimide-based polymer is a polymer having a structure derived from a diamine and a structure derived from a tetracarboxylic dianhydride as a repeating structure, and includes at least one diamine and at least one tetracarboxylic dianhydride. Polymerized.
  • the polyimide polymer includes a polyamic acid structure represented by the following chemical formula (P-1) and / or a polyimide structure represented by the following chemical formula (P-2).
  • X and Y may be one type or two or more types, respectively.
  • the polyimide polymer (the polyamic acid and the polyimide) those having a structure derived from a diamine having an azobenzene group and a structure derived from a tetracarboxylic dianhydride having a bent molecular structure are suitable.
  • the azobenzene group undergoes an isomerization reaction and a decomposition (cleavage) reaction upon irradiation with polarized ultraviolet rays (preferably linearly polarized ultraviolet rays).
  • the polyimide polymer is formed by polymerizing a diamine having an azobenzene group and a tetracarboxylic dianhydride having a bent molecular structure, an azobenzene group is present in the main chain of the polyimide polymer, Since the absorption efficiency of polarized ultraviolet rays of the polyimide-based polymer is improved, there is a concern that the burn-in derived from the AC voltage becomes significant as described above. However, in this embodiment, since the inclination angle ⁇ is set to 7 ° or more in plan view, even in such a case, the occurrence of image sticking due to the application of a high AC voltage is effectively suppressed. be able to.
  • a tetracarboxylic dianhydride having a bent molecular structure means that a plurality of conformations can be obtained and the molecular structure in at least the most energetically stable conformation is bent.
  • the molecular structure in a conformation other than the most energetically stable conformation may be bent or unbent.
  • the molecular structure is confirmed by mass spectrometry (ToF-SIMS, LC-MS, etc.), and the energy calculation by simulation is performed for the molecular structure. It can be determined by the method to be performed.
  • the tetracarboxylic dianhydride has a flexible (bent) molecular structure, so that the steric hindrance between the polyimide polymer molecules is suppressed, so that the isomerization reaction of the azobenzene group by light irradiation occurs efficiently.
  • a low molecular additive for improving the reaction efficiency is added in the photo-alignment film 50 (alignment agent therefor). There is no need to introduce it.
  • the low molecular additive When the low molecular additive is added, a part of the unreacted low molecular additive is eluted into the liquid crystal layer 30, and the orientation of the liquid crystal compound 31 is lowered or the VHR is lowered due to the increased concentration of ionic impurities. Therefore, in particular, in applications where the liquid crystal layer 30 needs to exhibit a liquid crystal phase even at high temperatures (preferably in-vehicle applications), a bent tetracarboxylic dianhydride is preferable. On the other hand, the steric hindrance between the azobenzene group-containing polyimide polymer molecules is suppressed, so that image sticking is likely to occur when an AC voltage is applied for a long time.
  • the low-molecular additive is a cross-linking agent that cross-links polyimide polymers and generally includes a low-molecular compound having 2 to 4 epoxy groups in one molecule.
  • a tetracarboxylic dianhydride that is not bent is used, if the polyimide polymer has a high molecular weight, intermolecular steric hindrance increases, and photoalignment control becomes difficult. Therefore, after performing photo-alignment treatment using a polyimide polymer with a relatively small molecular weight, the epoxy group of the low molecular additive and the carboxylic acid in the polyimide polymer are thermally reacted to increase the molecular weight of the polyimide polymer. .
  • the diamine having an azobenzene group (diamine for constituting Y in the above formulas (P-1) and (P-2)) is represented by any one of the following chemical formulas (Y-1) to (Y-5). It may be a compound. Any of these may be used alone or in combination of two or more.
  • the tetracarboxylic dianhydride having a bent molecular structure (tetracarboxylic dianhydride for constituting X in the above formulas (P-1) and (P-2)) is represented by the following chemical formula (X-1) It may be a compound represented by any one of (X-28). In particular, a compound represented by any of the following chemical formulas (X-6), (X-22), (X-23) or (X-27) is preferred. Any of these may be used alone or in combination of two or more.
  • the polyimide polymer (the polyamic acid and the polyimide) may have a structure derived from a cyclobutane ring.
  • the cyclobutane ring undergoes a decomposition (cleavage) reaction upon irradiation with polarized ultraviolet rays (preferably linearly polarized ultraviolet rays).
  • the cyclobutane ring is included in a structure derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the following chemical formula (Xa), and includes the above formulas (P-1) and (P-2). ) Included.
  • the structure derived from a diamine is not particularly limited, and is used for constituting Y in the above formulas (P-1) and (P-2).
  • the diamine may be, for example, a compound represented by the following chemical formula (Ya).
  • the photo-alignment film 50 further contains a polymer obtained by polymerizing at least one monomer (hereinafter also referred to as an alignment monomer), and the alignment monomer is subjected to at least isomerization reaction and dimerization reaction by irradiation with polarized ultraviolet rays. It is preferable that one of the reactions occurs to exhibit orientation.
  • the orientation monomer can be polymerized in a state in which the orientation is controlled and entangled with the main chain of the polyimide polymer, and the orientation state of the polyimide polymer can be more stably fixed, resulting in liquid crystal.
  • the orientation state of the compound 31 can be more stably fixed.
  • the polarized ultraviolet ray irradiated to the alignment monomer is preferably a linearly polarized ultraviolet ray.
  • the sealing material 40 when an unreacted component (for example, (meth) acrylic monomer or photo radical polymerization initiator) of the sealing material 40 eluted in the liquid crystal layer 30 is adsorbed on the surface of the photo-alignment film 50 without being controlled in orientation.
  • the alignment regulating force (azimuth angle anchoring strength) of the photo-alignment film 50 further decreases and causes burn-in due to further AC voltage application.
  • the photo-alignment film 50 is obtained by polymerizing the alignment monomer. By including the polymer, it is possible to effectively suppress image sticking resulting from application of the AC voltage.
  • the specific example of the said orientation monomer is not specifically limited, It has a monomer which has a chalcone group which may have a substituent, a monomer which has a cinnamate group which may have a substituent, and a substituent. It is preferable to include at least one photoreactive monomer selected from the group consisting of monomers having a good coumarin group.
  • the chalcone group, cinnamate group and coumarin group function as photofunctional groups.
  • the substituent preferably includes at least one substituent selected from the group consisting of a halogen group, a methyl group, a methoxy group, an ethyl group, and an ethoxy group.
  • the at least one alignment monomer may contain a photoreactive monomer having a photofunctional group having a substituent and a photoreactive monomer having a photofunctional group having no substituent.
  • halogen group a fluoro group and a chloro group are preferred.
  • a substituent is normally substituted by the at least 1 hydrogen atom which ring structures, such as a phenylene group of the said photofunctional group, have.
  • the photofunctional group may be a monovalent functional group, but is preferably a divalent cinnamate group represented by the following chemical formula (G-1), preferably represented by the following chemical formula (G-2).
  • G-1 divalent cinnamate group represented by the following chemical formula (G-2)
  • G-3 A divalent chalcone group and a divalent coumarin group represented by the following chemical formula (G-3).
  • the at least one orientation monomer preferably contains at least one monomer represented by the following chemical formula (1).
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different and each represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a direct bond. At least one hydrogen atom of each phenylene group may be substituted.
  • FIG. 5 is a schematic diagram illustrating a state of a polyimide polymer having an azobenzene group and a polymer of an alignment monomer in the photo-alignment film of the liquid crystal display device according to the first embodiment.
  • FIG. 6 is a schematic diagram illustrating a molecular state in the photo-alignment film of the liquid crystal display device according to the first embodiment.
  • FIG. 6A illustrates a polyimide polymer having an azobenzene group and an alignment monomer before irradiation with polarized ultraviolet rays.
  • B shows the polymer of the polyimide-type polymer which has an azobenzene group after polarized ultraviolet irradiation, and the polymer of an orientation monomer.
  • the orientation monomer represented by the chemical formula (1) has a chalcone group, and the chalcone group is oriented in the same direction as the azobenzene group by irradiation with linearly polarized ultraviolet rays, and is not only isomerized but also dimerized. Since the reaction also occurs, as shown in FIG. 5, the polymer 52 having a chalcone group is easily entangled in the main chain of the polyimide-based polymer 51 having an azobenzene group. Therefore, the alignment state of the liquid crystal compound 31 can be more stably fixed, and image sticking due to application of the AC voltage can be more effectively suppressed.
  • the chalcone group exhibits orientation by irradiation with linearly polarized ultraviolet rays
  • the orientation monomer 53 having a chalcone group is a polyimide having an azobenzene group. Similar to the system polymer 51, it is oriented in the direction of 90 ° (easily aligned) with respect to the polarization axis (polarization direction) of the linearly polarized ultraviolet light to be irradiated, and coincides with the orientation control direction of the azobenzene group by irradiation with the polarized ultraviolet light.
  • the chalcone group can cause isomerization reaction and dimerization reaction, but in particular, the orientation of the polyimide polymer 51 having an azobenzene group can be effectively fixed by dimerization of the orientation monomer 53 having the chalcone group. Can do. Furthermore, the orientation of the polyimide polymer 51 having an azobenzene group can also be fixed by polymerization of the orientation monomer 53 having a chalcone group. Accordingly, at least one kind of orientation monomer represented by the above chemical formula (1) is added to an orientation agent containing a polyimide polymer having an azobenzene group, and the orientation of the azobenzene group, the polymerization of the orientation monomer, and the chalconyl group. By performing the exposure for the orientation of the polyimide, the orientation state of the polyimide polymer having an azobenzene group can be more stably fixed.
  • the said effect by the orientation monomer represented by the said Chemical formula (1) can be acquired similarly, also when a polyimide-type polymer has a structure originating in a cyclobutane ring.
  • At least one hydrogen atom of the phenylene group is the same or different and is substituted with a halogen atom (preferably a fluorine atom or a chlorine atom), a methyl group, a methoxy group, an ethyl group, or an ethoxy group. May be.
  • a halogen atom preferably a fluorine atom or a chlorine atom
  • orientation monomer represented by the chemical formula (1) include a monomer represented by either the following chemical formula (1-1) or (1-2). Any of these may be used alone or in combination of two or more. Like these monomers, when an alkyl group is introduced between at least one polymerizable group and a chalconyl group, the flexibility in the molecular structure is improved and the degree of alignment control by irradiation with polarized ultraviolet rays can be improved. Is possible.
  • orientation monomer represented by the chemical formula (1) include monomers represented by any of the following chemical formulas (2-1) to (2-5). Any of these may be used alone or in combination of two or more.
  • a polarizing plate (linear polarizer) 60 may be disposed on the opposite side of the pair of substrates 10 and 20 from the liquid crystal layer 30.
  • the polarizing plate 60 typically includes a polyvinyl alcohol (PVA) film obtained by adsorbing and orienting an anisotropic material such as an iodine complex having dichroism.
  • PVA polyvinyl alcohol
  • a protective film such as a triacetyl cellulose film is laminated on both sides of the PVA film and put to practical use.
  • An optical film such as a retardation film may be disposed between the polarizing plate 60 and the pair of substrates 10 and 20.
  • the transmission axes of the pair of polarizing plates 60 are preferably orthogonal to each other. According to such a configuration, since the pair of polarizing plates 60 are arranged in crossed Nicols, a good black display state can be realized when no voltage is applied.
  • that two axes (directions) are orthogonal means that an angle (absolute value) between the two axes (direction) is within a range of 90 ⁇ 3 ° unless otherwise specified, preferably 90 ⁇ . It is within the range of 1 °, more preferably within the range of 90 ⁇ 0.5 °, and particularly preferably 90 ° (fully orthogonal).
  • the initial alignment direction 31 a of the liquid crystal compound 31 may be parallel to one polarization axis of the pair of polarizing plates 60 and may be orthogonal to the other polarization axis.
  • the control method of the liquid crystal display device 100 can be set to a so-called normally black mode in which black display is performed with no voltage applied.
  • a backlight 70 is disposed on the back side of the liquid crystal panel.
  • a liquid crystal display device having such a configuration is generally called a transmissive liquid crystal display device.
  • the backlight 70 is not particularly limited as long as it emits light including visible light, may emit light including only visible light, and emits light including both visible light and ultraviolet light. It may be.
  • the liquid crystal display device of the present embodiment includes an external circuit such as a TCP (tape carrier package) and a PCB (printed wiring board) in addition to the liquid crystal panel and the backlight 70; an optical film such as a viewing angle widening film and a brightness enhancement film.
  • An external circuit such as a TCP (tape carrier package) and a PCB (printed wiring board) in addition to the liquid crystal panel and the backlight 70; an optical film such as a viewing angle widening film and a brightness enhancement film.
  • a plurality of members such as a bezel (frame), and some members may be incorporated in other members.
  • Members other than those already described are not particularly limited, and those normally used in the field of liquid crystal display devices can be used, and thus description thereof is omitted.
  • the liquid crystal drive mode of the liquid crystal display device 100 is the FFS mode.
  • the liquid crystal drive mode according to the present embodiment is particularly limited as long as it is a horizontal electric field type horizontal alignment mode.
  • the IPS mode may be used.
  • a pair of comb electrodes is provided on at least one of the substrates 10 and 20, and a lateral electric field is formed in the liquid crystal layer 30.
  • the pair of comb-shaped electrodes for example, an electrode pair that includes a plurality of comb-tooth portions and is arranged so that the comb-tooth portions mesh with each other can be used.
  • a pair of comb electrodes functions as the pixel electrode 25 and the common electrode 26.
  • the linear part 27 is contained in each comb-tooth part of each comb-shaped electrode.
  • the manufacturing method of the liquid crystal display device of the present embodiment includes a preparation step of preparing a pair of substrates, at least one polymer of polyamic acid and polyimide, and at least one monomer on at least one surface of the pair of substrates.
  • Including at least one irradiation step, and the at least one monomer may be a method for producing a liquid crystal display device that exhibits orientation by causing at least one of an isomerization reaction and a dimerization reaction by irradiation with polarized ultraviolet rays.
  • a pair of substrates 10 and 20 are prepared.
  • At least one (preferably both) of the pair of substrates has at least one polymer (polyimide polymer) of polyamic acid and polyimide, and at least one monomer (alignment).
  • a film forming step of forming a photo-alignment film that is, a polyimide-based polymer has a photofunctional group
  • the at least one monomer is a polarized ultraviolet ray Irradiation causes at least one of an isomerization reaction and a dimerization reaction (preferably at least a dimerization reaction) to exhibit orientation.
  • an alignment agent is prepared by dissolving a polyimide polymer and an alignment monomer in a solvent (for example, an organic solvent).
  • the alignment agent may contain other optional components as necessary, and is preferably prepared as a solution-like composition in which each component is dissolved in a solvent.
  • a solvent for example, an organic solvent.
  • dissolves a polyimide-type polymer, an orientation monomer, and another arbitrary component, and does not react with these is suitable.
  • curing agent, a hardening accelerator, a catalyst etc. can be mentioned, for example.
  • Polymers other than the above polyimide-based polymers can be used to further improve the solution properties of the aligning agent and the electrical properties of the photo-alignment film. Examples of such polymers include no photofunctional groups.
  • General polymers for alignment films are listed.
  • the alignment monomer added to the alignment agent is 3% by weight or more and less than 30% by weight with respect to the polyimide polymer having a photofunctional group (when the polyimide polymer having a photofunctional group is 100% by weight). It is preferably 5 wt% or more and 25 wt% or less, more preferably 10 wt% or more and 20 wt% or less. If it is less than 3% by weight, there is a possibility that the effect of suppressing the AC image sticking is insufficient due to the orientation monomer, and if it exceeds 30% by weight, the contrast may be greatly lowered.
  • the coating method is not particularly limited, and examples thereof include a roll coater method, a spinner method, a printing method, and an ink jet method.
  • each substrate is heated.
  • the solvent in the aligning agent is volatilized and a photo-alignment film is formed.
  • Heating may be performed in two stages of pre-baking (pre-baking) and main baking (post-baking).
  • pre-baking pre-baking
  • post-baking main baking
  • the formed photo alignment film may have a two-layer structure, mainly from the alignment film polymer that does not have a photofunctional group.
  • You may have the comprised lower layer and the upper layer comprised mainly from the polyimide-type polymer which has a photofunctional group. The upper layer is in contact with the liquid crystal layer.
  • the photo-alignment film is irradiated with polarized ultraviolet rays to align the at least one polymer (polyimide polymer) and align the at least one monomer (orientation monomer). And an irradiation step for polymerization.
  • the orientation of the polyimide polymer having a photofunctional group is controlled, and the orientation monomer is polymerized in a controlled orientation, thereby fixing the orientation of the polyimide polymer having the photofunctional group. be able to. Therefore, since the azimuth anchoring strength of the photo-alignment film can be improved, it is possible to reduce image sticking due to application of an AC voltage.
  • the polarized ultraviolet light to be irradiated is preferably linearly polarized ultraviolet light.
  • the wavelength of the polarized ultraviolet light may be 200 nm or more and 430 nm or less. A more preferable lower limit of the wavelength is 250 nm, and a more preferable upper limit is 380 nm. Dose of the polarized ultraviolet is, 0.3 J / cm 2 or more, may be 20 J / cm 2 or less. A more preferable lower limit of the irradiation amount is 1 J / cm 2 , and a more preferable upper limit is 5 J / cm 2 .
  • One of the pair of substrates includes a pixel electrode and a common electrode, and at least one of the pixel electrode and the common electrode includes a linear portion.
  • the photo-alignment film is formed on the surface of the substrate including the pixel electrode and the common electrode (more preferably both substrates).
  • the angle formed by the polarization axis direction (polarization direction) with respect to the linear portion is 83. It is preferable to irradiate the above-mentioned photo-alignment film with polarized ultraviolet rays so that the temperature is not more than 0 °. Thereby, it can be easily made 7 ° or more in a plan view of the inclination angle of the linear portion with respect to the initial orientation direction of the liquid crystal compound. For this reason, it is possible to further reduce the burn-in resulting from the AC voltage application.
  • the irradiation step it is more preferable to irradiate the photo-alignment film with polarized ultraviolet rays so that an angle formed by a polarization axis direction (polarization direction) with respect to the linear portion is 77 ° or more.
  • an angle formed by a polarization axis direction (polarization direction) with respect to the linear portion is 77 ° or more.
  • the liquid crystal display device of this embodiment is completed through a liquid crystal layer forming step, a polarizing plate attaching step, and a control step, a power supply portion, a backlight attaching step, and the like.
  • a liquid crystal composition containing a liquid crystal material is usually sealed between a pair of substrates bonded by a sealing material.
  • the liquid crystal layer can be formed by, for example, filling a liquid crystal composition between a pair of substrates by a vacuum injection method or a drop injection method.
  • a liquid crystal layer is formed by applying a sealing material, bonding a pair of substrates, curing the sealing material, injecting a liquid crystal composition, and sealing the injection port in this order.
  • the dropping injection method is employed, a liquid crystal layer is formed by applying a sealing material, dropping a liquid crystal composition, bonding a pair of substrates, and curing the sealing material in this order.
  • the liquid crystal material has positive dielectric anisotropy.
  • the liquid crystal material may contain a liquid crystal compound having an alkenyl group.
  • the liquid crystal material may contain one or more liquid crystal compounds.
  • a pair of polarizing plates are arranged in crossed Nicols so that the absorption axes are orthogonal to each other, and the absorption axes of the pair of polarizing plates; It arrange
  • a voltage equal to or higher than the threshold is not applied to the liquid crystal layer, the light from the backlight does not pass through the liquid crystal layer and is displayed in black.
  • the angle formed between the absorption axis of the pair of polarizing plates arranged in the crossed Nicols and the liquid crystal director becomes larger than 0 ° (for example, 45 °), and the light from the backlight Transmits through the liquid crystal layer.
  • Example 1-1 (Production of liquid crystal panel) An FFS mode liquid crystal panel was actually produced by the following method. First, a planar electrode (lower layer electrode) having an FFS electrode structure made of indium tin oxide (ITO), a TFT substrate on which an insulating film and a slit electrode (upper layer electrode) are stacked, and a counter electrode having no electrode A substrate was prepared. Next, an aligning agent A containing polyamic acid having an azobenzene group in the main chain, represented by the following chemical formula (P-1a), was applied to both substrates.
  • ITO indium tin oxide
  • TFT substrate on which an insulating film and a slit electrode upper layer electrode
  • a counter electrode having no electrode A substrate was prepared.
  • an aligning agent A containing polyamic acid having an azobenzene group in the main chain represented by the following chemical formula (P-1a), was applied to both substrates.
  • preliminary baking is performed at 60 to 80 ° C. (2 minutes), followed by irradiation with 1 to 3 J / cm 2 of linearly polarized light (including 300 to 500 nm ultraviolet rays), and subsequently 170 to 180 ° C. (10 to 10 ° C.). 20 minutes) is performed (first stage firing) and 220 to 230 ° C. (20 to 30 minutes) firing (second stage firing).
  • first stage firing is performed (first stage firing)
  • second stage firing second stage firing
  • a UV and thermosetting sealant manufactured by Sekisui Chemical Co., Ltd., Photorec; this sealant is composed of (meth) acrylic monomer, photoradical polymerization initiator, epoxy monomer, epoxy A curing material, a silane coupling agent, and an inorganic filler are drawn.
  • This positive type liquid crystal material was composed of a compound having an alkenyl group and a positive type liquid crystal compound.
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 40 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 7 ° in plan view.
  • Example 1-2 A liquid crystal panel of this example was produced in the same manner as in Example 1-1, except that the inclination angle ⁇ was 10 ° in plan view.
  • Example 1-3 A liquid crystal panel of this example was produced in the same manner as in Example 1-1 except that the inclination angle ⁇ was 13 ° in plan view.
  • Example 1-4 A liquid crystal panel of this example was produced in the same manner as in Example 1-1 except that the inclination angle ⁇ was 15 ° in plan view.
  • Example 2-1> (Production of liquid crystal panel) An FFS mode liquid crystal panel was actually produced by the following method. First, a planar electrode (lower electrode) having an FFS electrode structure made of indium tin oxide (ITO), a TFT substrate on which an insulating film and a slit electrode (upper electrode) are stacked, and a counter substrate having no electrode are prepared. did. Next, an aligning agent A containing a polyamic acid containing an azobenzene group in the main chain represented by the following chemical formula (P-1b) was applied to both substrates.
  • ITO indium tin oxide
  • P-1b an aligning agent A containing a polyamic acid containing an azobenzene group in the main chain represented by the following chemical formula (P-1b) was applied to both substrates.
  • X contains at least a structure derived from X2, and Y contains at least a structure derived from Y2.
  • preliminary baking is performed at 60 to 80 ° C. (2 minutes), followed by irradiation with 3 to 5 J / cm 2 of linearly polarized light (including 300 to 500 nm ultraviolet rays), and subsequently 110 to 130 ° C. (10 to 10 ° C.).
  • a photo-alignment film was formed on each substrate by performing main firing including firing at 20 minutes (first stage firing) and firing at 230 ° C. (30 to 40 minutes) (second stage firing). .
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 30 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 7 ° in plan view.
  • Example 2-2 A liquid crystal panel of this example was fabricated in the same manner as in Example 2-1, except that the inclination angle ⁇ was 10 ° in plan view.
  • Example 2-3 A liquid crystal panel of this example was produced in the same manner as in Example 2-1, except that the inclination angle ⁇ was 13 ° in plan view.
  • Example 2-4 A liquid crystal panel of this example was produced in the same manner as in Example 2-1, except that the inclination angle ⁇ was 15 ° in plan view.
  • preliminary baking is performed at 60 to 80 ° C. (2 minutes), followed by irradiation with 1 to 3 J / cm 2 of linearly polarized light (including 300 to 500 nm ultraviolet rays), and subsequently 170 to 180 ° C. (10 to 10 ° C.). 20 minutes) is performed (first stage firing) and 220 to 230 ° C. (20 to 30 minutes) firing (second stage firing).
  • first stage firing is performed (first stage firing)
  • second stage firing second stage firing
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 40 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 10 ° in plan view.
  • Example 3-2 A liquid crystal panel of this example was produced in the same manner as in Example 3-1, except that the dielectric anisotropy ⁇ of the positive liquid crystal material was 3.3.
  • Example 3-3 A liquid crystal panel of this example was produced in the same manner as in Example 3-1, except that the dielectric anisotropy ⁇ of the positive liquid crystal material was set to 4.0.
  • ⁇ of the positive liquid crystal material is preferably less than 3.5.
  • Example 4-1 (Alignment agent adjustment) A monomer (orienting monomer) having a chalconyl group represented by the following chemical formula (2-2) is added to the aligning agent A containing a polyamic acid having an azobenzene group in the main chain represented by the chemical formula (P-1a).
  • the alignment agent B1 was prepared by adding 10% by weight to the total weight of the solute of the alignment agent A (total weight of the polyamic acid represented by the chemical formula (P-1a)).
  • An FFS mode liquid crystal panel was actually produced by the following method. First, a planar electrode (lower electrode) having an FFS electrode structure made of indium tin oxide (ITO), a TFT substrate on which an insulating film and a slit electrode (upper electrode) are stacked, and a counter substrate having no electrode are prepared. did. Next, the alignment agent B1 was applied to both substrates.
  • pre-baking is performed at 60 to 80 ° C. (2 minutes), followed by irradiation with 4 to 7 J / cm 2 of linearly polarized light (including 300 to 500 nm ultraviolet rays) to perform uniaxial alignment treatment of the azobenzene group.
  • the monomer represented by the chemical formula (2-2) was polymerized.
  • main firing including firing at 170 to 180 ° C. (20 to 30 minutes) (first stage firing) and firing at 220 to 230 ° C. (20 to 30 minutes) (second stage firing).
  • main firing including firing at 170 to 180 ° C. (20 to 30 minutes) (first stage firing) and firing at 220 to 230 ° C. (20 to 30 minutes) (second stage firing).
  • a photo-alignment film was formed on each substrate.
  • a UV and thermosetting sealant manufactured by Sekisui Chemical Co., Ltd., Photorec; this sealant is composed of (meth) acrylic monomer, photoradical polymerization initiator, epoxy monomer, epoxy A curing material, a silane coupling agent, and an inorganic filler are drawn.
  • This positive type liquid crystal material was composed of a compound having an alkenyl group and a positive type liquid crystal compound.
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 40 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 10 ° in plan view.
  • the aligning agent A containing a polyamic acid containing an azobenzene group in the main chain represented by the chemical formula (P-1a) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 4-1, except that B2 was used.
  • the aligning agent A containing a polyamic acid containing an azobenzene group in the main chain represented by the chemical formula (P-1a) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 4-1, except that B3 was used.
  • the aligning agent A containing a polyamic acid containing an azobenzene group in the main chain represented by the chemical formula (P-1a) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 4-1, except that B4 was used.
  • Example 4-0> In the same manner as in Example 4-1, except that the aligning agent A containing a polyamic acid containing an azobenzene group in the main chain, represented by the chemical formula (P-1a), was used instead of the aligning agent B1.
  • the liquid crystal panel of the example was produced.
  • the burn-in rate was greatly reduced by adding the monomer having the chalconyl group to the photo-alignment film material and polymerizing the monomer during exposure of the photo-alignment film. From this, it was confirmed that the alignment control of the liquid crystal compound is stabilized by forming a polymer of a monomer having a chalcone group in the photo-alignment film. This is presumably because the anchoring strength (particularly the azimuth anchoring strength) of the photo-alignment film has increased. On the other hand, the response characteristics were almost constant with respect to the added amount of the monomer, but the contrast was greatly reduced when 30% by weight of the monomer was added.
  • concentration of less than 30 weight% with respect to the solute (polyamic acid) of an orientation agent it turned out that it is preferable to add the monomer which has a chalconyl group with the density
  • Example 5-1 (Alignment agent adjustment) A monomer (orienting monomer) having a chalcone group represented by the above chemical formula (2-2) is added to the aligning agent C containing a polyamic acid having a cyclobutane ring in the main chain represented by the following chemical formula (P-1c).
  • the alignment agent D1 was prepared by adding 10% by weight to the total weight of the solute of the alignment agent C (total weight of the polyamic acid represented by the following chemical formula (P-1c)).
  • An FFS mode liquid crystal panel was actually produced by the following method. First, a planar electrode (lower electrode) having an FFS electrode structure made of indium tin oxide (ITO), a TFT substrate on which an insulating film and a slit electrode (upper electrode) are stacked, and a counter substrate having no electrode are prepared. did. Next, the alignment agent D1 was applied to both substrates.
  • main baking is performed at 190 to 200 ° C. (20 to 30 minutes), followed by 0.5 to 2 J / cm 2 linearly polarized light (250 (Including ultraviolet rays of up to 360 nm) and uniaxial orientation treatment of the cyclobutane ring, and at the same time, polymerization of the monomer represented by the chemical formula (2-2) was performed. Subsequently, by baking at 220 to 220 ° C. (30 to 40 minutes), a photo-alignment film was formed on each substrate.
  • a UV and thermosetting sealant manufactured by Sekisui Chemical Co., Ltd., Photorec; this sealant is composed of (meth) acrylic monomer, photoradical polymerization initiator, epoxy monomer, epoxy A curing material, a silane coupling agent, and an inorganic filler are drawn.
  • This positive type liquid crystal material was composed of a compound having an alkenyl group and a positive type liquid crystal compound.
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 40 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 10 ° in plan view.
  • the aligning agent C containing a polyamic acid containing a cyclobutane ring in the main chain represented by the chemical formula (P-1c) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 5-1, except that D2 was used.
  • the aligning agent C containing a polyamic acid containing a cyclobutane ring in the main chain represented by the chemical formula (P-1c) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 5-1, except that D3 was used.
  • the aligning agent C containing a polyamic acid containing a cyclobutane ring in the main chain represented by the chemical formula (P-1c) has a chalcone group represented by the chemical formula (2-2).
  • a liquid crystal panel of this example was produced in the same manner as in Example 5-1, except that D4 was used.
  • Example 5-0 In the same manner as in Example 5-1, except that the aligning agent C containing a polyamic acid containing a cyclobutane ring in the main chain, represented by the chemical formula (P-1c), was used instead of the aligning agent D1.
  • the liquid crystal panel of the example was produced.
  • the cyclobutane ring originally has a cyclobutane ring by adding the monomer having the chalconyl group to the photo-alignment film material having a cyclobutane ring and also polymerizing the monomer during the exposure of the photo-alignment film.
  • the degree of image sticking of the photo-alignment film was small, the image sticking rate was further reduced. From this, it was confirmed that the alignment control of the liquid crystal compound is stabilized also by forming a polymer of a monomer having a chalcone group in a photo-alignment film (decomposed type) having a cyclobutane ring.
  • the anchoring strength (particularly the azimuth anchoring strength) of the photo-alignment film is further increased.
  • the response characteristics were almost the same as in Example 4 and were almost constant with respect to the added amount of the monomer, but the contrast was greatly lowered when 30% by weight of the monomer was added. This is presumed that when the photo-alignment film having 30% by weight of the monomer was formed, it was not a transparent film but a white turbid film, so that a significant decrease in contrast due to scattering occurred.
  • the photo-alignment film having a cyclobutane ring was slightly lower than the photo-alignment film having an azobenzene group.
  • concentration of less than 30 weight% with respect to the solute (polyamic acid) of an orientation agent it turned out that it is preferable to add the monomer which has a chalconyl group with the density
  • preliminary baking is performed at 60 to 80 ° C. (2 minutes), followed by irradiation with 1 to 3 J / cm 2 of linearly polarized light (including 300 to 500 nm ultraviolet rays), and subsequently 170 to 180 ° C. (10 to 10 ° C.). 20 minutes) is performed (first stage firing) and 220 to 230 ° C. (20 to 30 minutes) firing (second stage firing).
  • first stage firing is performed (first stage firing)
  • second stage firing second stage firing
  • a UV and thermosetting sealant manufactured by Sekisui Chemical Co., Ltd., Photorec; this sealant is composed of (meth) acrylic monomer, photoradical polymerization initiator, epoxy monomer, epoxy A curing material, a silane coupling agent, and an inorganic filler are drawn.
  • This positive type liquid crystal material was composed of a compound having an alkenyl group and a positive type liquid crystal compound.
  • both the substrates were bonded together under vacuum, and the sealing material was cured by irradiating with ultraviolet rays (including 300 to 500 nm ultraviolet rays) to produce a liquid crystal panel.
  • the liquid crystal panel was heated at 110 to 140 ° C. for about 40 minutes to thermally cure the sealing material and to make the liquid crystal layer isotropic, and then the liquid crystal panel was cooled to room temperature.
  • a pair of polarizing plates was attached to the liquid crystal panel to complete a normally black mode and FFS mode liquid crystal panel.
  • the slit electrode 24 has a V-shaped structure, and the inclination angle ⁇ of the linear portion 27 with respect to the initial alignment azimuth 31a of the liquid crystal compound is 10 ° in plan view.
  • Example 6-2 Except for using a polyamic acid represented by the following chemical formula (P-1d) represented by the following chemical formula (P-1a), a polyamic acid comprising an azobenzene group contained in the main chain, instead of the polyamic acid represented by the chemical formula (P-1a).
  • P-1d a polyamic acid represented by the following chemical formula (P-1a)
  • P-1a a polyamic acid comprising an azobenzene group contained in the main chain
  • X includes at least a structure derived from X3, and Y includes at least a structure derived from Y3.
  • the seizure resulting from the application of AC voltage over a long period of time was higher (bad) when the polyamic acid represented by the chemical formula (P-1a) was used.
  • the polyamic acid represented by the above chemical formula (P-1a) has low molecular steric hindrance due to the bending of the polymer, and therefore has high molecular mobility, and as a result, there is a slight seizure resulting from application of AC voltage over a long period of time. It got worse.
  • One embodiment of the present invention includes a liquid crystal layer containing a liquid crystal material having a positive dielectric anisotropy, a sealant disposed so as to surround the liquid crystal layer in a plan view, and a pair of sandwiching the liquid crystal layer A substrate and a photo-alignment film provided on at least one surface of the pair of substrates, the photo-alignment film containing at least one of polyamic acid and polyimide (polyimide polymer), and the liquid crystal material
  • the liquid crystal compound in the substrate is aligned horizontally with respect to the substrate surface, and one of the pair of substrates includes a pixel electrode and a common electrode, and at least one of the pixel electrode and the common electrode is linear.
  • the liquid crystal display device may be characterized in that an inclination angle of the linear portion with respect to an initial alignment direction of the liquid crystal compound is 7 ° or more in plan view.
  • the liquid crystal display device includes a photo-alignment film that aligns the liquid crystal compound in a horizontal direction with respect to the substrate surface, and the inclination angle of the linear portion with respect to the initial alignment direction of the liquid crystal compound is 7 ° or more in plan view. Therefore, image sticking due to the application of the AC voltage can be suppressed.
  • the inclination angle may be 13 ° or less. Thereby, it is possible to suppress a decrease in transmittance and contrast.
  • the polyamic acid and the polyimide may have a structure derived from a diamine having an azobenzene group and a structure derived from a tetracarboxylic dianhydride having a bent molecular structure. Even in this case, it is possible to effectively suppress the occurrence of image sticking due to application of a high AC voltage.
  • the tetracarboxylic dianhydride having a bent molecular structure may include at least one tetracarboxylic dianhydride represented by any one of the following chemical formulas (X-1) to (X-28).
  • the tetracarboxylic dianhydride having a bent molecular structure is at least one tetracarboxylic dianhydride represented by any one of the chemical formulas (X-6), (X-22), (X-23) or (X-27). Carboxylic dianhydrides may be included.
  • the polyamic acid and the polyimide may have a structure derived from a cyclobutane ring.
  • the liquid crystal material may have a dielectric anisotropy of 1 or more and less than 3.5. Even in this case, it is possible to effectively suppress the occurrence of image sticking due to application of a high AC voltage. Further, the response performance of the liquid crystal material can be improved and the speed can be increased.
  • the nematic phase-isotropic phase transition point of the liquid crystal material may be 95 ° C. or higher.
  • the said liquid crystal display device can be made suitable for a vehicle-mounted use, a ship use, an aviation use, etc.
  • the sealing material may contain a (meth) acrylic monomer, a radical polymerization initiator, an epoxy monomer, and an epoxy curing material. Even in this case, it is possible to effectively suppress the occurrence of image sticking due to application of a high AC voltage.
  • the photo-alignment film further contains a polymer obtained by polymerizing at least one monomer (alignment monomer), and the at least one monomer reacts with at least one of an isomerization reaction and a dimerization reaction by irradiation with polarized ultraviolet rays. May be produced to show the orientation.
  • the alignment state of the polyimide-based polymer can be more stably fixed, and as a result, the alignment state of the liquid crystal compound can be more stably fixed. That is, the azimuth anchoring strength of the photo-alignment film can be improved, and image sticking due to application of AC voltage can be more effectively suppressed.
  • the at least one monomer is a monomer having a chalcone group which may have a substituent, a monomer having a cinnamate group which may have a substituent, and a monomer having a coumarin group which may have a substituent. It may contain at least one photoreactive monomer selected from the group consisting of:
  • the at least one monomer may include at least one monomer represented by the following chemical formula (1).
  • P 1 and P 2 are the same or different and each represents an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, or a vinyloxy group.
  • Sp 1 and Sp 2 are the same or different and each represents a linear, branched or cyclic alkylene group or alkyleneoxy group having 1 to 6 carbon atoms, or a direct bond. At least one hydrogen atom of each phenylene group may be substituted.
  • the at least one monomer represented by the chemical formula (1) may include at least one monomer represented by any one of the following chemical formulas (2-1) to (2-5).
  • the display mode of the liquid crystal display device may be a fringe field switching (FFS) mode.
  • FFS fringe field switching
  • Another embodiment of the present invention is a preparatory step of preparing a pair of substrates, at least one surface of the pair of substrates, at least one polymer of polyamic acid and polyimide (polyimide polymer), and at least one monomer
  • the manufacturing method of a display apparatus may be sufficient.
  • the method for manufacturing the liquid crystal display device includes an irradiation step of irradiating the photo-alignment film with polarized ultraviolet rays to align the polyimide polymer and aligning and polymerizing the orientation monomer.
  • the polyimide polymer having a group is controlled in orientation, and the orientation monomer is polymerized in a state in which the orientation is controlled, so that the orientation of the polyimide polymer having a photofunctional group can be fixed. Therefore, since the azimuth anchoring strength of the photo-alignment film can be improved, it is possible to reduce image sticking due to application of an AC voltage.
  • One of the pair of substrates includes a pixel electrode and a common electrode, and at least one of the pixel electrode and the common electrode includes a linear portion.
  • the photo-alignment film is formed on the surface of the substrate including the pixel electrode and the common electrode.
  • the photo-alignment film is polarized so that an angle formed by the polarization axis direction with respect to the linear portion is 83 ° or less.
  • the photo-alignment film may be irradiated with polarized ultraviolet rays so that an angle formed by a polarization axis direction with respect to the linear portion is 77 ° or more.
  • the inclination angle of the linear portion with respect to the initial alignment direction of the liquid crystal compound can be easily reduced to 13 ° or less in plan view. Therefore, it is possible to suppress a decrease in transmittance and contrast.
  • the polyamic acid and the polyimide may have a structure derived from a diamine having an azobenzene group and a structure derived from a tetracarboxylic dianhydride having a bent molecular structure. Even in this case, it is possible to effectively suppress the occurrence of image sticking due to application of a high AC voltage.
  • the polyamic acid and the polyimide may have a structure derived from a cyclobutane ring.
  • the at least one monomer is a monomer having a chalcone group which may have a substituent, a monomer having a cinnamate group which may have a substituent, and a monomer having a coumarin group which may have a substituent. It may contain at least one photoreactive monomer selected from the group consisting of:

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Abstract

La présente invention concerne un dispositif d'affichage à cristaux liquides grâce auquel un effet fantôme provoqué par l'application d'une tension alternative peut être supprimé, et un procédé de fabrication d'un dispositif d'affichage à cristaux liquides grâce auquel un tel dispositif d'affichage à cristaux liquides peut être fabriqué. La présente invention concerne un dispositif d'affichage à cristaux liquides comprenant une couche de cristaux liquides contenant un matériau à cristaux liquides ayant une anisotropie diélectrique positive, un matériau d'étanchéité disposé de façon à entourer la couche de cristaux liquides dans une vue en plan, une paire de substrats prenant en sandwich la couche de cristaux liquides, et un film d'alignement optique disposé sur une surface d'au moins l'un des deux substrats, le film d'alignement optique contenant un acide polyamique et/ou un polyimide et amenant un composé à cristaux liquides dans le matériau à cristaux liquides à s'aligner dans la direction horizontale par rapport à la surface du substrat, au moins l'un des deux substrats comprenant une électrode de pixel et une électrode partagée, l'électrode de pixel et/ou l'électrode partagée comprenant une partie linéaire, et l'angle d'inclinaison de la partie linéaire par rapport à la direction d'alignement initial du composé de cristaux liquides étant supérieur ou égal à 7° dans une vue en plan.
PCT/JP2018/019915 2017-05-31 2018-05-24 Dispositif d'affichage à cristaux liquides et son procédé de fabrication WO2018221360A1 (fr)

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CN111240104A (zh) * 2020-03-19 2020-06-05 Tcl华星光电技术有限公司 显示面板及其制备方法
CN111704717A (zh) * 2020-05-21 2020-09-25 东华大学 一种基于偶氮类聚酰亚胺的新型钠离子电池有机负极材料
CN111752048A (zh) * 2019-03-29 2020-10-09 夏普株式会社 液晶显示装置
WO2022147943A1 (fr) * 2021-01-05 2022-07-14 Tcl华星光电技术有限公司 Électrode de pixel, son procédé d'entraînement et écran d'affichage à cristaux liquides

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CN111752048A (zh) * 2019-03-29 2020-10-09 夏普株式会社 液晶显示装置
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CN111704717A (zh) * 2020-05-21 2020-09-25 东华大学 一种基于偶氮类聚酰亚胺的新型钠离子电池有机负极材料
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WO2022147943A1 (fr) * 2021-01-05 2022-07-14 Tcl华星光电技术有限公司 Électrode de pixel, son procédé d'entraînement et écran d'affichage à cristaux liquides
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