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WO2016006738A1 - Inducteur d'alignement vertical des cristaux liquides et production d'un dispositif d'affichage à cristaux liquides l'utilisant - Google Patents

Inducteur d'alignement vertical des cristaux liquides et production d'un dispositif d'affichage à cristaux liquides l'utilisant Download PDF

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Publication number
WO2016006738A1
WO2016006738A1 PCT/KR2014/006203 KR2014006203W WO2016006738A1 WO 2016006738 A1 WO2016006738 A1 WO 2016006738A1 KR 2014006203 W KR2014006203 W KR 2014006203W WO 2016006738 A1 WO2016006738 A1 WO 2016006738A1
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Prior art keywords
liquid crystal
group
acid
vertical alignment
compound
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English (en)
Korean (ko)
Inventor
강신웅
김진욱
김선수
이명훈
이승희
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INDUSTRIAL COOPERATION FOUNDATION
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INDUSTRIAL COOPERATION FOUNDATION
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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

Definitions

  • Liquid crystal vertical alignment guide and liquid crystal display manufactured using the same
  • the present invention relates to a liquid crystal vertical alignment inducer and a liquid crystal display device manufactured using the same.
  • FIG. 1 is a process diagram schematically illustrating a manufacturing process of a liquid crystal display device using a polyimide thin film for vertical alignment of a conventional liquid crystal.
  • the electrodes 2, 2 ′ are patterned and formed respectively (S1), and the polymer orientation thereon.
  • the agent After applying the agent in the form of a thin film in a solution state, it is baked by applying high temperature heat to form a polymer alignment layer (3, 3 ') (S2), and the first and second substrates on which the polymer alignment layer is formed are opposed to each other. After assembling at regular intervals, a liquid crystal was injected to form a liquid crystal layer (4) to manufacture a liquid crystal display (S3). At this time, the liquid crystal molecules in the liquid crystal layer 4 are arranged perpendicularly to the substrate surface under the influence of the polymer alignment agent.
  • the conventional method of manufacturing a vertically aligned liquid crystal display device separates the process of forming the alignment layers on both substrates before the process of forming the liquid crystal layer between the first and second substrates to control the alignment of the liquid crystals. It must be done.
  • the liquid crystal composition mixed with the solid nanoparticles as the liquid crystal alignment induction additive is injected into the liquid crystal display device, it is difficult to control to have a uniform alignment characteristic due to the non-uniform distribution of these additives on the inner surface of the substrate.
  • alignment defects due to agglomeration of nanoparticles are generated, which causes a decrease in performance and a low manufacturing yield of a liquid crystal display.
  • the nanoparticles are agglomerated or localized, resulting in poor uniformity of liquid crystal alignment and long-term reliability of the liquid crystal display.
  • the transparent conductive film is directly in contact with the liquid crystal layer without an insulating charge, the liquid crystal compound is deteriorated by an electrochemical reaction when the liquid crystal display is driven, thereby degrading the performance of the liquid crystal display.
  • An object of the present invention is to induce a vertical alignment of the liquid crystal without a line alignment treatment process, to stabilize the pretilt angle of the liquid crystal to improve the performance and reliability of the liquid crystal display liquid crystal vertical alignment inducer and liquid crystal layer comprising the same To provide a composition.
  • Another object of the present invention is to provide a liquid crystal display device using the liquid crystal vertical alignment guide and a manufacturing method thereof.
  • Still another object of the present invention is to provide a method of inducing vertical alignment of liquid crystals having alignment stability by using an emulsified liquid crystal forming composition.
  • Liquid crystal vertical alignment inducer according to an embodiment of the present invention, an amphiphilic compound comprising 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule; And monomolecular hydrophilic liquids.
  • the amphiphilic compound is a hydrophilic group, alcohol, polyhydric alcohol, amine, polyvalent amine, thiol, polyvalent, polyoxyethylene, carboxylic acid, polycarboxylic acid, sulfonic acid, polysulfonic acid, sulfonic acid one derived from a compound selected from the group consisting of sulfuric acid, polyhydric acid, phosphonic acid, polyphosphonic acid, phosphoric acid, and polyhydric acid It may be to include the above nonionic polar group.
  • the amphiphilic compound is 1- (l-ol), 1,2-diol (glycerol), glucose (glucose), textose (dextrose), sorbide ( sorbitol, pentaerythr itol, dipentaerythritol, tripentaerythritol, sorbitan, fructose, sucrose, sucrose, gal It may include a functional group derived from a compound selected from the group consisting of lic acid, glucopyranoside, ascorbic acid, mannide and maltoside. .
  • the amphiphilic compound is a hydrophilic group such as 1-amine (1-amine), 1,2-diamine (1,2 'diamine), 1,3-diamine (1,3-diamine), ethylene diamine ( ethylene diamine), ethylenediamine-di (diethyl ene diamine), tris (2-aminoethyl) amine (tris (2-aminoethyl) amine ), a cycloalkyl nucleic acid diamine (diamine eye lohexane), diethylenetriamine 0 min (diethylene triamine), Phenyl diamine, phenyltriamine, 1,3,5-triazine 4,6-diamine (1,3,5- ⁇ 1 & 2 ⁇ 4,6-diamine), 1,3,5— Triazine 2,4,6-triamine (1,3,5-triazine 2,4,6—triamine) and cyclic ethylene amine (cyclen; (CH 2 CH 2 NH) n ; integer
  • amphiphilic compound may include a functional group derived from linear polyoxyethylene having 4 to 40 carbon atoms of Formula 1 or cyclic polyethylene glycol having 4 to 10 carbon atoms of Formula 2 as a hydrophilic group.
  • n is an integer of 2 to 5
  • amphiphilic compound may include 1-thiol, 1,2-dithiol, thioglycerol, and thiopentathiopentaerythritol as hydrophilic groups. And dithio tray
  • amphiphilic compound is a 1-carboxylic acid as a hydrophilic group.
  • amphiphilic compound is a hydrocarbon group of 8 to 30 carbon atoms substituted or unsubstituted as a hydrophobic group;
  • it may be to include a functional group selected from the group consisting of a combination thereof.
  • the amphiphilic compound is sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate , Polyethylene glycol sorbitan monolaurate, Polyethylene sorbitan monolaurate, Polyethylene sorbitan monopalmitate, Polyoxy ethylene sorbitan monostearate Fullyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monool Latex, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan rate, pentaerythrite monostearate, pentaerythrite dartrelate monostearate, pentaerylate Three monoacrylate Monostearate, octyl gallate, lauryl gallate, gallate derivatives, stearoyl glycerol, dipalmitoyl g
  • the monomolecular hydrophilic liquid may include 1 to 6 hydrophilic groups consisting of hydroxy, thiol, amine, and carboxyl groups in a molecule, preferably water (0), glycerol (glycerol), diglycerol ( diglycerol, triglycerol, ethylene glycol, diethyleneglycol, triethylene glycol, thioglycero 1, dithioglycerol, ethanedithiol ethanedi thi ol, ethylene diamine, diaminopropane, diethylenetr iamine, triethyl enetet r amine, tris aminoethyl amine amine), pentaerythritol tetrakis (3-mercaptopropionate), monoglycerol (trimer) iglycero 1 monoacrylate, triglycerol monomethacrylate (tri iglycerol monomethacrylate), triglycerol diacryl
  • amphiphilic compound and the hydrophilic liquid may be included in a weight ratio of 1:99 to 99.9: 0.1.
  • At least one of the amphiphilic compound and the hydrophilic liquid vapor compound may be a photo-banung compound further comprising at least one photoreactive group in the compound, preferably in the compound, an acrylate group, methacrylate group, cinnamate group, Coumarin group, chacon group, vinyl group, thiol group, engi, diene group, thiol group And it may be a photo-banung compound further comprising one or more photoreactive groups selected from the group consisting of acetylene groups.
  • the photo-banung compound may be included in 5 to 100% by weight relative to the total weight of the liquid crystal vertical alignment inducer.
  • a liquid crystal vertical alignment inducing agent comprising an amphiphilic compound containing 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule, and a hydrophilic liquid of a single molecule; And it provides a composition for forming a liquid crystal layer containing a liquid crystal host.
  • the liquid crystal vertical alignment inducer is dispersed in the form of an emuls i on the liquid crystal host.
  • At least one of the amphiphilic compound and the hydrophilic liquid may be a photoreactive compound further comprising at least one photoreactive group in the compound.
  • the liquid crystal vertical alignment inducing agent may be included in an amount of 0 to 5% by weight based on the total weight of the composition for forming a liquid crystal layer.
  • the first substrate and the second substrate including the first and second electrodes, respectively, are bonded to each other so that the electrodes face each other, and then a liquid crystal layer forming composition is injected into the space between the first and second substrates.
  • the liquid crystal filling forming composition is dropped under vacuum to any one of the first substrate and the second substrate including the first and second electrodes, respectively, to form a liquid crystal layer, and the remaining substrates are bonded to face the electrodes.
  • the composition for forming a liquid crystal layer includes an amphiphilic compound including 1 to 3 hydrophobic groups including 8 to 30 intramolecular carbon atoms, and a liquid crystal vertical including a single molecule hydrophilic liquid.
  • Orientation inducing agent provides a method for manufacturing a liquid crystal display device comprising a liquid crystal host.
  • the liquid crystal vertical alignment guide agent is dispersed in the form of emuls i on in the liquid crystal host.
  • At least one of the amphiphilic compound and the hydrophilic liquid may be a photo-banung compound further comprising one or more photoreactive groups in the compound.
  • the liquid crystal vertical alignment inducing agent is 0. 0 to the total weight of the composition for liquid crystal layer formation. 01 to 5% by weight may be included.
  • the manufacturing method may further include applying an electric field between the first substrate and the second substrate and irradiating light after the assembly of the assembly.
  • the first substrate and the second substrate which are located facing each other; First and second electrodes formed on opposite surfaces of the first and second substrates, respectively; And a liquid crystal layer interposed between the first substrate and the second substrate, wherein the liquid crystal layer includes an amphiphilic compound including 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in a molecule, and Liquid crystal vertical alignment inducer containing a molecular hydrophilic liquid; And a liquid crystal display comprising a liquid crystal host.
  • the liquid crystal display device at least one of an amphiphilic compound and a hydrophilic liquid Any one is a photoreactive compound further comprising one or more photobanung groups in the compound, the liquid crystal layer may further include a photopolymer of the photoreactive compound.
  • the liquid crystal display may further include a vertical alignment and light stabilization layer of a liquid crystal including a liquid crystal vertical alignment inducing agent between the liquid crystal layer and the first and second electrodes.
  • a vertical alignment and light stabilization layer of a liquid crystal including a liquid crystal vertical alignment inducing agent between the liquid crystal layer and the first and second electrodes.
  • one or both of the first and second electrodes may be patterned.
  • a method of inducing vertical alignment of liquid crystals having alignment stability using an emulsified liquid crystal layer forming composition is provided.
  • a method of inducing vertical alignment and photo stabilization of liquid crystals using a light reflection emulsified liquid crystal layer-forming composition is provided.
  • the vertical alignment of the liquid crystal is induced without the linear alignment process, the pretilt angle of the liquid crystal is stabilized, and as a result, the manufacturing process of the liquid crystal display is simplified, and the performance of the liquid crystal display is improved. And reliability can be improved.
  • FIG. 1 is a process diagram schematically showing a manufacturing process of a conventional liquid crystal display device.
  • Figure 2a is a schematic diagram showing a composition for forming a liquid crystal layer according to an embodiment of the present invention
  • Figure 2b is a schematic diagram showing the structure of the microassembly dispersed in the composition
  • Figure 2c is an amphiphilic compound included in the composition It is a schematic diagram showing the structure of.
  • FIG. 3 is a flowchart schematically illustrating a manufacturing process of a liquid crystal display according to an exemplary embodiment of the present invention.
  • FIG. 4A is a photograph of the arrangement of liquid crystals in the liquid crystal display device of Example 1 using a polarization microscope
  • FIG. 4B is a photograph observed using conoscopy.
  • FIG. 5A is a photograph of the liquid crystal display device manufactured in Example 2 of Test Example 6, where the arrangement of liquid crystals in the liquid crystal layer before applying an electric field was observed with a polarization microscope;
  • Figure 5b is a photograph of the alignment state of the liquid crystal immediately after application of the electric field with a polarizing microscope,
  • Figure 5c is a photograph of the alignment state of the liquid crystal 30 seconds (sec) after applying the electric field by a polarization microscope.
  • FIG. 6A confirms the stabilization of the liquid crystal array state after applying an electric field to the liquid crystal display device in Example 2 of Test Example 6, performs light irradiation, and again observes the arrangement state of the liquid crystal before switching by applying an electric field with a polarizing microscope.
  • 6B is a photograph of the arrangement of the liquid crystals immediately after switching by applying an electric field with a polarization microscope
  • FIG. 6C shows the arrangement of the liquid crystals at 20 milliseconds (ms) after switching by an electric field. It is a photograph observed under a microscope.
  • FIG. 7A is a photograph showing the arrangement of liquid crystals in the liquid crystal layer before applying an electric field to the liquid crystal display device manufactured in Example 2 of Test Example 9.
  • FIG. 7B is a polarization microscope showing the arrangement of liquid crystals immediately after application of an electric field.
  • 7c is a photograph of the arrangement of the liquid crystals in a polarization microscope at 30 seconds (sec) after application of an electric field.
  • FIG. 8A illustrates the liquid crystal display device manufactured in Example 2 of Test Example 9 after stabilizing the liquid crystal array state after applying an electric field, performing light irradiation, and again showing the arrangement state of the liquid crystal before switching by applying an electric field.
  • FIG. 8B is a photograph of the arrangement of the liquid crystal immediately after switching by electric field application.
  • FIG. 8C is a view of the liquid crystal at about 20 milliseconds (ms) after switching by electric field application. It is a photograph observing the arrangement state of with a polarizing microscope.
  • 'substituted' means that at least one hydrogen in the molecule is a halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, amino group, thio group, methylthio group, alkoxy group, aldehyde group, epoxy group, ether group, ester group , Carbonyl group, acetal group, ketone group alkyl group, perfluoroalkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof and derivatives thereof and any combination thereof Means replaced.
  • a single bond, a double bond, a triple bond, an alkylene group having 1 to 20 carbon atoms for example, methylene (_CH 2- ), ethylene (_CH 2 CH 2- ), etc.
  • alkylene fluoride groups having 1 to 20 carbon atoms eg, methylene fluoride (_CF 2 —), ethylene fluoride (- CF 2 CF 2- ), etc.
  • the present invention provides a non-uniform dispersion of an additive for aligning the liquid crystal without inducing an alignment film by using a liquid crystal vertical alignment inducing agent capable of forming an emulsion having excellent dispersibility in the liquid crystal host when forming a liquid crystal layer in a liquid crystal display device. Or inducing vertical alignment of the liquid crystals without fear of alignment defects caused by agglomeration.
  • a photopolymerization group is introduced into the vertical alignment inducing agent of the liquid crystals, thereby performing photopolymerization reaction after inducing vertical alignment of the liquid crystal material.
  • the vertical alignment of the liquid crystal to stabilize the pretilt angle is another feature.
  • the liquid crystal vertical alignment inducing agent according to the embodiment of the present invention includes an amphiphilic compound including 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule, and a single molecule hydrophilic liquid.
  • liquid crystals are generally classified as hydrophobic substances, they are phase separated without being mixed with hydrophilic substances such as water and glycerol.
  • hydrophilic substances such as water and glycerol.
  • the hydrophilic substance or the hydrophobic liquid crystal may be uniformly dispersed in the form of fine spheres in the excess continuous liquid phase without macroscopic phase separation. That is, the liquid crystal can form a colloidal system with a polar hydrophilic liquid phase in the presence of an amphiphilic compound.
  • the excess liquid phase is a continuous phase and a small amount of the hydrophilic material phase is a dispersion phase, it is called a water-in-LC (W / LC) emulsion
  • the excess hydrophilic liquid phase forms a continuous phase and the hydrophobic liquid crystal is a dispersion phase.
  • LC / W LOin-water
  • the size and dispersion stability of the dispersed phase may vary depending on the mixing ratio of the two liquid phases, the type and content of the amphiphilic compound, and the temperature.
  • the spherical dispersed phase (sphere or drop) stabilized by the amphiphilic compound is referred to as a 'microassembly' or 'fine aggregate' generated by self-assembly of amphiphilic compound molecules.
  • the liquid crystal vertical alignment induction agent according to the present invention may induce vertical alignment of the liquid crystal material without forming a liquid crystal layer by forming an emulsified microassembly in the liquid crystal host without a pre-treated alignment layer.
  • the liquid crystal vertical alignment inducing agent has a higher hydrophilicity than a liquid crystal host, and independently a hydrophilic liquid of a monomolecular compound that is not dissolved or dispersed in a liquid crystal, and a parent capable of stabilizing an interface between the liquid crystal host and the hydrophilic liquid It consists of a mixture containing a solvent compound.
  • a single molecule means a single molecule excluding a polymer.
  • Figure 2a is a schematic diagram showing the composition for forming a liquid crystal layer according to an embodiment of the present invention
  • Figure 2b is a schematic diagram showing the microassembly dispersed in the composition for forming a liquid crystal layer
  • Figure 2c is the liquid crystal It shows the structure of the amphipathic compound used at the time of manufacture of a layer forming composition.
  • 2A to 2C are only examples for describing the present invention, but the present invention is not limited thereto.
  • hydrophilic liquid for example, water is mixed with the excess liquid crystal host (C), it is not mixed due to different polarities and is separated into different phases.
  • an amphiphilic compound (bl) including a hydrophilic group (bll) and a hydrophobic group (bl2) is added thereto in one molecule, a small amount of hydrophilic liquid water (b2) is uniform in the continuous liquid crystal host (C). It becomes the colloidal system which formed the dispersed powdery phase.
  • the added amphiphilic compound molecules form a self-assembly microassembly (B) spontaneously aligned at the interface between the continuous liquid crystal phase (C) and the dispersed hydrophilic liquid phase (b2) Lowering the energy (interfacial energy / tension) forms a stable W / LC emulsion system (A).
  • the diameter of the dispersed microassembly can be adjusted according to the mixing ratio of the amphiphilic compound and the hydrophilic liquid and the type of the amphiphilic compound, and the stability of the formed emulsion dog is the kind and properties of the amphiphilic compound used, and the hydrophilic and hydrophobic liquid. It depends a lot on the type.
  • the excess liquid crystal forms a hydrophobic continuous phase and a small amount of the hydrophilic liquid forms a boundary interface with a phase different from the emulsion phase when the W / LC emulsion forms a dispersed phase due to the stabilizing effect of the amphiphilic compound
  • the amphipathic compound surrounding it that is, the microassembly produced by the self-assembly of the amphipathic compound molecules, is adsorbed on the newly formed interface.
  • the liquid crystal molecules present on the liquid crystal are arranged in a direction perpendicular to the surface on the surface of the hydrophilic liquid adsorbed at the interface and the amphiphilic compound surrounding the liquid.
  • Induction of vertical alignment of liquid crystals by surface adsorption of such fine granules is possible without limitation to the kind of the compound forming the solid surface.
  • vertical alignment can be induced on the surface of various organic polymer compounds such as polyimide, polystyrene, polyacrylate, polyvinyl alcohol, as well as various inorganic oxides and nitrides.
  • organic polymer compounds such as polyimide, polystyrene, polyacrylate, polyvinyl alcohol, as well as various inorganic oxides and nitrides.
  • a change in characteristics may appear depending on the magnitude of the interfacial tension at the interface between the liquid crystal and the liquid crystal.
  • the amphiphilic compound may form a stable microassembly in consideration of the properties of the hydrophobic liquid crystal phase and the hydrophilic dispersion phase. It is desirable to select a compound which does not adversely affect the stability, reliability, and device characteristics of the final liquid crystal display device.
  • FIG. 2c schematically shows the structure of the amphipathic compound (b l) usable in the present invention.
  • the amphiphilic compound (bl) includes a hydrophilic group (bl) having a large polarity and a hydrophobic group (bl2) having a small polarity in the molecule.
  • the hydrophilic group and hydrophobic group may be bonded covalently.
  • each includes one hydrophilic group (bll) and a hydrophobic group (bl2), but may include one or more hydrophilic groups or hydrophobic groups in the molecule, and preferably include one to three hydrophobic groups in the molecule. Can be.
  • the hydrophobic group that can be included in the amphiphilic compound can be used without particular limitation as long as it is a hydrophobic group that satisfies the conditions of 8 to 30 carbon atoms.
  • the hydrophobic group is a linear, branched or cyclic substituted or unsubstituted hydrocarbon group having 8 to 30 carbon atoms, or at least one hetero atom selected from the group consisting of N, 0, P, S and Si in an intramolecular molecule It may be a substituted or unsubstituted heteroalkyl group having 8 to 30 carbon atoms, heterocycle group or heteroaromatic group containing a, or may be a combination group having 8 to 30 carbon atoms consisting of a combination of the hydrocarbon group and heteroatom-containing groups.
  • hydrocarbon group examples include substituted or unsubstituted alkyl group, alkenylalkyl group, alkynylalkyl group, cycloalkyl group or aryl group having 8 to 30 carbon atoms, and when the hydrocarbon group is substituted, a halogen atom, preferably fluorine It may be substituted by an atom.
  • the hydrophobic group may have a structure similar to that of the compound constituting the liquid crystal host, ie, a rigid-core group and a flexible chain group, in order to increase affinity with the liquid crystal host.
  • a hydrophilic group (bu) having a large polarity both ionic and nonionic hydrophilic groups may be used to induce vertical alignment through emulsification of the composition for forming a liquid crystal layer.
  • VHR voltage holding ratio
  • VHR voltage holding ratio
  • Hydrophilic groups containing ionic head groups may be more desirable in devices or materials that do not or do not require switching by an electric field.
  • hydrophilic group having a nonionic head group examples include, but are not limited to, functional groups derived from the following compounds:
  • Alcohol A functional group derived from a C1-C20 alcohol or a polyhydric alcohol containing 1 to 8 hydroxy groups. Specific examples thereof include 1- (1-01), 1,2-di (1,2- Glycerol, glucose, dextrose, sorbi tol, pentaerythritol (6), 3 ⁇ 71; 11 ⁇ 1: 01), dipentaerythrone (( ⁇ 6 3 ⁇ 1 ⁇ 1 " ⁇ 01), tripentaerythr itol, sorbi tan, fluctose, sucrose, gallic acid, gallate functional groups derived from gal late, glucopyranoside, ascorbic acid, mannide or maltoside;
  • n is an integer of 2 to 5
  • Thiol A functional group derived from a thiol or polyvalent thiol having 1 to 20 carbon atoms containing 1 to 8 thiol groups (-SH). Specific examples thereof include 1-thiol and 1,2-dithiol. functional groups derived from (l, 2-dithiol), thiogl ycerol, thiopentathiothraerythr itol or dithiothreitol;
  • Carboxylic acid It is a functional group derived from C1-C10 carboxylic acid or polyhydric carboxylic acid containing 1-4 carboxylic acid groups (-C00H), More specifically, 1-carboxylic acid (1-carboxylic acid), 1,2-dicarboxylic acid (1,2-dicarboxylyc acid), 1,3-dicarboxylic acid (1,3-dicarboxylyc acid), benzenecarboxylic acid, Benzenedicarboxylic acid
  • benzenedicarboxyl ic acid 1,2,3-tricarboxylic acid (1,2,3-tr icarboxyl ic acid), benzenetri carboxylic acid (malic acid), maleic acid (maleic acid), tartar acid citric acid, maleamic acid glutamic acid, agaric acid aconitic acid, tricarvalic acid functional groups derived from tricarballylic acid or amino acid;
  • Amphiphilic compounds usable in the present invention may include a hydrophilic group having a nonionic headgroup as described above, a nonionic headgroup derived from them, or a combination thereof. .
  • amphiphilic compound examples include, but are not limited to the following compounds:
  • Sorbitan monolaurate (Span TM 20) (Al) Sorbitan monopalmitate (Span TM 40) (A2) Sorbitan monost earate (Span TM 60) ( A3) Sorbitan tristearate (Span TM 65) (A4) Sorbitan monooleate (Span TM 80) (A5) Sorbitan sesqui olate (Span TM 83) ( A6) Sorbitan trioleate (Span TM 85) (A7)
  • Pentaerythritol a polyhydric alcohol, having a head group
  • amphiphilic compound is added to the hydrophilic group and hydrophobic group in order to stabilize the pretilt angle of the liquid crystal by using light irradiation after induction of vertical alignment of the liquid crystal by emulsification, acrylate group, methacrylate group, thinner
  • the mate group, coumarin group, chacon group, vinyl group, thiol group, en group, diene group, thiol group and acetylene group may further include at least one photo-banung group selected from the group.
  • amphiphilic compounds described above may be used alone, or when the effective concentration for vertical alignment induction, i.e., the mixing ratio of the liquid crystal vertical alignment inducing agent to the liquid crystal host needs to be adjusted, or the effective vertical alignment induction and light stabilization When it is necessary to independently control the photopolymerization density for the above, two or more of the above amphiphilic compounds may be mixed and used in an appropriate ratio.
  • any hydrophilic liquid of a single molecule may be used as long as it is a hydrophilic monomolecular liquid compound having a high polarity that is not dissolved or dispersed in a liquid crystal independently, such as water or glycerol, that is, phase separated from the liquid crystal. .
  • a hydrophilic monomolecular liquid compound having a high polarity that is not dissolved or dispersed in a liquid crystal independently, such as water or glycerol, that is, phase separated from the liquid crystal.
  • the hydrophilic polymer compound it is difficult to form a uniform microassembly in the liquid crystal, and the stability of the emulsion is low.
  • hydrophilic liquid a hydrophilic monomolecular compound containing one or more, preferably 1 to 6, hydrophilic groups selected from the group consisting of a hydroxy group, a thiol group, an amine group, and a carboxyl group
  • hydrophilic groups selected from the group consisting of a hydroxy group, a thiol group, an amine group, and a carboxyl group
  • water, alcohol, polyhydric alcohol, thiol, polyvalent thiol, amine, polyvalent amine, carboxylic acid, etc. are mentioned. More specific examples include, but are not limited to, the following compounds.
  • the hydrophilic liquid induces vertical alignment of the liquid crystal using a liquid microassembly in the manufacturing process of the liquid crystal display, and then solidifies the microassembly by additional processing such as light irradiation and stabilizes the pretilt angle of the liquid crystal. It may also include at least one or more photopolymerizable groups polymerizable in the molecule to enable.
  • examples of the light semi-cyclic group include an acrylate group, a methacrylate group, a cinnamate group, a coumarin group, a chacon group, a vinyl group, a thiol group, an en group, a diene group, a thiol group, and an acetylene group. It doesn't happen.
  • the hydrophilic liquid including the photobanung group may include, but is not limited to:
  • glycerol monomethacrylate (glycerol monomethacrylate)
  • the above-mentioned hydrophilic liquid may be used alone, or two or more thereof may be used in combination.
  • the amphiphilic compound and the hydrophilic liquid constituting the microassembly inducing the liquid crystal vertical alignment are preferably mixed in a weight ratio of 1:99 to 99.9: 0.1, and preferably in a weight ratio of 30:70 to 99.9: 0.1. It can be more uniformly mixed to effectively form the microassembly.
  • the ratio of the photoreactive compound that forms the photopolymer by photoirradiation so that the liquid crystal vertical alignment and the light stabilization layer have an appropriate surface density It is preferable to make it 5 to 100 weight% with respect to the total weight of this liquid crystal aligning derivative.
  • the liquid crystal vertical alignment inducer having the above configuration may be prepared by mixing an amphiphilic compound and a hydrophilic liquid according to a conventional method. In this case, heat or ultrasonication may be applied for efficient mixing.
  • Liquid crystal vertical alignment inducer according to an embodiment of the present invention and the liquid crystal host Since the microassembly of the amphiphilic compound formed by the self-assembly of the amphiphilic compound and the monomolecular hydrophilic liquid is uniformly dispersed in the liquid crystal host to form an emulsion, the liquid crystals induce vertical alignment of the liquid crystal. Poor orientation due to low dispersibility or aggregation of the orientation inducing agent can be significantly reduced.
  • the formed microassembly forms an insulating liquid crystal alignment and a light stabilization layer on the electrode layer, and then stabilizes through solidification by light irradiation, thereby manufacturing a highly reliable liquid crystal device.
  • At least one of the amphiphilic compound constituting the microassembly and the phase-like hydrophilic liquid further comprises a photobanung group, and the liquid crystal of a specific arrangement state by performing a photopolymerization process through light irradiation while applying an electric field Pre-tilt (pr et ilt) can be formed and stabilized, as a result can further improve the performance of the liquid crystal device.
  • liquid crystal vertical alignment guide by inducing the vertical alignment of the liquid crystal without the linear alignment process, stabilizing the pretilt angle of the liquid crystal and forming an insulating liquid crystal vertical alignment and light stabilization layer on the electrode layer A liquid crystal device excellent in performance and reliability can be manufactured.
  • composition for forming a liquid crystal layer comprising the liquid crystal vertical alignment guide.
  • composition for forming a liquid crystal layer includes the liquid crystal vertical alignment induction agent together with the liquid crystal host.
  • the liquid crystal host can be used without particular limitation as long as it is usually used in a liquid crystal display device. Specifically, a nematic liquid crystal having negative dielectric anisotropy can be used.
  • the liquid crystal vertical alignment guide is the same as described above.
  • the liquid crystal vertical alignment guide agent contained in the composition for forming a liquid crystal layer
  • the vertical alignment and surface stabilization effects on the liquid crystal host are insignificant.
  • the content is too high, a high density of misalignment and excessive light sadding may occur.
  • the liquid crystal vertical alignment inducing agent is 0. It is preferably contained in 01 to 5% by weight, more preferably 0. It is good that the inclusion of 05 to 3% by weight can obtain a more improved effect.
  • the liquid crystal vertical alignment guide agent When mixed with the liquid crystal host, the liquid crystal vertical alignment guide agent is dispersed in the liquid crystal host in the form of a microassembly.
  • the size of the formed microassembly may vary depending on the mixing ratio of the disperse phase liquid and the amphipathic compound. In general, the higher the ratio of the amphipathic compound to the disperse phase liquid is, the smaller the diameter of the microassembly becomes, and the smaller the ratio, the finer. The diameter of the assembly becomes large.
  • the minimum diameter of the microassembly may be limited by the length of the amphipathic compound used, and may not be smaller than twice the average length of the amphiphilic compound.
  • the diameter of the microassembly may vary depending on the nature and type of the amphipathic compound.
  • the diameter of the microassembly of the dispersed phase may be present in a wide range from several nanometers to several tens of microns.
  • the diameter of the microassembly is too small, it is difficult to form the microassembly itself.
  • the diameter of the microassembly is too large, many defects may occur to deteriorate the liquid crystal alignment characteristics. Therefore, the diameter of the microassembly that can be used for the purpose of controlling the vertical alignment of the liquid crystal is preferably 2nm to 800nm, more preferably 3nm to 600nm, even more preferably 3nm to
  • the composition for forming a liquid crystal layer may further include a monomer capable of photopolymerization in order to induce vertical alignment of liquid crystals and stabilize alignment and pretilt angles.
  • the photo-reflective monomer is used to fabricate a liquid crystal device using a substrate pre-treated with a vertical alignment polymer film and a liquid crystal layer-forming composition to which a small amount of reactive mesogen is added, and to stabilize the alignment under the application of an electric field. It acts similar to the function of reactive liquid crystals.
  • the photoreactive monomer it is preferable to use a compound which does not participate in the emulsification of the liquid crystal vertical alignment inducing agent, and which can stabilize the orientation of a specific state only after the vertical alignment induction of the liquid crystal by the liquid crystal vertical alignment inducing agent.
  • a compound which does not participate in the emulsification of the liquid crystal vertical alignment inducing agent 4,4'-biphenol diacrylate, 4,4'-biphenol dimethacrylate (4, 4'-biphenol dimethacrylate), 1,4 bis- [4- (6_acryloyloxynuxyloxy) benzoyloxy]-2 ⁇ methylbenzene (l, 4_bisS— [4_ (6— acryloyloxyhexyloxy) benzoyloxy] — 2 ⁇
  • 1,6-nucleic acid diol acrylate (1,6-hexanediol diacrylate) or the like can be used.
  • composition for forming a liquid crystal layer may further include a conventional photo-initiaror for inducing a photoreaction of surface reaction together with the liquid crystal host.
  • a liquid crystal display device manufactured using the composition for forming a liquid crystal layer and a method of manufacturing the same.
  • the liquid crystal display according to the embodiment of the present invention, the first substrate and the second substrate which are located facing each other; A first electrode and a second electrode formed on opposite surfaces of the first substrate and the second substrate, respectively; And a liquid crystal layer interposed between the first substrate and the second substrate, wherein the liquid crystal layer includes the liquid crystal host and the liquid crystal vertical alignment guide.
  • the liquid crystal layer is a liquid crystal perpendicular to the liquid crystal layer as the microassembly existing in the composition for forming a liquid crystal layer is solidified by a light irradiation process, which is an optional process for stabilizing liquid crystal alignment, thereby forming a passivation layer on the electrode layer. It may further comprise an alignment and light stabilization layer (see 14 and 24 of FIG. 3).
  • the liquid crystal layer is a photopolymerized light of the compound having the optical semi-cyclic group through a photopolymerization reaction process under an electric field applied after the liquid crystal vertical alignment is induced. It may further comprise a polymer.
  • the photopolymer is It is formed by photopolymerization of a photoreactive group contained in a compound having a photoreactive group, and by an action mechanism that memorizes a specific surface orientation of a liquid crystal by a photopolymer formed when the liquid crystal molecules are photopolymerized in a specific arrangement. Vertical alignment and pretilt angle stabilization of the liquid crystal material in the liquid crystal layer may be induced.
  • the photopolymer includes a polymer formed by photopolymerization of one photoreactive compound or a copolymer formed by photopolymerization of two or more photoreactive compounds.
  • any one or both of the first and second electrodes may be patterned.
  • the first substrate and the second substrate including the first and second electrodes, respectively, are bonded to each other so that the electrodes face each other, and then a composition for forming a liquid crystal layer is injected into the space between the first substrate and the second substrate, or
  • a liquid crystal layer was formed by dropping the liquid crystal layer forming composition under vacuum with respect to any one of the first substrate and the second substrate including the first electrode and the second electrode, respectively, and then bonding the remaining substrates to face the electrodes.
  • the manufacturing method may further include selectively irradiating light after applying an electric field between the first substrate and the second substrate of the assembly after fabrication of the assembly.
  • 3 is a process diagram schematically illustrating a manufacturing process of a liquid crystal display according to an exemplary embodiment of the present invention. 3 is only an example for describing the present invention and the present invention is not limited thereto.
  • Step 1 is a step of forming the first and second electrodes 12 and 22 for the first substrate 11 and the second substrate 21, respectively (S11).
  • the first and second substrates 11 and 21 may be used without particular limitation as long as they are generally used in liquid crystal displays, and specifically, glass or plastic substrates may be used.
  • a common electrode (or transparent electrode) is formed on one surface of the first substrate 11 as the first electrode 12, and pixel electrodes are formed on the one surface of the second substrate 21 as the second electrode 22, respectively.
  • the first substrate and the second substrate, and the common electrode and the pixel electrode are classified according to the position and the function thereof.
  • the common electrode may be formed on the second substrate or the pixel electrode may be formed on the first substrate.
  • the first and second electrodes 12 and 22 may be manufactured according to a conventional electrode forming method, and the first and second electrode forming materials may be particularly limited as long as they are materials used for forming electrodes in liquid crystal displays. Can be used without
  • the first and second electrodes 12 and 22 may include a metal oxide carbon-based electroconductive material and a mixture thereof, which may be selected from the group of yitusin.
  • a metal oxide carbon-based electroconductive material Preferably, indium tin oxide ( ⁇ ), zinc oxide (Z0), inindi zinc oxide (IZO), Tin oxide (TO), indium oxide (10), aluminum oxide (A1 2 0 3 , AO), silver oxide (AgO), titanium oxide (Ti0 2 ), fluorine-doped tin oxide (fluorine— doped tin oxide (FTO), aluminum doped zinc oxide (AZO), zinc indium tin oxide (ZITO), nickel oxide (NiO), nickel zinc tin oxide oxide, NZTO), nickel titanium oxide (NTO), nickel tin oxide, graphene, graphene oxide (GO), and combinations thereof It may include a compound selected.
  • first and second electrodes 12 and 22 may be formed over the entire surface of the substrates 11 and 21, or may be patterned in a predetermined form such as island, sprite, fishbone, or the like through a separate patterning process. (Not shown). Accordingly, according to another embodiment of the present invention, a liquid crystal display device in which at least one of the first and second electrodes 12 and 22 is patterned is provided. Further, at least one of the first and second substrates 11 and 21 before the electrode forming step, or on at least one of the first and second electrodes 12 and 22 after the electrode formation. The step of forming an electrically insulating compound layer (not shown) may be further performed, or the step of forming the electrically insulating compound layer may be performed both before and after forming the electrode.
  • an electrically insulating compound layer serving as a passivation layer or an insulating layer may be formed on the top or the bottom of the electrode, and the electrode may be formed by performing the step of forming the electrically insulating compound layer before and after forming the electrode.
  • An electrically insulating compound layer may be formed on both top and bottom of the. Accordingly, according to another embodiment of the present invention, a liquid crystal display device in which an electrically insulating compound layer is formed above, below, or both of at least one of the first and second electrodes 12 and 22. do.
  • the electrically insulating compound layer may include an organic insulating material, a nonmetal oxide, or a nonmetal nitride.
  • the electrically insulating compound layer may be a single layer composed of silicon oxide (SiOx) or silicon nitride (SiNx), or may be a dichroic layer or a multilayer structure composed of a silicon oxide layer and a silicon nitride layer.
  • Step 2 is performed by bonding the first and second substrates 11 and 21 including the first and second electrodes 12 and 22 to each other so that the electrodes face each other and then bonding the spaces between the first substrate and the second substrate.
  • Forming composition (13a) After dropping, the remaining substrates are bonded to each other under a special step of manufacturing an assembly (S12).
  • composition 13a for forming a liquid crystal layer is the same as described above.
  • pouring or dripping process of the composition for liquid crystal layer formation 13a can be performed by a conventional method.
  • the assembly is heated to a temperature of 5 to 20 ° C higher than the nematic-isotropic phase transition temperature of the mixture of the liquid crystal material and the liquid crystal vertical alignment inducing agent 0 minutes per minute.
  • the induction process may be further performed for the vertical alignment of the liquid crystal cooled at a rate of 1 to 10 ° C.
  • the electric field applying process is preferably performed under the condition that a direct current or alternating current electric field is applied such that the light transmittance of the liquid crystal display becomes 5% (T 05 ) to 100% ( ⁇ 100 ) of the maximum transmittance under the orthogonal polarizer.
  • a specific optical state is induced to the liquid crystal in the assembly by application of an electric field, and then light of a wavelength capable of chemically reflecting the photoreactive group is irradiated, preferably ultraviolet rays.
  • light stabilizers purification of the photoreactive group of the to light reflection male compound is irradiated with ultraviolet rays of 200 nm to 400 nm wavelength range, in 1 minute to 90 minutes intensity of 500 mW / cm 2 to about 50 ⁇ W / cm 2 for This is good because the surface stabilization effect of liquid crystal alignment can be obtained by maximizing the efficiency.
  • the light irradiation step may be carried out in two or more steps by varying the electric field to be applied or the intensity of light to be irradiated.
  • the light irradiation process is preferably performed after applying an electric field and waiting for the defect to be minimized before the arrangement of the liquid crystals becomes stable.
  • the liquid crystal layer is a passivation layer formed by the microassembly as the microassembly of the liquid crystal vertical alignment guider present in the liquid crystal layer forming composition is solidified by the light irradiation process to form a passivation layer on the electrode. It may further comprise purifying layers 14 and 24.
  • the compound forming the liquid crystal vertical alignment inducing agent is a photoreactive compound containing a photo-banung group
  • the photoreactive group of the photoreactive compound causes a photoreaction to form a photopolymer by the above light irradiation process, as a result
  • the arrangement and optical state of the liquid crystal can be further stabilized, and the surface pretilt angle induction of the liquid crystal and the surface stabilization of the pixel unit can be realized.
  • the liquid crystal molecules Transmittance increases as it rotates in a direction perpendicular to the electric field.
  • the rotation direction of the liquid crystal occurs irregularly according to the portion of the liquid crystal cell. Therefore, defects in the liquid crystal array are generated, which acts as a cause of deterioration of device characteristics.
  • the liquid crystal material is in the liquid crystal pretilt direction of the surface. It will be transferred to a vertical alignment state that remembers. As such, the alignment of the liquid crystal is stabilized to have a pretilt angle, thereby eliminating defects, thereby improving the response characteristic of the liquid crystal and the brightness and contrast ratio of the device.
  • the manufacturing method of the liquid crystal display device can induce the vertical alignment of the liquid crystal by applying a liquid crystal vertical alignment inducer capable of forming an emulsion with respect to the liquid crystal host, without the application of a separate polymer alignment layer and the high temperature baking process. have.
  • the manufacturing method unlike the conventional liquid crystal display device manufacturing method that achieves orientation stabilization by mixing a liquid crystal material, the reaction liquid is mixed with a reactive liquid crystal as a liquid crystal material to achieve alignment stabilization, using a photo-banung compound containing the photoreactive group
  • a photo-banung compound containing the photoreactive group This can induce the vertical alignment of the liquid crystal without forming the alignment layer, and also stabilizes the specific alignment state of the liquid crystal by solidifying the liquid microassembly adsorbed on the substrate surface through the photopolymerization process by light irradiation under electric field application. Defects that may occur after stabilization can be significantly reduced. As a result, the productivity of the liquid crystal display device manufacturing and the reliability of the liquid crystal display device can be improved.
  • the stabilization of the liquid crystal array it is possible to prevent defects in the liquid crystal generated when driving the device and to improve the reaction speed, thereby improving performance and reliability of the device.
  • the liquid crystal line tilt angle induction and director stabilization are possible in pixel units, optical / electro-optic characteristics such as brightness, contrast ratio, and reaction speed of the liquid crystal device may be further improved.
  • the manufacturing method is carried out at room temperature, the process temperature is significantly lower than the firing temperature of the conventional polymer alignment layer, and the process is simple. In particular, a flexible substrate having a high quality liquid crystal display device or a low temperature process is required. It is useful for manufacturing a liquid crystal display device using ex ible sub rat.
  • the manufacturing method of the liquid crystal display device may replace the conventional high temperature alignment layer coating and firing process with a room temperature process. Therefore, not only a high-quality liquid crystal display device using a glass substrate but also an alignment film firing step at a high temperature is omitted, which is useful for the manufacture of a liquid crystal display device having a high temperature process such as a flexible liquid crystal display device.
  • the liquid crystal display device according to the present invention manufactured by such a manufacturing method is TV, It can be applied to electro-optical device products using liquid crystal such as 3D-TV, monitor, tablet PC, various mobile devices, especially flat panel display.
  • the composition for forming an emulsified liquid crystal layer includes the liquid crystal vertical alignment guider together with the liquid crystal host, each of which is the same as described above.
  • the composition for forming a liquid crystal layer includes the liquid crystal vertical alignment inducing agent together with a liquid crystal host, wherein the liquid crystal vertical alignment inducing agent is photoreactive with at least one compound of an amphiphilic compound and a monomolecular hydrophilic liquid constituting the inducing agent.
  • Photoreactive compound containing a group Amphiphilic compounds comprising the photoreactive group and the hydrophilic liquid of a single molecule are the same as described above.
  • a method of forming an insulating liquid crystal vertical alignment and light stabilization layer between the electrode layer and the liquid crystal layer in a simplified process compared to the prior art without a line coating treatment of the substrate.
  • the liquid crystal vertical alignment and photostabilization layer forming method includes injecting a liquid crystal layer formation composition including a liquid crystal vertical alignment inducing agent dispersed in an emulsion state in the liquid crystal host together with a liquid crystal host into a liquid crystal layer, applying an electric field, and irradiating with light. This can be done by.
  • the fine granules present in the liquid crystal layer forming composition are solidified to form the liquid crystal vertical alignment and the light stabilization layer as a passivation layer on the electrode layer. Done.
  • the liquid crystal host, the liquid crystal vertical alignment guide and the light irradiation process are the same as described above.
  • a pentaerythride of Formula 5 as an amphiphilic compound was mixed with monostearate and glycerol of Formula 6 as a hydrophilic liquid at a weight ratio of 80:20 to prepare a liquid crystal vertical alignment inducing agent.
  • a homogeneous mixture of pentaerythritol monostearate and glycerol was added to the liquid crystal host with respect to the total weight of the liquid crystal host. Dispersed in an amount of 3% by weight to prepare a composition for forming a liquid crystal layer of a uniform emulsion.
  • Pentaerythritol dispersed in chloroform prepared above was added monostearate / glycerol to the liquid crystal host in 30% by weight based on the total weight of the liquid crystal host in the emulsion liquid of the microassembly, and then heated to 70 degrees Celsius to completely chloroform By removing the 0.3 wt% pentaerythritol monostearate / glycerol to prepare a composition for forming a liquid crystal layer in which the microassembly was emulsified uniformly in the liquid crystal host.
  • Test Example 1 Test Example 1
  • compositions for forming a liquid crystal layer prepared in Preparation Examples 1 and 2 were respectively injected into a liquid crystal cell prepared using a substrate not pre-aligned.
  • liquid crystal layer-forming compositions prepared in Preparation Examples 1 and 2 are the same type of emulsion dogs, and amphiphilicity as in Preparation Example 1 without using a third solvent such as chloroform in Preparation Example 2 It can be seen that an emulsion can be prepared by adding the compound-hydrophilic acid liquid mixture directly to the liquid crystal.
  • Preparation Example 3
  • the composition for forming a liquid crystal layer prepared in Preparation Example 3 includes a photobanung acrylate group in a hydrophilic dispersed phase liquid, after inducing liquid crystal vertical alignment, irrespective of whether an electric field is applied or not, a photoinitiator is used. Through the photopolymerization reaction by light irradiation, the microassembly of the liquid phase may be converted into a solid phase.
  • Preparation Example 4 A pentaerythride of formula (8) containing a photoreactive group as an amphiphilic compound is mixed with a diacrylate monostearate and a triglycerol diacrylate containing a photobanung group as a hydrophilic liquid at a weight ratio of 80:20. Vertical alignment inducers were prepared.
  • the liquid crystal vertical alignment induction agent prepared above was dispersed in the liquid crystal host in an amount of 0.3% by weight based on the total weight of the liquid crystal host to prepare a composition for forming a liquid crystal layer of a uniform emulsion.
  • Liquid crystal vertical alignment induction agent was carried out in the same manner as in Preparation Example 4, except that sorbitan monopalmitate represented by Chemical Formula 9 as an amphiphilic compound and triglycerol diacrylate having a photobanung group were used as a hydrophilic liquid. And to prepare a composition for forming a liquid crystal layer comprising the same.
  • a liquid crystal vertical alignment inducer prepared by mixing sorbitan monopalmitate and triglyceride in a weight ratio of 80:20 was added to chloroform. It was sonicated for 5 minutes after the addition of the content of 1% by weight. At this time, a stable emulsion showing a white light scattering state was produced while uniformly dispersing sorbitan monopalmitate / triglyceride diacrylate in a colorless transparent chloroform solvent.
  • the average particle diameter of the microassembly was about 200 nm.
  • the sorbitan monopalmitate / triglyceride dispersed in the above-mentioned chloroform was added to the emulsion of the microassembly of diacrylate in 30% by weight relative to the total weight of the liquid crystal host in the liquid crystal host, followed by heat of 70 degrees Celsius. 0 is added to remove chloroform completely.
  • a liquid crystal layer-forming composition was prepared in which 3 wt% pentaerythritol monostearate / glycerol was uniformly emulsified in a liquid crystal host.
  • the sorbitan monopalmitate used in the preparation of the liquid crystal vertical alignment guide in Preparation Examples 5 and 6 has a property of dissolving itself in the liquid crystal host, even when mixed with the liquid crystal host such as a hydrophilic liquid, Insoluble triglycerides were evenly dispersed in the liquid crystal host in the form of a disperse phase microassembly with diacrylate.
  • composition for liquid crystal layer formation manufactured in manufacture 5 and 6 was injected into the liquid crystal cell produced using the board
  • the liquid microassembly was converted into the solid phase through a photopolymerization reaction by light irradiation regardless of whether the electric field was applied after the vertical alignment of the liquid crystal.
  • sorbitan monopalmitate as an amphiphilic compound and glycerol without a photoreactive group as a hydrophilic liquid are mixed at various mixing ratios as shown in Table 1 to prepare a liquid crystal vertical alignment inducing agent, and with respect to the total weight of the liquid crystal host. 0 . It was mixed at 1% by weight to prepare a composition for forming a liquid crystal layer.
  • the prepared liquid crystal layer-forming composition was injected into a liquid crystal cell prepared by using a non-aligned substrate, and the vertical alignment of the liquid crystal was confirmed.
  • the vertical alignment of the liquid crystal was confirmed.
  • After inducing the vertical alignment of the liquid crystal by applying an electric field to the liquid crystal Sal The light was irradiated in a state in which the liquid crystals were arranged in the direction, and it was confirmed whether the liquid crystals induce the pretilt angle.
  • Table 1 The results are shown in Table 1 below.
  • Sorbitan monopalmitate or pentaerythrite as an amphiphilic compound and diacrylate monostearate as a hydrophilic liquid and triglycerides containing a photoreactive group as a hydrophilic liquid were mixed in various mixing ratios shown in Tables 2 and 3 below.
  • the liquid crystal vertical alignment induction agent was carried out in the same manner as in Test Example 3, except that the liquid crystal vertical alignment inducer was mixed with the liquid crystal host in the content as shown in Tables 2 and 3, The vertical alignment of and after the light irradiation was confirmed whether the pretilt angle of the liquid crystal. The results are shown in Tables 2 and 3 below.
  • the diameter of the microassembly was dependent on the mixing ratio of the amphiphilic compound and the hydrophilic dispersed phase liquid, the higher the ratio of the amphiphilic compound is the diameter of the microassembly Decreased.
  • the average particle diameter of the microassembly was about 200 nm, and in the case of Example No. 7, it was about 10 nm.
  • a liquid crystal display device according to the manufacturing process of the liquid crystal display device shown in FIG. 3, using the first and second substrates each having an unpatterned transparent electrode ITO and a pixel electrode ⁇ patterned in the form of fishbone, respectively. was prepared.
  • the unpatterned ⁇ ⁇ transparent electrode and the patterned ITO pixel electrode as the low U and second electrodes 12 and 22 for the first and second substrates 11 and 21, respectively. It was formed, and ultrasonically cleaned in distilled water using a detergent, and then washed with acetone and isopropyl alcohol, respectively, and dried. After assembling the transparent electrodes and the pixel electrodes on the first and second substrates to face each other without any other alignment treatment, 0.2 parts by weight of the liquid crystal vertical alignment guide is uniformly mixed with 100 parts by weight of the liquid crystal host having negative dielectric anisotropy. The granulated liquid crystal layer was prepared by injecting the composition for forming an emulsified liquid crystal layer.
  • the liquid crystal vertical alignment induction agent was used by uniformly mixing stearoyl glycerol (Amphiphilic compound) and glycerol (80%) in a ratio of 80:20 as a hydrophilic liquid.
  • Each compound used in the liquid crystal vertical alignment inducer was not dissolved or dispersed independently in the liquid crystal host, but it was confirmed that the mixture of the two compounds uniformly dispersed in the liquid crystal host.
  • the gap between the first substrate and the second substrate during the assembly formation was maintained at 4.0; urn, and the process of injecting the composition for forming a liquid crystal layer was performed at 90 ° C., which is an isotropic temperature of the composition for forming a liquid crystal layer. .
  • the assembly was cooled at a rate of 5 ° C. per minute.
  • liquid crystal vertical alignment inducer prepared by mixing stearoyl glycerol as an amphiphilic compound and glycerol as a hydrophilic liquid at a ratio as shown in Table 4 below, using an unpatterned ⁇ electrode as a transparent electrode and a pixel electrode.
  • a liquid crystal display device was manufactured in the same manner as in Example 1, except that the gap between the first substrate and the second substrate was maintained at ⁇ when the assembly was formed.
  • the polarization microscope and the conoscopy image were used to determine whether the liquid crystal was vertically aligned and whether the pretilt angle was formed by applying an electric field. The results are shown in Table 4.
  • Liquid crystal vertical alignment inducer prepared by mixing triglyceride diacrylate (tri gl yce ro l di acryl at e) with a stearoyl glycerol as an amphiphilic compound and a photoreactive group as a hydrophilic liquid at a ratio as shown in Table 5 below
  • a liquid crystal display device was manufactured in the same manner as in Example 1, except for using.
  • the polarization microscope and the conoscopy image were used to determine whether the liquid crystal was vertically aligned and whether the pretilt angle was formed by applying an electric field. The results are shown in Table 5.
  • FIG. 5A to 5C show the results of observing the change of the liquid crystal array before and after applying the electric field with the polarizing microscope for the liquid crystal display device manufactured in Example 2.
  • FIG. 5A to 5C show the results of observing the change of the liquid crystal array before and after applying the electric field with the polarizing microscope for the liquid crystal display device manufactured in Example 2.
  • a liquid crystal layer vertically aligned with respect to a substrate exhibits an extinction state as shown in FIG. 5A under a quadrature polarizer.
  • the liquid crystal molecules are diluted in a direction perpendicular to the electric field and transmittance increases.
  • the electrolysis direction of the liquid crystal occurs randomly at the portion of the liquid crystal sal.
  • FIG. 5B a large number of defects in the liquid crystal array may occur, thereby deteriorating characteristics of the liquid crystal display.
  • the defect shown in FIG. 5B is slowly removed as time passes, and transitions to a uniform bright state as shown in FIG. 5C when the arrangement of the liquid crystals is observed after 30 seconds (sec) after application of an electric field.
  • a liquid crystal display was manufactured in the same manner as in Example 1, except that a liquid crystal vertical alignment inducing agent was used.
  • the vertical alignment of the liquid crystal was not induced in the liquid crystal display of Example No. 1.
  • the length of the hydrophobic group of the propyl calrate used as the amphiphilic compound was not sufficient to form an emulsified liquid crystal composition, and as a result, the vertical alignment of the liquid crystal was not induced.
  • the liquid crystal display device of Examples 2 to 4 it can be confirmed that when the length of the hydrophobic hydrocarbon group is longer than or equal to 8 carbon atoms in length, it effectively induces vertical alignment.
  • the liquid crystal display device of Example No. 4 contained a photopolymerizable group in both the amphiphilic compound and the phase-phase hydrophilic liquid compound forming the emulsion, and thus the line tilt angle of the liquid crystal could be more efficiently stabilized.
  • Test Example 8
  • Example liquid crystals were carried out in the same manner as in Example 1, except that a glucoside derivative (Compounds A33 to A40) and a liquid crystal vertical alignment inducing agent prepared by mixing glycerol as a hydrophilic liquid were used.
  • a display device was manufactured.
  • a sorbitan derivative (compounds A1 to A7) having a cyclic polyalcohol-derived hydrophilic group as an amphiphilic compound at a ratio as shown in Table 8 below or using triglycerol diacrylate as a hydrophilic liquid Or, except that a liquid crystal vertical alignment inducer prepared using glycerol as a hydrophilic liquid and a polyoxyethylene sorbitan derivative (compounds A8 to A16) as an amphiphilic compound, The liquid crystal display device was manufactured by the same method.
  • A8 polyethyleneglycol sorbitan monolaurate, Tween TM 20
  • A12 polyoxyethylene sorbitan tristearate
  • A13 Polyoxyethylenesorbitan monooleate, Tween TM 80
  • A15 Polyoxyethylenesorbitan st ear ate, Tween TM 61
  • A16 Polyoxyethylenesorbitan oleate (Tween TM 81)
  • FIG. 7A to 7C are polarization micrographs showing electro-optic switching characteristics before light irradiation for Example No. 2.
  • FIG. 8A to 8C show polarization micrographs showing electro-optic switching characteristics after light stabilization of the same liquid crystal device under electric field application.
  • the prepared liquid crystal display device was subjected to the electric field application and light irradiation process in the same manner as in Test Example 6, and the liquid crystal alignment state and the pretilt angle were stabilized before and after the light irradiation process.
  • the results are shown in Table 9.
  • A24 Stearoyl glycerol
  • A29 Dihexadecanoyl glycerol, dipalmit in A30: Octadecyl glycerol (batyl alcohol)
  • Maltoside derivatives (compounds A41 to A48) having a bicyclic polyhydric alcohol hydrophilic group as an amphiphilic compound at a ratio as shown in Table 10 below, and a glycerol containing no photobanung group as a hydrophilic liquid.
  • A52 1-nuxadecanol
  • A53 1-octadecanol (1-Octadecanol)
  • the liquid crystal compositions of Examples 1 and 5 could not induce vertical alignment in the liquid crystal device. This is because the length of the hydrophobic groups of the amphiphilic compounds (A49, A50, and A54) used in the preparation of the liquid crystal composition is not sufficient to form an emulsified liquid crystal composition, thereby inducing vertical alignment of the liquid crystal.
  • the liquid crystal display device according to the exemplary embodiment of the present invention includes the amphiphilic compound having a length of the hydrophobic hydrocarbon group longer than the length corresponding to 8 carbon atoms.
  • the prepared liquid crystal display device was subjected to the electric field application and light irradiation process in the same manner as in Test Example 6, and the liquid crystal alignment state and the pretilt angle were stabilized before and after the light irradiation process.
  • the results are shown in Table 13.
  • A60 Hexadecanoic acid, Palmitic acid
  • A61 Octadecanoic acid (Stearic acid)
  • the liquid crystal display of the device is the application of an electric field in the induced vertically-oriented state after when subjected to stabilization of the orientation by light irradiation, the surface of the substrate by an a photo-polymerization comprising a hydrophilic liquid, a solid thin film eu Was formed, and as a result, it was found that the pretilt angle of the liquid crystal was effectively stabilized. .
  • Test Example 15 Preparation prepared by mixing a compound having a hydrophilic ethylene glycol or polyoxyethylene head group (A70 to A78) as an amphiphilic compound at a ratio as shown in Table 14, and triglycerol diacrylate having a photoreactive group as a hydrophilic liquid A liquid crystal display device was manufactured in the same manner as in Test Example 5, except that the prepared liquid crystal vertical alignment inducing agent was used.
  • the prepared liquid crystal display device was subjected to the electric field application and light irradiation process in the same manner as in Test Example 6, and the liquid crystal alignment state and the pretilt angle were stabilized before and after the light irradiation process.
  • the results are shown in Table 14.
  • A70 ethylene glycol stearate
  • A71 polyoxyethylene acid: Polyoxyethylene (8) stearate (Myr j TM 45)
  • A72 polyoxyethylene (2) stearyl ether (Brij TM S2)
  • A74 Polyoxyethylene (2) cetyl ether (Brij TM 52)
  • A75 polyoxyethylene (20) cetyl ether (Brij TM 58)
  • A78 polyoxyethylene (10) stearyl ether (Brij TM S10)
  • the amphiphilic compounds A4, A19, A25, A23, A33, A34, A36, A48, A61, A65 and A66
  • A4 sorbitan tristearate (Sorbitan tristearate, Span TM 65)
  • A19 pentaerythritol monoacrylate monostearyl zero rate (Pentaerythr itol monoacryl ate monostearate) in
  • A61 Octadecanoic acid (Octadecanoi c acid, Stearic acid)
  • the present invention relates to a liquid crystal vertical alignment inducing agent and a liquid crystal display device manufactured using the same, wherein the liquid crystal vertical alignment inducing agent induces vertical alignment of the liquid crystal without a line alignment treatment process and stabilizes the pretilt angle of the liquid crystal. It is possible to simplify the manufacturing process of the liquid crystal display and to improve the performance and reliability of the liquid crystal display.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)

Abstract

Cette invention concerne un inducteur d'alignement vertical des cristaux et la production d'un affichage à cristaux liquides l'utilisant, l'inducteur contenant un composé amphiphile, qui contient de un à trois groupes hydrophobes ayant chacun de 8 à 30 atomes de carbone par molécule, et un liquide hydrophile unimoléculaire, de façon que l'alignement vertical des cristaux liquides soit induit sans processus de pré-alignement et que l'angle de pré-inclinaison des cristaux liquides soit stabilisé, pour améliorer ainsi la performance et la fiabilité du dispositif d'affichage à cristaux liquides.
PCT/KR2014/006203 2014-07-10 2014-07-10 Inducteur d'alignement vertical des cristaux liquides et production d'un dispositif d'affichage à cristaux liquides l'utilisant Ceased WO2016006738A1 (fr)

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PCT/KR2014/006203 WO2016006738A1 (fr) 2014-07-10 2014-07-10 Inducteur d'alignement vertical des cristaux liquides et production d'un dispositif d'affichage à cristaux liquides l'utilisant

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PCT/KR2014/006203 WO2016006738A1 (fr) 2014-07-10 2014-07-10 Inducteur d'alignement vertical des cristaux liquides et production d'un dispositif d'affichage à cristaux liquides l'utilisant

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WO2016006738A1 true WO2016006738A1 (fr) 2016-01-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108587649A (zh) * 2017-12-28 2018-09-28 深圳市华星光电技术有限公司 辅助配向剂及其应用
TWI685713B (zh) * 2016-03-28 2020-02-21 韓商東友精細化工有限公司 著色感光性樹脂組合物、使用其製造的濾色器和圖像顯示裝置
WO2024204521A1 (fr) * 2023-03-31 2024-10-03 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides et leurs procédés de fabrication

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2002169015A (ja) * 2000-11-30 2002-06-14 Fuji Photo Film Co Ltd 光学フイルム、偏光素子、偏光素子の製造方法、偏光板および液晶表示装置
KR20050056326A (ko) * 2003-12-10 2005-06-16 제일모직주식회사 표면 관능화된 단분산성 고분자 미립자, 그 제조 방법, 및그 미립자를 이용한 스페이서
US7799391B2 (en) * 2006-06-15 2010-09-21 Dai Nippon Printing Co., Ltd. Liquid crystal composition, color filter and liquid crystal display
WO2014042389A1 (fr) * 2012-09-17 2014-03-20 전북대학교산학협력단 Inducteur permettant d'aligner verticalement des cristaux liquides et dispositif d'affichage à cristaux liquides fabriqué à l'aide de cet inducteur

Patent Citations (4)

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JP2002169015A (ja) * 2000-11-30 2002-06-14 Fuji Photo Film Co Ltd 光学フイルム、偏光素子、偏光素子の製造方法、偏光板および液晶表示装置
KR20050056326A (ko) * 2003-12-10 2005-06-16 제일모직주식회사 표면 관능화된 단분산성 고분자 미립자, 그 제조 방법, 및그 미립자를 이용한 스페이서
US7799391B2 (en) * 2006-06-15 2010-09-21 Dai Nippon Printing Co., Ltd. Liquid crystal composition, color filter and liquid crystal display
WO2014042389A1 (fr) * 2012-09-17 2014-03-20 전북대학교산학협력단 Inducteur permettant d'aligner verticalement des cristaux liquides et dispositif d'affichage à cristaux liquides fabriqué à l'aide de cet inducteur

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KIM, JIN UK.: "Emulsion Induced Homeotropic Alignment of Liquid Crystals and Photostabilization of Director Tilt.", MASTER'S THESIS., 21 February 2014 (2014-02-21), pages 1 - 97 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI685713B (zh) * 2016-03-28 2020-02-21 韓商東友精細化工有限公司 著色感光性樹脂組合物、使用其製造的濾色器和圖像顯示裝置
CN108587649A (zh) * 2017-12-28 2018-09-28 深圳市华星光电技术有限公司 辅助配向剂及其应用
WO2024204521A1 (fr) * 2023-03-31 2024-10-03 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides et leurs procédés de fabrication

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