WO2016006738A1 - Inducer for vertically aligning liquid crystals and liquid crystal display device manufactured using same - Google Patents

Inducer for vertically aligning liquid crystals and liquid crystal display device manufactured using same 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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WIPO (PCT)
Prior art keywords
liquid crystal
group
acid
vertical alignment
compound
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PCT/KR2014/006203
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French (fr)
Korean (ko)
Inventor
강신웅
김진욱
김선수
이명훈
이승희
Original Assignee
전북대학교산학협력단
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Priority to PCT/KR2014/006203 priority Critical patent/WO2016006738A1/en
Publication of WO2016006738A1 publication Critical patent/WO2016006738A1/en

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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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Abstract

The present invention provides an inducer for vertically aligning crystals and a liquid crystal display manufactured using the same, in which the inducer contains an amphiphilic compound, which contains one to three hydrophobic groups each having 8-30 carbon atoms in a molecule, and a unimolecular hydrophilic liquid, and thus vertical alignment of liquid crystals is induced without a pre-alignment process and the pretilt angle of liquid crystals is stabilized, thereby improving the performance and reliability of the liquid crystal display device.

Description

명세서  Specification
액정 수직배향 유도제 및 이를 이용하여 제조된 액정 표시장치  Liquid crystal vertical alignment guide and liquid crystal display manufactured using the same
기술분야 Technical Field
본 발명은 액정 수직배향 유도제 및 이를 이용하여 제조된 액정표시장 치에 관한 것이다.  The present invention relates to a liquid crystal vertical alignment inducer and a liquid crystal display device manufactured using the same.
배경기술 Background
종래 수직배향형 액정표시장치의 제조시， 기판 표면에서 액정의 수직배 향을 유도하기 위해 폴리이미드와 같은 수직 배향형 고분자를 용액 상태 로 도포한 후 소상하여 고체화한 박막을 이용하였다. 도 1은 종래 액정의 수직배향을 위해 폴리이미드 박막을 이용한 액정표시장치의 제조공정을 개략적으로 나타낸 공정도이다. 도 1을 참조하여 설명하면， 제 1 및 제 2 기판 ( 1 , Γ ) 위에 전기장 인가를 위한 투명 전도성 막으로서 전극 (2， 2 ' ) 을 패턴화하여 각각 형성하고 (S1) , 그 위에 고분자 배향제를 용액 상태에 서 박막 형태로 도포한 후 고온의 열을 가하여 소성시켜 고분자 배향막 (3， 3 ' )을 형성하고 (S2) , 고분자 배향막이 형성된 제 1 및 제 2 기판을 서로 대 향시킨 후 일정한 간격으로 조립한 후 액정을 주입하여 액정층 (4)을 형성 시켜 액정표시장치를 제조하였다 (S3) . 이때 고분자 배향제의 영향으로 액 정층 (4)내 액정 분자는 기판 면에 대해 수직으로 배열하게 된다. 이와 같 이 , 종래의 수직배향형 액정표시장치의 제조방법은 액정의 배향을 제어하 기 위하여 제 1 및 제 2 기판 사이에 액정층을 형성하는 공정 이전에 양 기판에 배향막을 형성하는 공정을 별도로 실시하여야 한다.  In the manufacturing of a conventional vertical alignment liquid crystal display device, in order to induce the vertical alignment of the liquid crystal on the surface of the substrate, a vertically oriented polymer such as polyimide was applied in a solution state and then used to thin and solidify. 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. Referring to FIG. 1, as a transparent conductive film for applying an electric field on the first and second substrates (1, Γ), the electrodes 2, 2 ′ are patterned and formed respectively (S1), and the polymer orientation thereon. 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. As such, 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.
그러나， 상기와 같은 방법으로 액정의 배향을 제어하는 액정표시장치를 제조하는 경우， 액정이 특정 방향으로 선경사각올 가지지 않기 때문에 전 기장 인가 시 반응하는 액정의 방향이 랜덤 ( r andom )하여 결함 발생， 시인 성 저하， 반웅속도 저하 등의 문제가 발생하였다.  However, when manufacturing a liquid crystal display device that controls the alignment of the liquid crystal in the same manner as described above, since the liquid crystal does not have a pretilt angle in a specific direction, the direction of the liquid crystal reacts when the electric field is applied (r andom) to generate a defect , Problems such as low visibility, low reaction speed.
이러한 문제점을 해결하기 위하여， 러빙 , 표면돌기， 패턴화된 전극， 등 의 기술을 이용하여 액정의 선경사각을 유도하거나, 액정이 전기장에 반 응하는 방향을 제어하는 방법들이 제안되었다. 그러나， 이러한 방법들은 반드시 액정의 배향제어를 위한 배향막의 선처리공정이 필요하고, 공정상 의 문제， 부가된 기술에 따른 부작용 등으로 인하여 완전한 기술적인 해 결방법을 제시하지 못하였다. 최근에는 기판에 대한 선배향 처리 공정없이 나노입자와 같은 액정 배 향 유도 첨가물을 액정 조성물에 흔합하여 사용함으로써 액정 배향을 제 어하는 방법이 보고되었다 . 이 경우 종래 폴리이미드와 같은 배향막 처리 공정이 불필요하기 때문에 제조공정상의 이점이 있고 생산비용을 절감할 수 있다. 그러나, 액정배향 유도 첨가물로서 고체 나노입자가 흔합된 액 정조성물이 액정표시장치에 주입되었을 때 기판의 내부 표면에서 이들 첨 가물들의 불균일한 분포로 인하여 균일한 배향특성을 갖도록 제어하는데 어려움이 있으며， 특히 나노입자의 뭉침 ( aggregat i on )에 기인하는 배향 불량이 발생하게 되어 액정표시장치의 성능저하 및 제조수율을 낮추는 원 인이 되고 있다. 또한， 기판표면에 흡착된 나노입자의 약한 접착력으로 인하여 나노입자들이 뭉치거나 편재화되어 액정배향의 균일성이 나빠지고 액정표시장치의 장기적인 신뢰성에 문제가 크다 . 또한 투명전도막과 액 정층이 절연충없이 직접 접촉하기 때문에 액정표시장치의 구동시 전기화 학적 반응에 의해 액정화합물이 열화됨으로써 액정표시장치의 성능이 저 하되는 문제가 있다. In order to solve this problem, methods for inducing the pretilt angle of the liquid crystal or controlling the direction in which the liquid crystal responds to the electric field using techniques such as rubbing, surface protrusion, patterned electrode, and the like have been proposed. However, these methods necessarily require a pretreatment process of the alignment layer for the alignment control of the liquid crystal, and did not provide a complete technical solution due to process problems and side effects due to the added technology. Recently, a method of controlling liquid crystal alignment has been reported by using a liquid crystal alignment induction additive such as nanoparticles in a liquid crystal composition without pre-orientation treatment on a substrate. In this case, since an alignment film treating process such as a polyimide is unnecessary, there is an advantage in the manufacturing process and the production cost can be reduced. However, when 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. In particular, 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. In addition, due to the weak adhesion of the nanoparticles adsorbed on the surface of the substrate, the nanoparticles are agglomerated or localized, resulting in poor uniformity of liquid crystal alignment and long-term reliability of the liquid crystal display. In addition, since 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.
[선행기술문헌]  [Preceding technical literature]
한국특허공개 제 2008-0070821호 ( 2008 .07 .31 공개)  Korean Patent Publication No. 2008-0070821 (2008.07.31 publication)
발명의 상세한 설명 Detailed description of the invention
기술적 과제 Technical challenges
본 발명의 목적은 선 배향처리 공정 없이 액정의 수직배향을 유도하고， 액정의 선경사각을 안정화시켜 액정표시장치의 성능 및 신뢰성을 향상시 킬 수 있는 액정 수직배향 유도제 및 이를 포함하는 액정층 형성용 조성 물을 제공하는 것이다.  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.
본 발명의 다른 목적은 상기 액정 수직배향 유도제를 이용한 액정표시 장치 및 그 제조방법을 제공하는 것이다.  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.
본 발명의 또 다른 목적은 에멀견화된 액정충 형성용 조성물을 이용하 여 배향 안정성을 갖는 액정의 수직배향을 유도하는 방법을 제공하는 것 이다.  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.
본 발명의 또 다른 목적은 광반웅성의 에멀견화된 액정층 형성용 조성 물을 이용하여 액정의 수직배향 및 광안정화를 유도하는 방법을 제공하는 것이다.  It is still another object of the present invention to provide a method of inducing vertical alignment and photo stabilization of liquid crystals by using a composition for forming an emulsified liquid crystal layer of light reflection.
본 발명의 또 다른 목적은 기판의 선코팅처리 없이 종래에 비해 단순화 된 공정으로 전극층과 액정층 사이에 절연성의 액정배향 및 광안정화 층 을 형성하는 방법을 제공하는 것이다.  It is still another object of the present invention to provide a method of forming an insulating liquid crystal alignment and photo stabilization layer between an electrode layer and a liquid crystal layer in a simplified process compared to the prior art without precoating a substrate.
과제 해결 수단 Challenge solution
본 발명의 일 구현예에 따른 액정 수직배향 유도제는， 분자내 탄소원자 를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합 물; 및 단분자의 친수성 액체를 포함한다. 상기 양친매성 화합물은 친수성기로서 알코올， 다가알코을 , 아민， 다가 아민， 티을， 다가티을， 폴리옥시에틸렌， 카르복실산, 다가카르복실산， 설 포닉산 (sulfonic acid) , 다가설포닉산, 설퍼릭산 (sul f ur ic acid), 다가 설퍼릭산， 포스포닉산 (phosphonic acid), 다가포스포닉산， 포스퍼릭산 (phosphoric acid) 및 다가포스퍼릭산으로 이루어진 군에서 선택되는 화 합물로부터 유도된 1종 이상의 비이온성의 극성기를 포함하는 것일 수 있 다. 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.
바람직하게는 상기 양친매성 화합물은 1-을 (l-ol), 1，2-디올 (1,2-diol) 글리세를 (glycerol)， 글루코오스 (glucose)， 텍스트로스 (dextrose)， 소르 비를 (sorbitol), 펜타에리스리를 (pentaerythr itol )， 디펜타에리스리를 (dipentaerythritol ) , 트리펜타에리스리롤 (tripentaerythritol )， 소르비 탄 (sorbitan), 플룩토스 (f luctose)， 수크로스 (sucrose)， 갤릭산 (gallic acid) , 글루코피라노사이드 (glucopyranoside)， 아스코르빅산 (ascorbic acid), 매나이드 (mannide) 및 말토사이드 (maltoside)로 이투어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것일 수 있다.  Preferably, 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. .
또한 바람직하게는 상기 양친매성 화합물은 친수성기로서 1-아민 (1- amine) , 1，2-디아민 (1,2ᅳ diamine)， 1,3-디아민 (1,3-diamine)， 에틸렌 디 아민 (ethylene diamine) , 디에틸렌 디아민 (diethyl ene diamine) , 트리스 (2-아미노에틸)아민 (tris(2-aminoethyl )amine)， 시클로핵산 디아민 (eye lohexane diamine), 디에틸렌 트리 0 민 (diethylene triamine) , 페닐 디아민 (phenyl diamine ) , 페닐트리아민 (phenyltriamine)， 1,3，5-트리아진 4,6-디아민(1,3，5-^1&2^ 4,6-diamine), 1，3，5—트리아진 2，4，6-트리아 민 (1,3,5-triazine 2，4，6— triamine) 및 고리형 에틸렌 아민 (cyclen; (CH2CH2NH)n; n=2 내지 6의 정수)로 이투어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것일 수 있다. Also preferably, 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 ; integers of n = 2 to 6 It may be to include a functional group derived from a compound selected from the group consisting of).
또한 바람직하게는 상기 양친매성 화합물은 친수성기로서 하기 화학식 1의 탄소수 4 내지 40의 선형 폴리옥시에틸렌 또는 하기 화학식 2의 탄소 수 4 내지 10의 고리형 폴리에틸렌글리콜로부터 유도되는 작용기를 포함 하는 것일 수 있다.  Also preferably, the 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.
[화학식 1]  [Formula 1]
-CH2CH2-0-H -CH 2 CH 2 -0-H
Figure imgf000004_0001
Figure imgf000004_0001
(상기 화학식 1 및 2에서， m은 2 내지 20의 정수이고， n은 2 내지 5의 정수이다)  (In Formulas 1 and 2, m is an integer of 2 to 20, n is an integer of 2 to 5)
또한 바람직하게는 상기 양친매성 화합물은 친수성기로서 1-티을 (1- thiol) , 1,2-디티올 (l,2-dithiol), 티오글리세를 (thioglycerol ) , 티오펜 타에리쓰리롤 (thiopentathiopentaerythritol) 및 디티오트레이틀 Also preferably, the amphiphilic compound may include 1-thiol, 1,2-dithiol, thioglycerol, and thiopentathiopentaerythritol as hydrophilic groups. And dithio tray
(dithiothreitol)로 이루어진 군에서 선택된 화합물로부터 유도된 작용기 를 포함하는 것일 수 있다. functional groups derived from compounds selected from the group consisting of (dithiothreitol) It may be to include.
또한 바람직하게는 상기 양친매성 화합물은 친수성기로서 1-카르복실산 Also preferably, the amphiphilic compound is a 1-carboxylic acid as a hydrophilic group.
(1-carboxylic acid), 1，2-디카르복실산 (1,2-dicarboxylyc acid) , 1，3-디 카르복실산 (1,3-dicarboxylyc acid) , 벤젠카르복실산 (benzenecarboxy 1 i c acid), 벤젠디카르복실산 (benzenedicarboxylic acid), 1，2，3—트리카르복 실산 (l,2,3-tricarboxyl ic acid) , 벤젠트리카르복실산(1-carboxylic acid), 1,2-dicarboxylic acid (1,2-dicarboxylyc acid), 1,3-dicarboxylic acid (1,3-dicarboxylyc acid), benzenecarboxylic acid (benzenecarboxy 1 ic acid ), Benzenedicarboxylic acid, 1,2,3-tricarboxylic acid (l, 2,3-tricarboxyl ic acid), benzenetricarboxylic acid
(benzenetr icarboxyl ic acid) , 말릭산 (malic acid) , 말레익산 (maleic acid), 타르타르산 (tartar acid), 시트릭산 (citric acid), 말레아믹산 (mal eami c acid) , 그루타믹산 (glutamic acid) , 아가릭산 (agaric acid) , 아코니틱산 (aconitic acid) , 트라이카르발릴릭산 (tricarballyl ic acid) 및 아미노산 (amino acid)로 이루어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것일 수 있다. (benzenetr icarboxyl ic acid), malic acid (maleic acid), maleic acid (maleic acid), tartar acid (tartar acid), citric acid (mal eami c acid), glutamic acid (glutamic acid) ), Agaric acid (agaric acid), aconic acid (aconitic acid), tricarballyl ic acid (tricarballyl ic acid) and may include a functional group derived from a compound selected from the group consisting of amino acids (amino acid).
또한 상기 양친매성 화합물은 소수성기로서 치환 또는 비치환된 탄소수 8 내지 30의 탄화수소기 ; 분자내 분자내에 N, 0， P, S 및 Si로 이루어진 군에서 선택되는 1 이상의 해테로 원자를 포함하는 치환 또는 비치환된 탄소수 8 내지 30의 헤테로알킬기 , 헤테로사이클기 및 헤테로아로마틱기 ; 및 이들의 조합기로 이루어진 군에서 선택되는 작용기를 포함하는 것일 수 있다.  In addition, the amphiphilic compound is a hydrocarbon group of 8 to 30 carbon atoms substituted or unsubstituted as a hydrophobic group; A substituted or unsubstituted heteroalkyl group having 8 to 30 carbon atoms, a heterocycle group and a heteroaromatic group containing at least one heteroatom selected from the group consisting of N, 0, P, S and Si in the intramolecular molecule; And it may be to include a functional group selected from the group consisting of a combination thereof.
바람직하게는 상기 양친매성 화합물은 소수성기로서 할로겐 원자로 치 환되거나 비치환된 탄소수 8 내지 30의 알킬기， 알케닐알킬기， 알키닐알 킬기， 사이클로알킬기 및 아릴기 ; 분자내 카르보닐기 (-c(=o)-), 에스테르 기 (-COO)O— )， 에테르기 (-0-), 에틸렌옥사이드기 (-CH2CH20-), 및 아조기 (一 N=N-)로 이루어진 군에서 선택되는 헤테로원자 함유 작용기를 포함하는 탄소수 8 내지 30의 헤테로알킬기， 헤테로사이클로알킬기， 및 헤테로아릴 기 ; 및 이들의 조합으로 이루어진 군에서 선택되는 작용기를 포함하는 것 일 수 있다. Preferably, the amphiphilic compound is an alkyl group having 8 to 30 carbon atoms, an alkenylalkyl group, an alkynylalkyl group, a cycloalkyl group, and an aryl group which is unsubstituted or substituted with a halogen atom as a hydrophobic group; Intramolecular carbonyl group (-c (= o)-), ester group (-COO) O—), ether group (-0-), ethylene oxide group (-CH 2 CH 2 0-), and azo group (一 N = C8-C30 heteroalkyl group, heterocycloalkyl group, and heteroaryl group containing hetero atom containing functional group selected from the group which consists of N-); And it may be to include a functional group selected from the group consisting of a combination thereof.
보다 바람직하게는 상기 양친매성 화합물은 소르비탄 모노라우레이트， 소르비탄 모노팔미테이트, 소르비탄 모노스테아레이트， 소르비탄 트리스 테아레이트， 소르비탄 모노올레이트， 소르비탄 세스퀴올레이트, 소르비탄 트리올레이트， 폴리에틸렌글리콜 소르비탄 모노라우레이트， 폴리에틸렌소 르비탄 모노라우레이트， 폴리에틸렌소르비탄 모노팔미테이트， 폴리옥시에 틸렌소르비탄 모노스테아레이트 풀리옥시에틸렌소르비탄 트리스테아레이 트， 폴리옥시에틸렌소르비탄 모노올레이트， 폴리옥시에틸렌소르비탄 트리 올레이트， 폴리옥시에틸렌소르비탄 스테아레이트， 폴리옥시에틸렌소르비 탄 을레이트， 펜타에리쓰리틀 모노스테아레이트， 펜타에리쓰리틀 디아크 릴레이트 모노스테아레이트, 펜타에리쓰리를 모노아크릴레이트 모노스테 아레이트， 옥틸 갈레이트， 라우릴 갈레이트， 갈레이트 유도체， 스테아로 일 글리세를， 디팔미토일 글리세를， 디옥타데카노일 글리세롤， 팔미토일 글리세롤， 모노핵사데카노일 글리세롤， 디핵사데카노일 글리세를， 옥타데 실 글리세를， 올레오일 글리세를, 트리글리세를 모노스테아레이트， 아스 코르빅산 6-괄미테이트， 매나이드 모노올레이트， 옥틸 글루코피라노사이 드， 도데실글루코피라노사이드, 메틸글루코사이드 세스퀴스테아레이트， 메틸글루코사이드 디올레이트， 글루코실옥시에틸 메타크릴레이트， 글루코 피라노사이드 유도체， 옥틸 말토사이드， 사이클로핵실핵실 말토사이드， 데실 말토사이드, 운데실 말토사이드， 도데실 말토사이드， 트리데실 말토 사이드， 테트라데실 말토사이드， 핵사데실 말토사이드， 1—도데칸올， 1-핵 사데칸올， 1-옥타데칸올， 1，2-도데칸디올, 1,2-핵사데칸디올， 옥탄산, 데 칸산， 도데칸산， 핵사데칸산， 옥타데칸산， 옥틸아민， 데실아민, 도데실아 민， 핵사데칸 1，2-디아민, 디핵사데실 포스페이트， 데실포스폰산， 1-도데 칸티올， 1-핵사데칸티올， 에틸렌 글리콜 스테아레이트, 폴리옥시에틸렌산 폴리옥시에틸렌 (2) 스테아릴 에테르， 폴리옥시에틸렌 (4) 라우릴 에테르， 폴리옥시에틸렌 (2) 세틸 에테르, 폴리옥시에틸렌 (20) 세틸 에테르, 폴리 옥시에틸렌 (2) 을레일 에테르， 폴리옥시에틸렌 (20) 올레일 에테르， 폴리 옥시에틸렌 (10) 스테아 ¾ 에테르 및 이들의 흔합물로 이루어진 군에서 선택되는 것일 수 있다. More preferably, 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 glycerol, dioctadecanoyl glycerol, palmitoyl glycerol, mononuclear decanoyl glycerol, dinuxadecanoyl Glycerol, octadecyl glycerol, oleoyl glycerol, triglycerol monostearate, ascorbic acid 6-sulfite, mannide monooleate, octyl glucopyranoside, dodecyl glucopyranoside, methylglucoside Sesquistearate, Methylglucoside Dioleate, Glucosyloxyethyl Methacrylate, Gluco Pyranoside derivatives, octyl maltoside, cyclonucleus nucleus chamber maltoside, decyl maltoside, undecyl maltoside, dodecyl maltoside, tridecyl maltoside, tetradecyl maltoside, nucleodecyl maltoside, 1—dodecanol, 1 Nucleic acid decanol, 1-octadecanol, 1,2-dodecanediol, 1,2-nuxadecanediol, octanoic acid, decanoic acid, dodecanoic acid, nucleodecanoic acid, octadecanoic acid, octylamine, decylamine , Dodecylamine, nuxadecane 1,2-diamine, dinuxadecyl phosphate, decylphosphonic acid, 1-dodecanethiol, 1-nuxadecanethiol, ethylene glycol stearate, polyoxyethylene acid polyoxyethylene (2) ste Aryl ether, polyoxyethylene (4) lauryl ether, polyoxyethylene (2) cetyl ether, polyoxyethylene (20) cetyl ether, polyoxyethylene (2) oleyl ether, polyoxyethylene (20) oleyl Ether, polyoxyethylene (10) stea ¾ ether, and combinations thereof.
상기 단분자의 친수성 액체는 분자내에 히드록시기， 티을기， 아민기 , 및 카르복실기로 이루어진 친수성기를 1 내지 6개 포함하는 것일 수 있으 며 , 바람직하게는 물 ( 0) , 글리세롤 (glycerol)， 디글리세롤 (diglycerol), 트리글리세률 (triglycerol ) , 에틸렌 글리콜 (ethylene glycol), 디에틸렌 글리콜 (diethyleneglycol), 트리에틸렌 글리콜 (triethylene glycol) , 티오글리세를 (thi oglycero 1 )， 디티오글리세롤 (dithioglycerol), 에탄디티을 (ethanedi thi ol ) , 에틸렌 디아민 (ethylene diamine) , 디아미^프로판 (diaminopropane)， 디에틸렌트리아민 (diethylenetr iamine) , 트리에틸렌테트라아민 (t r i ethyl enetet r amine)， 트 리스아미노에틸 아민 (tris(aminoethyl) amine) , 펜타에리쓰리틀 테트라키 스 (3-멀캡토프로피오네이트) [Pentaerythritol tetrakis(3- mercaptopropionate)] , 트리글리세를 모노아크릴레이트 ( t r iglycero 1 monoacrylate) , 트리글리세를 모노메타아크릴레이트 ( tr iglycerol monomethacrylate) , 트리글리세롤 디아크릴레이트 (triglycerol diacrylate), 트리글리세롤 디메타아크릴레이트 (triglycerol dimethacrylate) , 펜타에리쓰리를 모노아크릴레이트 (pentaerytyhritol monoacrylate) , 펜타에리쓰리를 모노메타아크릴레이트 (pentaerytyhritol monomethacrylate) , 펜타에리쓰리롤 디아크릴레이트 (pentaerytyhritol diacrylate) , 펜타에리쓰리롤 디메타아크릴레이트 (pentaerythritol dimethacrylate), 아크릴산 (acrylic acid) , 메타크릴산 (methacryl i c acid) , 2-히드록시에틸 아크릴레이트 (2-hydroxyethyl acrylate) , 2-히드 록시에틸 메타크릴레이트 (2-hydroxyethyI methacryl ate) , 글리세를 모노 아크릴레이트 (glycerol monoacrylate) , 글리세롤 모노메타아크릴레이트 (glycerol monomethacrylate) 및 이들의 흔합물로 이루어진 군에서 선택 되는 것일 수 있다.  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 diacrylate, triglycerol dimethacrylate (triglycerol dimethacrylate), pentaerythrone monoacrylate (pentaerytyhritol monoacrylate) , Pentaerythritol monomethacrylate, pentaerytyhritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, acrylic acid, methacrylic acid ic acid), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (2-hydroxyethyI methacrylate), glycerol monoacrylate, glycerol monomethacrylate ( glycerol monomethacrylate) and combinations thereof May be.
상기 양친매성 화합물과 친수성 액체는 1:99 내지 99.9:0.1의 중량비로 포함될 수 있다.  The amphiphilic compound and the hydrophilic liquid may be included in a weight ratio of 1:99 to 99.9: 0.1.
상기 양친매성 화합물 및 친수성 액체 증 적어도 어느 하나의 화합물은 화합물 내에 1 이상의 광반응성기를 더 포함하는 광반웅성 화합물일 수 있으며， 바람직하게는 화합물내에 아크릴레이트기， 메타크릴레이트기 , 신 나메이트기， 쿠마린기， 차콘기， 비닐기， 티을기 , 엔기 , 디엔기， 티올엔기 및 아세틸렌기로 이루어진 군에서 선택되는 1 이상의 광반응성기를 더 포 함하는 광반웅성 화합물일 수 있다. 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.
상기 광반웅성 화합물은 액정 수직배향 유도제 총 중량에 대하여 5 내 지 100증량 %로 포함될 수 있다.  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.
본 발명의 다른 일 구현예에 따르면， 분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합물， 및 단분자의 친수성 액체를 포함하는 액정 수직배향 유도제 ; 그리고 액정호스트를 포 함하는 액정층 형성용 조성물을 제공한다.  According to another embodiment of the present invention, 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.
상기 액정 수직배향 유도제는 액정호스트 증에 에멀견 ( emu l s i on)의 형 태로 분산되어 있다.  The liquid crystal vertical alignment inducer is dispersed in the form of an emuls i on the liquid crystal host.
상기 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물은 화합물 내에 1 이상의 광반응성기를 더 포함하는 광반웅성 화합물일 수 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.
01다 01
상기 액정 수직배향 유도제는 액정층 형성용 조성물 총 중량에 대하여 0 .이 내지 5증량 %로 포함될 수 있다.  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.
본 발명의 또 다른 일 구현예에 따르면 , 제 1기판 및 제 2기판에 대해 각 각 제 1 및 제 2전극을 형성하는 전극형성단계; 그리고 상기 제 1 및 계 2전 극을 각각 포함하는 제 1기판과 제 2기판을 전극들끼리 대면하도록 하여 접 합한 후 제 1기판과 제 2기판 사이의 공간에 액정층 형성용 조성물을 주입 하거나， 또는 상기 제 1 및 제 2전극을 각각 포함하는 제 1기판과 제 2기판 중 어느 하나에 대해 진공 하에서 액정충 형성용 조성물을 적하하여 액정 층을 형성한 후 나머지 기판을 전극들끼리 대면하도록 접합하여 조립체를 제조하는 단계를 포함하며， 상기 액정층 형성용 조성물은 분자내 탄소원 자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화 합물， 및 단분자의 친수성 액체를 포함하는 액정 수직배향 유도제 ; 그리 고 액정호스트를 포함하는 것인 액정표시장치의 제조방법을 제공한다 . 상기 제조방법에 있어서， 액정 수직배향 유도제는 액정호스트 중에 에 멀견 ( emu l s i on)의 형태로 분산되어 있는 것이다.  According to another embodiment of the present invention, an electrode forming step of forming the first and second electrodes for each of the first substrate and the second substrate; 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. Alternatively, 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. And a step of preparing an assembly, wherein 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; And it provides a method for manufacturing a liquid crystal display device comprising a liquid crystal host. In the above production method, the liquid crystal vertical alignment guide agent is dispersed in the form of emuls i on in the liquid crystal host.
상기 제조방법에 있어서， 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물은, 화합물 내에 1 이상의 광반응성기를 더 포함하는 광반웅성의 화합물일 수 있다.  In the above production method, 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.
상기 제조방법에 있어서， 액정 수직배향 유도제는 액정층 형성용 조성 물 총 중량에 대하여 0 . 01 내지 5중량 %로 포함될 수 있다.  In the above production method, 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.
상기 제조방법은 조립체의 제조 후 제 1기판과 제 2기판 사이에 전기장을 인가하고， 광 조사하는 단계를 더 포함할 수 있다.  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.
본 발명의 또 다른 일 구현예에 따르면, 서로 대향하여 위치하는 제 1기 판과 제 2기판; 상기 제 1기판과 제 2기판의 상호 대향되는 면에 각각 형성 된 제 1전극과 제 2전극; 그리고 상기 제 1기판과 상기 제 2기판 사이에 개재 되어 위치하는 액정층을 포함하며 , 상기 액정층은 분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합물， 및 단분자의 친수성 액체를 포함하는 액정 수직배향 유도제 ; 그리고 액정 호스트를 포함하는 것인 액정표시장치를 제공한다 .  According to another embodiment of the invention, 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.
상기 액정표시장치에 있어서 , 양친매성 화합물 및 친수성 액체 중 적어 도 어느 하나는 화합물 내에 1 이상의 광반웅성기를 더 포함하는 광반응 성 화합물이며 , 상기 액정층은 상기 광반응성 화합물의 광증합체를 더 포 함할 수 있다. In 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.
상기 액정표시장치는 액정층과 제 1 및 제 2전극 사이에 액정 수직배향 유도제를 포함하는 액정의 수직배향 및 광안정화 층을 더 포함할 수 있다. 상기 액정표시조사에 있어서 , 제 1 및 제 2 전극 중 어느 하나 또는 둘 모두가 패턴화된 것일 수 있다.  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. In the liquid crystal display irradiation, one or both of the first and second electrodes may be patterned.
본 발명의 또 다른 일 구현예에 따르면， 에멀젼화된 액정층 형성용 조 성물을 이용하여 배향 안정성을 갖는 액정의 수직배향을 유도하는 방법을 제공한다 .  According to another embodiment of the present invention, a method of inducing vertical alignment of liquid crystals having alignment stability using an emulsified liquid crystal layer forming composition is provided.
본 발명의 또 다른 일 구현예에 따르면, 광반웅성의 에멀견화된 액정층 형성용 조성물을 이용하여 액정의 수직배향 및 광안정화를 유도하는 방법 을 제공한다.  According to still another embodiment of the present invention, a method of inducing vertical alignment and photo stabilization of liquid crystals using a light reflection emulsified liquid crystal layer-forming composition is provided.
본 발명의 또 다른 일 구현예에 따르면， 광반웅성의 에멀견화된 액정층 형성용 조성물에 대하여 전기장을 인가하고， 광을 조사함으로써 액정충과 전극층의 사이에 절연성의 액정 수직배향 및 광안정화 층을 형성하는 방 법을 제공한다.  According to another embodiment of the present invention, by applying an electric field to the light semi-emulsifying emulsified liquid crystal layer forming composition, and irradiating light to form an insulating liquid crystal vertical alignment and light stabilization layer between the liquid crystal filling and the electrode layer Provide a way to do it.
기타 본 발명의 구현예들의 구체적인 사항은 이하의 상세한 설명에 포 함되어 있다.  Other specific details of the embodiments of the present invention are included in the following detailed description.
발명의 효과 Effects of the Invention
본 발명에 따른 액정 수직배향 유도제를 이용하여 선 배향처리 공정 없 이 액정의 수직배향을 유도하고, 액정의 선경사각을 안정화시키며， 그 결 과로 액정표시장치의 제조공정을 단순화하고 액정표시장치의 성능 및 신 뢰성을 향상시킬 수 있다.  By using the liquid crystal vertical alignment guide according to the present invention, 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.
도면의 간단한 설명 Brief description of the drawings
도 1은 종래 액정표시장치의 제조공정을 개략적으로 나타낸 공정도이다. 도 2a는 본 발명의 일 구현예에 따른 액정층 형성용 조성물을 나타낸 모식도이고， 도 2b는 상기 조성물내에 분산된 미세조립체의 구조를 나타 낸 모식도이며， 도 2c는 상기 조성물내 포함되는 양친매성 화합물의 구조 를 나타낸 모식도이다.  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.
도 3은 본 발명의 일 구현예에 따른 액정표시장치의 제조공정을 개략적 으로 나타낸 공정도이다.  3 is a flowchart schematically illustrating a manufacturing process of a liquid crystal display according to an exemplary embodiment of the present invention.
도 4a는 실시예 1에서 제조한 액정표시장치의 액정충내 액정의 배열상 태를 편광현미경으로 관찰한 사진이고， 도 4b는 코노스코피 ( conoscopy) 를 이용하여 관찰한 사진이다.  FIG. 4A is a photograph of the arrangement of liquid crystals in the liquid crystal display device of Example 1 using a polarization microscope, and FIG. 4B is a photograph observed using conoscopy.
도 5a는 시험예 6의 실시번호 2에서 제조한 액정표시장치에 대해 전기 장 인가 전 액정층내 액정의 배열상태를 편광현미경으로 관찰한 사진이고， 도 5b는 전기장 인가 직후 액정의 배열상태를 편광현미경으로 관찰한 사 진이며， 도 5c는 전기장 인가 이후 30초 ( sec )에 액정의 배열상태를 편광 현미경으로 관찰한 사진이다. 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.
도 6a는 시험예 6의 실시번호 2에서 액정표시장치에 대해 전기장 인가 후 액정 배열상태의 안정화를 확인하고， 광조사를 실시하고, 다시 전기장 인가에 의한 스위칭 전 액정의 배열상태를 편광현미경으로 관찰한 사진이 고， 도 6b는 전기장 인가에 의한 스위칭 직후 액정의 배열상태를 편광현 미경으로 관찰한 사진이며， 도 6c는 전기장 인가에 의한 스위칭 후 20 밀 리초 (ms )에 액정의 배열상태를 편광현미경으로 관찰한 사진이다.  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, and 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.
도 7a는 시험예 9의 실시번호 2에서 제조한 액정표시장치에 대해 전기 장 인가 전 액정층내 액정의 배열상태를 편광현미경으로 관찰한 사진이고ᅳ 도 7b는 전기장 인가 직후 액정의 배열상태를 편광현미경으로 관찰한 사 진이며 , 도 7c는 전기장 인가 이후 30초 ( sec )에 액정의 배열상태를 편광 현미경으로 관찰한 사진이다.  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.
도 8a는 시험예 9의 실시번호 2에서 제조된 액정표시장치에 대해 전기 장 인가 후 액정 배열상태의 안정화를 확인하고， 광조사를 실시하고， 다 시 전기장 인가에 의한 스위칭 전 액정의 배열상태를 편광현미경으로 관 찰한 사진이고， 도 8b는 전기장 인가에 의한 스위칭 직후 액정의 배열상 태를 편광현미경으로 관찰한 사진이며， 도 8c는 전기장 인가에 의한 스위 칭 후 약 20밀리초 ( ms )에 액정의 배열상태를 편광현미경으로 관찰한 사진 이다.  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.
발명의 실시를 위한 최선의 형태 Best Mode for Carrying Out the Invention
이하 본발명의 구현예를 상세히 설명하기로 한다. 다만， 이는 예시로서 제시되는 것으로， 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다.  Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 명세서에서 특별한 언급이 없는 한 모든 화합물 또는 치환기는 치환되거나 비치환된 것일 수 있다. 여기서， '치환된'이란 분자내 1 이상의 수소가 할로겐 원자， 하이드록시기， 카르복시기， 시아노기， 니트로기， 아미노기， 티오기， 메틸티오기， 알콕시기， 알데하이드기， 에폭시기， 에테르기， 에스테르기， 카르보닐기， 아세탈기， 케톤기 알킬기， 퍼플루오로알킬기， 시클로알킬기， 헤테로시클로알킬기， 알릴기， 벤질기， 아릴기 , 헤테로아릴기， 이들의 유도체 및 이들의 조합으로 이루어진 군에서 선택되는 어느 하나로 대체된 것을 의미한다.  Unless stated otherwise in the specification, all compounds or substituents may be substituted or unsubstituted. Herein, '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.
본 명세서에서 '이들의 조합'이란 특별한 언급이 없는 한， 둘 이상의 작용기가 단일결합， 이중결합， 삼중결합， 탄소수 1 내지 20의 알킬렌기 (예를 들면， 메틸렌 ( _CH2- ) , 에틸렌 ( _CH2CH2- ) , 등)， 탄소수 1 내지 20의 불화알킬렌기 (예를들면, 불화 메틸렌 ( _CF2— )， 불화에틸렌 ( - CF2CF2-) 등)， , 0， P, S, 또는 Si와 같은 헤테로 원자 또는 이를 포함하는 작용기 (구체적으로는， 분자내 카르보닐기 (-C( ))-), 에테르 (ether, -0— )， 에스테르 (ester, -C00-) , -S―， 아민기 (― NH-) 또는 - N=N- 등을 포함하는 헤테로알킬렌기)와 같은 연결기에 의해 결합되어 있거나， 또는 둘 이상의 작용기가 축합， 연결되어 있는 것을 의미한다. 또한, 본 명세서에서 층， 막， 영역， 기판 등의 부분이 다른 부분 '위에 ' 있다고 할 때， 이는 다른 부분 '바로 위에 ' 있는 경우뿐 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 한편, 어떤 부분이 다른 부분 '바로 위에 ' 있다고 할 때에는 중간에 다른 부분이 없는 것을 뜻한다. 반대로 충, 막， 영역 , 기판 등의 부분이 다른 부분 '아래에 ' 있다고 할 때 , 이는 다른 부분 '바로 아래에 ' 있는 경우뿐 아니라 그 증간에 또 다른 부분이 있는 경우도 포함한다. 한편， 어떤 부분이 다른 부분 '바로 아래에 ' 있다고 할 때에는 중간에 다른 부분이 없는 것을 뜻한다. In the present specification, 'combination thereof', unless otherwise specified, 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.),, a hetero atom such as 0, P, S, or Si or a functional group containing the same (specifically, an intramolecular carbonyl group (-C ())-), ether (ether, -0 —), Bound by a linking group such as ester (ester, -C00-), -S-, amine group (-NH-) or -N = N-, etc.) or two or more functional groups Is condensed and connected. In addition, in the present specification, when a part such as a layer, a film, an area, or a substrate is 'above' another part, this includes not only the case where the other part is 'just above' but also another part in the middle thereof. On the other hand, when one part is "just above" another part, there is no other part in the middle. On the contrary, when parts such as filling, film, region, and substrate are 'underneath' another part, this includes not only the case where the other part is 'underneath', but also when there is another part between the parts. On the other hand, when one part is just below another part, it means that there is no other part in the middle.
본 발명은 액정표시장치에서의 액정층 형성시 , 액정호스트내에서 분산성이 우수한 에멀견을 형성할 수 있는 액정 수직배향 유도제를 사용함으로써， 배향막 형성 공정없이 그리고 액정 배향유도용 첨가제의 불균일한 분산 또는 뭉침에 의한 배향 불량 발생의 우려 없이， 액정의 수직배향을 유도하는 것을 일 특징으로 하며， 또한 추가로 상기 액정의 수직배향 유도제에 광반웅성기를 도입함으로써 액정물질의 수직배향 유도 후 광중합 반응을 통해 액정의 수직배향 유도와 더불어 선경사각을 안정화시키는 것을 또 다른 일 특징으로 한다.  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. In addition, 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. In addition to the vertical alignment of the liquid crystal to stabilize the pretilt angle is another feature.
즉， 본 발명의 일 구현예에 따른 액정 수직배향 유도제는， 분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합물과， 단분자의 친수성 액체를 포함한다.  That is, 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.
액정은 일반적으로 소수성 물질로 분류되기 때문에 물， 글리세를 등과 같은 친수성 물질과 흔합되지 않고 상분리된다. 그러나， 양친매성 화합물을 첨가하게 되면 거시적으로 상분리 되지 않고 친수성 물질 또는 소수성의 액정이 과량의 연속 액체상에서 미세한 구의 형태로 균일하게 분산될 수 있다. 즉， 액정 또한 양친매성 화합물의 존재하에서 극성이 큰 친수성의 액체상과 콜로이드계를 형성할 수 있다. 이때 , 과량의 액정상이 연속상이고 소량의 친수성 물질상이 분산상을 이를 때를 W/LC(water-in- LC) 에멀견이라 하고， 과량의 친수성 액체상이 연속상을 형성하고 소수성의 액정이 분산상을 이를 때를 LC/W(LOin-water) 에멀견이라고 한다. 분산상의 크기 및 분산 안정도는 흔합시 두 액체상의 흔합비 , 양친매성 화합물의 종류와 함량， 온도 등에 따라 다양하게 변화할 수 있다. 이하 본 명세서에서는 이와 같이 양친매성 화합물에 의해 안정화된 구형의 분산상 (sphere 또는 drop)을 양친매성 화합물 분자의 자기조립에 의해 생성된 '미세 조립체 ' 또는 '미세 집합체 '라고 한다 . Since liquid crystals are generally classified as hydrophobic substances, they are phase separated without being mixed with hydrophilic substances such as water and glycerol. However, when the amphiphilic compound is added, 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. At this time, when 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, and the excess hydrophilic liquid phase forms a continuous phase and the hydrophobic liquid crystal is a dispersion phase. When it is called LC / W (LOin-water) emulsion dog do. 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. Hereinafter, in the present specification, 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.
본 발명에 따른 액정 수직배향 유도제는 액정호스트 내에서 에멀견화된 미세조립체를 형성함으로써 액정층 형성시 선처리된 배향층 없이도 액정물질의 수직배향을 유도할 수 있다 . 상기 액정 수직배향 유도제는 액정 호스트에 비해 친수성이 높아 독립적으로는 액정에 용해되거나 분산되지 않고 상분리되는 단분자 (monomolecular) 화합물의 친수성 액체와, 액정 호스트와 상기 친수성 액체의 경계면을 안정화시킬 수 있는 양친매성 화합물을 포함하는 흔합물로 이루어진다. 이때 단분자란 단일 분자로서 고분자를 배제한 의미이다.  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. In this case, a single molecule means a single molecule excluding a polymer.
도 2a는 본 발명의 일 구현예에 따른 액정층 형성용 조성물을 도식화하여 나타낸 모식도이고， 도 2b는 상기 액정층 형성용 조성물내에 분산되어 존재하는 미세조립체를 도식화하여 나타낸 것이고, 도 2c는 상기 액정층 형성용 조성물의 제조시 사용되는 양친매성 화합물의 구조를 도식화하여 나타낸 것이다. 도 2a 내지 2c는 본 발명을 설명하기 위한 일 례일 뿐 본 발명이 이에 한정되는 것은 아니다.  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.
도 2a 내지 2c를 참조하여 설명하면， 과량의 액정 호스트 (C)에 소량의 친수성 액체， 예를 들어 물을 흔합하면 서로 상이한 극성으로 인하여 흔합되지 못하고 서로 다른 상으로 분리된다. 그러나， 여기에 1분자 내에 친수성기 (bll)와 소수성기 (bl2)를 포함하는 양친매성 화합물 (bl)을 첨가하게 되면， 소량의 친수성 액체인 물 (b2)은 연속상인 액정 호스트 (C) 중에 균일하게 분산된 분상상을 형성한 콜로이드계가 된다. 이때 , 첨가한 양친매성 화합물의 분자는 연속상인 액정상 (C)과 분산상인 친수성 액체상 (b2)의 경계면에 자발적으로 정렬된 자기조립 (self-assembly) 상태의 미세조립체 (B)를 형성하고 계면에너지 (interfacial energy/tension)를 낮춤으로써 안정적인 W/LC 에멀젼계 (A)를 형성한다 . 분산된 미세조립체의 직경은 양친매성 화합물과 친수성 액체의 흔합비 및 양친매성 화합물의 종류에 따라 조절될 수 있으며 , 형성된 에멀견의 안정도는 사용된 양친매성 화합물의 종류 및 특성， 그리고 친수성 및 소수성 액체의 종류에 따라 크게 달라진다. 과량의 액정이 소수성의 연속상을 이루고 소량의 친수성 액체가 양친매성 화합물의 안정화 효과에 의하여 분산상을 이루는 W/LC 에멀젼이 에멀젼상과 상이한 상과 만나 경계면을 형성하게 되면， 분산상을 이루는 친수성 액체와 이를 감싸고 있는 양친매성 화합물， 즉 양친매성 화합물 분자의 자기조립에 의해 생성된 미세조립체가 새로이 형성된 경계면에 흡착되게 된다. 이 결과 액정상에 존재하는 액정분자는 경계면에 흡착된 친수성 액체와 이를 감싸고 있는 양친매성 화합물의 표면에서 이 표면에 수직인 방향으로 배열하게 된다 . Referring to FIGS. 2A to 2C, when a small amount of 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. However, when 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. At this time, 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. When 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. As a result, 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.
이러한 미세 조립체의 표면흡착에 의한 액정의 수직배향 유도는 고체표면을 이루는 화합물의 종류에 제한없이 가능하다. 예를 들어， 다양한 무기산화물 및 질화물뿐만 아니라 폴리이미드， 폴리스틸렌， 폴리아크릴레이트， 폴리비닐알코올 등 다양한 유기고분자 화합물의 표면에서도 수직배향의 유도가 가능하다. 단지， 액정과 이루는 경계면에서의 계면장력의 크기에 따라 특성의 변화가 나타날 수 있다. 이와 같이 양친매성 화합물 분자의 자기조립에 의해 생성된 미세 조립체를 이용하여 액정의 수직배향을 제어하고자 할 경우ᅳ 양친매성 화합물로는 소수성 액정상 및 친수성 분산상의 특성을 고려하여 안정적인 미세조립체를 형성할 수 있으며， 최종 액정표시장치의 안정성， 신뢰성， 및 소자의 특성에 나쁜 영향을 미치지 않는 화합물을 선택하는 것이 바람직하다 .  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. For example, 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. However, 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. As described above, in order to control the vertical alignment of the liquid crystal using the microassembly generated by the self-assembly of the amphiphilic compound molecule, 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.
도 2c는 본 발명에서 사용 가능한 양친매성 화합물 ( b l )의 구조를 도식적으로 나타낸 것이다. 도 2c에 나타난 바와 같이 상기 양친매성 화합물 ( b l )은 분자내에 극성이 큰 친수성기 ( b l l )와 극성이 작은 소수성기 ( bl2)를 포함한다 . 또한， 상기 친수성기와 소수성기는 공유결합으로 결합될 수 있다. 도 2c에서는 각각 하나의 친수성기 ( b l l ) 및 소수성기 ( bl2 )를 포함하는 것으로 제시되어 있으나， 분자내에 1개 이상의 친수성기 또는 소수성기를 포함할 수 있으며， 바람직하게는 분자 내에 1 내지 3개의 소수성기를 포함할 수 있다.  Figure 2c schematically shows the structure of the amphipathic compound (b l) usable in the present invention. As shown in FIG. 2C, 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. In addition, the hydrophilic group and hydrophobic group may be bonded covalently. In FIG. 2C, it is shown that 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.
상기 양친매성 화합물에 포함될 수 있는 소수성기는 탄소수 8 내지 30의 조건을 충족하는 소수성의 기라면 특별한 제한없이 사용가능하다. 구체적으로 상기 소수성기는 선형， 분지형 또는 고리형의 치환 또는 비치환된 탄소수 8 내지 30의 탄화수소기이거나， 분자내 분자내에 N , 0， P , S 및 Si로 이루어진 군에서 선택되는 1 이상의 헤테로 원자를 포함하는 치환 또는 비치환된 탄소수 8 내지 30의 헤테로알킬기 , 헤테로사이클기 또는 헤테로아로마틱기일 수 있으며， 또는 상기 탄화수소기와 헤테로원자 함유기들의 조합으로 이루어진 탄소수 8 내지 30의 조합기일 수 있다.  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. Specifically, 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.
상기 탄화수소기의 구체적인 예로는 치환된거나 비치환된 탄소수 8 내지 30의 알킬기， 알케닐알킬기 , 알키닐알킬기， 사이클로알킬기 또는 아릴기를 들 수 있으며， 상기 탄화수소기가 치환될 경우 할로겐원자， 바람직하게는 불소원자로 치환될 수 있다. 또한 상기 헤테로 원자를 포함하는 치환 또는 비치환된 헤테로알킬기， 헤테로사이클기 또는 헤테로아로마틱기의 구체적인 예로는， 분자내 카르보닐기 (-c(=o)-)， 에스테르기 (-C(=0)0-), 에테르기 (-0-)， 에틸렌옥사이드기 (_CH2CH20-) 및 아조기 (-N=N-)로 이루어진 군에서 선택되는 헤테로원자 함유 작용기를 포함하는 탄소수 8 내지 30의 헤테로알킬기 , 헤테로사이클로알킬기 또는 해테로아릴기를 들 수 있다. Specific examples of the hydrocarbon group 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. In addition, the hetero atom Specific examples of the substituted or unsubstituted heteroalkyl group, heterocycle group or heteroaromatic group containing include, an intramolecular carbonyl group (-c (= o)-), ester group (-C (= 0) 0-), ether group Heteroalkyl group having 8 to 30 carbon atoms, heterocycloalkyl group including a hetero atom-containing functional group selected from the group consisting of (-0-), ethylene oxide group (_CH 2 CH 2 0-) and azo group (-N = N-) Or a heteroaryl group.
상기 소수성기는 액정호스트와의 친화성을 높이기 위하여 액정호스트를 구성하는 화합물의 구조와 유사한， 즉 리지드ᅳ코어 (rigid-core) 그룹과 유연성 사슬 (flexible chain) 그룹으로 이루어진 구조를 가질 수도 있다. 한편， 극성이 큰 친수성기 (bu)로는 액정층 형성용 조성물의 에멀견화를 통한 수직배향 유도를 위해 이온성 및 비이온성 친수성기가 모두 사용될 수 있다. 그러나， 이온성 헤드그룹이 포함된 친수성기를 갖는 양친매성 화합물을 액정호스트에 첨가할 경우， 액정의 비저항이 현저히 저하하고 그 결과로 전압유지율 (voltage holding ratio, VHR)이 낮아질 우려가 있다. 따라서， 액정표시장치의 구동시 요구되는 특성， 즉 전압유지율 (Voltage Holding Ratio, VHR)에 따라 높은 비저항을 유지할 필요가 있는 경우에는 비이온성 헤드 그룹을 갖는 친수성기가 보다 바람직하고， 높은 전압유지율이 요구되지 않거나 전기장에 의한 스위칭이 요구되지 않는 소자 또는 소재에서는 이온성 헤드 그룹을 포함하는 친수성기가 보다 바람직할 수도 있다.  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. On the other hand, as 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. However, when an amphiphilic compound having a hydrophilic group containing an ionic head group is added to the liquid crystal host, the specific resistance of the liquid crystal is significantly lowered, and as a result, there is a concern that the voltage holding ratio (VHR) is lowered. Therefore, when it is necessary to maintain a high specific resistance according to characteristics required for driving the liquid crystal display, that is, voltage holding ratio (VHR), a hydrophilic group having a nonionic head group is more preferable, and a high voltage holding ratio is required. 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.
비이온성 헤드 그룹을 갖는 친수성기의 구체적인 예로는 하기의 화합물로부터 유도된 작용기들을 들 수 있으나， 이에 한정되는 것은 아니다:  Specific examples of the hydrophilic group having a nonionic head group include, but are not limited to, functional groups derived from the following compounds:
알코올 (alcohol): 히드록시기를 1 내지 8개 포함하는 탄소수 1 내지 20의 알코올 또는 다가알코올로부터 유도되는 작용기로서 , 구체적인 예로는 1-을 (1-01)， 1,2-디을(1，2- 01)， 글리세롤 (glycerol), 글루코오스 (glucose)， 덱스트로스 (dextrose), 소르비를 (sorbi tol ) , 펜타에리스리톨( )6 3^71;11^1:01)， 디펜타에리스리를((^ 6 3^ 1±1"^01) , 트리펜타에리스리를 (tripentaerythr itol) , 소르비탄 (sorbi tan)， 플룩토스 (fluctose)， 수크로스 (sucrose)， 갤릭산 (gallic acid) , 갈레이트 (gal late)， 글루코피라노사이드 (glucopyranoside)， 아스코르빅산 (ascorbic acid) , 매나이드 (mannide) 또는 말토사이드 (maltoside)로부터 유도된 작용기 ;  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;
아민 (amine): 아민기를 1 내지 6개 포함하는 탄소수 1 내지 20의 아민 또는 다가아민으로부터 유도되는 작용기로서， 보다 구체적인 예로는 1- 아민 (1-amine)， 1,2-디아민 (1,2-diamine)， 1，3-디아민 (1,3-diamine) , 에틸렌 디아민 (ethylene diamine) , 디에틸렌 디아민 (diethylene diamine) , 트리스 (2-아미노에틸 )아민 (tr is(2— aminoethyl)amine)， 시클로핵산 디아민 (cyclohexane diamine) , 디에틸렌 트리아민 (di ethyl ene tr iamine) , 페닐디아민 (phenyldiamine)， 페닐트리아민 (phenyltr iamine) , 1,3,5- 트리아진 4，6- 아민(1，3,5- 32^6 4,6-diamine) , 1,3，5_트리아진 2，4，6-트리아민 (1,3,5-tr iazine 2,4,6-tr iamine) 또는 고리형 에틸렌 아민 (cyclen; (CH2CH2NH)n; n=2 내지 6의 정수)으로부터 유도된 작용기 ; 폴리옥시에틸렌: 에틸렌옥사이드 (ethyleneoxide)기를 2 내지 20개 포함하는 하기 화학식 1의 탄소수 4 내지 40의 선 ^ 폴리옥시에틸렌 또는 하기 화학식 2의 탄소수 4 내지 10의 고리형 풀리에틸렌글리콜 (crown ether)로부터 유도되는 작용기 ; Amine: A functional group derived from an amine or a polyvalent amine having 1 to 20 carbon atoms containing 1 to 6 amine groups, and more specifically, 1-amine (1-amine), 1,2-diamine (1,2) -diamine), 1,3-diamine, 1,3-diamine, ethylene diamine, diethylene diamine, tris (2-aminoethyl) amine ， Cyclohexane diamine, diethyl ene tr iamine, phenyldiamine, phenyltriamine, 1,3,5-triazine 4，6-amine (1 ， 3,5- 32 ^ 6 4,6-diamine), 1,3,5_triazine 2,4,6-triamine (1,3,5-tr iazine 2,4,6-tr iamine) or Functional groups derived from cyclic ethylene amines (cyclen; (CH 2 CH 2 NH) n ; integers of n = 2 to 6); Polyoxyethylene: from 4 to 40 carbon atoms of formula (1) containing 2 to 20 ethylene oxide groups from polyoxyethylene or cyclic pulley ethylene glycol (crown ether) having 4 to 10 carbon atoms of formula (2) Induced functional group;
Figure imgf000014_0001
Figure imgf000014_0001
(상기 화학식 1 및 2에서 , m은 2 내지 20의 정수이고， n은 2 내지 5의 정수이다)  (In Formulas 1 and 2, m is an integer of 2 to 20, n is an integer of 2 to 5)
티올 (thiol): 티올기 (-SH)를 1 내지 8개 포함하는 탄소수 1 내지 20의 티올 또는 다가티올로부터 유도되는 작용기로서 , 구체적인 예로는 1- 티을 (1-thiol), 1,2-디티을 (l,2-dithiol), 티오글리세롤 ( thiogl ycerol ) , 티오펜타에리쓰리를 (thiopentathiopentaerythr itol ) 또는 디티오트레이를 (dithiothreitol)로부터 유도된 작용기 ;  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;
카르복실산 (carboxylic acid)： 카르복실산기 (-C00H)를 1 내지 4개 포함하는 탄소수 1 내지 10의 카르복실산 또는 다가 카르복실산으로부터 유도되는 작용기로서， 보다 구체적인 예로는 1-카르복실산 (1-carboxylic acid) , 1,2-디카르복실산 (1,2-dicarboxylyc acid) , 1,3- 디카르복실산 (1,3-dicarboxylyc acid) , 벤젠카르복실산 (benzenecarboxylic acid), 벤젠디카르복실산 Carboxylic acid (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-트리카르복실산 (1，2，3- tr icarboxyl ic acid), 벤젠트리카르복실산 (benzenetr i carboxyli c acid) 말릭산 (malic acid) , 말레익산 (maleic acid), 타르타르산 (tartar acid) 시트릭산 ( c i t r i c acid) , 말레아믹산 (maleamic acid) 그루타믹산 (glutamic acid), 아가릭산 (agaric acid) 아코니틱산 (aconitic acid), 트라이카르발릴릭산 (tricarballylic acid) 또는 아미노산 (amino acid)으로부터 유도된 작용기 ; (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;
설포닉산 (sul fonic acid): 설포닉산이기 [_S(=0)20H] 를 1 내지 3개 포함하는 탄소수 1 내지 10의 설포닉산 또는 다가설포닉산으로부터 유도되는 작용기； Sulfonic acid: a functional group derived from a sulfonic acid or a polysulfonic acid having 1 to 10 carbon atoms containing 1 to 3 sulfonic acid groups [_S (= 0) 2 0H];
설퍼릭산 (sul fur i c acid): 설퍼릭산기 [-0-S( =0)20H] 를 1 내지 3개 포함하는 탄소수 1 내지 10의 설퍼릭산 또는 다가 설퍼릭산으로부터 유^되 작용기； Sulfuric acid: A functional group derived from a sulfuric acid having 1 to 3 carbon atoms or a polyhydric sulfuric acid containing 1 to 3 sulfuric acid groups [-0-S (= 0) 2 0H];
포스포닉산 (phosphonic acid): 포스포닉산기 (-P =0)(0H)2. 내지 3개 포함하는 탄소수 1 내지 10의 포스포닉산 또는 다가포스포닉산으로부터 유도되는 작용기； 그리고 Phosphonic acid: phosphonic acid group (-P = 0) (0H) 2 . Functional groups derived from phosphonic acids or polyvalent phosphonic acids having from 1 to 3 carbon atoms; and
포스퍼릭산 (phosphoric acid): 포스퍼릭산기 (-0-P(=0)(0H)2)를 내지 3개 포함하는 탄소수 1 내지 10의 포스퍼릭산 또는 다가포스퍼릭산으로부터 유도되는 작용기 . Phosphoric acid: a phosphoric acid having 1 to 10 carbon atoms containing 3 to 3 phosphoric acid groups (-0-P (= 0) (0H) 2 ) or Functional groups derived from polyphosphoric acid.
본 발명에서 사용가능한 양친매성 화합물은 상기한 비이온성 헤드그룹을 가지거나, 이들로부터 유도된 비이온성 헤드그룹을 가지거나， 또는 이들의 조합으로 이루어진 비이온성 헤드그룹을 포함하는 친수성기를 포함할 수 있다.  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. .
상기 양친매성 화합물의 구체적인 예로는 하기의 화합물들을 들 수 있으나， 이들에 한정되는 것은 아니다:  Specific examples of the amphiphilic compound include, but are not limited to the following compounds:
(극성 헤드기에 따른 분류)  (Classification according to polar head group)
고리형 다가알코올인 소르비탄 헤드그룹을 가진 화합물;  Compounds having a sorbitan headgroup which is a cyclic polyhydric alcohol;
소르비탄 모노라우레이트 (Sorbitan monolaurate, Span™ 20) (Al) 소르비탄 모노팔미테이트 (Sorbitan monopalmi t at e , Span™ 40) (A2) 소르비탄 모노스테아레이트 (Sorbitan monost earate , Span™ 60) (A3) 소르비탄 트리스테아레이트 (Sorbitan tristearate, Span™ 65) (A4) 소르비탄 모노올레이트 (Sorbitan monooleate, Span™ 80) (A5) 소르비탄 세스퀴을레이트 (Sorbitan sesqui ol eate , Span™ 83) (A6) 소르비탄 트리올레이트 (Sorbitan trioleate, Span™ 85) (A7)  Sorbitan monolaurate (Span ™ 20) (Al) Sorbitan monopalmitate (Span ™ 40) (A2) Sorbitan monost earate (Span ™ 60) ( A3) Sorbitan tristearate (Span ™ 65) (A4) Sorbitan monooleate (Span ™ 80) (A5) Sorbitan sesqui olate (Span ™ 83) ( A6) Sorbitan trioleate (Span ™ 85) (A7)
고리형 다가알코올인 소르비탄 헤드 그룹 및 폴리옥시에틸렌 (polyoxyethylene)기를 극성 헤드 그룹으로 갖는 화합물;  A compound having a sorbitan head group and a polyoxyethylene group as a cyclic polyhydric alcohol as a polar head group;
폴리에틸렌글리콜 소르비탄 모노라우레이트 (Polyethyleneglycol sorbitan monolaurate , Tween™ 20) (Α8)  Polyethyleneglycol sorbitan monolaurate (Tween ™ 20) (Α8)
폴리에틸렌소르비탄 모노라우레이트 (Polyoxyethylenesorbitan monolaurate, Tween™ 21) (A9)  Polyoxyethylenesorbitan monolaurate, Tween ™ 21 (A9)
폴리에틸렌소르비탄 모노팔미테이트 (Polyoxyethylenesorbitan monopa Imitate, Tween™ 40) (A10)  Polyoxyethylenesorbitan monopa Imitate, Tween ™ 40 (A10)
폴리옥시에틸렌소르비탄 모노스테아레이트 (Polyoxyethylenesorbitan monostearate , Tween™ 60) (All)  Polyoxyethylenesorbitan monostearate, Tween ™ 60 (All)
폴리옥시에틸렌소르비탄 트리스테아레이트 (Polyoxyethylenesorbitan tristearate, Tween™ 65) (A12)  Polyoxyethylenesorbitan tristearate, Tween ™ 65 (A12)
폴리옥시에틸렌소르비탄 모노올레이트 (Polyoxyethylenesorbitan monooleate, Tween™ 80) (A13)  Polyoxyethylenesorbitan monooleate, Tween ™ 80 (A13)
폴리옥시에틸렌소르비탄 트리올레이트 (Polyoxyethylenesorbitan trioleate, Tween™ 85) (A14)  Polyoxyethylenesorbitan trioleate, Tween ™ 85 (A14)
폴리옥시에틸렌소르비탄 스테아레이트 (Polyoxyethylenesorbitan stearate, Tween™ 61) (A15)  Polyoxyethylenesorbitan stearate, Tween ™ 61 (A15)
폴리옥시에틸렌소르비탄 을레이트 (Polyoxyethylenesorbitan oleate, Tween™ 81) (A16)  Polyoxyethylenesorbitan oleate, Tween ™ 81 (A16)
다가알코올인 펜타에리쓰리를 헤드 그룹을 가진 화합물;  Pentaerythritol, a polyhydric alcohol, having a head group;
펜타에리쓰리를 모노스테아레이트 (Pentaerythr itol monostearate) (A17)  Pentaerythr itol monostearate (A17)
펜타에리쓰리를 디아크릴레이트 모노스테아레이트 (Pentaerythritol diacrylate monostearate ) (A18)  Pentaerythritol diacrylate monostearate (A18)
펜 에리쓰리를 모노아크릴레이트 모노스테아레이트 (Pentaerythritol monoacryl ate monostearate) (A19) 옥사친데Penerythritol monoacrylate monostearate (A19) Oxachinde
실수틸이  Real number
방향족 다가알코올인 갈릭산 (gallic acid) 헤드 그룹을 가진 화합물; 옥틸 갈레이트 (Octyl gallate) (A21)  Compounds having a gallic acid head group which is an aromatic polyhydric alcohol; Octyl gallate (A21)
라우릴 갈레이트 (Lauryl gallate) (A22)  Lauryl gallate (A22)
하기 화학식 3의 갈레이트 유도체 (Gal late derivative) (A23)  Gal late derivative (A23)
Figure imgf000016_0001
Figure imgf000016_0001
친수성 글리세롤 헤드 그룹을 가진 화합물;  Compounds having a hydrophilic glycerol head group;
스테아로일 글리세롤 (Stearoyl glycerol) (A24)  Stearoyl glycerol (A24)
디팔미토일 글리세롤 (Dipalmitoyl glycerol) (A25)  Dipalmitoyl glycerol (A25)
디옥타데카노일 글리세룰 (Dioctadecanoyl glycerol ) (A26)  Dioctadecanoyl glycerol (A26)
팔미토일 글리세를 (Palmitoyl glycerol) (A27)  Palmitoyl glycerol (A27)
모노핵사데카노일 글리세롤 (Monohexadecanoyl glycerol , palmit in) (A28)  Monohexadecanoyl glycerol, palmit in (A28)
디핵入 ]·데^ "노일 글리서 1를 (Dihexadecanoyl glycerol , dipalmit in) (A29) 옥타데실 글리세를 (Octadecyl glycerol , batyl alcohol ) (A30) 올레오일 글리세를 (Oleoyl glycerol) (A31)  Dihexadecanoyl glycerol, dipalmit in (A29) Octadecyl glycerol, batyl alcohol (A30) Oleoyl glycerol (A31)
트리글리세를 모노스테아레이트 (Triglycerol monostearate) (A32) 친수성 아스코르빅산， 매나이드, 또는 글루코실 헤드그룹을 가진 화합물;  Triglycerol monostearate (A32) compounds with hydrophilic ascorbic acid, mannide, or glucosyl headgroup;
아스코르빅산 6—팔미테이트 (Ascorbic acid 6-palmi tate) (A33) 매나이드 모노올레이트 (M謹 ide monooleate) (A34)  Ascorbic acid 6-palmitate (A33) M 謹 ide monooleate (A34)
옥틸 글루코피라노사이드 (Octyl glucopyranoside) (A35)  Octyl glucopyranoside (A35)
도데실글루코피라노사이드 (Dodecyl glucopyranoside) (A36)  Dodecyl glucopyranoside (A36)
메틸글루코사이드 세스퀴스테아레이트 (Methyl glucoside sesqui stearate) (A37)  Methyl glucoside sesqui stearate (A37)
메틸글루코사이드 디을레이트 (Methyl glucoside dioleate) (A38) 글리코실옥시에틸 메타크릴레이트 (Glycosyloxyethyl methacrylate) (A39)  Methyl glucoside dioleate (A38) Glycosyloxyethyl methacrylate (A39)
하기 화학식 4의 글루코피라노사이드 유도체 (Glucopyranoside derivative) (A40)  Glucopyranoside derivative of Formula 4 (A40)
CH2 CH 2
Figure imgf000016_0002
Figure imgf000016_0002
성 말토사이드 헤드그룹을 가진 화합물;  Compounds with a sex maltoside headgroup;
말토사이드 (Octyl matoside) (A41)  Octal matoside (A41)
클로핵실핵실 말토사이드 (Cyclohexylhexyl maltoside) (A42) 말토사이드 (Decyl maltoside) (A43) 운데실 말토사이드 (Undecyl maltoside) (A44) Cyclohexylhexyl maltoside (A42) Decyl maltoside (A43) Undecyl maltoside (A44)
도데실 말토사이드 (Dodecyl maltoside) (A45)  Dodecyl maltoside (A45)
트리데실 말토사이드 (Tr idecyl maltoside) (A46)  Tridecyl maltoside (A46)
테트라데실 말토사이드 (Tetradecyl maltoside) (A47)  Tetradecyl maltoside (A47)
핵사데실 말토사이드 (Hexadecyl maltoside) (A48)  Hexadecyl maltoside (A48)
친수성 1가 알코올 헤드 그룹을 가진 화합물;  Compounds having a hydrophilic monohydric alcohol head group;
1-도데칸을 (1-Dodecanol) (A51)  1-dodecane (1-Dodecanol) (A51)
1-핵사데칸올 (1-Hexadecanol) (A52)  1-Hexadecanol (A52)
1-옥타데칸올 (1-Octadecanol) (A53)  1-octadecanol (A53)
친수성 1，2-디올 헤드 그룹을 가진 화합물;  Compounds having a hydrophilic 1,2-diol head group;
1,2-도데칸디을 (1,2-Dodecanediol) (A55)  1,2-dodecanediol (A55)
1， 2-핵사데칸디올 ( 1， 2-Hexadecanediol ) (A56)  1,2-nuxadecanediol (1,2-Hexadecanediol) (A56)
친수성 카르복실산 헤드 그룹을 가진 화합물;  Compounds having a hydrophilic carboxylic acid head group;
옥탄산 (Octanoic acid) (A57)  Octanoic acid (A57)
데칸산 (Decanoic acid) (A58)  Decanoic acid (A58)
도데칸산 (Dodecanoic acid) (A59)  Dodecanoic acid (A59)
핵사데칸산 (Hexadecanoic acid, Palmitic acid) (A60)  Hexadecanoic acid (palmitic acid) (A60)
옥타데칸산 (Octadecanoic acid, Stearic acid) (A61)  Octadecanoic acid (Stearic acid) (A61)
친수성 1가 또는 2가 아민 해드 그룹을 가진 화합물;  Compounds having a hydrophilic monovalent or divalent amine head group;
옥틸아민 (Octylamine) (A62)  Octylamine (A62)
데실아민 (Decylamine) (A63)  Decylamine (A63)
도데실아민 (Dodecylamine) (A64)  Dodecylamine (A64)
핵사데칸 1,2-디아민 (Hexadecane 1,2-diamine) (A65)  Hexadecane 1,2-diamine (A65)
친수성 포스폰산 또는 티을 헤드 그룹을 가진 화합물;  Compounds having a hydrophilic phosphonic acid or a thir head group;
디핵사데실 포스페이트 (Dihexadecyl phosphate) (A66)  Dihexadecyl phosphate (A66)
데실포스폰산 (Decylphosphonic acid) (A67)  Decylphosphonic acid (A67)
1-도데칸티올 (l-Dodecanethiol) (A68)  L-Dodecanethiol (A68)
1-핵사데칸티올 (1-Hexadecanethiol ) (A69)  1-Hexadecanethiol (A69)
친수성 에틸렌글리콜 또는 폴리옥시에틸렌 헤 --- 그룹을 가진 화합물; 에틸렌 글리콜 스테아레이트 (Ethylene glycol stearate) (A70) 폴리옥시에틸렌산 (Polyoxyethylene acid: Polyoxyethylene (8) stearate (Myrj™ 45)) (A71)  Compounds having a hydrophilic ethylene glycol or polyoxyethylene he --- group; Ethylene glycol stearate (A70) Polyoxyethylene acid: Polyoxyethylene (8) stearate (Myrj ™ 45)) (A71)
폴리옥시에틸렌 (2) 스테아릴 에테르 (Poly, Lene (2) stearyl ether (Brij™ S2)) (A72)  Poly, Lene (2) stearyl ether (Brij ™ S2) (A72)
풀리옥시에틸렌 (4) 라우릴 어 1테르 (Polyoxyethylene (4) lauryl ether Polyoxyethylene (4) lauryl ether
(Brij™ L4)) (A73) (Brij ™ L4)) (A73)
플리옥시에틸렌 (2) 세틸 에테르 (Polyoxyethylene (2) cetyl ether (Brij™ 52)) (A74)  Polyoxyethylene (2) cetyl ether (Brij ™ 52) (A74)
폴리옥시에틸렌 (20) 세틸 에테르0)01 0 ^ 171^6 (20) cety 1 ether (Brij™ 58)) (A75) Polyoxyethylene (20) Cetyl Ether0 ) 01 0 ^ 171 ^ 6 (20) cety 1 ether (Brij ™ 58)) (A75)
폴리옥시에틸렌 (2) 을레일 에테르(150^^" €1；11 1^6 (2) oleyl ether (Brij™ 93)) (A76) Polyoxyethylene (2) oleyl ether (1 5 0 ^^ "€ 1; 11 1 ^ 6 (2) oleyl ether (Brij ™ 93)) (A76)
폴리옥시에틸렌 (20) 올레일 에테르 (Polyoxyethylene (20) oleyl ether (Brij™ 98)) (A77) Polyoxyethylene (20) oleyl ether (Brij ™ 98)) (A77)
폴리옥시에틸렌 (10) 스테아릴 에테르 (Polyoxyethylene (10) stearyl ether (Brij™ S10)) (A78)  Polyoxyethylene (10) stearyl ether (Brij ™ S10) (A78)
또한， 상기 양친매성 화합물은 에멀견화에 의한 액정의 수직배향 유도 후에 광조사를 이용하여 액정의 선경사각을 안정화시키기 위해， 친수성기 및 소수성기 증 적어오 어느 하나에 아크릴레이트기， 메타크릴레이트기， 신나메이트기， 쿠마린기， 챠콘기， 비닐기， 티올기， 엔기 , 디엔기 , 티올엔기 및 아세틸렌기로 이루어진 군에서 선택되는 적어도 하나의 광반웅성기를 더 포함할 수 있다.  In addition, the 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.
상기한 양친매성 화합물은 1종 단독으로 사용될 수도 있고， 또는 수직배향 유도를 위한 유효농도， 즉 액정호스트에 대한 액정 수직배향 유도제의 흔합비를 조절할 필요가 있을 때, 또는 효과적인 수직배향 유도 및 광안정화를 위한 광중합 밀도를 독립적으로 조절할 필요가 있을 때 상기한 양친매성 화합물중 2종 이상을 적정 비율로 혼합하여 사용할 수도 ΰΐ다  The 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.
본 발명에서 사용가능한 분산상으로서 단분자의 친수성 액체로는, 물， 글리세롤 등과 같이 독립적으로는 액정에 용해되거나 또는 분산되지 않는 즉 액정과 상분리되는 극성이 큰 친수성의 단분자 액체 화합물이라면 모두 사용할 수 있다. 친수성의 고분자 화합물의 경우 액정내에서 균일한 미세조립체를 형성하기 어렵고, 에멀전의 안정성이 낮다.  As the dispersible phase usable in the present invention, 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. . In the case of the hydrophilic polymer compound, it is difficult to form a uniform microassembly in the liquid crystal, and the stability of the emulsion is low.
구체적으로 상기 친수성 액체로는， 히드록시기， 티올기， 아민기， 및 카르복실기로 이루어진 군에서 선택되는 친수성기를 1개 이상， 바람직하게는 1 내지 6개 포함하는 친수성의 단분자 화합물을 사용할 수 있다. 보다 구체적으로는, 물， 알코올， 다가알코올， 티올， 다가티올， 아민， 다가아민, 카르복실산 등을 들 수 있다. 보다 더 구체적인 예로는 하기 화합물들을 수 있으나， 이들에 한정되는 것은 아니다.  Specifically, as the 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 can be used. More specifically, 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.
B1: 물 ( 0)  B1: water (0)
Β2: 글리세롤 (glycerol)  Β2: glycerol
B3: 디글리세를 (diglycerol)  B3: diglycerol
B4: 트리글리세를 (trig  B4: triglycerides
B5: 에틸렌 글리콜 (ethylene glycol)  B5: ethylene glycol
B6: 디에틸렌 글리콜 (diethyleneglycol)  B6: diethyleneglycol
B7: 트리에틸렌 글리콜 (triethylene glycol)  B7: triethylene glycol
B10: 티오글리세를 (thioglycerol)  B10: thioglycerol
B11: 디티오글리세를 (dithioglycerol)  B11: dithioglycerol
B12: 에탄디티올 (ethanedithiol )  B12: ethanedithiol
B13: 에틸렌 디아민 (ethylene diamine)  B13: ethylene diamine
B14： 디아미노프로판 (diaminopropane)  B14 ： diaminopropane
B15: 디에틸렌트리아민 (diethylenetriamine)  B15: diethylenetriamine
B16: 트리에틸렌테트라아민 (triethylenetetramine)  B16: triethylenetetramine
ΒΓ7: 트리스아미노에틸 아민 (tr is(aminoethyl) amine)  ΒΓ7: trisaminoethyl amine (tr is (aminoethyl) amine)
B18: 펜타에리쓰리틀 테트라키스 (3-멀캡토프로피오네이트) B18: pentaerythrite tetrakis (3-mercaptopropionate)
[Pentaerythr itol tetrakis(3-mercaptopropionate) ] . 또한 상기 친수성 액체는 액정표시장치의 제작과정에서 액체상태의 미세조립체를 이용하여 액정의 수직배향을 유도한 후， 광조사 등의 부가적인 처리에 의해 미세조립체를 고체화하고， 액정의 선경사각을 안정화시킬 수 있도록 분자내에 중합가능한 광반웅성기를 적어도 1개 이상 더 포함할 수도 있다. 이때 상기 광반웅성기로는 아크릴레이트기， 메타아크릴레이트기， 신나메이트기， 쿠마린기， 챠콘기， 비닐기 , 티올기 , 엔기， 디엔기， 티올엔기 및 아세틸렌기 등을 들 수 있으나 이에 제한되는 것은 아니다. Pentaerythr itol tetrakis (3-mercaptopropionate). In addition, 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. In this case, 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.
이와 같이 광반웅성기를 포함하는 친수성 액체로는 하기의 화합물들을 들 수 있으나， 이들에 한정되는 것은 아니다:  As such, the hydrophilic liquid including the photobanung group may include, but is not limited to:
C1: 트리글리세롤 모노아크릴레이트 (triglycerol monoacryl ate) C1: triglycerol monoacrylate
C2: 트리글리세롤 모노메타아크릴레이트 (triglycerol monomethacrylate) C2: triglycerol monomethacrylate
C3: 트리글리세를 디아크릴레이트 (triglycerol diacrylate)  C3: triglycerol diacrylate
C4: 트리글리세롤 디메타아크릴레이트 (triglycerol dimethacryl ate) C4: triglycerol dimethacryl ate
C5: 펜타에리쓰리를 모노아크릴레이트 (pentaerytyhr itol monoacryl ate) C5: pentaerythri monoacrylate (pentaerytyhr itol monoacryl ate)
C6: 펜타에리쓰리를 모노메타아크릴레이트 (pentaerytyhritol monomethacrylate)  C6: pentaerythritol monomethacrylate (pentaerytyhritol monomethacrylate)
C7: 펜타에리쓰리롤 디아크릴레이트 (pentaerytyhritol diacrylate) C7: pentaerytyhritol diacrylate
C8: 펜타에리쓰리를 디메타아크 i레이트 (pentaerythr itol dimethacryl ate) C8: pentaerythr itol dimethacryl ate
C9: 아크릴산 (acrylic acid) ■ C9: acrylic acid ■
CIO: 메타크릴산 (methacrylic acid)  CIO: methacrylic acid
Cll: 2-히드록시에틸 아크릴레이트 (2-hydroxyethyl acrylate)  Cll: 2-hydroxyethyl acrylate
C12: 2-히드록시에틸 데타크릴레이트 (2-hydroxyethyl methacryl ate) C13: 글리세롤 모노아크릴레이트 (glycerol monoacryl ate) ,  C12: 2-hydroxyethyl methacrylate C13: glycerol monoacrylate,
C14: 글리세를 모노메타아크릴레이트 (glycerol monomethacrylate) 상기와 같은 친수성 액체를 1종 단독으로 사용될 수도 있고, 2종 이상 흔합하여 사용될 수도 있다.  C14: glycerol monomethacrylate (glycerol monomethacrylate) The above-mentioned hydrophilic liquid may be used alone, or two or more thereof may be used in combination.
상기 액정 수직배향을 유도하는 미세조립체를 구성하는 양친매성 화합물과 친수성 액체는 1:99 내지 99.9:0.1의 중량비로 흔합되는 것이 좋으며， 바람직하게는 30:70 내지 99.9:0.1의 중량비로 흔합될 때 보다 균일하게 흔합되어 효과적으로 미세조립체를 형성할 수 있다.  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.
또한， 양친매성 화합물 또는 친수성 액체로서 광반웅성기를 포함하는 광반응성 화합물을 사용하는 경우， 액정 수직배향 및 광안정화 층이 적절한 표면밀도를 갖도록 광조사에 의해 광증합체를 형성하는 광반응성 화합물의 비율이 액정 수직배향 유도체 총 중량에 대하여 5 내지 100중량 %가 되도록 하는 것이 바람직하다 .  In addition, in the case of using an amphiphilic compound or a photoreactive compound containing a photobanung group as a hydrophilic liquid, 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.
상기와 같은 구성을 갖는 액정 수직배향 유도제는 양친매성 화합물과 친수성 액체를 통상의 방법에 따라 흔합하여 제조될 수 있는데， 이때 효율적인 흔합을 위하여 열을 가하거나 초음파처리를 할 수도 있다.  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.
본 발명의 일 구현예에 따른 액정 수직배향 유도제는 액정호스트와의 흔합시 양친매성 화합물의 자기조립에 의해 형성된 양친매성 화합물과 단분자의 친수성 액체의 미세조립체가 액정호스트 중에 균일하게 분산되어 에멀견을 형성하고 그 결과로 액정의 수직배향을 유도하기 때문에 , 종래 액정 배향 유도제의 낮은 분산성 또는 뭉침에 의한 배향 불량을 현저하게 감소시킬 수 있다. 또한, 형성된 미세조립체는 전극층 위에 절연성의 액정 배향 및 광안정화 층을 형성하고， 이후 광조사에 의한 고체화 과정을 거쳐 안정화됨으로써 신뢰성이 높은 액정소자를 제작할 수 있다. 또한， 상기 미세조립체를 구성하는 양친매성 화합물 및 분상상의 친수성 액체 중 적어도 어느 하나에 광반웅성기를 더욱 포함시키고， 전기장을 인가한 상태에서 광조사를 통해 광중합 과정을 실시함으로써 특정 배열상태의 액정 프리틸트 ( pr et i l t )를 형성하고 안정화할 수 있으며， 그 결과로 액정소자의 성능을 더욱 개선시킬 수 있다. 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. In addition, 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. In addition, 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.
따라서， 본 발명의 일 구현예에 따른 액정 수직배향 유도제를 이용하여 선 배향처리 공정 없이 액정의 수직배향을 유도하고 액정의 선경사각을 안정화시키며 전극층 위에 절연성의 액정 수직배향 및 광안정화 층을 형성함으로써 성능 및 신뢰성이 우수한 액정소자를 제작할 수 있다.  Therefore, by using the liquid crystal vertical alignment guide according to the embodiment of the present invention, 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.
본 발명의 다른 일 구현예에 따르면 상기 액정 수직배향 유도제를 포함하는 액정층 형성용 조성물을 제공한다.  According to another embodiment of the present invention provides a composition for forming a liquid crystal layer comprising the liquid crystal vertical alignment guide.
상세하게는， 상기 액정층 형성용 조성물은 액정호스트와 함께， 상기한 액정 수직배향 유도제를 포함한다.  In detail, the composition for forming a liquid crystal layer includes the liquid crystal vertical alignment induction agent together with the liquid crystal host.
상기 액정호스트로는 통상 액정표시장치에 사용되는 것이라면 특별한 한정없이 사용가능하다 . 구체적으로는 음의 유전율 이방성을 가지는 네마틱 액정을 사용할 수 있다.  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.
상기 액정 수직배향 유도제는 앞서 설명한 바와 동일하다.  The liquid crystal vertical alignment guide is the same as described above.
다만， 액정층 형성용 조성물 중에 포함되는 액정 수직배향 유도제의 함량이 지나치게 낮으면， 액정호스트에 대한 수직배향 및 표면안정화 효과가 미미하고， 반면 함량이 지나치게 높으면， 높은 밀도의 배향불량 및 과도한 광안장화 발생에 따른 액정표시장치의 성능 저하의 우려가 있다. 이에 따라 상기 액정 수직배향 유도제는 액정층 형성용 조성물 총 중량에 대하여 0 . 01 내지 5 중량 %로 포함되는 것이 바람직하고， 보다 바람직하게는 0 . 05 내지 3 중량 %로 포함되는 것이 보다 향상된 효과를 얻을 수 있어 좋다.  However, when the content of the liquid crystal vertical alignment guide agent contained in the composition for forming a liquid crystal layer is too low, the vertical alignment and surface stabilization effects on the liquid crystal host are insignificant. On the other hand, when the content is too high, a high density of misalignment and excessive light sadding may occur. There is a risk of deterioration of the performance of the liquid crystal display device. Accordingly, 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.
액정호스트와 흔합시 액정 수직배향 유도제는 미세조립체의 형태로 액정호스트 중에 분산되어 존재한다. 이때 형성되는 미세조립체의 크기는 분산상 액체 및 양친매성 화합물의 흔합비에 따라 달라질 수 있으며， 일반적으로 양친매성 화합물의 분산상 액체에 대한 비율이 높을수톡 미세조립체의 직경은 작아지고, 비율이 낮을수록 미세조립체의 직경은 커지게 된다. 또한， 미세조립체의 최소 직경은 사용하는 양친매성 화합물의 길이에 의해 제한될 수 있으며， 양친매성 화합물의 평균길이의 두 배보다 작아질 수 없다. 또한， 미세조립체의 직경은 양친매성 화합물의 특성 및 종류에 따라 달라질 수 있다. 본 발명에 따른 에멀젼 상태의 액정층 형성용 조성물에서 분산상의 미세조립체의 직경은 수 나노미터 내지 수십 미크론까지 광범위하게 존재할 수 있다. 그러나 미세조립체의 직경이 지나치게 작은 경우에는 미세조립체 형성 자체가 어렵고， 반면 미세조립체의 직경이 지나치게 큰 경우에는 결함이 많이 발생하여 액정 배향 특성이 나빠질 수 있다. 따라서 , 액정의 수직배향을 제어할 목적으로 이용될 수 있는 미세조립체의 직경은 2nm 내지 800nm 인 것이 바람직하고， 보다 바람직하게는 3nm 내지 600nm, 보다 더 바람직하게는 3nm 내지When 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. In this case, 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. In addition, 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. In addition, the diameter of the microassembly may vary depending on the nature and type of the amphipathic compound. In the composition for forming a liquid crystal layer in an emulsion according to the present invention, the diameter of the microassembly of the dispersed phase may be present in a wide range from several nanometers to several tens of microns. However, when the diameter of the microassembly is too small, it is difficult to form the microassembly itself. On the other hand, when 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
400nm이다 , 400nm,
또한 상기 액정층 형성용 조성물은 액정의 수직배향을 유도한 후, 배향 및 선경사각을 안정화시키기 위하여 광중합 반응이 가능한 모노머를 더 포함할 수 있다. 이때， 광반웅성 모노머는 수직배향 고분자막을 선처리한 기판과 반웅성 액정 (reactive mesogen)을 소량 첨가한 액정층 형성용 조성물을 사용하여 액정소자를 제작하고 전기장의 인가하에서 배향을 광안정화 시킬 때 사용되는 반응성 액정의 기능과 유사한 작용을 한다. 상기 광반응성 모노머로는 액정 수직배향 유도제의 에멀견화에 관여하지 않으며 , 단지 액정 수직배향 유도제에 의한 액정의 수직배향 유도 후 특정상태의 배향을 안정화시킬 수 있는 화합물을 사용하는 것이 바람직하다. 구체적으로는 4, 4'-바이페놀 디아크릴레이트 (4,4'-biphenol diacrylate), 4,4'-바이페놀 디메타아크릴레이트 (4， 4 ' -biphenol dimethacrylate), 1，4_비스 -[4-(6_아크릴로일옥시핵실옥시 )벤조일옥시 ] - 2一메틸벤젠 (l,4_bisS—[4_(6— acryloyloxyhexyloxy)benzoyloxy]— 2一  In addition, 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. In this case, 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. As 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. Specifically, 4,4'-biphenol diacrylate, 4,4'-biphenol dimethacrylate (4, 4'-biphenol dimethacrylate), 1,4 bis- [4- (6_acryloyloxynuxyloxy) benzoyloxy]-2 一 methylbenzene (l, 4_bisS— [4_ (6— acryloyloxyhexyloxy) benzoyloxy] — 2 一
methyl benzene ) , 또는 1,6-핵산디올 아크릴레이트 ( 1， 6-hexanedi ol diacrylate) 등을 사용할 수 있다. methyl benzene), or 1,6-nucleic acid diol acrylate (1,6-hexanediol diacrylate) or the like can be used.
또한 상기 액정층 형성용 조성물은 액정호스트와 함께 표면 반웅기의 광반응을 유도하기 위한 통상의 광 개시제 (photo-initiaror)를 더 포함할 수도 있다.  In addition, the 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.
본 발명의 또 다른 일 구현예에 따르면 상기 액정층 형성용 조성물을 이용하여 제조된 액정표시장치 및 그의 제조방법을 제공한다 .  According to still another embodiment of the present invention, there is provided a liquid crystal display device manufactured using the composition for forming a liquid crystal layer and a method of manufacturing the same.
구체적으로， 본 발명의 일 구현예에 따른 액정표시장치는 서로 대향하여 위치하는 제 1기판과 제 2기판; 상기 계 1기판과 제 2기판의 상호 대향되는 면에 각각 형성된 제 1전극과 제 2전극; 그리고 상기 제 1기판과 상기 제 2기판 사이에 개재되어 위치하는 액정층을 포함하며， 상기 액정층은 상기한 액정호스트 및 액정 수직배향 유도제를 포함한다 .  Specifically, 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.
또한 상기 액정층은， 이후 액정 배향 안정화를 위한 선택적 실시공정인 광조사 공정에 의해 액정층 형성용 조성물 내 존재하는 미세조립체가 고체화되어 전극층 위에 패시베이션층을 형성함에 따라， 미세조립체를 포함하는 액정 수직배향 및 광안정화 층 (도 3의 14 및 24 참조 )을 더 포함할 수 있다.  In addition, 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).
또한， 액정 수직배향 유도제가 광반응성기를 포함하는 화합물을 포함하는 경우， 상기 액정층은 액정의 수직배향 유도 후 실시되는 전기장 인가하에서의 광증합 반웅 공정을 통해 상기 광반웅성기를 갖는 화합물이 광중합된 광중합체를 더 포함할 수도 있다. 상기 광중합체는 광반웅성기를 갖는 화합물에 포함된 광반응성기의 광중합에 의해 형성되는 것으로， 액정 분자가 특정한 배열을 이루고 있는 상태에서 광중합될 경우 형성된 광중합체에 의해 액정의 특정한 표면 배향을 기억하는 작용메카니즘에 의해 액정층내 액정물질의 수직배향 및 선경사각 안정화를 유도할 수 있다. 상기 광증합체는 1종의 광반웅성 화합물의 광중합에 의해 형성되는 중합체， 또는 2종 이상의 광반응성 화합물의 광중합에 의해 형성되는 공중합체를 포함한다. In addition, when the liquid crystal vertical alignment guide includes a compound including a photoreactive group, 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.
또한 상기 액정표시장치에 있어서， 상기 제 1 및 제 2 전극 중 어느 하나 또는 둘 모두는 패턴화된 것일 수 있다.  In the liquid crystal display, any one or both of the first and second electrodes may be patterned.
본 발명의 또 다른 일 구현예에 따르면， 제 1기판 및 제 2기판에 대해 각각 제 1 및 제 2전극을 형성하는 전극형성단계 ; 상기 제 1 및 제 2전극을 각각 포함하는 제 1기판과 제 2기판을 전극들끼리 대면하도록 하여 접합한 후 제 1기판과 제 2기판 사이의 공간에 액정층 형성용 조성물을 주입하거나 또는 상기 제 1 및 제 2전극올 각각 포함하는 제 1기판과 제 2기판 중 어느 하나에 대해 진공 하에서 액정층 형성용 조성물을 적하하여 액정층을 형성한 후 나머지 기판을 전극들끼리 대면하도록 접합하여 조립체를 제조하는 단계를 포함하는 액정표시장치의 제조방법을 제공한다. 또한 상기 제조방법은 조립체의 제조 후 상기 조립체의 제 1기판과 제 2기판 사이에 전기장을 인가한 후 광 조사하는 단계를 선택적으로 더 포함할 수 있다.  According to another embodiment of the present invention, an electrode forming step of forming the first and second electrodes for the first substrate and the second substrate, respectively; 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. It provides a method of manufacturing a liquid crystal display device comprising the step of. In addition, 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.
도 3 은 본 발명의 일 구현예에 따른 액정표시장치의 제조공정을 개략적으로 나타낸 공정도 이다. 도 3 은 본 발명을 설명하기 위한 일 례일 뿐 본 발명이 이에 한정되는 것은 아니다.  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.
이하 도 3을 참조하여 각 단계별로 상세히 설명한다.  Hereinafter, each step will be described in detail with reference to FIG. 3.
단계 1 은 제 1 기판 (11) 및 제 2 기판 (21)에 대해 각각 제 1 및 제 2전극 (12 및 22)을 형성하는 단계이다 (S11).  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).
상기 제 1 및 제 2 기판 (11 및 21)으로는 통상 액정표시장치에서 사용되는 것이라면 특별한 한정 없이 사용할 수 있으며 , 구체적으로 유리 또는 플라스틱 기판을 사용할 수 있다.  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.
상기 제 1 기판 (11)의 일면에는 제 1 전극 (12)으로서 공통전극 (또는 투명전극)을 형성하고， 제 2 기판 (21)의 일면에는 제 2 전극 (22)으로서 화소전극을 각각 형성한다. 이때 제 1 기판과 제 2 기판， 그리고 공통전극과 화소전극은 위치 및 그 기능에 따라 구분한 것으로 제 2 기판에 공통전극이 형성될 수도 있고 제 1 기판에 화소전극이 형성될 수도 있다.  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. . In this case, 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.
상기 제 1 및 제 2 전극 (12 및 22)은 통상의 전극 형성 방법에 따라 제조될 수 있으며 , 상기 제 1 및 제 2 전극 형성 물질로는 통상 액정표시장치의 전극 형성에 사용되는 물질이라면 특별한 제한없이 사용할 수 있다.  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
구체적으로는， 상기 제 1 및 제 2 전극 (12 및 22)은 금속산화물 탄소계 전기전도성 물질 및 이들의 흔합물로 이투진 군에서 선택되는 것을 포함할 수 있다. 바람직하게는， 인듐주석산화물 (indium tin oxide, ΠΌ)， 산화아연 (zinc oxide, Z0) , 인듐아연산화물 (inindi zinc oxide, IZO) , 산화주석 (tin oxide, TO), 산화인듐 (indium oxide, 10), 산화알루미늄 (A1203, AO), 산화은 (AgO), 산화티타늄 (Ti02), 불소 도핑된 주석 산화물 (fluorine— doped tin oxide, FTO) , 알루미늄 도핑된 아연 산화물 (aluminum doped zinc oxide, AZO)， 아연인듐주석 산화물 (zinc indium tin oxide, ZITO) , 니켈 산화물 (nickel oxide, NiO), 니켈 아연 주석 산화물 (nickel zinc tin oxide, NZTO), 니켈티타늄 산화물 (nickel titanium oxide, NTO) , 니켈주석 산화물 (nickel tin oxide) , 그래핀 (graphene), 그래핀 산화물 (graphene oxide, GO) 및 이들의 흔합물로 이루진 군에서 선택되는 화합물을 포함할 수 있다. Specifically, 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. Preferably, indium tin oxide (ΠΌ), 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.
또한 상기 제 1 및 제 2 전극 (12 및 22)은 기판 (11， 21) 전면에 걸쳐 형성될 수도 있고， 또는 별도의 패턴화 공정을 통해 아일랜드， 스프라이트， 피시본 등의 소정의 형태로 패턴화 (미도시)될 수도 있다. 이에 따라 본 발명의 다른 일 구현예에 따르면 상기 제 1 및 제 2 전극 (12 및 22) 중 적어도 어느 하나의 전극이 패턴화된 액정표시장치를 제공한다. 또한, 상기 전극 형성 단계 전 제 1 및 제 2 기판 (11 및 21)중 적어도 어느 하나의 기판에 대해， 또는 상기 전극 형성 후 제 1 및 제 2 전극 (12 및 22) 중 적어도 어느 하나의 전극 상에 전기절연성 화합물층 (미도시)을 형성하는 단계를 더 실시할 수 있으며， 또는 상기 전극 형성 단계 전과 전극 형성 후 둘 모두에 대해 전기절연성 화합물층을 형성하는 단계를 실시할 수 있다.  In addition, the 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.
상기 공정의 결과로 전극의 상부 또는 하부에는 패시베이션층 (passivation layer) 또는 절연층의 역할을 하는 전기절연성 화합물층이 형성될 수 있으며 , 또한 전극 형성 전 및 전극 형성 후 전기절연성 화합물층 형성 공정을 실시함으로써 전극의 상부 및 하부 들 모두에 전기절연성 화합물층이 형성될 수 있다. 이에 따라 본 발명의 또 다른 일 구현예에 따르면， 상기 제 1 및 제 2 전극 (12 및 22) 중 적어도 어느 하나의 전극에 대해 위나 아래， 또는 둘 모두에 전기절연성 화합물층이 형성된 액정표시장치를 제공한다.  As a result of the above process, 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.
상기 전기절연성 화합물층은 유기 절연성 물질， 비금속 산화물 또는 비금속 질화물을 포함할 수 있다. 구체적으로는 상기 전기 절연성 화합물층은 실리콘 산화물 (SiOx) 또는 실리콘 질화물 (SiNx)로 구성된 단일막이거나， 또는 실리콘산화물막 및 실리콘질화물막으로 구성된 이증막 내지는 다층구조체일 수 있다.  The electrically insulating compound layer may include an organic insulating material, a nonmetal oxide, or a nonmetal nitride. Specifically, 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.
또한, 전극 (12 및 22)이 형성된 각각의 기판 (11 및 21)에 대해 선택적으로 세제를 이용한 수용액 ; 아세톤, 이소프로필알코을 등의 유기용매 ; 오존; 또는 플라즈마 등을 이용하여 세정 후 건조하여 전극 표면의 불순물 및 수분을 제거하는 공정올 실시할 수도 있다.  Further, an aqueous solution using a detergent selectively for each of the substrates 11 and 21 on which the electrodes 12 and 22 are formed; Organic solvents such as acetone and isopropyl alcohol; ozone; Alternatively, a process of removing impurities and water from the surface of the electrode by washing and drying using plasma or the like may be performed.
단계 2 는 상기 제 1 및 제 2 전극 (12 및 22)을 포함하는 제 1 기판 및 제 2기판 (11 및 21)을 전극들끼리 대면하도록 하여 접합한 후 제 1기판과 제 2 기판 사이의 공간에 액정층 형성용 조성물 (13a)을 주입하거나， 또는 상기 제 1 및 제 2전극 (12 및 22)을 포함하는 제 1 기판과 제 2기판 (11 및 21) 증 어느 하나에 대해 진공하에서 액정층 형성용 조성물 (13a)을 적하한 후 나머지 기판을 전극끼리 대면하도특 접합하여 조립체를 제조하는 단계이다 ( S12) . 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. Injecting the liquid crystal layer-forming composition 13a into the liquid crystal layer, or under the vacuum of either the first substrate and the second substrate 11 and 21 including the first and second electrodes 12 and 22. Forming composition (13a) After dropping, the remaining substrates are bonded to each other under a special step of manufacturing an assembly (S12).
상기 액정층 형성용 조성물 ( 13a)은 앞서 설명한 바와 동일하다.  The composition 13a for forming a liquid crystal layer is the same as described above.
상기 제 1 기판과 제 2 기판 ( 11， 21 )의 접합 공정과, 액정층 형성용 조성물 ( 13a)의 주입 또는 적하 공정은 통상의 방법에 따라 실시할 수 The bonding process of the said 1st board | substrate and the 2nd board | substrates 11 and 21, and the injection | pouring or dripping process of the composition for liquid crystal layer formation 13a can be performed by a conventional method.
01다 01
상기와 같은 공정에 따라 액정층 형성용 조성물 ( 13a)을 주입하게 되면， 도 2 에 나타난 바와 같이 액정은 통상적인 배향막의 코팅 없이도 수직 배향하게 된다 ( S12) .  Injecting the liquid crystal layer forming composition (13a) according to the above process, as shown in Figure 2, the liquid crystal is vertically aligned without coating the conventional alignment layer (S12).
이때 액정의 수직배향을 효과적으로 유도하기 위해 상기 액정층 형성용 조성물의 주입 또는 적하 후 액정물질과 액정 수직배향 유도제의 흔합물의 네마틱 -아이소트로픽 상전이 온도 보다 5 내지 20 °C 높은 온도로 조립체를 가열한 후 분당 0 . 1 내지 10 °C의 속도로 냉각시키는 액정의 수직배열을 유도 공정을 더 실시할 수도 있다. At this time, after injecting or dropping the composition for forming the liquid crystal layer to effectively induce the vertical alignment of the liquid crystal, 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.
또한 상기 조립체의 제조 단계 이후 선택적으로 상기 조립체의 제 1 기판과 제 2 기판 ( 11 , 21 ) 사이에 전기장을 인가한 후 광 조사하여 액정표시장치를 제조하는 단계를 더 실시할 수도 있다 ( S13 ) .  In addition, after the fabrication step of the assembly, optionally applying an electric field between the first substrate and the second substrate (11, 21) of the assembly and then irradiated with light to manufacture a liquid crystal display device (S13) .
상기 전기장 인가 공정은 액정표시장치의 광투과율이 직교편광자 하에서 최대 투과도의 5% (T05 ) 내지 100% (Τ100)가 되는 직류 또는 교류 전기장을 인가한 조건에서 실시되는 것이 바람직하다. 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% (Τ 100 ) of the maximum transmittance under the orthogonal polarizer.
상기와 같은 조건에서 전기장 인가에 의해 조립체 내 액정에 대해 특정 광학상태를 유도한 후 광반웅성기를 화학반웅시킬 수 있는 파장의 광， 바람직하게는 자외선을 조사한다 . 바람직하게는 200 nm 내지 400 nm 파장 범위의 자외선을， 1 분 내지 90 분 동안 500 mW/cm2 내지 50 μ W/cm2 의 세기로 조사하는 것이 광반웅성 화합물에 있어서의 광반응성기의 광안정화 효율을 최대화하여 액정배향의 표면안정화 효과를 얻을 수 있기 때문에 좋다. 또한， 광 조사 공정은 인가하는 전기장이나 조사하는 광의 세기를 다르게 하여 2가지 이상의 단계로 실시할 수도 있다. Under the above conditions, 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. Preferably, 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 μ W / cm 2 for This is good because the surface stabilization effect of liquid crystal alignment can be obtained by maximizing the efficiency. In addition, 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.
상기 광 조사 공정은 전기장을 인가한 후 결함이 최소화될 때까지 기다렸다가 액정의 배열상태가 안정된 상태가 된 후 실시하는 것이 바람직하다 .  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.
상기 광 조사 공정에 의해 액정층 형성용 조성물내 존재하는 액정 수직배향 유도제의 미세조립체가 고체화되어 전극 위에 패시베이션층을 형성함에 따라 상기 액정층은 상기 미세조립체에 의해 형성된 패시베이션층으로서 액정 수직배향 및 광안정화 층 ( 14 및 24 )을 더 포함할 수 있다.  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.
또한 액정 수직배향 유도제를 형성하는 화합물이 광반웅성기를 포함하는 광반응성 화합물인 경우， 상기와 같은 광 조사 공정에 의해 광반응성 화합물의 광반응성기가 광반응을 일으켜 광중합체를 형성하며 , 그 결과로 액정의 배열 및 광학상태가 더욱 안정화되고， 액정의 표면 선경사각 유도 및 화소 단위의 표면 안정화를 실현할 수 있다.  In addition, when 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.
구체적으로， 광안정화 처리가 되지 않은 액정표시장치에 제 1 및 제 2 기판 ( 11， 21 )을 통해 기판에 수직인 전기장을 인가하게 되면 액정분자가 전기장에 수직인 방향으로 회전하면서 투과도가 증가하게 된다. 이때 액정분자는 특정 방향으로의 선경사각이 형성되어 있지 않으므로 액정의 회전방향은 액정 셀의 부위에 따라 불규칙적으로 일어나게 된다. 따라서 액정배열의 결함이 생기게 되고 이것은 소자의 특성을 악화시키는 원인으로 작용하게 된다. 그러나 상기와 같은 광 조사 및 광반웅 공정을 통해 액정물질에 대해 표면에 특정 방향으로 선경사각을 유도하고， 이후 인가된 전기장을 제거하면 단계 S13 에 나타난 바와 같이， 액정물질은 표면의 액정 프리틸트 방향을 기억하는 수직 배향 상태로 전이되게 된다 . 이와 같이 액정의 배향이 표면 안정화됨으로써 선경사각을 가지게 되어 결함의 발생을 제거할 수 있으므로 액정의 반응특성 및 소자의 밝기 및 대비비를 향상 시킬 수 있다. 따라서， 본 발명에서 제안된 액정배열의 표면 안정화 기술 즉， 광반응성 화합물의 광 반웅성 유기기의 화학반응을 통한 액정 배열 안정화 방법을 이용하여 액정표시장치를 제조할 경우 액정표시장치의 휘도 및 대비비 ( cont r as t rat i o )가 향상되고 액정의 스위칭 속도를 빠르게 할 수 있다. Specifically, when an electric field perpendicular to the substrate is applied to the liquid crystal display device which is not subjected to the light stabilization process through the first and second substrates 11 and 21, the liquid crystal molecules Transmittance increases as it rotates in a direction perpendicular to the electric field. In this case, since the liquid crystal molecules do not have a pretilt angle in a specific direction, 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. However, when the light inclination and the light reflection process as described above induce a pretilt angle to the surface of the liquid crystal material in a specific direction, and then remove the applied electric field, as shown in step S13, 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. Therefore, when manufacturing a liquid crystal display device using the liquid crystal array stabilization method through the surface stabilization technology of the liquid crystal array proposed in the present invention, that is, the chemical reaction of the photo-banung organic group of the photoreactive compound, the brightness and contrast of the liquid crystal display device The ratio (cont r as t rat io) is improved and the switching speed of the liquid crystal can be increased.
상기와 같이 본 발명에 따른 액정표시장치의 제조방법은 액정호스트에 대하여 에멀견 형성이 가능한 액정 수직배향 유도제를 이용함으로써 별도의 고분자 배향막의 도포 및 고온 소성 공정없이， 액정의 수직배향을 유도할 수 있다. 또한 상기 제조방법은， 배향제가 처리된 액정샐에 액정물질로서 반응성 액정을 흔합하여 광반웅시킴으로써 배향 안정화를 달성하는 종래 액정표시장치 제조방법과는 달리 , 상기 광반응성기를 포함하는 광반웅성 화합물을 사용함으로써 배향층 형성공정 없이 액정의 수직배향을 유도할 수 있고， 또한 이후 전기장 인가 하에서 광 조사에 의한 광중합 과정을 통하여 기판표면에 흡착된 액체 미세조립체를 고체화시킴으로써 액정의 특정 배향 상태를 안정화 시키는 동시에 광 안정화 후 발생할 수 있는 불량을 획기적으로 감소시킬 수 있다. 그 결과 액정표시장치 제조의 생산성 및 액정표시장치의 신뢰성을 향상시킬 수 있다.  As described above, the manufacturing method of the liquid crystal display device according to the present invention 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. In addition, 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 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.
또한 상기 액정 배열의 안정화로 인해 소자 구동시 발생하는 액정의 결함 발생을 방지하고 반응속도를 개선하여 소자의 성능 및 신뢰성을 향상시킬 수 있다 . 특히 화소 단위의 표면 액정 선경사각 유도 및 방향자 안정화가 가능하므로 액정소자의 휘도， 명암 대비율， 반응속도 등 광학 /전기광학 특성을 더욱 향상시킬 수 있다. 또한, 상기 제조방법은 상온에서 공정이 실시되기 때문에 공정온도가 종래 고분자 배향막의 소성 온도보다 현저히 낮고，ᅳ공정이 단순하며， 특히， 고품위 액정표시장치나 저온공정이 요구되는 플랙서블기재 기판 ( f l ex i b l e subst rat e )을 사용한 액정표시장치의 제작에 유용하다 .  In addition, due to 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. In particular, since 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. In addition, since 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.
상기 액정표시장치의 제조방법은 상온 공정으로 종래 고온 배향막 코팅 및 소성 공정을 대체할 수 있다. 따라서， 유리기판을 이용한 고품위 액정 표시장치뿐만 아니라， 고온에서의 배향막 소성 공정이 생략됨으로써 플렉서블 액정표시장치와 같은 고온 공정이 어려운 액정표시장치의 제작에 유용하다.  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.
이와 같은 제조방법에 의해 제조된 본 발명에 따른 액정표시장치는 TV , 3D-TV , 모니터， 태블릿 PC , 각종 모바일 기기 등 액정을 이용한 전기광학 소자 제품， 특히 평관 디스플레이에 다양하게 적용될 수 있다. 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.
본 발명의 또 다른 일 구현예에 따르면， 에멀견화된 액정층 형성용 조성물을 이용하여 배향 안정성을 갖는 액정의 수직배향을 유도하는 방법을 제공한다. 이때 상기 에멀견화된 액정층 형성용 조성물은 액정 호스트와 함께 상기한 액정 수직배향 유도제를 포함하몌 그 각각은 앞서 설명한 바와 동일하다.  According to another embodiment of the present invention, there is provided a method of inducing vertical alignment of a liquid crystal having alignment stability by using the composition for forming an emulsified liquid crystal layer. In this case, 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.
본 발명의 또 다른 일 구현예에 따르면， 광반응성의 에멀젼화된 액정층 형성용 조성물을 이용하여 액정의 광안정화를 유도하는 방법을 제공한다. 이때 상기 액정층 형성용 조성물은 액정 호스트와 함께 상기한 액정 수직배향 유도제를 포함하되 , 상기 액정 수직배향 유도제는 유도제를 구성하는 양친매성 화합물 및 단분자의 친수성 액체 중 적어도 어느 하나의 화합물이 광반응성기를 포함하는 광반응성 화합물이다. 상기 광반응성기를 포함하는 양친매성 화합물 및 단분자의 친수성 액체는 앞서 설명한 바와 동일하다.  According to another embodiment of the present invention, a method of inducing photostabilization of a liquid crystal using a photoreactive emulsified liquid crystal layer forming composition is provided. In this case, 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.
본 발명의 또 다른 일 구현예에 따르면， 기판의 선 코팅처리 없이 종래에 비해 단순화된 공정으로 전극층과 액정층 사이에 절연성의 액정 수직배향 및 광안정화 층을 형성하는 방법을 제공한다 .  According to another embodiment of the present invention, there is provided 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.
상기 액정 수직배향 및 광안정화 층 형성방법은， 액정 호스트와 함께 상기 액정 호스트 중에 에멀전 상태로 분산된 액정 수직배향 유도제를 포함하는 액정층 형성용 조성물을 액정층내에 주입한 후 전기장을 인가하고 광조사함으로써 실시될 수 있다.  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.
상기 에멀견 상태의 액정층 형성용 조성물을 액정층 내에 주입한 후 광조사를 실시하면, 액정층 형성용 조성물내 존재하는 미세 조립체가 고체화되어 전극층 위에 패시베이션층으로서 액정 수직배향 및 광안정화층을 형성하게 된다. 이때， 상기 액정 호스트 및 액정 수직배향 유도제 그리고 광조사 공정은 앞서 설명한 바와 동일하다 .  When the liquid crystal layer forming composition in the emulsion state is injected into the liquid crystal layer and subjected to light irradiation, 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. In this case, the liquid crystal host, the liquid crystal vertical alignment guide and the light irradiation process are the same as described above.
이하， 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.  Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
제조예 1  Preparation Example 1
양친매성 화합물로서 하기 화학식 5의 펜타에리쓰리를 모노스테아레이트와 친수성 액체로서 하기 화학식 6의 글리세를을 80 : 20의 중량비로 혼합하여 액정 수직배향 유도제를 제조하였다.  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.
액정호스트에 펜타에리쓰리롤 모노스테아레이트과 글리세롤의 균일 흔합물을 액정호스트 총 중량에 대하여 0 . 3% 중량의 양으로 분산시켜 균일한 에멀젼의 액정층 형성용 조성물을 제조하였다.  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.
[화학식 5 ]
Figure imgf000027_0001
[Formula 5]
Figure imgf000027_0001
[화학식 6 ]  [Formula 6]
OH OH
II
CH, - CH - CH CH,-CH-CH
OH OH 제조예 2  OH OH Preparation Example 2
펜타에리쓰리를 모노스테아레이트과 글리세를을 80 : 20의 중량비로 혼합하여 제조한 액정 수직배향 유도제를 클로로포름에 1% 증량비로 흔합한 후 5분간 초음파 처리하였다. 이때 무색 투명하던 클로로포름 용매에 미세조립체가 균일하게 분산되면서 흰색의 광산란 상태를 나타내는 안정적인 에멀젼이 생성되었다 . 또한 에멀견에 분산된 미세조립체의 크기를 광산란을 이용한 입도 분석기로 측정한 결과 미세조립체의 평균 입자 직경은 약 180nm이었다.  A liquid crystal vertical alignment inducer prepared by mixing monostearate and glycerol in a weight ratio of 80:20 was mixed with chloroform in a 1% increase ratio and sonicated for 5 minutes. At this time, as the microassembly was uniformly dispersed in the colorless transparent chloroform solvent, a stable emulsion showing a white light scattering state was produced. In addition, when the size of the microassembly dispersed in the emulsion was measured by the particle size analyzer using light scattering, the average particle diameter of the microassembly was about 180 nm.
상기에서 제조된 클로로포름에 분산된 펜타에리쓰리를 모노스테아레이트 /글리세를 미세조립체의 에멀견을 액정호스트 중에 액정호스트 총 증량에 대하여 30중량 %로 첨가한 후 , 섭씨 70도의 열을 가하여 클로로포름을 완전히 제거함으로써 0 .3중량%의 펜타에리쓰리롤 모노스테아레이트 /글리세를 미세조립체가 액정호스트에 균일하게 에멀젼화된 액정층 형성용 조성물을 제조하였다. 시험예 1  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
상기 제조예 1 및 2에서 액정 수직배향 유도제의 제조에 사용된 각각의 화합물을 양 또는 음의 유전율 이방성을 가지는 액정호스트에 흔합하였을 경우， 두 화합물 모두 액정호스트와 전혀 섞이지 않고 상분리되었다. 또한， 이들 각각의 흔합물을 각각 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였을 경우， 액정호스트만을 따로 주입하였을 경우와 동일하게 랜덤수평 배향상태가 관찰되었다.  When each compound used in the preparation of the liquid crystal vertical alignment guide in Preparation Examples 1 and 2 was mixed with a liquid crystal host having positive or negative dielectric anisotropy, both compounds were phase-separated without mixing at all with the liquid crystal host. In addition, when each of these mixtures were injected into a liquid crystal cell fabricated using a non-aligned substrate, random horizontal alignment states were observed in the same manner as in the case where only the liquid crystal host was separately injected.
그러나， 상기 제조예 1에서 제조한 액정 수직배향 유도제를 액정호스트와 흔합했을때， 액정 수직배향 유도제는 액정호스트에 쉽게 용해되었다. 이 같은 결과는 액정호스트와 글리세를의 경계면에서 펜타에리쓰리롤 모노스테아레이트 분자가 자기조립에 의해 글리세롤 /펜타에리쓰리를 모노스테아레이트 미세조립체를 형성하고， 이들 미세조립체가 액정호스트에 안정적으로 분산된 에멀젼을 형성하였기 때문이다.  However, when the liquid crystal vertical alignment guide prepared in Preparation Example 1 was mixed with the liquid crystal host, the liquid crystal vertical alignment guide was easily dissolved in the liquid crystal host. These results indicate that the pentaerythritol monostearate molecule forms a monostearate microassembly of glycerol / pentaerythride by self-assembly at the interface between the liquid crystal host and glycerol, and these microassemblies are stably dispersed in the liquid crystal host. This is because an emulsion is formed.
이어서 상기 제조예 1 및 2에서 제조된 액정층 형성용 조성물을 각각 독립적으로 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였다. Subsequently, the 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.
사조실Thread
성친용시  Sexual intercourse
Φ丁 <  Φ 丁 <
그 결성는을여과， 두 경우 모두에서 액정의 수직배향이 유도되었다. 이 같은 결과는， 액정호스트에 분산되어 펜타에리쓰리롤 모노스테아레이트의 분자 자기조립에 의해 생성된 펜타에리쓰리를 모노스테아레이트 /글리세롤 미세조립체가 액정셀에 주입되었을 때 기판의 표면에 흡착되어 기판의 표면을 액정의 수직배열 상태로 개질하였기 때문이다. 따라서， 제조예 1 및 2에서 제조된 액정층 형성용 조성물은 동일한 형태의 에멀견임을 알 수 있고， 제조예 2에서의 클로로포름과 같이 제 3의 용매를 사용하지 않고도 제조예 1에서와 같이 양친매성화합물 -친수성분산상액체 흔합물을 직접 액정에 첨가하여 에멀젼을 제조할 수 있음을 알 수 있다. 제조예 3  The formation resulted in vertical alignment of the liquid crystal in both cases. The result is that when the monostearate / glycerol microassembly is injected into the liquid crystal cell, the pentaerythri, which is dispersed in the liquid crystal host and produced by molecular self-assembly of the pentaerythriol monostearate, is adsorbed onto the surface of the substrate and the substrate This is because the surface of was modified in the vertically aligned state of the liquid crystal. Therefore, it can be seen that the 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
액체로서 하기 화학식 ^리세롤 디아크릴레이트를 것을 제외하고는 상기 7 7 except that the liquid of the general formula ^ glycerol diacrylate
및의제 1에서와 동일한 방법으로 액정 수직배향 유도제 포함하는 액정층 형성용 제조하였다. 이트예  And prepared in the same manner as in the first liquid crystal layer comprising a liquid crystal vertical alignment inducing agent. Yye
1를리
Figure imgf000028_0001
1
Figure imgf000028_0001
제조예 3의 액정 수직배향 화합물의 제조에 사용된 각각의 화합물을 액정호스트에 흔합하였을 때， 두 화합물 모두 액정과 전혀 섞이지 않고 상분리 됨을 관찰 하였다. 따라서， 이들 흔합물을 각각 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였을 경우， 액정호스트만을 따로 주입하였을 경우와 동일하게 랜덤수평 배향상태가 관찰되었다. 그러나, 펜타에리쓰리롤 모노스테아레이트와 트리글리세 * 디아크릴레이트의 흔합물을 액정호스트와 혼합했을 때 액정호스트에 쉽게 용해되었다.  When each compound used in the preparation of the liquid crystal vertical alignment compound of Preparation Example 3 was mixed with the liquid crystal host, it was observed that both compounds phase separated without mixing with the liquid crystal at all. Therefore, when these mixtures were injected into liquid crystal cells fabricated using substrates not pre-aligned, random horizontal alignment states were observed in the same manner as in the case where only liquid crystal hosts were separately injected. However, when a mixture of pentaerythritol monostearate and triglyceride diacrylate was mixed with the liquid crystal host, it was easily dissolved in the liquid crystal host.
또한 이후 에멀견화된 액정층 형성용 조성물을 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였을 때， 액정호스트만을 주입하였을 경우와는 다르게 액정의 수직배향이 유도되었다. 이 같은 결과 역시， 앞서 제조예 1 및 2에서와 마찬가지로， 펜타에리쓰리톨 모노스테아레이트 분자의 자기조립에 의해 생성된 펜타에리쓰리롤 모노스테아레이트 /트리글리세롤 디아크릴레이트의 미세조립체가 액정셀에 주입되었을 때 기판의 표면에 흡착되어 기판 표면을 액정의 수직배열 상태로 개질하였기 때문이다.  In addition, when injecting the emulsified composition for forming a liquid crystal layer into a liquid crystal cell manufactured using a non-aligned substrate, vertical alignment of the liquid crystal was induced differently from when only the liquid crystal host was injected. As described above, the microassembly of pentaerythritol monostearate / triglycerol diacrylate produced by the self-assembly of pentaerythritol monostearate molecules was prepared in the liquid crystal cell as in the preparation examples 1 and 2. This is because when injected, the substrate is adsorbed onto the surface of the substrate to modify the surface of the substrate to a vertical arrangement of liquid crystals.
또한， 제조예 3에서 제조된 액정층 형성용 조성물은 친수성 분산상 액체에 광반웅성 아크릴레이트기가 포함되어 있기 때문에 , 액정의 수직배향 유도 후， 전기장의 인가여부에 상관없이 또한 광개시제의 사용여부에 상관없이 광조사에 의한 광증합 반웅을 통하여 액체상의 미세조립체를 고체상으로 변환시킬 수 있다. 제조예 4 양친매성 화합물로 광반응성기를 포함하는 하기 화학식 8의 펜타에리쓰리를 디아크릴레이트 모노스테아레이트를， 그리고 친수성 액체로서 광반웅성기를 포함하는 트리글리세롤 디아크릴레이트를 80 :20의 중량비로 흔합하여 액정 수직배향 유도제를 제조하였다. In addition, since 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.
액정호스트에 상기에서 제조된 액정 수직배향 유도제를 액정호스트 총 중량에 대하여 0.3% 중량의 양으로 분산시켜 균일한 에멀견의 액정층 형성용 조성물을 제조하였다.  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.
[화학식 8]  [Formula 8]
0 0  0 0
H2C^AD > O人 ( CH2(CH2)15CH3H 2C ^ AD> O ( CH2 (CH2) 15CH3
Figure imgf000029_0001
Figure imgf000029_0001
o  o
이후 에멀젼화된 액정층 형성용 조성물을 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였을 때 , 액정호스트만을 주입하였을 경우와는 다르게 액정의 수직배향이 유도되었다.  Then, when the emulsified liquid crystal layer-forming composition is injected into a liquid crystal cell manufactured using a substrate that has not been pre-aligned, a vertical alignment of the liquid crystal is induced, unlike when only the liquid crystal host is injected.
또한 액정의 수직배향 유도 후 광조사 했을 때, 광반응성기의 중합반웅에 의해 기판 표면에 홉착된 펜타에리쓰리롤 디아크릴레이트 모노스테아레이트 / 트리글리세롤 디아크릴레이트의 미세조립체가 고체화됨으로써 보다 안정적이고 신뢰성 높은 특성을 갖는 액정표시장치를 제조할 수 있었다.  In addition, when the light is irradiated after induction of the vertical alignment of the liquid crystal, the microassembly of pentaerythriol diacrylate monostearate / triglycerol diacrylate, which is bound to the surface of the substrate by the polymerization reaction of the photoreactive group, becomes more stable, A liquid crystal display device having high reliability characteristics could be manufactured.
추가로, 상기 액정의 수직배향 유도 후 액정 샐에 전기장을 인가하여 특정한 방향으로 액정을 배열시킨 상태에서 광 조사하여 광중합반웅을 유도함으로써， 소자의 특성향상에 요구되는 액정의 특정 선경사각이 유도되고 안정화되었다. 제조예 5  In addition, after inducing the vertical alignment of the liquid crystal, an electric field is applied to the liquid crystal sal to induce photopolymerization by irradiating light in a state in which the liquid crystals are arranged in a specific direction, thereby inducing a specific pretilt angle of the liquid crystal required for improving the characteristics of the device. Stabilized. Preparation Example 5
양친매성 화합물로 하기 화학식 9의 소르비탄 모노팔미테이트를， 그리고 친수성 액체로서 광반웅성기를 가진 트리글리세롤 디아크릴레이트를 사용하는 것을 제외하고는ᅳ 제조예 4에서와 동일한 방법으로 실시하여 액정 수직배향 유도제 및 이를 포함하는 액정층 형성용 조성물을 제조하였다.  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.
[화학식 9]  [Formula 9]
Figure imgf000029_0002
제조예 6
Figure imgf000029_0002
Preparation Example 6
소르비탄 모노팔미테이트와 트리글리세를 디아크릴레이트를 80 : 20의 중량비로 흔합하여 제조한 액정 수직배향 유도제를 클로로포름에 1중량 %의 함량으로 첨가한 후 5분간 초음파 처리하였다. 이때， 무색 투명하던 클로로포름 용매에 소르비탄 모노팔미테이트 /트리글리세를 디아크릴레이트의 미세조립체가 균일하게 분산되면서 흰색의 광산란 상태를 나타내는 안정적인 에멀전이 생성되었다. 또한, 에멀견에 분산된 미세조립체의 크기를 광산란을 이용한 입도 분석기로 측정한 결과 미세조립체의 평균 입자 직경은 약 200nm이었다. 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. In addition, as a result of measuring the size of the microassembly dispersed in the emulsion by a particle size analyzer using light scattering, the average particle diameter of the microassembly was about 200 nm.
상기에서 제조된 클 S로포름에 분산된 소르비탄 모노팔미테이트 /트리글리세를 디아크릴레이트의 미세조립체의 에멀견을 액정호스트 중에 액정호스트 총 중량에 대하여 30 중량 %로 첨가한 후 섭씨 70도의 열을 가하여 클로로포름을 완전히 제거함으로써 0 . 3중량%의 펜타에리쓰리롤 모노스테아레이트 /글리세를 미세조립체가 액정호스트에 균일하게 에멀견화된 액정층 형성용 조성물을 제조하였다. 시험예 2  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. Test Example 2
상기 제조예 5 및 6에서 액정 수직배향 유도제의 제조에 사용된 소르비탄 모노팔미테이트는 그 자체로도 액정호스트에 대해 용해되는 특성이 있지만， 친수성 액체와 같이 액정호스트와 흔합한 경우에도 액정호스트에 용해되지 않는 트리글리세를 디아크릴레이트와 함께 분산상의 미세조립체 형태로 액정호스트내에 고르게 분산되었다.  Although 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.
또한 제조에 5 및 6에서 제조한 액정층 형성용 조성물을, 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하였다. 두 경우 모두 양호한 액정의 수직배향이 유도되었다.  In addition, the composition for liquid crystal layer formation manufactured in manufacture 5 and 6 was injected into the liquid crystal cell produced using the board | substrate which was not pre-aligned. In both cases, good vertical alignment of the liquid crystal was induced.
또한, 액정의 수직배향을 유도한 후 광조사를 실시했을 때， 액정의 수직배향 후 전기장의 인가여부에 무관하게 광조사에 의한 광중합 반응을 통하여 액체상의 미세조립체가 고체상으로 변환되었다.  In addition, when the light irradiation was induced after inducing the vertical alignment of the liquid crystal, 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.
또한, 액정의 수직배향을 유도한 후에 액정 셀에 전기장을 인가하여 특정한 방향으로 액정배향을 유도한 상태에서 광중합시킴으로써 소자의 특성향상에 요구되는 액정의 특정 선경사각을 유도하고 안정화시킬 수 있다. 시험예 3  In addition, after inducing the vertical alignment of the liquid crystal, by applying an electric field to the liquid crystal cell and photopolymerizing in a state in which the liquid crystal alignment is induced in a specific direction, it is possible to induce and stabilize a specific pretilt angle of the liquid crystal required for improving the characteristics of the device. Test Example 3
분자의 자기조립에 의해 생성된 미세 조립체의 형성에 관여하는 양친매성 화합물과 친수성 분산상 액체의 흔합비율에 따른 액정의 수직배향 유도 및 선경사각 안정화 여부를 확인하기 위하여 흔합비율에 따른 실험을 실시하였다.  Experiments were carried out according to the mixing ratio to determine whether the alignment of the liquid crystals and the pretilt angle were stabilized according to the mixing ratio of the amphiphilic compound and the hydrophilic dispersed phase liquid involved in the formation of the microassembly produced by the self-assembly of the molecules.
상세하게는 양친매성 화합물로서 소르비탄 모노팔미테이트와 친수성 액체로서 광반응성기가 없는 글리세를을 하기 표 1에 나타난 바와 같은 다양한 흔합비로 흔합하여 액정 수직배향 유도제를 제조하고， 액정호스트 총 중량에 대하여 0 . 1중량%로 흔합하여 액정층 형성용 조성물을 제조하였다.  Specifically, 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.
제조한 액정층 형성용 조성물을 선배향처리 되지 않은 기판을 이용하여 제작한 액정 셀에 주입하고， 액정의 수직배향 여부를 확인하였다. 또한， 상기 액정의 수직배향 유도 후 액정 샐에 전기장을 인가하여 특정한 방향으로 액정을 배열시킨 상태에서 광 조사하고 액정의 선경사각 유도 여부를 확인하였다. 그 결과를 하기 표 1에 나타내었다. 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. In addition, 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. The results are shown in Table 1 below.
[표 1]  TABLE 1
Figure imgf000031_0001
시험예 4
Figure imgf000031_0001
Test Example 4
양친매성 화합물로서 소르비탄 모노팔미테이트 또는 펜타에리쓰리를 디아크릴레이트 모노스테아레이트를, 그리고 친수성 액체로서 광반응성기를 포함하는 트리글리세를 디아크릴레이트를 하기 표 2 및 3에 나타난 다양한 혼합비로 흔합하여 제조한 액정 수직배향 유도제를 사용하고, 제조된 액정 수직배향 유도제를 하기 표 2 및 3에 나타난 바와 같은 함량으로 액정호스트와 흔합하는 것을 제외하고는 상기 시험예 3에서와 동일한 방법으로 실시하고, 액정의 수직배향 여부 및 광조사 후 액정의 선경사각 유도여부를 확인하였다. 그 결과를 하기 표 2 및 3에 나타내었다.  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. Using the prepared liquid crystal vertical alignment inducer, 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.
[표 2]  TABLE 2
실시번호 양친매성 친수성 액체 액정층 수직배향 선경사각 화합물 (증량%) 형성용 여부 안정화 NO. Amphiphilic hydrophilic liquid crystal layer Vertical alignment Line inclination compound (increase%) Formation stabilization
(중량 ¾) 조성물 증 여부 액정수직배향 (Weight ¾) composition increase liquid crystal vertical orientation
유도제의  Inducer
함량 (중량 %) 1 70 30 0.3 0 0Content (% by weight) 1 70 30 0.3 0 0
2 80 20 0.3 0 02 80 20 0.3 0 0
3 90 10 0.3 0 03 90 10 0.3 0 0
4 95 5 0.3 0 04 95 5 0.3 0 0
5 98 2 0.3 0 X5 98 2 0.3 0 X
6 99 1 0.3 0 X 6 99 1 0.3 0 X
[표 3] TABLE 3
실시번호 양친매성 친수성 액체 액정층 수직배향 선경사각 화합물 (증량 %) 형성용 안정화Example No. Amphiphilic Hydrophilic Liquid Liquid Crystal Vertical Orientation Pretilt Compound Stabilization for Formation
(중량 %) 조성물 중 여부 (% By weight) in the composition
액정수직배향  Liquid Crystal Vertical Orientation
유도제의  Inducer
함량 (중량 ¾)  Content (weight ¾)
1 70 30 0.2 0 0 1 70 30 0.2 0 0
2 80 20 0.2 0 02 80 20 0.2 0 0
3 90 10 0.2 0 03 90 10 0.2 0 0
4 95 5 0.2 0 04 95 5 0.2 0 0
5 98 2 0.2 0 05 98 2 0.2 0 0
6 99 1 0.2 0 0 상기 표 1 내지 3에 나타난 바와 같이 , 양친매성 화합물과 친수성 액체의 흔합시 양친매성 화합물의 비율을 50 내지 99증량 %로 첨가한 모든 액정조성물에서 액정의 수직배향이 유도됨을 확인하였다. 6 99 1 0.2 0 0 As shown in Tables 1 to 3, the vertical alignment of the liquid crystal was induced in all liquid crystal compositions in which the ratio of the amphiphilic compound was added in an amount of 50 to 99% by weight was mixed. Confirmed.
또한， 표 2의 실시번호 5 및 6의 결과로부터 액정층 형성용 조성물내 광반응성기를 포함하는 화합물의 비율이 지나치게 낮을 경우 액정의 선경사각 안정화가 효율적으로 달성되기 어려움을 알 수 있다 . 따라서 , 이들 실시예에서의 흔합비에서는 미세조립체를 구성하는 모든 화합물이 광반웅성기를 함유하는 것이 선경사각 안정화에 유리하게 작용할 수 있다 . 이는 상기 표 3의 실험결과에 의해서도 뒷받침된다. 표 3에 나타난 바와 같이， 미세조립체를 구성하는 모든 화합물이 광반응성기를 함유하는 경우 실시한 모든 흔합비율에서 액정의 수직배향 유도 및 선경사각 안정화가 실현되었다. 또한 분자의 자기조립에 의해 생성된 미세 조립체의 직경을 측정한 결과， 미세조립체의 직경은 양친매성 화합물과 친수성 분산상 액체의 흔합비에 따라 달라졌으며 , 양친매성 화합물의 비율이 높을수록 미세 조립체의 직경은 감소하였다. 구체적으로， 표 1에서의 실시번호 3의 경우 미세조립체의 평균입자직경은 약 200nm이었으며， 실시번호 7의 경우 약 10nm이었다. 실시예 1 In addition, it can be seen from the results of Examples 5 and 6 in Table 2 that when the ratio of the compound containing the photoreactive group in the composition for forming a liquid crystal layer is too low, the pretilt angle stabilization of the liquid crystal is difficult to be efficiently achieved. Therefore, in the mixing ratios in these examples, it is possible that all compounds constituting the microassembly contain a light semi-animal group can advantageously act to stabilize the pretilt angle. This is also supported by the experimental results of Table 3 above. As shown in Table 3, the vertical alignment induction and the pretilt angle stabilization of the liquid crystal were realized at all mixing ratios performed when all the compounds constituting the microassembly contained photoreactive groups. In addition, as a result of measuring the diameter of the microassembly generated by the self-assembly of the molecules, 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. Specifically, in the case of Example No. 3 in Table 1, the average particle diameter of the microassembly was about 200 nm, and in the case of Example No. 7, it was about 10 nm. Example 1
패턴화되지 않은 투명전극 (ITO) 및 피쉬본 형태로 패턴화된 화소전극 (ΠΌ)이 각각 형성된 제 1 및 제 2기판을 사용하여， 도 3에 제시된 액정표시장치의 제조공정에 따라 액정 표시 장치를 제조하였다.  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 ΠΌ patterned in the form of fishbone, respectively. Was prepared.
도 3을 참조하여 상세히 설명하면 , 제 1 및 제 2 기판 (11， 21)에 대해 저 U및 제 2전극 (12， 22)으로서 패턴화되지 않은 ΠΌ 투명전극 및 패턴화된 ITO 화소전극을 각각 형성하고， 세정제를 사용하여 증류수에서 초음파 세정한 후， 아세톤 및 이소프로필알코을로 각각 세정하고， 건조하였다. 별도의 배향처리 없이 상기 제 1 및 제 2기판에서의 투명전극과 화소전극이 서로 대향하도록 조립한 후, 음의 유전율 이방성을 가지는 액정호스트 100중량부에 대하여 액정 수직배향 유도제를 0.2중량부로 균일 혼합하여 제조한 에멀견화된 액정층 형성용 조성물을 주입하여 조립체를 제조하였다. 이때 , 액정 수직배향 유도제는 양친매성 화합물로서 스테아로일 글리세롤 (Stearoyl glycerol)과 친수성 액체로서 글리세를 (glycerol)을 80:20의 증량비로 균일하게 흔합하여 사용하였다. 액정 수직배향 유도제에 사용된 각각의 화합물은 액정호스트에 독립적으로는 용해되거나 분산되지 않았으나， 두 화합물을 균일하게 섞은 혼합물은 액정호스트에 쉽게 분산됨을 확인하였다. 또한， 상기 조립체 형성시 계 1기판과 제 2기판 사이의 간극은 4.0 ； urn로 유지하였으며， 액정층 형성용 조성물의 주입 공정은 상기 액정층 형성용 조성물의 등방상 온도인 90°C에서 실시하였다. 또한， 액정층 형성용 조성물의 주입 후， 분당 5°C의 속도로 상기 조립체를 냉각시켰다. Referring to FIG. 3 in detail, the unpatterned π 전극 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. In this case, 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. In addition, 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. . In addition, after the injection of the composition for forming a liquid crystal layer, the assembly was cooled at a rate of 5 ° C. per minute.
제조된 액정표시장치의 액정충내 액정의 배열상태를 편광현미경 및 코노스코피 (conoscopy) 를 이용하여 관찰하였다. 그 결과를 도 4a 및 도 4b에 각각 나타내었다.  The arrangement of the liquid crystal in the liquid crystal filling device of the manufactured liquid crystal display device was observed using a polarizing microscope and conoscopy. The results are shown in FIGS. 4A and 4B, respectively.
도 4a 및 도 4b에 나타난 바와 같이， 제조된 액정표시장치에서의 액정층은 직교 편광자 하에서 완전한 소광상태를 보였으며 . 코노스코피 이미지를 통해 액정분자가 기판 표면에 수직으로 배열되었음을 확인하였다. 이 같은 결과로부터 별도의 배향처리공정 없이도 액정 샐 내부에서 액정이 기판에 대하여 수직 방향으로 배열 가능함을 알 수 있다. 또한 상기 액정표시장치에 대해 T100 (최대 투과도 대비 투과율 100%)에 해당되는 세기의 전기장을 인가한 후 액정분자의 배향 상태를 관찰하였다. 그 결과， 전기장 인가 직후 액정 배열의 결함이 다수 발생하게 되었으나, 시간이 경과함에 따라 이들 결함이 천천히 제거됨을 확인하였다. 이는 액정분자가 전기장에 반응하여 전기장에 수직인 방향으로 재배열할 때 전기장에 반웅하는 방향이 랜덤하게 나타나기 때문에 발생하는 현상으로서 액정배열에 있어서 특정 방향으로의 균일한 선경사각이 형성되지 않았음을 나타내는 현상이다. 시험예 5 As shown in Figure 4a and 4b, in the liquid crystal display device manufactured The liquid crystal layer was completely quenched under orthogonal polarizer. Conoscopy images confirmed that the liquid crystal molecules were arranged perpendicular to the substrate surface. From this result, it can be seen that the liquid crystal can be arranged in the vertical direction with respect to the substrate in the liquid crystal sal without a separate alignment treatment process. In addition, the alignment state of the liquid crystal molecules was observed after applying an electric field having an intensity corresponding to T 100 (100% transmittance to maximum transmittance) with respect to the LCD. As a result, many defects in the liquid crystal array occurred immediately after the electric field was applied, but it was confirmed that these defects were slowly removed as time passed. This phenomenon occurs when the liquid crystal molecules are rearranged in a direction perpendicular to the electric field in response to the electric field, and the direction in which the reaction is reflected in the electric field appears randomly. Thus, there is no uniform pretilt angle in a specific direction in the liquid crystal array. It is a phenomenon exhibited. Test Example 5
하기 표 4에 나타난 바와 같은 비율로 양친매성 화합물로서 스테아로일 글리세롤과 친수성 액체로서 글리세롤을 흔합하여 제조된 액정 수직배향 유도제를 사용하고， 투명전극 및 화소전극으로서 패턴화되지 않은 ΠΌ 전극을 이용하며， 조립체 형성시 제 1기판과 제 2기판 사이의 간극을 ΙΟμιη로 유지하는 것을 제외하고는, 상기 실시예 1에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Using a 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 πΌ 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 ΙΟμιη when the assembly was formed.
제조된 액정표시장치에 대해 편광현미경 및 코노스코피 이미지를 이용하여 액정의 수직배향 여부 및 전기장 인가를 통한 선경사각 형성 여부를 확인하였다. 그 결과를 표 4에 나타내었다.  For the liquid crystal display, 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.
[표 4]  TABLE 4
Figure imgf000034_0001
4 90 10 0 .3 0 X
Figure imgf000034_0001
4 90 10 0 .3 0 X
5 95 5 0 .3 0 X 시험예 6 5 95 5 0.3 0 X Test Example 6
하기 표 5에 나타난 바와 같은 비율로 양친매성 화합물로서 스테아로일 글리세롤과 친수성 액체로서 광반응성기를 갖는 트리글리세를 디아크릴레이트 ( t r i gl ycero l di acryl at e )를 흔합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는, 상기 실시예 1에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  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.
제조된 액정표시장치에 대해 편광현미경 및 코노스코피 이미지를 이용하여 액정의 수직배향 여부 및 전기장 인가를 통한 선경사각 형성 여부를 확인하였다. 그 결과를 표 5에 나타내었다.  For the liquid crystal display, 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.
또한, 상기 제조된 액정표시장치에 대해 광 조사를 통한 배향 안정화 공정 실시 전， 액정표시장치에 대해 T100 (최대 투과도 대비 투과율 100%)에 해당되는 세기의 교류 전기장을 인가하고 전기장 인가 직후의 액정분자의 배향 상태를 관찰하였다 . 그 결과를 표 5에 나타내었다 . In addition, before performing the alignment stabilization process through light irradiation on the manufactured liquid crystal display device, an alternating current electric field having an intensity corresponding to T 100 (100% transmittance to maximum transmittance) is applied to the liquid crystal display device and the liquid crystal immediately after application of the electric field. The orientation state of the molecules was observed. The results are shown in Table 5.
또한， 추가적으로 상기 액정표시장치의 제 1 및 제 2기판 사이에 Τ100 (최대 투과도 대비 투과율 100%) 조건의 교류 전기장을 인가하여 , 결함이 최소화되고， 액정의 배열상태가 안정된 것올 확인한 후， 전기장이 인가된 조립체에 대해 320 내지 380nm 파장의 자외선을 100 mW/cm2 세기로 30분간 조사하였다. 이 같은 광조사에 의해 액정층 형성용 조성물 증에 에멀견화되어 분산되어 있던 광반웅성의 분산상 액체 화합물 중의 광반응성기가 광중합되어 기판 표면에 고체 박막화된다. In addition, by applying an alternating current electric field of Τ 100 (100% transmittance to maximum transmittance) condition between the first and second substrates of the liquid crystal display, after confirming that defects are minimized and the arrangement of the liquid crystals is stable, This applied assembly was irradiated with ultraviolet light of 320-380 nm wavelength for 30 minutes at 100 mW / cm 2 intensity. By such light irradiation, the photoreactive group in the photoreactive dispersed liquid compound emulsified and dispersed in the composition for forming a liquid crystal layer is photopolymerized to form a solid thin film on the substrate surface.
상기와 같은 광조사 공정 후 액정 표시 장치에 대해 전기장을 인가하여 스위칭시 액정 결함의 발생 여부를 관찰하였다. 그 결과를 표 5에 나타내었다.  After the above light irradiation process, an electric field was applied to the liquid crystal display to observe whether a liquid crystal defect occurred during switching. The results are shown in Table 5.
[표 5]  TABLE 5
Figure imgf000035_0001
1 70 30 0 . 3 0 0 0
Figure imgf000035_0001
1 70 30 0. 3 0 0 0
2 80 20 0 . 3 0 0 02 80 20 0. 3 0 0 0
3 90 10 0 . 3 0 0 03 90 10 0. 3 0 0 0
4 95 5 0 . 3 0 0 0 실험결과， 실시번호 1 내지 4에서 제작된 액정표시장치는 전기장 인가 하에서의 광조사 공정을 통해 모두 동일한 선경사각의 안정화 결과를 나타내었다. 4 95 5 0. 3 0 0 0 Experimental results, the liquid crystal display device produced in Examples 1 to 4 all showed the stabilization result of the same pretilt angle through the light irradiation process under the application of an electric field.
도 5a 내지 도 5c는 실시번호 2에서 제조된 액정표시장치에 대해 전기장 인가 전후 액정 배열의 변화를 편광현미경으로 관찰한 결과를 나타낸 것이다.  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.
일반적으로 기판에 대해 수직 배열된 액정층은 직교편광자 하에서 도 5a에 나타난 바와 같이 소광상태를 나타내며 , 이에 대해 전기장을 인가하면 액정분자가 전기장에 수직인 방향으로 희전하면서 투과도가 증가하게 된다 . 그러나 광 조사를 통한 배향 안정화 이전에는 액정분자가 특정 방향으로의 선경사각이 형성되어 있지 않기 때문에， 액정의 희전방향은 액정 샐의 부위에서 무작위로 일어나게 된다. 이 경우， 도 5b에 나타난 바와 같이 액정 배열의 결함이 다수 발생하게 되고, 이로 인한 액정표시장치의 특성 악화가 발생할 수 있다 . 그러나， 도 5b에 나타난 결함은 시간이 경과함에 따라 천천히 제거되며， 전기장 인가 이후 30초 ( sec )에 액정의 배열상태를 관찰했을 때 도 5c에서와 같이 균일한 밝음상태로 전이된다.  In general, a liquid crystal layer vertically aligned with respect to a substrate exhibits an extinction state as shown in FIG. 5A under a quadrature polarizer. When an electric field is applied thereto, the liquid crystal molecules are diluted in a direction perpendicular to the electric field and transmittance increases. However, since the liquid crystal molecules do not have a pretilt angle in a specific direction before the alignment stabilization through light irradiation, the electrolysis direction of the liquid crystal occurs randomly at the portion of the liquid crystal sal. In this case, as shown in FIG. 5B, a large number of defects in the liquid crystal array may occur, thereby deteriorating characteristics of the liquid crystal display. However, 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.
도 6a 내지 6c는 실시번호 2에서 제조된 액정표시장치에 대한 전기장 인가 후 결함이 최소화되고, 액정의 배열상태가 안정된 것을 확인하고， 이어서 320 내지 380nm 파장의 자외선을 100 mW/cm2 세기로 30분간 광 조사하고， 전기장 인가에 따른 스위칭시 액정 결함의 발생여부를 관찰한 결과를 나타낸 것이다. 6A to 6C confirm that defects are minimized after application of the electric field to the liquid crystal display device manufactured in Example 2, and that the arrangement of the liquid crystals is stabilized. Then, the ultraviolet rays of the 320 to 380 nm wavelength are reduced to 30 mW / cm 2 intensity. It shows the result of observing the occurrence of liquid crystal defects during the light irradiation for a minute, and switching when applying the electric field.
도 6a에 나타난 바와 같이， 초기 어둠상태 ( dark , b l ack )에서 위와 동일하게 T100 (최대 투과도 대비 투과율 100%)에 해당되는 세기의 전기장을 인가하면 액정이 반웅하여 배열상태가 바뀌게 되고， 이에 따라 액정의 광축이 기판면에서 편광자의 투과축과 45도의 각을 이루게 됨으로써 액정결함의 생성과정 없이 도 6b 및 도 6c에서와 같은 밝음 상태로 바로 전이됨을 관찰하였다. 이는 액정의 수직배향올 유도했던 액정 수직배향 유도제가 포함하고 있는 광반웅성기가 광 조사 과정에서 중합반웅을 통해 셀 내부 표면에서 액정분자가 전기장에 의해 형성된 특정방향으로의 선경사각을 안정화함으로써 나타나는 현상으로， 이를 통하여 액정의 반응속도 개선 및 소자의 밝기 및 대비비가 향상됨을 알 수 있다. As shown in FIG. 6A, when an electric field of an intensity corresponding to T 100 (100% transmittance to 100% transmittance) is applied in an initial dark state (dark, bl ack), the liquid crystal reacts to change the arrangement state. Accordingly, it was observed that the optical axis of the liquid crystal forms an angle of 45 degrees with the transmission axis of the polarizer on the substrate surface, thereby immediately transitioning to the bright state as shown in FIGS. 6B and 6C without generating a liquid crystal defect. This led to the vertical alignment of the liquid crystal This phenomenon occurs when the photoreaction device included in the liquid crystal vertical alignment inducing agent stabilizes the pretilt angle in the specific direction formed by the electric field on the inner surface of the cell through polymerization reaction during light irradiation. It can be seen that the improvement and the brightness and contrast ratio of the device are improved.
또한 앞서 광조사에 의한 안정화 처리가 되지 않은 도 5b와 광조사에 의한 안정화 처리가 된 도 6b를 비교했을 때， 안정화 처리가 된 도 6b는 결함의 발생이 제거되고， 반응속도도 빠르게 되므로 안정화 처리에 의해 소자의 전기광학적 특성을 향상시킬 수 있음을 알 수 있다. 시험예 7  In addition, when comparing FIG. 5B without stabilization by light irradiation with FIG. 6B with stabilization by light irradiation, stabilization is performed in FIG. 6B where stabilization is eliminated, and the reaction speed is also increased. It can be seen that it is possible to improve the electro-optical properties of the device. Test Example 7
하기 표 6에 나타난 바와 같은 비율로 양친매성 화합물로서 갤릭산 (gal l i c ac i d) 친수성기를 갖는 화합물 (A20 내지 A23 )과， 친수성 액체로서 광반응성기를 가지는 트리글리세를 디아크릴레이트를 흔합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는 상기 실시예 1에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Prepared by mixing a compound having a gallic acid (gal lic ac id) hydrophilic group (A20 to A23) as the amphiphilic compound and a triglyceride having a photoreactive group as a hydrophilic liquid at a ratio as shown in Table 6 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.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정올 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 6에 나타내었다.  With respect to the manufactured liquid crystal display device, the same method as in Test Example 6 was conducted, 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 6.
[표 6]  TABLE 6
Figure imgf000037_0001
A20 프로필 갈레이트 (Propyl gallate)
Figure imgf000037_0001
A20 Propyl gallate
A21 옥틸 갈레이트 (Octyl gallate)  A21 octyl gallate
A22 라우릴 갈레이트 (Lauryl gallate)  A22 Lauryl gallate
A23 하기 화학식 3의 갈레이트 유도체 (Gal late derivative)  A23 gal late derivative
Figure imgf000038_0001
Figure imgf000038_0001
실험결과, 실시번호 1의 액정표시장치에서는 액정의 수직배향이 유도되지 않았다. 이는 양친매성 화합물로서 사용된 프로필 칼레이트의 소수성기의 길이가 층분하지 못하여 효과적으로 에멀견화된 액정 조성물이 형성되지 못하였으며， 그 결과로 액정의 수직배향 유도가 되지 않음을 알 수 있다 . 한편， 실시번호 2 내지 4의 액정표시장치는 소수성 탄화수소기의 길이가 탄소수 8개 이상에 해당하는 길이이거나 이보다 긴 길이 일 때는 효과적으로 수직배향을 유도함을 확인할 수 있었다 .  As a result of the experiment, the vertical alignment of the liquid crystal was not induced in the liquid crystal display of Example No. 1. This shows that 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. On the other hand, 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.
또한， 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시했을때 , 분산상 액체에 포함된 광중합기에 의해 기판표면에 고체박막이 형성되고 액정의 선경사각을 효과적으로 안정화함을 알 수 있었다. 특히， 실시번호 4의 액정표시장치는 에멀견을 형성하는 양친매성 화합물과 분상상 친수성 액체 화합물 모두에 광증합성기가 포함되어 있어 보다 효율적으로 액정의 선경사각을 안정화시킬 수 있었다. 시험예 8  In addition, when stabilization of the orientation by light irradiation after applying the electric field in the induced vertical alignment state, a solid thin film is formed on the surface of the substrate by the photopolymerizer included in the dispersed phase liquid, and effectively stabilizes the pretilt angle of the liquid crystal. Could know. In particular, 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
하기 표 7에 나타난 바와 같은 비율로 양친매성 화합물로서 고리형의 다가알코올 유래 친수성기를 가지는 아스코르빅산 (arscorbic acid), 매나이드 (mannide) 글루코피라노사이드 (glucopyranoside)  Ascorbic acid and mannide glucopyranoside having a cyclic polyalcohol-derived hydrophilic group as an amphiphilic compound at a ratio as shown in Table 7 below.
글루코사이드 (glucoside) 유도체 (화합물 A33 내지 A40)과， 친수성 액체로서 글리세를 (glycerol)을 흔합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 실시예 1에서와 동일한 방법으로 실시하예 액정표시장치를 제조하였다. 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.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 7에 나타내었다. In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, and the liquid crystal alignment state and pretilt angle stabilization before and after light irradiation treatment were confirmed. The results are shown in Table 7. Indicated.
[표 7]  TABLE 7
Figure imgf000039_0002
Figure imgf000039_0002
•A33 아스코르빅산 6-팔미테이트 (Ascorbic acid 6-palmitate) • A33 Ascorbic acid 6-palmitate
A34 매나이드 모노올레이트 (Mannide monooleate)  A34 Mannide monooleate
A35 옥틸 글투코피라노사이드 (Octyl glucopyranoside)  A35 Octyl Glucopyranoside
A36 도데실글루코피라노사이드 (Dodecyl glucopyranoside)  A36 Dodecyl glucopyranoside
A37 메틸글루코사이드 세스퀴스테아레이트 (Methyl glucoside sesqui stearate)  A37 Methyl Glucoside Sesqui Stearate
A38: 메틸글루코사이드 디올레이트 (Methyl glucoside dioleate)  A38: methyl glucoside dioleate
A39： 글리코실옥시에틸 메타크릴레이트 (Glycosyloxyethyl methacrylate)  A39 ： Glycosyloxyethyl methacrylate
A40: 하기 화학식 글루코피라노사이드 유도체 (Glucopyranoside der i vat ive) - = CH, A40: Glucopyranoside der i vat ive of the formula:-CH,
Figure imgf000039_0001
Figure imgf000039_0001
CH3 (4) CH 3 (4)
실험결과， 실시번호 1 내지 8의 액정표시장치 모두에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 그러나 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 때， 분산상 액체 화합물이 광중합성기를 포함하지 않으므로 양친매성 화합물이 광중합성기를 가지는 실시번호 7 및 8의 액정표시장치에서만 액정의 선경사각 안정화 효과가 나타났다. 시험예 9 As a result of the experiment, it was confirmed that the liquid crystal composition emulsified in all of the liquid crystal display devices of Examples 1 to 8 induced vertical alignment in the liquid crystal device. But Liquid crystal display apparatuses of Nos. 7 and 8, wherein the amphiphilic compound has a photopolymerizable group because the liquid phase compound does not contain a photopolymerizable group when stabilization of the orientation by light irradiation after applying an electric field in the induced vertical alignment state. Only the pretilt angle stabilization effect of the liquid crystal appeared. Test Example 9
하기 표 8에 나타난 바와 같은 비율로 양친매성 화합물로서 고리형의 다가알코올 유래 친수성기를 가지는 소르비탄 (sorbitan)유도체 (화합물 A1 내지 A7)와 친수성 액체로서 트리글리세롤 디아크릴레이트 (triglycerol diacrylate)를 사용하거나, 또는 양친매성 화합물로서 폴리옥시에틸렌 소르비탄 유도체 (화합물 A8 내지 A16)과 친수성 액체로서 글리세를 (glycerol)을 사용하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Using 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.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 8에 나타내었다.  In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, and the liquid crystal alignment state and pretilt angle stabilization before and after light irradiation treatment were confirmed. The results are shown in Table 8.
[표 8]  TABLE 8
Figure imgf000040_0001
7 A7 80 20 0.1 0 0 0
Figure imgf000040_0001
7 A7 80 20 0.1 0 0 0
8 A8 80 20 0.1 0 - X8 A8 80 20 0.1 0-X
9 A9 70 30 0.3 0 - X9 A9 70 30 0.3 0-X
10 A10 70 30 0.3 0 - X10 A10 70 30 0.3 0-X
11 All 70 30 0.3 0 - X11 All 70 30 0.3 0-X
12 A12 70 30 0.3 0 - X12 A12 70 30 0.3 0-X
13 A13 70 30 0.3 0 ― X13 A13 70 30 0.3 0-X
14 A14 70 30 0.3 0 - X14 A14 70 30 0.3 0-X
15 A15 70 30 0.3 0 - X15 A15 70 30 0.3 0-X
16 A16 70 30 0.3 0 - X 16 A16 70 30 0.3 0-X
A1: 소르비탄 모노라우레이트 (Sorbitan monolaurate, Span™ 20)A1: Sorbitan monolaurate (Span ™ 20)
A2: 소르비탄 모노팔미테이트 (Sorbitan monopa Imitate, Span™ 40)A2: Sorbitan monopa Imitate (Span ™ 40)
A3: 소르비탄 모노스테아레이트 (Sorbitan monostearate, Span™ 60)A3: Sorbitan monostearate (Span ™ 60)
A4: 소르비탄 트리스테아레이트 (Sorbitan tristearate, Span™ 65)A4: Sorbitan tristearate (Span ™ 65)
A5: 소르비탄 모노올레이트 (Sorbitan monooleate, Span™ 80) A5: Sorbitan monooleate (Span ™ 80)
A6: 소르비탄 세스퀴올레이트 (Sorbitan sesquioleate, Span™ 83) A6: Sorbitan sesquioleate (Span ™ 83)
A7: 소르비탄 트리올레이트 (Sorbitan trioleate, Span™ 85) A7: Sorbitan trioleate (Span ™ 85)
A8: 폴리에틸렌글리콜 소르비탄 모노라우레이트 (Polyethyleneglycol sorbitan monolaurate, Tween™ 20)  A8: polyethyleneglycol sorbitan monolaurate, Tween ™ 20
A9: 폴리에틸렌소르비탄 모노라우레이트 (Polyoxyethylenesorbitan monolaurate, Tween™ 21)  A9: Polyoxyethylenesorbitan monolaurate, Tween ™ 21
A10: 폴리에틸렌소르비탄 모노팔미테이트 (Polyoxyethylenesorbitan monopa Imitate, Tween™ 40)  A10: Polyoxyethylenesorbitan monopa Imitate, Tween ™ 40
All: 폴리옥시에틸렌소르비탄 모노스테아레이트 All: polyoxyethylene sorbitan monostearate
(Polyoxyethylenesorbitan monostearate , Tween™ 60) (Polyoxyethylenesorbitan monostearate, Tween ™ 60)
A12: 폴리옥시에틸렌소르비탄 트리스테아레이트 A12: polyoxyethylene sorbitan tristearate
(Polyoxyethylenesorbitan tristearate, Tween™ 65) (Polyoxyethylenesorbitan tristearate, Tween ™ 65)
A13: 폴리옥시에틸렌소르비탄 모노올레이트 (Polyoxyethylenesorbitan monooleate , Tween™ 80)  A13: Polyoxyethylenesorbitan monooleate, Tween ™ 80
A14: 폴리옥시에틸렌소르비탄 트리을레이트 (Polyoxyethylenesorbitan trioleate, Tween™ 85)  A14: Polyoxyethylenesorbitan trioleate, Tween ™ 85
A15: 폴리옥시에틸렌소르비탄 스테아레이트 (Polyoxyethylenesorbitan st ear ate, Tween™ 61)  A15: Polyoxyethylenesorbitan st ear ate, Tween ™ 61
A16: 폴리옥시에틸렌소르비탄 을레이트 (Polyoxyethylenesorbitan oleate, Tween™ 81)  A16: Polyoxyethylenesorbitan oleate (Tween ™ 81)
실험결과， 실시번호 1 내지 16의 액정표시장치 모두에서 에멀젼화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. Experimental results, emulsified in all of the liquid crystal display device of Examples 1 to 16 It was confirmed that the liquid crystal composition induces vertical alignment in the liquid crystal device.
그러나, 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 때， 광중합성 친수성액체를 사용한 실시번호 1 내지 7의 경우에만 선경사각 안정화 효과가 나타고， 광중합성기를 포함하지 않는 액정조성물을 사용한 실시번호 8 내지 16에서는 액정의 선경사각 안정화 효과가 나타나지 않음을 확인하였다.  However, when stabilization of the orientation by light irradiation after application of the electric field in the induced vertical orientation state, the pretilt angle stabilization effect was exhibited only in the case of Run Nos. 1 to 7 using the photopolymerizable hydrophilic liquid. In Examples Nos. 16 to 16 using the liquid crystal composition not included, it was confirmed that the pretilt angle stabilization effect of the liquid crystal did not appear.
도 7a 내지 7c는 실시번호 2에 대하여 광조사하기 이전의 전기광학 스위칭 특성을 나타낸 편광현미경 사진이다. 동일한 액정소자에 대해 전기장 인가 하에서 광안정화를 실시한 후의 전기광학 스위칭 특성을 나타낸 편광현미경 사진을 도 8a 내지 도 8c에 나타내었다.  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.
광조사에 의한 안정화 처리가 되지 않은 도 7a 내지 7c와 광조사에 의한 안정화 처리가 된 도 8a 내지 8c를 비교했을 때， 이전의 시험예에서와 같이 안정화 처리가 된 도 8b 및 8c에서는 결함의 발생이 제거되고, 반응속도가 빠르게 되며 휘도가 증가하게 되므로 안정화 처리에 의해 소자의 전기광학적 특성을 향상시킬 수 있음을 알 수 있다. 시험예 10  When comparing Figs. 7A to 7C without stabilization by light irradiation with Figs. 8A to 8C with stabilization by light irradiation, defects are generated in Figs. 8B and 8C where stabilization is performed as in the previous test example. It can be seen that the electro-optical properties of the device can be improved by the stabilization process since the removal, the reaction speed is increased, and the brightness is increased. Test Example 10
하기 표 9에 나타난 바와 같은 비율로 양친매성 화합물로서 글리세롤 유도체 유래 친수성기를 가지는 화합물 (A24 내지 A32 )과, 친수성 액체로서 광반웅성기를 가지는 트리글리세를 모노메타아크릴레이트 ( t r i g l ycero l monomethacry l at e )를 혼합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 실시예 1에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Compounds having a glycerol derivative-derived hydrophilic group (A24 to A32) as an amphiphilic compound at a ratio as shown in Table 9 below, and triglyceride having a photobanung group as a hydrophilic liquid are monomethacrylate (trigl ycero l monomethacry l at e A liquid crystal display was manufactured in the same manner as in Example 1, except that the liquid crystal vertical alignment inducing agent prepared by mixing the same) was used.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고 , 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 9에 나타내었다.  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.
[표 9]  TABLE 9
Figure imgf000042_0001
함량
Figure imgf000042_0001
content
(중량 %)  (weight %)
1 A24 80 20 0.3 0 0 0 1 A24 80 20 0.3 0 0 0
2 A25 80 20 0.3 0 0 02 A25 80 20 0.3 0 0 0
3 A26 80 20 0.3 0 0 03 A26 80 20 0.3 0 0 0
4 A27 80 20 0.3 0 0 04 A27 80 20 0.3 0 0 0
5 A28 80 20 0.3 0 0 05 A28 80 20 0.3 0 0 0
6 A29 80 20 0.3 0 0 06 A29 80 20 0.3 0 0 0
7 A30 80 20 0.3 0 0 07 A30 80 20 0.3 0 0 0
8 A31 80 20 0.3 0 0 08 A31 80 20 0.3 0 0 0
9 A32 70 30 0.3 0 0 0 9 A32 70 30 0.3 0 0 0
A24: 스테아로일 글리세롤 (Stearoyl glycerol) A24: Stearoyl glycerol
A25: 디팔미토일 글리세를 (Dipalmitoyl glycerol )  A25: Dipalmitoyl glycerol
A26: 디옥타데카노일 글리세를 (Dioctadecanoyl glycerol)  A26: Dioctadecanoyl glycerol
A27: 팔미토일 글리세롤 (Palmitoyl glycerol )  A27: Palmitoyl glycerol
A28: 모노핵人 ]·데 ^ 1"노일 글리세를 (Monohexadecanoyl glycerol , palmi t in)  A28: mononuclear man] de ^ 1 "monoglycerides (Monohexadecanoyl glycerol, palmi t in)
A29: 디핵사데카노일 글리세를 (Dihexadecanoyl glycerol , dipalmit in) A30: 옥타데실 글리세를 (Octadecyl glycerol , batyl alcohol)  A29: Dihexadecanoyl glycerol, dipalmit in A30: Octadecyl glycerol (batyl alcohol)
A31: 올레오일 글리세롤 (Oleoyl glycerol)  A31: Oleoyl glycerol
A32: 트리글리세를 모노스테아레이트 (Tr iglycerol monost earat e) 실험결과， 실시번호 1 내지 9의 액정표시장치 모두에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 또한， 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시했올 때에도 안정화된 선경사각을 나타내었다. 이 같은 결과는 친수성 액체에 포함된 광증합기에 의해 기판 표면에 고체 박막이 형성되고， 이로 인해 액정의 선경사각이 효과적으로 안정화된 것임을 알 수 있다. 시험예 11  A32: Triglyceride monostearate (Tr iglycerol monost earat) Experimental results, it was confirmed that the liquid crystal composition emulsified in all of the liquid crystal display device of Examples 1 to 9 induce vertical alignment in the liquid crystal device. In addition, the stabilized pretilt angle was also observed when the alignment was stabilized by light irradiation after the electric field was applied in the induced vertical alignment state. This result indicates that a solid thin film is formed on the surface of the substrate by the photopolymerizer included in the hydrophilic liquid, and thus, the pretilt angle of the liquid crystal is effectively stabilized. Test Example 11
하기 표 10에 나타난 바와 같은 비율로 양친매성 화합물로서 이중고리형의 다가알코올 친수성기를 갖는 말토사이드 (maltoside)유도체 (화합물 A41 내지 A48)과， 친수성 액체로서 광반웅성기를 포함하지 않는 글리세롤 (glycerol)을 혼합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제초하였다. 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. Using liquid crystal vertical alignment inducer prepared by mixing Except that, the liquid crystal display was herbicized in the same manner as in Test Example 5.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고 , 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다 . 그 결과를 표 10에 나타내었다.  In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, 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 10.
[표 10]  TABLE 10
Figure imgf000044_0001
Figure imgf000044_0001
A41: 옥틸 말토사이드 (Octyl matoside)  A41: Octyl matoside
A42: 사이클로핵실핵실 말토사이드 (Cyclohexylhexyl maltoside)  A42: Cyclohexylhexyl maltoside
A43: 데실 말토사이드 (Decyl maltoside)  A43: Decyl maltoside
A44: 운데실 말토사이드 (Undecyl maltoside)  A44: Undecyl maltoside
A45: 도데실 말토사이드 (Dodecyl maltoside)  A45: Dodecyl maltoside
A46: 트리데실 말토사이드 (Tridecyl maltoside)  A46: Tridecyl maltoside
A47: 테트라데실 말토사이드 (Tetradecyl maltoside)  A47: Tetradecyl maltoside
A48: 핵사데실 말토사이드 (Hexadecyl maltoside)  A48: Hexadecyl maltoside
실험결과， 실시번호 1 내지 8의 액정표시장치 모두에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 그러나, 액정 조성물 내에 광중합성기를 포함하는 화합물이 존재하지 않으므로， 광조사를 이용한 배향의 안정화를 실시하지 않았다. 그 결과 모든 실시예에서 선경사각은 안정화되지 않았다. 시험예 12 As a result of the experiment, it was confirmed that the liquid crystal composition emulsified in all of the liquid crystal display devices of Examples 1 to 8 induced vertical alignment in the liquid crystal device. However, since the compound containing a photopolymerizable group does not exist in a liquid crystal composition, stabilization of the orientation using light irradiation was not performed. As a result all In the examples the pretilt angle was not stabilized. Test Example 12
하기 표 11에 나타난 바와 같은 비율로 양친매성 화합물로서 1가 알코을 유래 친수성기를 가지는 화합물 (A49 내지 A53) 또는 2가 알코을 유래 친수성기를 가지는 화합물 (A54 내지 A56)과， 친수성 액체로서 광반웅성기를 가지는 트리글리세를 디아크릴레이트 (triglycerol diacrylate)를 흔합하여 제조된 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Compounds having a hydrophilic group derived from monohydric alcohol (A49 to A53) or compounds having a hydrophilic group derived from divalent alcohol (A54 to A56) as an amphiphilic compound at a ratio as shown in Table 11 below, and having a photobanic group as a hydrophilic liquid Triglycerides were prepared in the same manner as in Test Example 5, except that the prepared liquid crystal vertical alignment inducing agent prepared by mixing triglycerol diacrylate was manufactured to manufacture a liquid crystal display device.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 11에 나타내었다.  In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, and the liquid crystal alignment state and pretilt angle stabilization before and after light irradiation treatment were confirmed. The results are shown in Table 11.
[표 11] TABLE 11
Figure imgf000045_0001
Figure imgf000045_0001
A49: 1-핵산올 (1-Hexanol) A49: 1-nuxol (1-Hexanol)
A51: 1-도데칸올 (l-Dodecanol)  A51: 1-dodecanol
A52: 1-핵사데칸올 (1-Hexadecanol) A53: 1-옥타데칸올 (1-Octadecanol) A52: 1-nuxadecanol A53: 1-octadecanol (1-Octadecanol)
A54: 1,2-핵산디올 (l,2-Hexanediol)  A54: 1,2-nucleic acid diol (l, 2-Hexanediol)
A55: 1，2-도데칸디올 (1,2-Dodecanediol)  A55: 1,2-dodecanediol
A56： 1 , 2-핵사데칸디올 ( 1， 2-Hexadecaned iol)  A56: 1, 2-nuxadecanediol (1, 2-Hexadecaned iol)
실험결과， 실시번호 1 및 5의 액정표시장치의 경우 액정 조성물이 액정장치 내에서 수직배향을 유도하지 못하였다. 이는 액정조성물의 제조시 사용된 양친매성 화합물 (A49, A50, 및 A54)의 소수성기의 길이가 충분하지 못하여 효과적으로 에멀견화된 액정 조성물을 형성하지 못함에 따라 액정의 수직배향 유도가 되지 않았기 때문이다. 그러나, 소수성 탄화수소기의 길이가 탄소수 8개에 해당하는 길이보다 긴 양친매성 화합물을 포함하는 이외 실시예들에서의 액정표시장치의 경우에는 액정의 수직배향을 유도됨을 확인할 수 있었다. 또한， 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 경우， 친수성 액체에 포함된 광중합기에 의해 기판 표면에 고체박막이 형성되고， 그 결과로 액정의 선경사각이 효과적으로 안정화되었음을 알 수 있었다. 시험예 13  As a result of the experiment, 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. However, it was confirmed that 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. In addition, when the alignment is stabilized by light irradiation after applying an electric field in the induced vertical alignment state, a solid thin film is formed on the surface of the substrate by a photopolymerizer included in the hydrophilic liquid, and as a result, the pretilt angle of the liquid crystal is increased. It was found to be effectively stabilized. Test Example 13
하기 표 12에 나타난 바와 같은 비율로 양친매성 화합물로서 1-아민 (1-amine) 유래 친수성기를 가지는 화합물 (A62 내지 A64) 또는 1， 2- 디아민 (l,2-diamine) 유래 친수성기를 가지는 화합물 (A65)과， 친수성 액체로서 광반웅성기를 가지는 트리글리세롤 디아크릴레이트를 흔합하여 제조된 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는, 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다. 제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 12에 나타내었다.  Compounds having a 1-amine (1-amine) -derived hydrophilic group (A62 to A64) or a 1, 2-diamine (l, 2-diamine) -derived hydrophilic group in the ratio as shown in Table 12 ( A65) and a liquid crystal display apparatus, which was carried out in the same manner as in Test Example 5, except that a liquid crystal vertical alignment inducing agent prepared by mixing triglycerol diacrylate having a photobanung group as a hydrophilic liquid was used. Was prepared. In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, and the liquid crystal alignment state and pretilt angle stabilization before and after light irradiation treatment were confirmed. The results are shown in Table 12.
[표 12]  TABLE 12
Figure imgf000046_0001
함량
Figure imgf000046_0001
content
(중량 ¾)  (Weight ¾)
1 A62 80 20 0.3/1.0 0 0 0 1 A62 80 20 0.3 / 1.0 0 0 0
2 A63 80 20 0.4 0 0 02 A63 80 20 0.4 0 0 0
3 A64 80 20 0.3 0 0 03 A64 80 20 0.3 0 0 0
4 A65 80 20 0.2 0 0 0 4 A65 80 20 0.2 0 0 0
A62: 옥틸아민 (Octylamine) A62: octylamine
A63: 데실아민 (Decylamine)  A63: Decylamine
A64: 도데실아민 (Dodecylamine)  A64: Dodecylamine
A65: 핵사데칸 1,2—디아민 (Hexadecane 1 , 2-diamine)  A65: nuxadecane 1,2-diamine
실험결과， 실시번호 1 내지 4의 액정표시장치에서 에멀젼화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 또한， 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 경우， 친수성 액체에 포함된 광중합기에 의해 기판표면에 고체박막이 형성되고， 그 결과로 액정의 선경사각이 효과적으로 안정화됨올 알 수 있었다 . 시험예 14  Experimental results, it was confirmed that the liquid crystal composition emulsified in the liquid crystal display device of Examples 1 to 4 induce vertical alignment in the liquid crystal device. In addition, when the orientation is stabilized by light irradiation after applying an electric field in the induced vertical alignment state, a solid thin film is formed on the surface of the substrate by the photopolymerizer included in the hydrophilic liquid, and as a result, the pretilt angle of the liquid crystal is increased. It was found to be effectively stabilized. Test Example 14
하기 표 13에 나타난 바와 같은 비율로 양친매성 화합물로서 카르복실산 유래 친수성기를 가지는 화합물 (A57 내지 A61) 또는 포스페이트 유래 친수성기를 가지는 화합물 (A66 및 A67) 또는 1-티을 유래 친수성기를 가지는 화합물 (A68 및 A69)과， 친수성 액체로서 광반웅성기를 가지는 트리글리세를 디아크릴레이트를 혼합하여 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Compounds having carboxylic acid-derived hydrophilic groups (A57 to A61) or phosphate-derived hydrophilic groups (A66 and A67) or compounds having a hydrophilic group derived from 1-T as the amphiphilic compound at a ratio as shown in Table 13 below (A68 and A69) and a liquid crystal display device in the same manner as in Test Example 5 except for using a liquid crystal vertical alignment inducing agent prepared by mixing diacrylate with triglyceride having a photobanung group as a hydrophilic liquid. Prepared.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고, 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 13에 나타내었다.  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.
[표 13]
Figure imgf000047_0001
번 화합물 화합물 함량 조성물 중 광조 광조 안정화 호 方 ¾ Ξ TABLE 13
Figure imgf000047_0001
Light compound stabilization in the composition
ΤΓ 의 함량 (중량 % 액정수직배 사 전 사 후 여부 Content of ΤΓ (Weight% before or after
(중량 ) 향 유도제의 (Weight) of fragrance inducer
함량  content
(중량 %)  (weight %)
1 A57 80 20 0.5 0 0 0 1 A57 80 20 0.5 0 0 0
2 A58 80 20 0.4 0 0 02 A58 80 20 0.4 0 0 0
3 A59 80 20 0.4 0 0 03 A59 80 20 0.4 0 0 0
4 A60 80 20 0.3 0 0 04 A60 80 20 0.3 0 0 0
5 A61 80 20 0.3 0 0 05 A61 80 20 0.3 0 0 0
6 A66 80 20 0.3 0 0 06 A66 80 20 0.3 0 0 0
7 A67 80 20 0.3 0 0 07 A67 80 20 0.3 0 0 0
8 A68 80 20 0.3 0 0 08 A68 80 20 0.3 0 0 0
9 A69 80 20 0.3 0 0 0 9 A69 80 20 0.3 0 0 0
A57: 옥탄산 (Octanoic acid) A57: Octanoic acid
A58: 데칸산 (Decanoic acid)  A58: Decanoic acid
A59: 도데칸산 (Dodecanoic acid)  A59: Dodecanoic acid
A60: 핵사데칸산 (Hexadecanoic acid, Palmitic acid)  A60: Hexadecanoic acid, Palmitic acid
A61: 옥타데칸산 (Octadecanoic acid, Stearic acid)  A61: Octadecanoic acid (Stearic acid)
A66: 디핵人 1"데실 포스페이트 (Dihexadecyl phosphate)  A66: Dihexadecyl phosphate
A67: 데실포스폰산 (Decylphosphonic acid)  A67: Decylphosphonic acid
A68: 1-도데칸티올 (1-Dodecanethiol)  A68: 1-dodecanethiol
A69: 1-핵사데칸티을 ( l-Hexadecanethiol )  A69: l-Hexadecanethiol
실험결과， 모든 실시예 (실시번호 1 내지 9)의 액정표시장치에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 이 같은 결과는 소수성 탄화수소기의 길이가 모두 탄소수 8개 이상인 양친매성 화합물을 포함함에 따라 효과적으로 액정호스트내에서 에멀견화되었기 때문이다. 또한， 실시번호 1 내지 9의 액정표시장치는 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 때， 친수성 액체에 포함된 광중합기에 의해 기판표면에' 고체박막ᅳ이 형성되고, 그 —결과로 액정의 선경사각이 효과적으로 안정화됨을 알 수 있었다. . 시험예 15 하기 표 14에 나타난 바와 같은 비율로 양친매성 화합물로서 친수성 에틸렌 글리콜 또는 폴리옥시에틸렌 헤드그룹을 가지는 화합물 (A70 내지 A78)과， 친수성 액체로서 광반응성기를 가지는 트리글리세롤 디아크릴레이트를 흔합하여 제조된 제조된 액정 수직배향 유도제를 사용하는 것을 제외하고는， 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다. As a result of the experiment, it was confirmed that the liquid crystal compositions emulsified in the liquid crystal display devices of all the examples (Examples 1 to 9) induce vertical alignment in the liquid crystal device. This result is because the hydrophobic hydrocarbon group was all emulsified in the liquid crystal host as including the amphiphilic compound having all eight or more carbon atoms. Further, in Nos. 1 to 9. 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.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로， 전기장 인가 및 광조사 공정을 실시하고 , 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 14에 나타내었다.  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.
[표 14]  TABLE 14
Figure imgf000049_0001
Figure imgf000049_0001
A70: 에틸렌 글리콜 스테아레이트 (Ethylene glycol stearate)  A70: ethylene glycol stearate
A71: 폴리옥시에틸렌산 (Polyoxyethylene acid: Polyoxyethylene (8) stearate (Myr j™ 45))  A71: polyoxyethylene acid: Polyoxyethylene (8) stearate (Myr j ™ 45)
A72: 폴리옥시에틸렌 (2) 스테아릴 에테르 (Polyoxyethylene (2) stearyl ether (Brij™ S2))  A72: polyoxyethylene (2) stearyl ether (Brij ™ S2)
A73: 폴리옥시에틸렌 (4) 라우릴 에테르 (Polyoxyethylene (4) lauryl 표 A73: polyoxyethylene (4) lauryl ether table
1  One
ether (B 5ri j™ L4))  ether (B 5ri j ™ L4))
A74: 폴리옥시에틸렌 (2) 세틸 에테르 (Polyoxyethylene (2) cetyl ether (Brij™ 52))  A74: Polyoxyethylene (2) cetyl ether (Brij ™ 52)
A75: 폴리옥시에틸렌 (20) 세틸 에테르 (Polyoxyethylene (20) cetyl ether (Brij™ 58))  A75: polyoxyethylene (20) cetyl ether (Brij ™ 58)
A76: 폴리옥시에틸렌 (2) 올레일 에테르 (Polyoxyethylene (2) oleyl ether (Brij™ 93))  A76: Polyoxyethylene (2) oleyl ether (Brij ™ 93)
A77: 폴리옥시에틸렌 (20) 올레일 에테르 (Polyoxyethylene (20) oleyl ether (Brij™ 98))  A77: Polyoxyethylene (20) oleyl ether (Brij ™ 98)
A78: 폴리옥시에틸렌 (10) 스테아릴 에테르 (Polyoxyethylene (10) stearyl ether (Brij™ S10))  A78: polyoxyethylene (10) stearyl ether (Brij ™ S10)
실험결과， 모든 실시예 (실시번호 1 내지 9)의 액정표시장치에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 또한， 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 때， 친수성 액체에 포함된 광중합기에 의해 기판표면에 고체박막이 형성되고 그 결과로 액정의 선경사각이 효과적으로 안정화됨을 알 수 있었다. 시험예 16  As a result of the experiment, it was confirmed that the liquid crystal compositions emulsified in the liquid crystal display devices of all the examples (Examples 1 to 9) induce vertical alignment in the liquid crystal device. In addition, when stabilization of the orientation by irradiation with light after applying the electric field in the induced vertical alignment state, a solid thin film is formed on the surface of the substrate by the photopolymerizer contained in the hydrophilic liquid, and as a result, the pretilt angle of the liquid crystal is effectively It was found to be stabilized. Test Example 16
하기 표 15에 나타난 바와 같은 비율로 하기 표 15에 기재된 양친매성 화합물 (A4, A19, A25, A23， A33, A34, A36, A48, A61, A65 및 A66)과 친수성 액체로서 광반옹성기를 가지는 트리글리세를 디아크릴레이트를 흔합하여 제조된 액정 수직배향 유도제를 사용하고, 조립체의 형성시 제 1기판과 제 2기판 사이의 간격을 10.0/Λΐι로 유지하는 것을 제외하고는, 상기 시험예 5에서와 동일한 방법으로 실시하여 액정표시장치를 제조하였다.  Triglycerides having a photoreflective group as a hydrophilic liquid with the amphiphilic compounds (A4, A19, A25, A23, A33, A34, A36, A48, A61, A65 and A66) shown in Table 15 below at a ratio as shown in Table 15 below. Is the same as in Test Example 5 except for using a liquid crystal vertical alignment guide prepared by mixing diacrylate, and maintaining the distance between the first substrate and the second substrate at 10.0 / Λΐι at the time of forming the assembly The liquid crystal display device was manufactured by the method.
제조된 액정표시장치에 대해 상기 시험예 6에서와 동일한 방법으로, 전기장 인가 및 광조사 공정을 실시하고， 광조사 처리 전 후의 액정배향 상태 및 선경사각 안정화 여부를 확인하였다. 그 결과를 표 15에 나타내었다.
Figure imgf000050_0001
번 화합물 화합물 함량 조성물 중 광조 광조 안정화 호 조方 a In the same manner as in Test Example 6, an electric field application and light irradiation process were performed on the manufactured liquid crystal display device, 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 15.
Figure imgf000050_0001
Light compound light composition stabilization
ΤΓ 의 함량 (중량 % 액정수직배 사 전 사 후 여부 (중량 ¾>) ) 향 유도제의  Content of ΤΓ (Weight% before or after liquid crystal vertical vertical (weight ¾>))
함량  content
(중량 %)  (weight %)
1 A36 95 5 0.1 0 0 0 1 A36 95 5 0.1 0 0 0
2 A48 95 5 0.1 0 0 02 A48 95 5 0.1 0 0 0
3 A23 95 5 0.2 0 0 03 A23 95 5 0.2 0 0 0
4 A4 95 5 2.0 0 0 04 A4 95 5 2.0 0 0 0
5 A19 95 5 0.3 0 0 05 A19 95 5 0.3 0 0 0
6 A25 95 5 1.5 0 0 06 A25 95 5 1.5 0 0 0
7 A65 95 5 2.0 0 0 07 A65 95 5 2.0 0 0 0
8 A33 95 5 1.5 0 0 08 A33 95 5 1.5 0 0 0
9 A34 95 5 1.5 0 0 09 A34 95 5 1.5 0 0 0
10 A61 95 5 2.0 0 0 010 A61 95 5 2.0 0 0 0
11 A66 95 5 2.0 0 0 0 11 A66 95 5 2.0 0 0 0
A4: 소르비탄 트리스테아레이트 (Sorbitan tristearate, Span™ 65) A19: 펜타에리쓰리톨 모노아크릴레이트 모노스테 0 레이트 (Pentaerythr itol monoacryl ate monostearate) A4: sorbitan tristearate (Sorbitan tristearate, Span ™ 65) A19: pentaerythritol monoacrylate monostearyl zero rate (Pentaerythr itol monoacryl ate monostearate) in
A23: 하기 화학식 3의 갈레이트 유도체 (Gal late derivative)  A23: gal late derivative of Formula 3
Figure imgf000051_0001
Figure imgf000051_0001
A25: 디팔미토일 글리세롤 (Dipalmitoyl glycerol)  A25: Dipalmitoyl glycerol
A33: 아스코르빅산 6-팔미테이트 (Ascorbic acid 6-palmitate)  A33: Ascorbic acid 6-palmitate
A34: 매나이드 모노올레이트 (Mannide monooleate)  A34: Mannide monooleate
A36: 도데실글루코피라노사이드 (Dodecyl glucopyranoside)  A36: Dodecyl glucopyranoside
A48: 핵사데실 말토사이드 (Hexadecyl maltoside)  A48: Hexadecyl maltoside
A61： 옥타데칸산 (Octadecanoi c acid, Stearic acid)  A61 ： Octadecanoic acid (Octadecanoi c acid, Stearic acid)
A65: 핵人! "데칸 1,2—디 ο|·민 (Hexadecane 1,2— diamine)  A65: A nuclear man! Decane 1,2—di ο | · min (Hexadecane 1,2— diamine)
A66: 디핵사데실 포스페이트 (Dihexadecyl phosphate) 실험결과, 모든 실시예 (실시번호 1 내지 11 )의 액정표시장치에서 에멀견화된 액정 조성물이 액정장치 내에서 수직배향을 유도함을 확인하였다. 또한, 유도된 수직배향 상태에서 전기장을 인가한 후 광조사에 의한 배향의 안정화를 실시하였을 때， 친수성 액체에 포함된 광중합기에 의해 기판표면에 고체박막이 형성되고 그 결과로 액정의 선경사각이 효과적으로 안정화됨을 알 수 있었다 . A66: Dihexadecyl phosphate As a result of the experiment, it was confirmed that the liquid crystal compositions emulsified in the liquid crystal display devices of all Examples (Examples 1 to 11) induce vertical alignment in the liquid crystal device. In addition, when stabilization of the orientation by light irradiation after application of an electric field in the induced vertical alignment state, a solid thin film is formed on the surface of the substrate by the photopolymerizer included in the hydrophilic liquid, and as a result, the pretilt angle of the liquid crystal is effectively It was found to be stabilized.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.  Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.
[부호의 설명 ]  [Description of the code]
1， 11 게 1기판  1, 11 Crab 1 Board
1 '， 21 제 2기판  1 ′, 21 2nd board
2， 12 제 1전극  2, 12 first electrode
2 ' , 22 제 2전극  2 ', 22 2nd electrode
3， 3 ' 고분자 배향막  3 ， 3 'polymer alignment film
4， 13a 액정층 형성용 조성물  4, 13a liquid crystal layer forming composition
13b 액정층  13b liquid crystal layer
14， 24 액정 수직배향 및 광안정화 층  14, 24 vertical alignment and light stabilization layer
산업상 이용가능성  Industrial availability
본 발명은 액정 수직배향 유도제 및 이를 이용하여 제조된 액정표시장치에 관한 것으로서， 상기 액정 수직배향 유도제는 선 배향처리 공정 없이 액정의 수직배향을 유도하고， 액정의 선경사각을 안정화시키며 , 그 결과로 액정표시장치의 제조공정을 단순화하고 액정표시장치의 성능 및 신뢰성을 향상시킬 수 있다 .  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.

Claims

청구범위 Claims
[청구항 1] [Claim 1]
분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함 하는 양친매성 화합물 ; 및 Amphipathic compounds containing 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule; and
단분자의 친수성 액체 Monomolecular hydrophilic liquid
를 포함하는 액정 수직배향 유도제 . A liquid crystal vertical alignment inducing agent containing a.
[청구항 2] [Claim 2]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 친수성기로서 알코올, 다가알코올, 아민, 다가 아민 , 티올， 다가티올， 폴리옥시에틸렌 , 카르복실산， 다가카르복실산， 설 포닉산 (sulfonic acid), 다가설포닉산， 설퍼릭산 (sulfuric acid) , 다가 설퍼릭산， 포스포닉산 (phosphonic acid), 다가포스포닉산， 포스퍼릭산 The amphiphilic compound is a hydrophilic group such as alcohol, polyalcohol, amine, polyamine, thiol, polythiol, polyoxyethylene, carboxylic acid, polycarboxylic acid, sulfonic acid, polysulfonic acid, sulfuric acid. (sulfuric acid), polyvalent sulfuric acid, phosphonic acid (phosphonic acid), polyphosphonic acid, phosphoric acid
(phosphoric acid) 및 다가포스퍼릭산으로 이루어진 군에서 선택되는 화 합물로부터 유도된 1종 이상의 비이온성의 극성기를 포함하는 것인 액정 수직배향 유도제 . A liquid crystal vertical alignment inducing agent containing at least one nonionic polar group derived from a compound selected from the group consisting of (phosphoric acid) and polyphosphoric acid.
[청구항 3] [Claim 3]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 친수성기로서 1—올 (l-ol), 1,2-디올 (1,2-diol), 글리세를 (glycerol)， 글루코오스 (glucose) , 덱스트로스 ( dext rose)， 소르 비롤 (sorbitol)， 펜타에리스리를 (pentaerythritol )， 디펜타에리스리를 (dipentaerythr itol ) , 트리펜타에리스리톨 (tripentaerythritol )， 소르비 탄 (sorbitan), 플룩토스 ( f luctose)， 수크로스 (sucrose)， 갤릭산 (gallic acid) , 글루코피라노사이드 (glucopyranos ide)， 아스코르빅산 (ascorbic acid) , 매나이드 (mannide) 및 말토사이드 (mal tos i de )로 이루어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것인 액정 수직배향 유도 제 . The amphiphilic compound is a hydrophilic group such as 1—ol (l-ol), 1,2-diol (1,2-diol), glycerol, glucose, dextrose, sorbirol ( sorbitol), pentaerythritol, dipentaerythr itol, tripentaerythritol, sorbitan, fructose, sucrose, gallic acid Containing a functional group derived from a compound selected from the group consisting of (gallic acid), glucopyranoside (glucopyranos ide), ascorbic acid, mannide, and maltoside (mal tos i de) Phosphorus liquid crystal vertical alignment inducing agent.
[청구항 4] [Claim 4]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 친수성기로서 1-아민 (1-amine) , 1，2_디아민 (1，2— diamine)， 1 ,3-디아민 ( 1 ,3-diamine)， 에틸렌 디아민 (ethylene diamine) , 디에틸렌 디아민 (diethylene diamine) , 트리스 (2—아미노에틸) 아민 (tris(2一 aminoethyl)amine)， 시클로핵산 디아민 (cyclohexane diamine) , 디에틸렌 트리아민 (diethylene triamine) , 페닐디아민 (phenyldiamine) , 페닐트리아민 (phenyl tri amine)， 1,3,5-트리아진 4,6-디 아민 (l,3,5-triazine 4,6· -diamine) , 1,3, 5-트리아진 2, 4, 6-트리아민 (1,3,5-triazine 2,4,6-tr iamine) 및 고리형 에틸렌 아민 (cyclen; (CH2CH2NH)n; n=2 내지 6의 정수)로 이루어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것인 액정 수직배향 유도제. The amphiphilic compound is a hydrophilic group such as 1-amine, 1,2-diamine, 1,3-diamine, ethylene diamine, diamine, Ethylene diamine, tris(2—aminoethyl)amine, cyclohexane diamine), diethylene triamine, phenyldiamine, phenyl triamine, 1,3,5-triazine 4,6-diamine (l,3,5-triazine 4) ,6· -diamine), 1,3, 5-triazine 2, 4, 6-triamine (1,3,5-triazine 2,4,6-tr iamine) and cyclic ethylene amine (cyclen; (CH A liquid crystal vertical alignment inducing agent comprising a functional group derived from a compound selected from the group consisting of 2 CH 2 NH) n ; n=an integer of 2 to 6.
[청구항 5] [Claim 5]
계 1항에 있어서， In paragraph 1,
상기 양친매성 화합물이 친수성기로서 하기 화학식 1의 탄소수 4 내 40의 선형 폴리옥시에틸렌 또는 하기 화학식 2의 탄소수 4 내지 10의 리형 폴리에틸렌글리콜로부터 유도되는 작용기를 포함하는 것인 액정 직배향 유도제.
Figure imgf000054_0001
 A liquid crystal direct orientation inducing agent wherein the amphiphilic compound contains a functional group derived from linear polyoxyethylene having 4 to 40 carbon atoms of the following formula (1) or linear polyethylene glycol having 4 to 10 carbon atoms of the formula (2) as a hydrophilic group.
Figure imgf000054_0001
[화학식 2]
Figure imgf000054_0002
 [Formula 2]
Figure imgf000054_0002
(상기 화학식 1 및 2에서， tn은 2 내지 20의 정수이고， n은 2 내지 5의 정수이다) (In Formulas 1 and 2, tn is an integer from 2 to 20, and n is an integer from 2 to 5)
[청구항 6] [Claim 6]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 친수성기로서 1-티을 (l-thiol), 1，2-디티을 (1,2-dithiol), 티오글리세롤 (thioglycerol), 티오펜타에리쓰리를 (thi opentathiopentaerythr it ol ) 및 디티오트레이틀 (dithiothreitol )로 이루어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것인 액 정 수직배향 유도제 . The amphiphilic compound is a hydrophilic group such as 1-thiol, 1,2-dithiol, thioglycerol, thi opentathiopentaerythr it ol, and dithiothre. A liquid crystal vertical alignment inducing agent containing a functional group derived from a compound selected from the group consisting of dithiothreitol.
[청구항 7] [Claim 7]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 친수성기로서 1-카르복실산 (1-carboxyl ic acid), 1,2-디카르복실산 (1,2-dicarboxylyc acid), 1,3-디카르복실산 (1,3-dicarboxylyc acid), 밴젠카르복실산 (benzenecarboxyl i c acid) , 벤 젠디카르복실산 (benzenedicarboxylic acid) , 1 2 3 트리카르복실산 (1,2,3-tricarboxyl ic acid) , 벤젠트리카르복실산 (benzenet r i carboxyl i c acid) , 말릭산 (malic acid) , 말레익산 (maleic acid) , 타르타르산 (tartar acid) , 시트릭산 (citric acid) , 말레아믹산 (mal eami c acid) , 그루타믹산 (glutamic acid) , 아가릭산 (agaric acid) , 아코니틱산 (aconit ic acid) , 트라이카르발릴릭산 (tricarballylic acid) 및 아미노산 (amino acid)로 이 루어진 군에서 선택된 화합물로부터 유도된 작용기를 포함하는 것인 액정 수직배향 유도제 . The amphiphilic compound is a hydrophilic group such as 1-carboxyl ic acid, 1,2-dicarboxylyc acid, 1,3-dicarboxylic acid (1,3- dicarboxylyc acid), benzenecarboxyl ic acid, ben benzenedicarboxylic acid, 1 2 3 tricarboxylic acid (1,2,3-tricarboxyl ic acid), benzene tricarboxyl ic acid, malic acid, maleic acid maleic acid, tartaric acid, citric acid, maleic acid, glutamic acid, agaric acid, aconitic acid A liquid crystal vertical alignment inducing agent containing a functional group derived from a compound selected from the group consisting of acid, tricarballylic acid, and amino acid.
[청구항 8] [Claim 8]
제 1항에 있어서 , In clause 1,
상기 양친매성 화합물이 소수성기로서 치환 또는 비치환된 탄소수 8 내 지 30의 탄화수소기 ; 분자내 분자내에 N, 0 P, S 및 Si로 이루어진 군에 서 선택되는 1 이상의 해테로 원자를 포함하는 치환 또는 비치환된 탄소 수 8 내지 30의 해테로알킬기， 해테로사이클기 및 헤테로아로마틱기 ; 및 이들의 조합기로 이루어진 군에서 선택되는 작용기를 포함하는 것인 액정 수직배향 유도제 . The amphiphilic compound is a hydrophobic group and is a substituted or unsubstituted hydrocarbon group having 8 to 30 carbon atoms; A substituted or unsubstituted heteroalkyl group having 8 to 30 carbon atoms, a heterocyclic group, and a heteroaromatic group containing one or more heteroatoms selected from the group consisting of N, 0P, S, and Si within the molecule. ; and a liquid crystal vertical alignment inducing agent comprising a functional group selected from the group consisting of a combination thereof.
[청구항 9] [Claim 9]
제 1항에 있어서 , In clause 1,
상기 양친매성 화합물이 소수성기로서 할로겐 원자로 치환되거나 비치 환된 탄소수 8 내지 30의 알킬기， 알케닐알킬기， 알키닐알킬기 , 사이클로 알킬기 및 아릴기 ; 분자내 카르보닐기 (-c(=o)-), 에스테르기 (-C(=0)0-), 에테르기 (-0— )， 에틸렌옥사이드기 (_CH2CH20-) 및 아조기 (-N=N— )로 이루어 진 군에서 선택되는 헤테로원자 함유 작용기를 포함하는 탄소수 8 내지 30의 헤테로알킬기 , 해테로사이클로알킬기， 및 해테로아릴기 ; 및 이들의 조합으로 이루어진 군에서 선택되는 작용기를 포함하는 것인 액정 수직배 향 유도제 . The amphiphilic compound is a hydrophobic group, such as an alkyl group having 8 to 30 carbon atoms substituted or unsubstituted with a halogen atom, an alkenyl alkyl group, an alkynyl alkyl group, a cycloalkyl group, and an aryl group; Intramolecular carbonyl group (-c(=o)-), ester group (-C(=0)0-), ether group (-0—), ethylene oxide group (_CH 2 CH 2 0-) and azo group (-N =N— ), a heteroalkyl group having 8 to 30 carbon atoms containing a heteroatom-containing functional group selected from the group consisting of a heterocycloalkyl group, and a heteroaryl group; and a liquid crystal vertical alignment inducing agent comprising a functional group selected from the group consisting of combinations thereof.
[청구항 10] [Claim 10]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물이 소르비탄 모노라우레이트, 소르비탄 모노팔미 테이트， 소르비탄 모노스테아레이트, 소르비탄 트리스테아레이트， 소르비 탄 모노올레이트， 소르비탄 세스퀴올레이트， 소르비탄 트리올레이트， 폴 리에틸렌글리콜 소르비탄 모노라우레이트， 폴리에틸렌소르비탄 모노라우 레이트， 폴리에틸렌소르비탄 모노팔미테이트， 폴리옥시에틸렌소르비탄 모 노스테아레이트， 폴리옥시에틸렌소르비탄 트리스테아레이트， 폴리옥시에 틸렌소르비탄 모노을레이트， 풀리옥시에틸렌소르비탄 트리올레이트， 폴리 옥시에틸렌소르비탄 스테아레이트, 폴리옥시에틸렌소르비탄 을레이트， 펜 타에리쓰리를 모노스테아레이트， 펜타에리쓰리를 디아크릴레이트 모노스 테아레이트， 펜타에리쓰리틀 모노아크릴레이트 모노스테아레이트， 옥틸 갈레이트， 라우릴 갈레이트， 갈레이트 유도체， 스테아로일 글리세롤， 디 팔미토일 글리세를， 디옥타데카노일 글리세롤， 팔미토일 글리세를, 모노 핵사데카노일 글리세를， 디핵사데카노일 글리세를, 옥타데실 글리세를， 올레오일 글리세롤, 트리글리세를 모노스테아레이트， 아스코르빅산 6-팔 미테이트， 매나이드 모노을레이트, 옥틸 글루코피라노사이드， 도데실글루 코피라노사이드， 메틸글루코사이드 세스퀴스테아레이트， 메틸글투코사이 드 디을레이트， 글루코실옥시에틸 메타크릴레이트, 글루코피라노사이드 유도체， 옥틸 말토사이드， 사이클로핵실핵실 말토사이드, 데실 말토사이 드， 운데실 말토사이드， 도데실 말토사이드， 트리데실 말토사이드， 테트 라데실 말토사이드, 핵사데실 말토사이드， 1-도데칸올， 1-핵사데칸올， 1- 옥타데칸을， 1，2—도데칸디올， 1,2-핵사데칸디올， 옥탄산， 데칸산， 도데칸 산， 핵사데칸산， 옥타데칸산， 옥틸아민， 데실아민， 도데실아민， 핵사데칸 1,2-디아민, 디핵사데실 포스페이트, 데실포스폰산， 1-도데칸티을， 1-핵 사데칸티올, 에틸렌 글리콜 스테아레이트 폴리옥시에틸렌산， 폴리옥시에 틸렌 (2) 스테아릴 에테르， 풀리옥시에틸렌 (4) 라우릴 에테르， 폴리옥시 에틸렌 (2) 세틸 에테르， 폴리옥시에틸렌 (20) 세틸 에테르, 폴리옥시에틸 렌 (2) 올레일 에테르， 폴리옥시에틸렌 (20) 올레일 에테르, 폴리옥시에틸 렌 (10) 스테아릴 에테르 및 이들의 흔합물로 이루어진 군에서 선택되는 것인 액정 수직배향 유도제 . The amphiphilic compounds include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, poly Ethylene glycol sorbitan monolaurate, polyethylene sorbitan monolaurate, polyethylene sorbitan monopalmitate, polyoxyethylene sorbitan parent Nostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monoate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan sulfate, pentaerythate. Three monostearate, pentaerythrylate diacrylate monostearate, pentaerythrylate monoacrylate monostearate, octyl gallate, lauryl gallate, gallate derivatives, stearoyl glycerol, dipalmitoyl Glycerol, dioctadecanoyl glycerol, palmitoyl glycerol, monohexadecanoyl glycerol, dihexadecanoyl glycerol, octadecyl glycerol, oleoyl glycerol, triglycerol monostearate, ascorbic acid 6-arm Mitate, manide monoate, octyl glucopyranoside, dodecylglucopyranoside, methylglucoside sesquistearate, methylglucoside diylate, glucosyloxyethyl methacrylate, glucopyranoside derivatives, Octyl maltoside, cyclonucleus nucleyl maltoside, decyl maltoside, undecyl maltoside, dodecyl maltoside, tridecyl maltoside, tetradecyl maltoside, hexadecyl maltoside, 1-dodecanol, 1-hexadecane All, 1-octadecane, 1,2-dodecanediol, 1,2-hexadecanediol, octanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, octylamine, decylamine, dodecyl Amine, hexadecane 1,2-diamine, dihexadecyl phosphate, decylphosphonic acid, 1-dodecanethiol, 1-nuclear tetradecanethiol, ethylene glycol stearate polyoxyethylene acid, polyoxyethylene (2) stearyl Ether, polyoxyethylene (4) Lauryl ether, polyoxyethylene (2) Cetyl ether, polyoxyethylene (20) Cetyl ether, polyoxyethylene (2) Oleyl ether, polyoxyethylene (20) Oleyl ether A liquid crystal vertical alignment inducing agent selected from the group consisting of polyoxyethylene (10) stearyl ether and mixtures thereof.
[청구항 11] [Claim 11]
제 1항에 있어서， In clause 1,
상기 단분자의 친수성 액체는 분자내에 히드록시기 , 티올기， 아민기， 및 카르복실기로 이루어진 친수성기를 1 내지 6개 포함하는 것인 액정 수 직배향 유도제 . The single-molecule hydrophilic liquid is a liquid crystal vertical alignment inducing agent containing 1 to 6 hydrophilic groups consisting of a hydroxyl group, a thiol group, an amine group, and a carboxyl group in the molecule.
[청구항 12] [Claim 12]
제 1항에 있어서， In clause 1,
상기 친수성 액체는 물 (¾0)， 글리세를 (glycerol), 디글리세를 (diglycerol), 트리글리세롤 ( t r iglycerol )， 에틸렌 글리콜 (ethylene glycol), 디에틸렌 글리콜 (diethyleneglycol), 트리에틸렌 글리콜 (triethylene glycol) , 티오글리세를 ( thi oglycerol )， 디티오글리세롤 (dithioglycerol) , 에탄디티올 (ethanedithiol ) , 에틸렌 디아민 (ethylene diamine) , 디아미노프로판 (di aminopropane)， 디에틸렌트리아민 (diethylenetr iamine) , 트리에틸렌테트라아민 ( t r i ethylenet et ramine )， 트 리스아미노에틸 아민 (tris(aminoethyl) amine) , 펜타에리쓰리톨 테트라키 스 (3—멀캡토프로피오네이트) [Pentaerythritol tetrakis(3- mercaptopropionate)] , 트리글리세를 모노아크릴레이트 (tr iglycerol monoacrylate), 트리글리세롤 모노메타아크릴레이트 (tr iglycerol monomethacrylate) , 트리글리세를 디아크릴레이트 (triglycerol diacrylate), 트리글리세롤 디메타아크릴레이트 (triglycerol dimethacrylate), 펜타에리쓰리롤 모노아크릴레이트 (pent aerytyhr i tol monoacrylate), 펜타에리쓰리를 모노메타아크릴레이트 (pent aerytyhr i tol monomethacrylate) , 펜타에리쓰리틀 디아크릴레이트 (pentaerytyhri tol diacrylate) , 펜타에리쓰리를 디메타아크릴레이트 (pentaerythr i tol dimethacrylate) , 아크릴산 (acrylic acid) , 메타크릴산 (methacryl i c acid) , 2-히드록시에틸 아크릴레이트 (2-hydroxyethyl acrylate) , 2-히드 특시에틸 메타크릴레이트 (2-hydroxyethyl methacryl ate) , 글리세를 모노 아크릴레이트 (glycerol monoacrylate) , 글리세를 모노메타아크릴레이트 (glycerol monomethacrylate) 및 이들의 흔합물로 이루어진 군에서 선택 되는 것인 액정 수직배향 유도제. The hydrophilic liquid is water (¾0), glycerol, diglycerol, triglycerol, ethylene glycol glycol), diethylene glycol, triethylene glycol, thioglycerol, dithioglycerol, ethanedithiol, ethylene diamine, diaminopropane (di aminopropane), diethylenetriamine (diethylenetr iamine), triethylenet et ramine, tris(aminoethyl) amine, pentaerythritol tetrakis (3—mercapto) propionate) [Pentaerythritol tetrakis(3- mercaptopropionate)], triglycerol monoacrylate, triglycerol monomethacrylate, triglycerol diacrylate, triglycerol diacrylate Glycerol dimethacrylate, pentaerythrol monoacrylate, pentaerythri monomethacrylate, pentaerythril diacrylate tol diacrylate), pentaerythr i tol dimethacrylate, acrylic acid, methacryl ic acid, 2-hydroxyethyl acrylate, 2- Liquid crystal vertical alignment selected from the group consisting of 2-hydroxyethyl methacryl ate, glycerol monoacrylate, glycerol monomethacrylate, and mixtures thereof. Inducing agent.
[청구항 13] [Claim 13]
제 1항에 있어서， In clause 1,
상기 양친매성 화합물과 친수성 액체는 1:99 내지 99.9:0.1의 중량비로 포함되는 것인 액정 수직배향 유도제 . A liquid crystal vertical alignment inducing agent wherein the amphiphilic compound and the hydrophilic liquid are included in a weight ratio of 1:99 to 99.9:0.1.
[청구항 14] [Claim 14]
저 U항에 있어서， In that U port,
상기 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물이 , 화합물 내에 1 이상의 광반응성기를 더 포함하는 광반웅성 화합물인 액정 수직배향 유도제 . A liquid crystal vertical alignment inducing agent wherein at least one of the amphipathic compound and the hydrophilic liquid is a photoreactive compound further containing one or more photoreactive groups in the compound.
[청구항 15] [Claim 15]
제 14항에 있어서， In clause 14,
상기 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물이 , 화합물내에 아크릴레이트기， 메타크릴레이트기， 신나메이트기， 쿠마린기， 챠콘기， 비닐기 , 티올기， 엔기, 디엔기 , 티올엔기 및 아세틸렌기로 이루 어진 군에서 선택되는 1 이상의 광반응성기를 더 포함하는 광반웅성 화합 물인 액정 수직배향 유도제. At least one of the amphipathic compounds and hydrophilic liquids, In the compound, one or more photoreactive groups selected from the group consisting of an acrylate group, a methacrylate group, a cinnamate group, a coumarin group, a chacone group, a vinyl group, a thiol group, an en group, a diene group, a thiol-ene group, and an acetylene group are added. A liquid crystal vertical alignment inducing agent containing a photoreactive male compound.
[청구항 16] [Claim 16]
제 14항에 있어서 , In clause 14,
상기 광반응성 화합물이 액정 수직배향 유도제 총 중량에 대하여 5 내 지 100중량 %로 포함되는 것인 액정 수직배향 유도제 . A liquid crystal vertical alignment inducing agent wherein the photoreactive compound is included in an amount of 5 to 100% by weight based on the total weight of the liquid crystal vertical alignment inducing agent.
[청구항 17] [Claim 17]
분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함 하는 양친매성 화합물， 및 단분자의 친수성 액체를 포함하는 액정 수직배 향 유도제; 그리고 an amphipathic compound containing 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule, and a liquid crystal vertical alignment inducing agent containing a single molecule hydrophilic liquid; and
액정호스트 LCD host
를 포함하는 액정층 형성용 조성물. A composition for forming a liquid crystal layer comprising.
[청구항 18] [Claim 18]
제 17항에 있어서， In clause 17,
상기 액정 수직배향 유도제가 액정호스트 중에 에멀견 (emu l s i on)의 형 태로 분산되어 있는 것인 액정층 형성용 조성물. A composition for forming a liquid crystal layer, wherein the liquid crystal vertical alignment inducing agent is dispersed in the form of an emulsion in a liquid crystal host.
[청구항 19 ] [Claim 19]
제 17항에 있어서 \ In clause 17\
상기 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물이 화합물 내에 1 이상의 광반응성기를 더 포함하는 광반응성 화합물인 액정 층 형성용 조성물. A composition for forming a liquid crystal layer, wherein at least one of the amphipathic compound and the hydrophilic liquid is a photoreactive compound further comprising one or more photoreactive groups in the compound.
[청구항 20 ] [Claim 20]
제 17항에 있어서， In clause 17,
상기 액정 수직배향 유도제가 액정층 형성용 조성물 총 중량에 대하여 0. 01 내지 5중량 ¾로 포함되는 것인 액정층 형성용 조성물. A composition for forming a liquid crystal layer, wherein the liquid crystal vertical alignment inducing agent is included in an amount of 0.01 to 5% by weight based on the total weight of the composition for forming a liquid crystal layer.
[청구항 21 ] [Claim 21]
제 1기판 및 제 2기판에 대해 각각 제 1및 제 2전극을 형성하는 전극형성단 계 ; 그리^ _ An electrode forming step of forming first and second electrodes on the first and second substrates, respectively; So ^ _
상기 제 1 및 제 2전극을 각각 포함하는 제 1기판과 제 2기판을 전극들끼리 대면하도록 하여 접합한 후 제 1기판과 제 2기판 사이의 공간에 액정층 형 성용 조성물을 주입하거나， 또는 상기 제 1 및 제 2전극을 각각 포함하는 제 1기판과 계 2기판 중 어느 하나에 대해 진공 하에서 액정층 형성용 조성 물을 적하하여 액정층올 형성한 후 나머지 기판을 전극들끼리 대면하도톡 접합하여 조립체를 제조하는 단계를 포함하며 , After bonding the first and second substrates, each including the first and second electrodes, with the electrodes facing each other, a composition for forming a liquid crystal layer is injected into the space between the first and second substrates, or Comprising first and second electrodes, respectively It includes the step of forming a liquid crystal layer by dropping a composition for forming a liquid crystal layer under vacuum on either the first substrate or the second substrate, and then bonding the remaining substrates with the electrodes facing each other to manufacture an assembly,
상기 액정층 형성용 조성물은 분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합물， 및 단분자의 친수성 액체를 포함하는 액정 수직배향 유도제 ; 그리고 액정호스트를 포함하는 것인 액정표시장치의 제조방법 . The composition for forming a liquid crystal layer includes an amphipathic compound containing 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule, and a liquid crystal vertical alignment inducing agent containing a single molecule hydrophilic liquid; and a method of manufacturing a liquid crystal display device including a liquid crystal host.
[청구항 22 ] [Claim 22]
제 21항에 있어서， In clause 21,
상기 액정 수직배향 유도제가 액정호스트 중에 에멀견 (emu l s i on)의 형 태로 분산되어 있는 것인 액정표시장치의 제조방법 . A method of manufacturing a liquid crystal display device in which the liquid crystal vertical alignment inducing agent is dispersed in the form of emulsions in the liquid crystal host.
[청구항 23 ] [Claim 23]
제 21항에 있어서， In clause 21,
상기 양친매성 화합물 및 친수성 액체 중 적어도 어느 하나의 화합물이 화합물 내에 1 이상의 광반웅성기를 더 포함하는 광반웅성 화합물인 액정 표시장치의 제조방법 . A method of manufacturing a liquid crystal display device wherein at least one of the amphipathic compound and the hydrophilic liquid is a photoreactive compound further containing one or more photoreactive male groups in the compound.
[청구항 24] [Claim 24]
제 21항에 있어서， In clause 21,
상기 액정 수직배향 유도제가 액정층 형성용 조성물 총 중량에 대하여 0. 01 내지 5중량 %로 포함되는 것인 액정표시장치의 제조방법 . A method of manufacturing a liquid crystal display device, wherein the liquid crystal vertical alignment inducing agent is included in an amount of 0.01 to 5% by weight based on the total weight of the composition for forming a liquid crystal layer.
[청구항 25 ] [Claim 25]
제 21항에 있어서 , In clause 21,
상기 조립체의 제조 후 계 1기판과 제 2기판 사이에 전기장을 인가하고， 광 조사하는 단계를 더 포함하는 액정표시장치의 제조방법 . A method of manufacturing a liquid crystal display device further comprising applying an electric field between the first and second substrates and irradiating light after manufacturing the assembly.
[청구항 26] [Claim 26]
서로 대향하여 위치하는 제 1기판과 제 2기판; A first substrate and a second substrate positioned opposite to each other;
상기 게 1기판과 제 2기판의 상호 대향되는 면에 각각 형성된 계 1전극과 제 2전극; 그리고 a first electrode and a second electrode respectively formed on opposite surfaces of the first and second substrates; and
상기 제 1기판과 상기 제 2기판 사이에 개재되어 위치하는 액정층을 포함 하며 , It includes a liquid crystal layer positioned between the first substrate and the second substrate,
상기 액정층은 분자내 탄소원자를 8 내지 30개 포함하는 소수성기를 1 내지 3개 포함하는 양친매성 화합물， 및 단분자의 친수성 액체를 포함하 는 액정 수직배향 유도제 ; 그리고 액정호스트를 포함하는 것인 액정표시 장치 . The liquid crystal layer includes an amphipathic compound containing 1 to 3 hydrophobic groups containing 8 to 30 carbon atoms in the molecule, and a liquid crystal vertical alignment inducing agent containing a single molecule hydrophilic liquid; And a liquid crystal display that includes a liquid crystal host. Device .
[청구항 27 ] [Claim 27]
제 26항에 있어서， In clause 26,
상기 양친매성 화합물 및 친수성 액체 증 적어도 어느 하나는 화합물 내에 1 이상의 광반웅성기를 더 포함하는 광반웅성 화합물이며， At least one of the amphipathic compounds and the hydrophilic liquid is a photoreactive compound further comprising one or more photoreactive groups in the compound,
상기 액정층은 상기 광반웅성 화합물의 광중합체를 더 포함하는 것인 액정표시장치 . The liquid crystal display device wherein the liquid crystal layer further includes a photopolymer of the photoreactive male compound.
[청구항 28 ] [Claim 28]
제 26항에 있어서， In clause 26,
상기 액정표시장치는 액정층과 제 1 또는 제 2전극 사이에 액정 수직배향 유도제를 포함하는 액정의 수직배향 및 광안정화 층을 더 포함하는 것인 액정표시장치 . The liquid crystal display device further includes a liquid crystal vertical alignment and light stabilization layer containing a liquid crystal vertical alignment inducing agent between the liquid crystal layer and the first or second electrode.
[청구항 29 ] [Claim 29]
제 26항에 있어서， In clause 26,
상기 제 1 및 제 2 전극 중 어느 하나 또는 들 모두가 패턴화된 것인 액 정표시장치 . A liquid crystal display device in which one or both of the first and second electrodes are patterned.
[청구항 30 ] [Claim 30]
에멀젼화된 액정층 형성용 조성물을 이용하여 배향 안정성을 갖는 액정 의 수직배향을 유도하는 방법 . A method of inducing vertical alignment of liquid crystals with orientation stability using an emulsified liquid crystal layer forming composition.
[청구항 31 ] [Claim 31]
광반응성의 에멀견화된 액정층 형성용 조성물을 이용하여 액정의 수직 배향 및 광안정화를 유도하는 방법 . A method of inducing vertical alignment and light stabilization of liquid crystals using a photoreactive, emulsified liquid crystal layer forming composition.
[청구항 32 ] [Claim 32]
광반응성의 에멀견화된 액정층 형성용 조성물에 대하여 전기장을 인가 하고 광 조사를 실시함으로써 액정층과 전극층의 사이에 절연성의 액정 수직배향 및 광안정화 층을 형성하는 방법 . A method of forming an insulating liquid crystal vertical alignment and light stabilization layer between a liquid crystal layer and an electrode layer by applying an electric field to a photoreactive emulsionized liquid crystal layer forming composition and performing light irradiation.
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