WO2003005113A1 - Agent d'alignement de cristaux liquides permettant d'obtenir un alignement vertical de cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides permettant d'obtenir un alignement vertical de cristaux liquides Download PDF

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Publication number
WO2003005113A1
WO2003005113A1 PCT/JP2002/006758 JP0206758W WO03005113A1 WO 2003005113 A1 WO2003005113 A1 WO 2003005113A1 JP 0206758 W JP0206758 W JP 0206758W WO 03005113 A1 WO03005113 A1 WO 03005113A1
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liquid crystal
group
dianhydride
formula
bis
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PCT/JP2002/006758
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English (en)
Japanese (ja)
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Toshiyuki Akiike
Masaki Obi
Tsuyoshi Hirai
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Jsr Corporation
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Priority to KR1020037002712A priority Critical patent/KR100842156B1/ko
Publication of WO2003005113A1 publication Critical patent/WO2003005113A1/fr

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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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

Definitions

  • Liquid crystal vertical alignment liquid crystal alignment agent Liquid crystal vertical alignment liquid crystal alignment agent
  • the present invention relates to a liquid crystal vertical alignment liquid crystal alignment agent. More specifically, the liquid crystal display is particularly suitable for the MVA (Mu1ti-doma inverticala 1 ig nment) type liquid crystal display element, because the liquid crystal display element has a short vertical orientation, printability, and a short after-image erasing time of the liquid crystal display element.
  • the present invention relates to a vertical alignment liquid crystal light-directing agent.
  • a liquid crystal display element As a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, or the like is formed on the surface of the substrate on which the transparent conductive film is provided, and a liquid crystal display element substrate is formed. A nematic liquid crystal layer with positive dielectric anisotropy is formed in the gap to form a sandwich structure cell, and the major axis of the liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other.
  • a TN type liquid crystal display element having a so-called TN (Twisted Negative) type liquid crystal cell is known.
  • STN Super Twisted Nematic liquid crystal display elements and vertical alignment type liquid crystal display elements that have higher contrast than TN type liquid crystal display elements and are less dependent on the viewing angle
  • This STN-type liquid crystal display element uses a nematic liquid crystal blended with an optically active substance, a chiral agent, as the liquid crystal, and the long axis of the liquid crystal molecules is continuously twisted over 180 degrees between the substrates. This utilizes the birefringence effect caused by the above.
  • the MVA-type liquid crystal display element is excellent in the manufacturing process, such as being excellent in viewing angle, contrast, etc., and requiring no rubbing treatment in forming a liquid crystal alignment film.
  • the liquid crystal display element is required to have excellent performance such as excellent elimination time and a short afterimage erasing time. Disclosure of the invention
  • An object of the present invention is to provide a liquid crystal vertical alignment liquid crystal alignment agent which is excellent in vertical alignment of liquid crystal and has a short afterimage erasing time of a liquid crystal display element and is suitably used for an MVA type liquid crystal display element.
  • P 1 is a tetravalent organic group
  • Q 1 represents a divalent organic group
  • P 2 is a tetravalent organic group
  • Q 2 is a divalent group represented by the following formula (Q-1) or the following formula (Q-2).
  • X 1 is a single bond, — ⁇ , —CO_, —COO—, — ⁇ C ⁇ -1, —NHC —1, CONH—, —S— or arylene
  • R 1 Is an alkyl group having 10 to 20 carbon atoms, a monovalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms, or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms.
  • X 2 and X 3 are the same or different and are a single bond, —O—, —CO—, one C ⁇ , one CO—, one NHC0—, one C0NH—, one S—, or an arylene group
  • R 2 is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms.
  • FIG. 1 is a schematic view of an MVA type liquid crystal cell used in an embodiment of the present invention.
  • Embodiment of the Invention is a schematic view of an MVA type liquid crystal cell used in an embodiment of the present invention.
  • the liquid crystal vertical alignment liquid crystal aligning agent of the present invention is constituted by dissolving the polymer component, preferably in an organic solvent.
  • the polymer component in the present invention includes: (A) a polyamic acid having a repeating unit represented by the above formula (1-1) (hereinafter also referred to as “component (A)”); It contains an imidized polymer having a repeating unit represented by 1-2) (hereinafter, also referred to as “component (B)”), or 2 (A) a repeating unit represented by the above formula (1-1)
  • the block copolymer preferably contains a block copolymer comprising an acid acid prepolymer having units and (B) an imidoblepolymer having a repeating unit represented by the formula (1-2).
  • the polyamic acid of the component (A) is obtained by reacting tetracarboxylic dianhydride with diamine, and the imidized polymer of the component (B) is tetracarboxylic dianhydride and H 2 N-Q 2 - NH 2 (wherein, Q 2 is formula (I one 2) the same definition as) Jiamin (hereinafter also referred to as "specific Jiamin”) having the structure represented by reacting the obtained The resulting polyamic acid is obtained by dehydration and ring closure.
  • Water 1,2-dimethyl_1,2,3,4-cyclobutanetetrahydroluponate dihydrate, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarponic acid dihydrate 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetrahydroluponic anhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride,
  • R 3 and R 6 represent a divalent organic group having an aromatic ring
  • R 4 and R 5 represent a hydrogen atom or an alkyl group
  • a plurality of R 4 and R 5 are the same, respectively. But they may be different.
  • Aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride; pyromellitic dianhydride, 3, 3,, 4, 4'-benzophenone tetracarboxylic dianhydride, 3, 3,, 4,4, -Biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-Naphthene lentetratetracarboxylic acid dianhydride 1,3,3,4,4,1-biphenylethertetracarboxylic dianhydride, 3,3,4,4, -dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3,4,4 , -Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dica
  • 1,2,3,4-cis dianhydride 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3 4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tripropoxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydrofural) -1,3-methyl-3-cyclohexene-1,1, 2-dicarboxylic dianhydride, cis-1,3,1-dibutylcyclohexyl 1,5-gen-1,2,5,6-tetracarboxylic dianhydride, 3,5,6 2-loo 2 _carpoxy norporanane 1: 2,3,5: 6-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-
  • Examples of the diamine used for the synthesis of the polyamic acid as the component (A) include p-phenylenediamine, m-phenylenediamine, 4,4, -diaminodiphenylmethane, 4,4, -diaminodiphenylethane, and 4 , 4 'diaminodiphenyl sulfide, 4,4, diaminodiphenyl sulfone, 2,2, -dimethyl-1,4,4' diaminobiphenyl, 3,3,1-dimethyl-4,4'-diaminobiphenyl, 4,4, Diaminobenzanilide, 4,4, -diaminodiphenyl ether, 1,5-diaminonaphthylene, 3,3-dimethyl-4,4, diamy Noviphenyl, 5-amino-1- (4,1-aminophenyl) 1,1,3,3-trimethylindane, 6-amino-11- (4'-aminophen
  • diaminoorganosiloxane represented by the following formula (IV) can be used alone or in combination of two or more.
  • R 7 represents a hydrocarbon group having 1 to 12 carbon atoms, a plurality of R 7 may be the same or different, p is an integer of 1 to 3, and q is 1 to It is an integer of 20.
  • the tetracarboxylic dianhydride used in the synthesis of the imidized polymer of the component (B) is the same as the tetracarboxylic dianhydride used in the synthesis of the polyamic acid of the component (A) described above. Can be mentioned.
  • alicyclic tetracarboxylic dianhydrides are preferred, and specifically, 1,2,3,4-cyclobutanetetracarponic dianhydride, 1,3-dimethyl-1,2,3,4 -Ciglobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) 1,3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride Cis-3,7-dibutylcyclooctanol 1,5-diene 1,2,5,6-tetracarponic dianhydride, 3,5,6-tripropanol 2--2-propoxynorpornan 1 2: 3,5: 6-dian
  • the compound represented by (8) is preferable from the viewpoint of exhibiting good liquid crystal alignment and electrical properties, and particularly preferable are 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1 To 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tripropoxycyclopentyl acetic dianhydride, 1,3,3a, 4,5,9b— Xahydro-5- (tetrahydro 2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione 1,3,3a, 4,5,9b-hexahydro-8 —Methyl— 5 _ (tetrahydro-1,2,5-dioxo-13-furanyl) naphtho [1,2, c] furan-1,3-dione, cis-1,3,7-dibutylcycloocta-1, 5-Gen _ 1,2,5,6-
  • these tetracarboxylic dianhydrides are such that the alicyclic tetracarboxylic dianhydride is
  • the repeating unit in which the tetravalent organic group represented by P 2 is a group having an alicyclic structure accounts for 50 mol% of all the repeating units in the component (B). It is preferable that it is above.
  • Preferred tetracarboxylic dianhydrides other than the alicyclic tetracarboxylic dianhydride include: Aromatic tetracarboxylic dianhydrides having a steroid skeleton represented by the above formulas (1) to (4) can be mentioned.
  • the specific diamine used for the synthesis of the imidized polymer of the component (B) is a diamine having a group represented by the above formula (Q-1) and the above formula (Q-2). These are used alone or in combination of two or more.
  • examples of the alkyl group having 10 to 20 carbon atoms represented by R 1 include n-decyl group, n-dodecyl group, n-pentadecyl group, and n- Examples include a xadecyl group, an n_octadecyl group, and an n-eicosyl group.
  • Examples of the organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R 1 in the above formula (Q-1) and R 2 in the above formula (Q-2) include cyclobutane and cyclo Groups having an alicyclic skeleton derived from cycloalken such as pentane, cyclohexane and cyclodecane; groups having a steroid skeleton such as cholesterol and cholesterol; groups having a bridged alicyclic skeleton such as norpolpolene and adamantane. And the like. Among these, a group having a steroid skeleton is particularly preferred.
  • the organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom, or a fluoroalkyl group, preferably a trifluoromethyl group.
  • Examples of the group having a fluorine atom having 6 to 20 carbon atoms represented by R 1 in the above formula (Q-1) include, for example, n-hexyl group, n-octyl group, n-decyl group and the like. Linear alkyl group having 6 or more carbon atoms; alicyclic hydrocarbon group having 6 or more carbon atoms such as cyclohexyl group and cyclooctyl group; and aromatic hydrocarbon having 6 or more carbon atoms such as phenyl group and biphenyl group. Examples thereof include groups in which part or all of the hydrogen atoms in an organic group such as a hydrogen group are substituted with a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group.
  • X 1 in the above formula (Q-1) and X 2 and X 3 in the above formula (Q-2) are each independently a single bond, 110-1, —CO—, —CO —,- OC is one, one NHCO—, one CONH—, one S— or arylene group.
  • the len group include a phenylene group, a tolylene group, a biphenylene group, and a naphthylene group. Of these, a group represented by one O—, one COO—, —OCO— is particularly preferred.
  • diamine having a group represented by the above formula (Q-1) examples include dodecanoloxy 2,4 diaminobenzene, pendecanoxy-1,2,4 diaminobenzene, hexadecanoxy 1,2,4 —Diaminobenzene, octadecanoloxy-1,4 diaminobenzene, and compounds represented by the following formulas (9) to (14) are preferred.
  • diamine having a group represented by the above formula (Q-2) diamines represented by the following formulas (15) to (17) can be preferably mentioned.
  • the proportion of the specific diamine used in the synthesis of the component (B) is preferably at least 5 mol%, more preferably at least 10 mol%, based on the total diamine used for the synthesis of the component (B).
  • the proportion of the repeating unit represented by the above formula (1-2) is preferably at least 5 mol%, particularly preferably at least 10 mol%.
  • the ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of the polyamic acid is as follows: 1 equivalent of amino group of diamine and tetracarboxylic acid
  • the ratio is preferably such that the acid anhydride group of the dianhydride becomes 0.2 to 2 equivalents, and more preferably the ratio becomes 0.3 to 1.2 equivalents.
  • the synthesis reaction of the polyamic acid is carried out in an organic solvent, preferably at a temperature of from 120 ° C to 150 ⁇ , more preferably from 0 to 10 ° C.
  • the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid.
  • Non-protocols such as carboxylolactone, tetramethylurea, hexamethylphosphortriamide Polar solvents
  • phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol.
  • the amount of the organic solvent used (h) is such that the total amount of the tetracarboxylic dianhydride and the diamine compound (3) is 0.1 to 30% by weight based on the total amount of the reaction solution (h + 3). It is preferred that the amount be such.
  • organic solvent alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for the polyamic acid, are used in combination as long as the generated polyamic acid does not precipitate. be able to.
  • such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-14-methyl-21-pentanone (diacetone alcohol), ethylene glycol, propylene glycol, , 4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate , Ethyl ethoxy propionate, getyl oxalate, getyl malonate, getyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n- Propyl ether, ethylene glycol i-propyl ether,
  • a reaction solution obtained by dissolving the polyamic acid is obtained.
  • the reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure.
  • a polyamic acid can be obtained.
  • the polyamic acid can be purified by dissolving the polyamic acid in an organic solvent again and then performing the step of precipitating with a poor solvent once or several times.
  • the component (B) can be synthesized by subjecting part or all of the above polyamic acid to dehydration and ring closure.
  • the component (B) used in the present invention preferably has a proportion of the repeating unit having an imide ring in all the repeating units (hereinafter, also referred to as “imidation ratio”), more preferably 40 mol% or more, more preferably. 70 mol% or more.
  • the dehydration and ring closure of the polyamic acid can be performed by (i) heating the polyamic acid or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as necessary. It is done by the method of doing.
  • the reaction temperature in the method of heating the polyamic acid of (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C.
  • the reaction temperature is lower than 50 ° C, the dehydration ring-closing reaction does not easily proceed sufficiently.
  • the reaction temperature exceeds 200 ° C the molecular weight of the imidized polymer obtained may decrease.
  • the dehydrating agent for example, an acid anhydride such as acetic anhydride, propionic anhydride, and anhydrous trifluoroacetic acid is used. be able to.
  • the amount of the dehydrating agent used depends on the desired imidation ratio, but is preferably 0.01 to 20 mol per 1 mol of the repeating unit of the polyamic acid.
  • the dehydration ring-closing catalyst for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used.
  • the amount of the dehydration ring-closing catalyst used is preferably from 0.01 to 10 mol per 1 mol of the dehydrating agent used.
  • the imidation ratio can be increased as the amount of the above-mentioned dehydrating agent and dehydrating ring-closing agent increases.
  • Examples of the organic solvent used for the dehydration ring closure reaction include the same organic solvents as those exemplified above as those used for the synthesis of polyamic acid.
  • the reaction temperature of the water ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C.
  • the obtained imidized polymer can be purified by subjecting the reaction solution thus obtained to the same operation as in the method for purifying polyamic acid.
  • the components (A) and (B) used in the present invention may be of a terminal-modified type having a controlled molecular weight.
  • this terminal-modified polymer By using this terminal-modified polymer, the coating characteristics of the liquid crystal aligning agent can be improved without impairing the effects of the present invention.
  • Such a terminal-modified polymer can be synthesized by adding an acid monohydrate, a monoamine compound, a monoisocyanate compound, or the like to the reaction system when synthesizing the polyamic acid.
  • examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, and n-tetradecylsuccinic anhydride. And n-hexadecyl succinic anhydride.
  • Monoamine compounds include, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-noeramine, n-decylamine, n-Pindecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-hepdecylamine, n-octadecylamine, n-eicosylamine and the like.
  • examples of the monodisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
  • the polymer used in the present invention has a logarithmic viscosity (77 ln ) value of preferably from 0.05 to: L 0 d 1 / g, more preferably from 0.05 to 5 dl / g.
  • the value of the logarithmic viscosity (77 ln ) in the present invention is determined by measuring the viscosity at 30 ° C. of a solution having a concentration of 0.5 g / 100 ml using N-methyl-2-pyrrolidone as a solvent. And it is obtained by the following equation (i). 1 n (solution flowing time Z solvent flowing time)
  • Block copolymer (Polymer concentration by weight) Block copolymer
  • a block copolymer can be produced by synthesizing an imidoble polymer having an amino group, respectively, and binding the terminal amino group and acid anhydride group of each prepolymer.
  • the method for synthesizing the preamic polymer is the same as the above-described method for synthesizing the polyamic acid
  • the method for synthesizing the imidoblepolymer is the same as the method for synthesizing the imidized polymer described above.
  • the selection of the functional group at the terminal can be made by adjusting the amounts of tetracarboxylic dianhydride and diamine during the synthesis of the polyamic acid.
  • the liquid crystal aligning agent of the present invention is constituted as a solution in which the above-mentioned polymer component, preferably the component (A) and the component (B), are usually dissolved in an organic solvent.
  • the mixing ratio of the polyamic acid as the component (A) and the imidized polymer as the component (B) is preferably 99.9 / 0.01-10 / 90, and particularly preferably 99.9 / 0/10. 1 to 40/60.
  • the temperature for preparing the liquid crystal aligning agent of the present invention is preferably from 0 nC to 200 ° C, more preferably from 20 ° C to 60 ° C.
  • Examples of the organic solvent constituting the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, a-butyrolactone, a-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4 -Methyl-2-nonene, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether , Ethylene glycol i-propyl ether, ethyl N-Butyl ether (ethylene glycol dimethyl ether), ethylene glycol dimethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and ethylene glycol monomethyl ether And ethylene glycol monoe
  • the solid content concentration in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, and the like, but is preferably in the range of 1 to 10% by weight.
  • the liquid crystal aligning agent of the present invention is applied to a substrate surface to form a coating film to be a liquid crystal alignment film.
  • the thickness of the coating film is too small. It is difficult to obtain a good liquid crystal alignment film because the solid content concentration exceeds 10% by weight. It becomes difficult, and the viscosity of the liquid crystal aligning agent increases, thereby deteriorating the coating properties.
  • the liquid crystal aligning agent of the present invention may contain a functional silane-containing compound or an epoxy compound from the viewpoint of improving the adhesiveness to the substrate surface as long as the desired physical properties are not impaired.
  • a functional silane-containing compound include, for example, 3-amino
  • Mouth pilltriethylenetriamine N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl 1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9- Trimethoxysilyl-1,3-diazanyonylacetate, 9-triethoxysilyl-1,3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N— Propyltrimethoxysilane, N-phenyl 3-aminopropyltriethoxysilane, N-bis (oxyethylene) -13-aminopropyltrimethoxysilane, N-bis (oxyethylene) -13-aminopropyltriethoxysilane And so on.
  • epoxy compounds examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol didalidicyl ether, tripropylene dalicol diglycidyl ether, polypropylene dalicol diglycidyl ether, and neopentyl glycol diglycidyl.
  • the mixing ratio of these functional silane-containing compounds and epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer.
  • the addition of an epoxy compound can further improve the scratch resistance of the obtained liquid crystal alignment film.
  • Particularly preferred epoxy compounds are N, N, N,, ⁇ ,, —tetraglycidyl m-xylene diamine, 1,3-bis
  • N N-diglycidylaminomethyl cyclohexane, N, N, ⁇ ,, N,, —tetraglycidyl—4,4 ′ diaminodiphenylmethane, 3 -— (N-aryl-1N-glycidyl) N-containing epoxy compounds such as aminopropyl trimethoxysilane and 3- (N, N-diglycidyl) aminopropyltrimethoxysilane.
  • At least one substrate forming a liquid crystal cell has a projection shape.
  • the liquid crystal display element include an MVA type liquid crystal display element.
  • the MVA mode is a vertical alignment mode in which projections are used as alignment control means, as shown in "Liquid Crystal Vol. 3 No. 2117 (1999)", JP-A-11-258605.
  • the projection may be formed on each of the TFT substrate side and the color filter side, and may have a projection on the color filter side and a slit on the TFT side.
  • a 1 Peak area derived from proton of NH group (l O ppm)
  • a liquid crystal aligning agent was printed on the glass substrate with ITO (A) and the glass substrate with ITO pattern (B) having protrusions formed using a positive resist, respectively.
  • the film was dried at 80 ° C for 1 minute and then at 180 ° C for 1 hour to produce a 600 ⁇ film thickness.
  • 1, 1 is a color filter side electrode (ITO), 2 is a liquid crystal alignment film, 3 is a pixel electrode (ITO), 4 is an alignment regulating means (projection), and 5 is an alignment regulating means (slit).
  • And 6 are liquid crystal molecules.
  • the liquid crystal display device was observed under crossed Nicols at the voltage OFF and at AC 12 V (peak to peak).
  • the voltage holding ratio was measured 167 ms after the application was canceled.
  • the measuring device used was VHR-1 manufactured by Toyo Corporation.
  • a 30 Hz, 3.0 V rectangular wave with 3.0 V DC and 6.0 V AC (peak-to-peak) superimposed on the liquid crystal display element is applied for 20 hours at an ambient temperature of 70 ° C. Then, the voltage was turned off, and the time until the afterimage disappeared was visually measured.
  • N-Methyl-2-pyrrolidone was added in the order shown in Table 1 in the order of diamine and tetracarboxylic dianhydride.
  • Synthesis Examples 3, 4, 6, 8, and 9 were 30 weight percent solids. %, At 60 ° C for 6 hours.
  • Synthesis Examples 1, 2, 5, 7, and 10 were reacted at room temperature for 20 hours at a solid content of 20% by weight and reacted at room temperature for 6 hours.
  • Citrate I ⁇ table 1
  • T C AAH 2, 3, 5-tricarpoxycyclopentyl acetic acid dianhydride
  • Diamine diamine represented by formula (9)
  • Diamine diamine represented by formula (10)
  • Diamine 3 diamine represented by formula (13)
  • Each of the polyamic acids shown in Table 2 was diluted to a solid concentration of 5% by weight with N-methyl-2-pyrrolidone, and the amount of pyridine added was as shown in Table 2 for each mole of diamine used in the synthesis of each polyamic acid. And acetic anhydride at 110 ° C for 4 hours By stirring for a while, imidized polymers 1 to 8 were synthesized. The polymer solution was reprecipitated with dimethyl ether to obtain a white powder of an imidized polymer. The imidation ratio of the obtained polymer is also shown in Table 2. Table 2
  • Solvent % by weight of each solvent type based on the total solvent
  • the amount of additives is parts by weight of additives with respect to 100 parts by weight of polymer.
  • the vertical alignment of a liquid crystal is favorable and the afterimage elimination time is short, and a liquid crystal alignment film suitable for an MVA-type liquid crystal display element can be obtained.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un agent d'alignement de cristaux liquides permettant d'obtenir un alignement vertical de cristaux liquides, et comprenant un polymère avec deux types spécifiques d'unités répétitives d'acide amique et une unité répétitive d'imitation. L'agent d'alignement de cristaux liquides présente une excellente capacité d'alignement vertical de cristaux liquides, et est réduit par rapport au temps nécessaire pour effacer une image postérieure, pouvant ainsi être adéquatement utilisé pour un élément d'affichage à cristaux liquides de type MVA.
PCT/JP2002/006758 2001-07-03 2002-07-03 Agent d'alignement de cristaux liquides permettant d'obtenir un alignement vertical de cristaux liquides WO2003005113A1 (fr)

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JP2001202282A JP2003015135A (ja) 2001-07-03 2001-07-03 垂直配向型液晶配向剤
JP2001-202282 2001-07-03

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CN100345050C (zh) * 2003-10-21 2007-10-24 精工爱普生株式会社 液晶显示装置和电子设备

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JP2003073471A (ja) * 2001-08-31 2003-03-12 Jsr Corp 垂直配向型液晶配向剤およびそれを用いた液晶表示素子
JP4671015B2 (ja) * 2003-12-17 2011-04-13 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
JP4645823B2 (ja) * 2004-06-18 2011-03-09 Ｊｓｒ株式会社 垂直液晶配向剤、および垂直液晶表示素子
JP4372648B2 (ja) * 2004-09-13 2009-11-25 シャープ株式会社 液晶表示装置およびその製造方法
JP4604707B2 (ja) * 2004-12-22 2011-01-05 チッソ株式会社 液晶配向膜用ワニス組成物および液晶表示素子
JP5041123B2 (ja) * 2005-07-12 2012-10-03 Ｊｓｒ株式会社 垂直液晶配向剤
CN100520537C (zh) * 2005-07-12 2009-07-29 Jsr株式会社 垂直液晶取向剂
JP4788899B2 (ja) * 2006-03-24 2011-10-05 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
KR101879834B1 (ko) 2015-11-11 2018-07-18 주식회사 엘지화학 액정 배향막의 제조 방법, 이를 이용한 액정 배향막 및 액정 표시소자
KR101856727B1 (ko) 2016-06-21 2018-05-10 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
CN108885375B (zh) 2016-11-28 2021-05-18 株式会社Lg化学 液晶取向膜、用于制备其的方法和使用其的液晶显示装置
TWI662112B (zh) * 2017-04-21 2019-06-11 友達光電股份有限公司 藍相液晶顯示器、其製造方法、以及其所使用的對掌性材料
KR102065718B1 (ko) 2017-10-17 2020-02-11 주식회사 엘지화학 액정 배향막 및 이를 이용한 액정표시소자

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JPH11212097A (ja) * 1998-01-22 1999-08-06 Jsr Corp 液晶配向剤
JP2001027759A (ja) * 1999-07-13 2001-01-30 Fujitsu Ltd 液晶表示装置

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JP3840717B2 (ja) * 1996-10-25 2006-11-01 Ｊｓｒ株式会社 液晶配向剤および液晶表示素子
TWI271590B (en) * 1997-06-12 2007-01-21 Sharp Kk Liquid crystal display device

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JPH11212097A (ja) * 1998-01-22 1999-08-06 Jsr Corp 液晶配向剤
JP2001027759A (ja) * 1999-07-13 2001-01-30 Fujitsu Ltd 液晶表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100345050C (zh) * 2003-10-21 2007-10-24 精工爱普生株式会社 液晶显示装置和电子设备

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TW556030B (en) 2003-10-01
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KR100842156B1 (ko) 2008-06-27

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