WO2008114846A1 - Agent d'alignement de cristaux liquides et afficheur à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides et afficheur à cristaux liquides Download PDF

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Publication number
WO2008114846A1
WO2008114846A1 PCT/JP2008/055180 JP2008055180W WO2008114846A1 WO 2008114846 A1 WO2008114846 A1 WO 2008114846A1 JP 2008055180 W JP2008055180 W JP 2008055180W WO 2008114846 A1 WO2008114846 A1 WO 2008114846A1
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WIPO (PCT)
Prior art keywords
liquid crystal
aligning agent
crystal aligning
dianhydride
formula
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PCT/JP2008/055180
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English (en)
Japanese (ja)
Inventor
Tsubasa Abe
Yusuke Uesaka
Eiji Hayashi
Michinori Nishikawa
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Jsr Corporation
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Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to JP2009505249A priority Critical patent/JP5403261B2/ja
Priority to KR1020097005763A priority patent/KR101450923B1/ko
Priority to CN2008800091889A priority patent/CN101652707B/zh
Publication of WO2008114846A1 publication Critical patent/WO2008114846A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—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
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133784—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by rubbing

Definitions

  • the present invention relates to a liquid crystal display element and a liquid crystal aligning agent therefor. More specifically, the present invention relates to a liquid crystal display element excellent in liquid crystal alignment and storage stability and a liquid crystal aligning agent therefor. Background Technology ''
  • a nematic liquid crystal layer having a positive dielectric anisotropy is formed between two substrates having a liquid crystal alignment film formed on the surface thereof via a transparent conductive film to form a cell having a SANDENCHI structure.
  • a TN liquid crystal display element having a TN liquid crystal cell in which the major axis of liquid crystal molecules is continuously twisted 90 degrees from one substrate to the other is known.
  • the alignment of liquid crystal in a liquid crystal display element such as this TN type liquid crystal display element is usually realized by a liquid crystal alignment film provided with alignment ability of liquid crystal molecules by rubbing treatment.
  • resins such as polyimide, polyamide, and polyester, and an epoxy-based crosslinking agent are conventionally known.
  • polyimide is used in many liquid crystal display elements because of its excellent heat resistance, affinity with liquid crystals, and mechanical strength.
  • the rubbing resistance can be improved by adding an epoxy crosslinking agent to the resin.
  • the addition of an epoxy crosslinking agent is effective in achieving a high voltage holding ratio.
  • the present invention has been made on the basis of the circumstances as described above, and the first object of the present invention is to provide excellent adhesion to a substrate and to prevent rubbing scratches even by rubbing treatment performed under various conditions.
  • a liquid crystal aligning agent that can form a tough film that is difficult to stick, and can form a liquid crystal alignment film with excellent alignment regulating power of liquid crystal molecules by rubbing the surface of the film. It is in.
  • a second object of the present invention is to provide a liquid crystal aligning agent having excellent storage stability.
  • the third object of the present invention is to provide a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.
  • R Q 1 is a hydrogen atom or a monovalent organic group having 6 to 30 carbon atoms bonded to the N atom represented in the above formula by an aliphatic carbon.
  • a liquid crystal display device comprising a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.
  • the polyamic acid constituting the liquid crystal aligning agent of the present invention can be obtained by reacting tetracarboxylic dianhydride with a diamine compound.
  • tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5- (2,5-dixotetrahydro-3-furanyl, 1) 3-Methyl _ 3-Cyclohexene 1, 2, 2-dicarboxylic anhydride, 1, 2_dimethyl-1, 2, 3, 4-cyclobutantetracarboxylic dianhydride, 1, 3-dimethyl-1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-tetramethyl-1, 2, 3 , 4-cyclobutanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride, 3, 3 ', 4, 4
  • Aliphatic and alicyclic tetracarboxylic dianhydrides such as 6,8-tetracarboxylic dianhydride, compounds represented by the following formulas (I) and (I I);
  • R 1 and R 3 represent a divalent organic group having an aromatic ring
  • R 2 and R 4 represent a hydrogen atom or an alkyl group
  • a plurality of R 2 and R 4 each represent They may be the same or different.
  • diamine compounds used in the synthesis of the polyamic acid include P-phenylenediamine, m-phenylenediamine, 4, 4'-diaminodiphenyl methane, 4, 4'-diaminodiphenylethane, 4, 4 '-Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'- Diaminodiphenyl, 1,5-diaminonaphtholene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-11 (1,4'-aminominophenyl) -1,3,3-trimethylindane 6-Amino 1- (4, 1-aminophenol) 1 1, 3, 3-Trimethylindane, 3, 4'-Diaminodiphenyl ether Le, 3, 3
  • R 5 represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, lyrazine, piperidine and piperazine, and X represents a divalent organic group.
  • R 6 represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine
  • X represents a divalent organic group
  • the existing X may be the same or different.
  • R 7 represents a divalent organic group selected from 1 O—, —COO—, _OCO_, 1 NHCO—, —CONH —, and 1 CO—
  • R 8 represents a steroid skeleton, trifluoro
  • R 9 represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 9 may be the same or different, p is an integer of 1 to 3, and q is 1) It is an integer of ⁇ 20.
  • Examples thereof include compounds represented by the following formulas (9) to (13). These diamine compounds can be used alone or in combination of two or more.
  • the proportion of tetracarboxylic dianhydride and diamine compound used in the polyamic acid synthesis reaction is such that the amount of acid anhydride group of tetracarboxylic dianhydride is 1 equivalent to the amino group contained in the diamine compound.
  • the ratio force S to be 0.2 to 2 equivalents S is preferable, and the ratio to be 0.3 to 1.2 equivalents is more preferable.
  • the synthesis reaction of the polyamic acid is performed in an organic solvent under a temperature condition of preferably 1 20 to 15 50 t: more preferably 0 to 100.
  • the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid.
  • N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Sulfoxide, aptilolactone, tetrame examples include aprotic polar solvents such as tyluurea and hexamethylphosphoric triamide; and phenolic solvents such as m-cresol, xylenol, phenol, and nonogenated phenol.
  • the amount of organic solvent used (a) is 0.1 to 30% by weight based on the total amount of tetraforce rubonic acid dianhydride and diamine compound (b) and the total amount of reaction solution (a + b). Such an amount is preferred.
  • alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc. which are poor solvents for polyamic acid, can be used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate.
  • poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butyl diol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, Butyl Lactate, Acetone, Methyl Ethyl Ketone, Methyl Isoptyl Ketone, Cyclohexanone, Methyl Acetate, Ethyl Acetate, Ptyl Acetate, Methyl Methyl Cypropionate, Ethyl Ethoxy Propionate, Jetyl Succinate, Jetyl Malon, Jetyl Ether , Ethylene glycol
  • reaction solution obtained by dissolving polyamic acid is obtained. Then, this reaction solution is poured into a large amount of a poor solvent to obtain a precipitate, and this precipitate is dried under reduced pressure.
  • a polyamic acid can be obtained by drying. Further, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.
  • the imidized polymer used in the liquid crystal aligning agent of the present invention can be synthesized by dehydrating and ring-closing the polyamic acid.
  • the imidized polymer referred to here includes a partially imidized polymer obtained by partially imidizing the polyamic acid and a polymer obtained by immobilizing 100%. “Combined”.
  • Dehydration and ring closure of polyamic acid is required by (i) heating the polyamic acid or (i 1) dissolving polyamic acid in an organic solvent and adding a dehydrating agent and dehydration ring closure catalyst to this solution. According to the method of heating according to this.
  • the reaction temperature in the above method (i) of heating the polyamic acid is preferably 50 to 200, more preferably 60 to 170. If the reaction temperature is less than 50, the dehydration ring-closing reaction does not proceed sufficiently, and if the reaction temperature exceeds 20 Ot :, the molecular weight of the resulting imidized polymer may decrease.
  • an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent.
  • the amount of the dehydrating agent used is preferably from 0.01 to 20 mol per 1 mol of the polyamic acid repeating unit.
  • tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these.
  • the amount of the dehydration ring closure catalyst used is preferably from 0.01 to 10 mol per mol of the dehydrating agent used.
  • the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature of the dehydration cyclization reaction is preferably 0 to 180, more preferably 10 to 15:50.
  • the imidized polymer can be purified by performing the same operation as the polyamic acid purification method on the reaction solution thus obtained. ⁇ End-modified polymer>
  • the polyamic acid and the imidized polymer may be of a terminal modified type with a controlled molecular weight.
  • a terminal-modified polymer By using this terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be improved without impairing the effects of the present invention.
  • Such a terminal-modified type can be synthesized by adding an acid monoanhydride, a monoamine compound, a monoisocyanate compound or the like to the reaction system when the polyamic acid is synthesized.
  • the acid monoanhydride for example, maleic anhydride, anhydrous fuuric acid, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride And n-hexadecyl succinic anhydride.
  • Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pendecylamine, n-hexadecylamine, n-heptdecylamine, n-decylamine, n-eicosylamine, etc. it can.
  • Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
  • the polyamic acid and imidized polymer obtained as described above preferably have a value of logarithmic viscosity ( ⁇ ? ⁇ ⁇ ) of preferably 0.05 to 10 d 1 /, more preferably 0.05 to 5 d 1.
  • the value of the logarithmic viscosity ( ⁇ ? 1 ⁇ ) in the present invention was measured at 30 for a solution having a concentration of 0.5 g Zl 0 ml using N-methyl-2-pyrrolidone as a solvent. It is obtained by the following formula (i). 1 n (solution flow time / solvent flow time)
  • the epoxy compound used in the present invention is represented by the following formula (A).
  • R Q 1 is a hydrogen atom or a monovalent organic group having 6 to 30 carbon atoms bonded to the N atom represented by the above formula and an aliphatic carbon.
  • Examples of the monovalent organic group of R Q 1 include an alicyclic hydrocarbon group having a cyclohexane ring, a norbornene ring, an adamantane ring, an aromatic hydrocarbon such as a benzene ring and a naphthenic ring. It preferably contains a group.
  • Examples of the epoxy compound represented by the above formula (A) include compounds represented by the following formulas (A) — 1, (A) 1-2, and (A) -3.
  • R G 2 is a hydrogen atom or a monovalent organic group such as an alkyl group or a phenyl group. It may be a ring structure. R 0 2 may combine with the ring-forming carbon of the cyclohexane ring or benzene ring shown in (A) — 1, (A) 1 2 and (A) — 3 to form a ring structure. . R Q 3 is a hydrogen atom or a monovalent organic group such as an alkyl group or a phenyl group, and a plurality of R Q 3 may be different from each other. R Q 2 and R Q 3 may be cross-linked in the same molecule.
  • epoxy compounds include N, N-diglycidylcyclohexylamine, N, N-diglycidyl-2-methylcyclohexylamine, N, N-diglycidyl 4-methylcyclohexylamine, N, N-diglycidyl 2, 3-dimethylcyclohexylamine, N, N-diglycidyl 3, 3, 5-trimethylcyclohexyl, N, N-diglycidyl 4-tert-butylcyclohexylamine, N, N-diglycidyl 2-aminonorbornane, N , N-diglycidyl 1-ethynylcyclohexylamine, N, N-diglycy 1-adadamantane methylamine, 1,2,3,4-tetrahydro-1-mononaphthylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidyl-1-adadamantanemethylamine, N,
  • the liquid crystal aligning agent of the present invention comprises at least one selected from the [a] component comprising at least one polymer selected from polyamic acids and imidized polymers thereof, and an epoxy compound represented by the above formula (A).
  • the component [b] composed of seed is dissolved and contained in an organic solvent.
  • the ratio of the component [b] to 100 parts by weight of the component [a] is preferably 0.01 to 40 parts by weight, The amount is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight.
  • the organic solvent for dissolving the [a] component and the [b] component these can be dissolved.
  • the solvent is not particularly limited as long as it can be used, and examples thereof include the same solvents as exemplified for use in the synthesis of polyamic acid and dehydration ring closure.
  • liquid crystal aligning agent of the present invention may contain a functional silane-containing compound for the purpose of further improving the adhesion to the substrate.
  • functional silane-containing compounds include 3-aminomino trimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyl trimethoxysilane,
  • 2-Aminopropyltriethoxysilane N- (2-Aminoethyl) 1 3-Aminopropyl trimethoxysilane, N_ (2-Aminoethyl) 1 3-Aminopropylmethyldimethoxysilane, 3_Ureidopropyl Methoxysilane, 3-uredopropyltriethoxysilane, N-ethoxycarbonyl tri-aminotrimethoxysilane, N-ethoxycarbonyl 3-aminopropylenetoxisilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene-amine, 10-trimethoxysilyl-1,4- 4,7-triazadecane, 10-triethoxysilyl-1,4-, 7-triazadecane, 9-trimethoxysilyl-1,3, 6-diazanonyl acetate, 9-triethoxysilyl-1
  • Examples thereof include 3-aminopropyltriethoxysilane.
  • the solid concentration (total concentration of [a] component, [b] component and additive) in the liquid crystal aligning agent of the present invention is selected in consideration of viscosity, volatility, etc. It is in the range of ⁇ 20% by weight.
  • the solid content concentration is less than 0.1% by weight, the coating film (film) becomes too thin to obtain a good liquid crystal alignment film, and the solid content concentration is less than 20% by weight. If it exceeds the upper limit, it is difficult to obtain a good liquid crystal alignment film due to excessive film thickness, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating characteristics. There is a match.
  • the liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example with the following method.
  • a liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention on one surface of a substrate on which a patterned transparent conductive film is provided for example, a roll coater method, a spinner method, a printing method, an ink jet method, etc. Then, the coated surface is formed by heating the coated surface.
  • a substrate for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.
  • NESA film made of tin oxide (S N_ ⁇ 2) (US PPG registered trademark), oxidation in Jiumu tin monoxide - from (ln 2 0 3 S n 0 2)
  • An ITO film or the like can be used.
  • a photo-etching method or a method using a mask in advance is used.
  • a functional silane-containing compound, a functional titanium-containing compound, etc. Can also be applied in advance.
  • the heating temperature after application of the liquid crystal aligning agent is preferably 80 to 30 O :, more preferably 120 to 25.50.
  • the liquid crystal aligning agent of the present invention containing a polyamic acid has a force to form a coating film that becomes an alignment film by removing the organic solvent after coating, and further proceeds with dehydration ring closure by further heating, and is further imidized. It can also be a coating film.
  • the film thickness of the coating film to be formed is preferably from 0.01 to 1 m, more preferably from 0.05 to 0.5 m.
  • a rubbing process is performed in which the surface of the film formed of the liquid crystal aligning agent is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton. Thereby, the alignment ability of the liquid crystal molecules is imparted to the film to form a liquid crystal alignment film.
  • the surface of the resin film is irradiated with polarized ultraviolet rays, ion beams, electron beams, etc. to give alignment ability, uniaxial stretching method, Langmuir-
  • the liquid crystal alignment film can also be formed by a method of obtaining a film by a blow jet method or the like.
  • a resist film is partially formed on the substrate, and a rubbing process is performed in a direction different from the previous rubbing process, and then the resist film is removed to change the alignment ability of the liquid crystal alignment film (for example, a special
  • the viewing angle characteristics of the manufactured liquid crystal display element can also be improved by performing Kaihei 5- 10 7 5 4 4).
  • sealant for example, an epoxy resin containing a hardener and aluminum oxide spheres as a spacer can be used.
  • liquid crystals examples include nematic liquid crystals such as Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, and pyrimidine liquid crystals.
  • nematic liquid crystals such as Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, and pyrimidine liquid crystals.
  • Liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, and the like can be used.
  • these liquid crystals include, for example, cholestyl chloride, Cholesteryl type liquid crystals such as cholesteryl nonate and cholesteryl carbonate may be used with the addition of chiral agents such as those sold under the trade names “C-15” and “CB-15” (Merck). it can.
  • a polarizing film in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between a protective film of roulose acetate or A polarizing plate made of the H film itself can be mentioned.
  • the liquid crystal aligning agent of the present invention is excellent in storage stability, and according to this, it can form a tough film that is not easily damaged by rubbing treatment performed under various conditions. It is possible to form a liquid crystal alignment film having excellent alignment regulating power. For this reason, a liquid crystal display element free from alignment failure can be obtained.
  • the liquid crystal display element of the present invention can be effectively used in various devices, for example, display devices such as desk calculators, watches, table clocks, mobile phones, counting display boards, word processors, personal computers, and liquid crystal televisions. Can be suitably used.
  • Example 1 Example 1
  • Example ⁇ The presence or absence of anomalous domains when the voltage was turned on / off (applied / released) in the liquid crystal display element prepared in the comparative example was observed with a polarizing microscope. Table 1 summarizes the results of the evaluation of the liquid crystal alignment for each alignment agent.
  • the liquid crystal aligning agent is allowed to stand at room temperature for one week, and the viscosity of the liquid crystal aligning agent before and after being left is measured using an E-type viscometer.
  • the change rate of the viscosity calculated based on the following formula (ii) is The cases within% were judged as good and the other cases were judged as bad.
  • Viscosity reduction rate (%) (i i) Initial viscosity (mPs) Synthesis example 1
  • the deposited salt was removed by filtration, the filtrate was transferred to NASFlasco, and ethanol was removed by evaporation.
  • 30 ml of toluene was added, followed by separation and washing four times with 15 ml of pure water and once with 15 ml of a saturated aqueous sodium chloride solution.
  • the organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was filtered.
  • the organic layer was concentrated by evaporation.
  • the precipitated salt was removed by filtration, the filtrate was transferred to an eggplant flask, and ethanol was removed by evaporation. To the residue, 30 ml of toluene was added, followed by separation and washing four times with 15 ml of pure water and once with 15 ml of a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous magnesium sulfate, the magnesium sulfate was filtered, and the organic layer was concentrated by evaporation.
  • 2,3,5-tricarboxycyclopentyl succinic dianhydride as tetracarboxylic dianhydride 224. 17 g (0.5 mol) and 1, 3, 3 a, 4, 5, 9 b —hexahydro —Methyl-5— (Tetrahydro-1,2,5-Dioxo1,3-Frael) One naphtho [1, 2— c] —Furan 1,3-Dione 157. 14 g (0.5 mol), p as diamine compound —Phenylene diamine 93. 27 g (0.8 625 mol), bisaminopropyltetramethyldisiloxane 24.
  • polyimide (A-2) a polyimide having a logarithmic viscosity of 0.77 dlZg
  • polyamic acid (B— 1) “)” 360 g was obtained.
  • polyamic acid (B-2) After washing with methyl alcohol and drying at 40 under reduced pressure for 15 hours, 365 g of polyamic acid having a logarithmic viscosity of 0.90 d lZg (referred to as “polyamic acid (B-2)”) was obtained. .
  • polyamic acid (B-2) 365 g of polyamic acid having a logarithmic viscosity of 0.90 d lZg
  • An amount of a part was added to obtain a solution having a solid content of 4% by weight. After sufficient stirring, the solution was filtered using a filter having a pore size of 0.2 to prepare the liquid crystal aligning agent of the present invention.
  • the above liquid crystal aligning agent is applied onto a transparent conductive film made of an ITO film on one side of a 1 mm thick glass substrate using an inkjet printer (rotation speed: 2,000 rpm, application time: 1 And dried at 200 for 1 hour to form a film with a dry film thickness of 0.08 m.
  • a rubbing machine having a roll in which a rayon cloth was wrapped around this film was subjected to a rubbing treatment with a roll rotation speed of 400 rpm, a stage moving speed of 3 cm nosec, and a hair foot indentation length of 0.4 mm.
  • the liquid crystal alignment film coated substrate was immersed in isopropyl alcohol for 1 minute and then dried on a hot plate at 100 for 5 minutes.
  • the liquid crystal alignment film coated substrate After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 // m to each outer edge of the liquid crystal alignment film coated substrate of the pair of transparent electrodes, the liquid crystal alignment film coated substrate.
  • the liquid crystal alignment film surface is opposite
  • the adhesives were cured by overlapping and pressing.
  • a nematic liquid crystal (MLC-6221, MLC-6221) is filled between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic photo-curing adhesive, and polarized on both sides of the substrate.
  • the plates were laminated to make a liquid crystal display element.
  • the voltage holding ratio and liquid crystal orientation of the obtained liquid crystal display element were evaluated.
  • the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.
  • the liquid crystal aligning agent obtained in the present invention was confirmed to have good voltage holding ratio and liquid crystal alignment.
  • -Butyrolactone / N-methyl-2-pyrrolidone-nobutylcetosolve mixed solvent (weight ratio 70Z20-10) and N, N-diglycidylaminomethylcyclohexane obtained in Synthesis Example 1 was polymerized. Ten parts by weight were added to one to obtain a solution with a solid content of 4% by weight. After sufficient stirring, this solution was filtered using a filter having a pore size of 0.2 // m to prepare the liquid crystal aligning agent of the present invention.
  • Example 1 Using the liquid crystal aligning agent thus prepared, a film was formed on the substrate surface in the same manner as in Example 1, and a liquid crystal display element was produced using the substrate on which the liquid crystal aligning film was formed. Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.
  • 10 parts by weight was added to obtain a solution having a solid concentration of 4% by weight. After sufficient stirring, this solution was filtered using a filter having a pore size of 0.2 zm to prepare the liquid crystal aligning agent of the present invention.
  • Example 1 Using the liquid crystal aligning agent thus prepared, a film was formed on the substrate surface in the same manner as in Example 1. And a liquid crystal display element was manufactured using the substrate on which the liquid crystal alignment film was formed. Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.
  • polyimides (A-1) to (A-2) and polyamic acids (B-1) to (B-2) obtained in Synthesis Examples 3 to 6 and Synthesis Example 2 were obtained.
  • 10 parts by weight of the obtained N, N-diglycidyl benzylamine with respect to the polymer was added to the alpha-ptyrolactone ZN-methyl-2-pyrrolidone Z-ptylcetosolve solvent mixture (weight ratio 70/200).
  • a liquid crystal aligning agent of the present invention was prepared by dissolving and obtaining a solution having a solid content concentration of 4.0% and filtering this solution through a filter having a pore size of 0.2 / xm.
  • Example 1 Using each of the thus prepared liquid crystal alignment agents, a film was formed on the substrate surface in the same manner as in Example 1, and a liquid crystal display element was manufactured using the substrate on which the liquid crystal alignment film was formed. . Then, voltage holding ratio and liquid crystal alignment were evaluated. In addition, the storage stability of the prepared liquid crystal aligning agent was evaluated. The results are shown in Table 1.
  • Example 1 A-1 B-1 20/80 N, N-Cyclic aminomethylcyclohexane 10 Good Good Good Good
  • Example 2 A-1 B-2 20/80 N, N- Quaricyl'laminomethylcyclohexane 10 Good Good Good
  • Example 3 A-2 B-1 20/80 N, N-Silicy's lyaminomethylcyclohexane 10 Good Good Good
  • Example 4 A -1 B-1 20/80 N, N-squeeze to squeeze lumamine 10 Good Good Good Good
  • Example 5 A-1 B-2 20/80 N, N-squeeze lysyl
  • Example 6 A-2 B-1 20/80 N, N-SiC Rishi-he-Lumin 10 Good Good Good Good Good

Abstract

L'invention se rapporte à un agent d'alignement de cristaux liquides contenant (a) au moins un polymère sélectionné dans le groupe constitué par des acides polyamiques et leurs polymères imidés, et (b) un composé représenté par la formule (A) ci-dessous et comportant deux groupes époxydiques dans une molécule. Dans la formule, R01 représente un atome d'hydrogène ou un groupe organique monovalent qui comprend 6 à 30 atomes de carbone et qui est lié à l'atome N grâce à un carbone aliphatique.) Cet agent d'alignement de cristaux liquides présente une excellente stabilité au stockage ainsi qu'une excellente adhérence à un substrat, et permet de former une pellicule protectrice résistante qui n'est presque pas rayée lors des processus de frottement exécutés dans diverses conditions. Par conséquent, grâce audit agent d'alignement de cristaux liquides, il est possible de former un film d'alignement de cristaux liquides doté d'une excellente capacité d'alignement de cristaux liquides en appliquant un processus de frottement sur la surface de la pellicule protectrice.
PCT/JP2008/055180 2007-03-19 2008-03-14 Agent d'alignement de cristaux liquides et afficheur à cristaux liquides WO2008114846A1 (fr)

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JP2009505249A JP5403261B2 (ja) 2007-03-19 2008-03-14 液晶配向剤および液晶表示素子
KR1020097005763A KR101450923B1 (ko) 2007-03-19 2008-03-14 액정 배향제 및 액정 표시 소자
CN2008800091889A CN101652707B (zh) 2007-03-19 2008-03-14 液晶取向剂以及液晶显示元件

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140086816A (ko) 2012-12-28 2014-07-08 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP7355007B2 (ja) 2018-04-27 2023-10-03 日産化学株式会社 ゲストホスト型液晶調光素子用の液晶配向剤

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* Cited by examiner, † Cited by third party
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WO2013081064A1 (fr) * 2011-11-29 2013-06-06 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant
CN105190414B (zh) * 2013-03-12 2018-02-06 日产化学工业株式会社 包含具有光反应性基团的交联性化合物的液晶取向剂
KR102135493B1 (ko) * 2013-05-01 2020-08-26 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
KR102069288B1 (ko) 2013-08-28 2020-01-23 삼성디스플레이 주식회사 액정 배향제 및 액정 표시 장치
JP6372200B2 (ja) * 2013-10-07 2018-08-15 Jsr株式会社 液晶配向膜の製造方法、光配向剤及び液晶表示素子
CN108700778B (zh) * 2015-12-25 2022-07-19 日产化学工业株式会社 液晶表示元件、液晶光学元件和液晶结构体稳定化膜用组合物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10333153A (ja) * 1997-06-03 1998-12-18 Jsr Corp 液晶配向剤
JP2002541277A (ja) * 1999-04-06 2002-12-03 ロリク アーゲー 感光性ポリマー

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10333153A (ja) * 1997-06-03 1998-12-18 Jsr Corp 液晶配向剤
JP2002541277A (ja) * 1999-04-06 2002-12-03 ロリク アーゲー 感光性ポリマー

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140086816A (ko) 2012-12-28 2014-07-08 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자
JP7355007B2 (ja) 2018-04-27 2023-10-03 日産化学株式会社 ゲストホスト型液晶調光素子用の液晶配向剤

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KR20090127865A (ko) 2009-12-14
TW200903116A (en) 2009-01-16
KR101450923B1 (ko) 2014-10-14
CN101652707A (zh) 2010-02-17
TWI437330B (zh) 2014-05-11

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