WO2009054545A1 - Agent d'alignement de cristaux liquides, procédé de formation de film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, procédé de formation de film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2009054545A1
WO2009054545A1 PCT/JP2008/069821 JP2008069821W WO2009054545A1 WO 2009054545 A1 WO2009054545 A1 WO 2009054545A1 JP 2008069821 W JP2008069821 W JP 2008069821W WO 2009054545 A1 WO2009054545 A1 WO 2009054545A1
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Prior art keywords
liquid crystal
group
formula
above formula
acid
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PCT/JP2008/069821
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English (en)
Japanese (ja)
Inventor
Igor Rozhanskii
Shoichi Nakata
Eiji Hayashi
Michinori Nishikawa
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Jsr Corporation
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Priority to JP2009538296A priority Critical patent/JP5177450B2/ja
Priority to CN200880113146XA priority patent/CN101836155B/zh
Priority to KR1020107008894A priority patent/KR101169862B1/ko
Publication of WO2009054545A1 publication Critical patent/WO2009054545A1/fr

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    • 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
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a liquid crystal aligning agent, a method for forming a liquid crystal aligning film, and a liquid crystal display element.
  • a nematic fine type liquid crystal having positive dielectric anisotropy is made into a sandwich structure with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of the liquid crystal molecules is between the substrates as required.
  • a liquid crystal display element having a liquid crystal cell is known (see Japanese Patent Laid-Open No. 56-91277 and Japanese Patent Laid-Open No. 1-120528).
  • liquid crystal alignment film In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface.
  • This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon.
  • rubbing method if the liquid crystal alignment film is formed by rubbing, dust and static electricity are likely to be generated in the process, so that dust adheres to the alignment film surface and causes display defects.
  • TFT Thin Film Transistor
  • a radiation-sensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface is used.
  • a photo-alignment method that imparts liquid crystal alignment ability by irradiating polarized or non-polarized radiation is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (Japanese Patent Laid-Open Nos. 6-287453, 10-251646, 11-2815).
  • JP-A-11-152475 JP-A-2000-144136, JP-A-2000-319510, JP-A-2000-281724, JP-A-9-297313, JP-A-2003-307736, (See JP 2004-163646 and JP 2002-250924).
  • the liquid crystal alignment film tilts the liquid crystal molecules at a predetermined angle with respect to the substrate surface. It must have pre-tilt angle characteristics.
  • the pretilt angle characteristic is usually imparted by tilting the incident direction of irradiated radiation to the substrate surface from the substrate normal.
  • the photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal cell. That is, it is known that the tilt direction of liquid crystal molecules during voltage application can be uniformly controlled by using a vertical alignment film imparted with alignment regulating ability and pretilt angle characteristics by a photo-alignment method (Japanese Patent Laid-Open No. 2000-003). No. 307736, JP-A 2004-163646, JP-A 2004-83810, JP-A 9-211468 and JP-A 2003-11 4437).
  • the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements.
  • conventionally known liquid crystal aligning agents applicable to the photo-alignment method have a problem that a large amount of radiation is required to obtain a large pretilt angle.
  • the optical axis force S UV rays with a wavelength of 365 nm tilted from the substrate normal line are used. , 000 J / m 2 or more has been reported (Japanese Patent Laid-Open No. 2002-250924) (See Japanese Patent Publication No. 2004-83810 and J. oft he SID 11/3, 2003, p 579).
  • the applicant of the present application can obtain a sufficient pretilt depression angle by irradiating only about 1,000 J / m 2 of ultraviolet rays with a wavelength of 313 nm by using a specific cinnamate derivative.
  • Proposed a new technique (see JP 2007-224273 A).
  • This technology is an excellent technology that breaks the limits of the conventional technology, but the cinnamate derivative has a wavelength that is widely used because it is easy to obtain a high-intensity light source because the absorption wavelength is biased toward the short wavelength side.
  • the 365 nm ultraviolet light cannot be used. Disclosure of the invention
  • the object of the present invention is to provide a liquid crystal alignment ability with a small radiation dose even when using a light source in a long wavelength region where a high-intensity light source is easily obtained by irradiation with polarized or non-polarized radiation without rubbing treatment.
  • a liquid crystal aligning agent capable of imparting S, a method of forming a liquid crystal alignment film from the liquid crystal aligning agent, a diammine suitably used for manufacturing the liquid crystal aligning agent, a manufacturing method thereof, display characteristics, and reliability It is to provide a liquid crystal display element excellent in various performances.
  • Ar represents a divalent aromatic group
  • 3 1 and 3 2 each independently represent a divalent linking group or a single bond
  • Y represents a monovalent organic group
  • Z is a trivalent organic group
  • D 1 and D 2 each independently represent an oxygen atom, a sulfur atom or —NR— (wherein R is a hydrogen atom or an alkyl group).
  • liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyamic acid obtained by using a diamine represented by formula (I) and an imidized product thereof.
  • the liquid crystal aligning agent is applied on a substrate to form a coating film, and the liquid crystal alignment film is formed by irradiating the coating film with radiation.
  • the object of the present invention is
  • Fig. 1 shows the 1 H-NMR spectrum of the diamine (14a) obtained in Synthesis Example 1.
  • the liquid crystal aligning agent of the present invention comprises a compound represented by the above formula (1) (hereinafter “diamin”).
  • the polyamic acid that can be used in the liquid crystal aligning agent of the present invention is a polymer obtained by using diamine (1), and preferably a tetracarboxylic dianhydride and diamine containing diamine (1) are reacted. It is a polymer obtained. [Jiamin (1)]
  • the divalent aromatic group of Ar in the above formula (1) is preferably a divalent aromatic group having 5 to 20 carbon atoms, specifically, for example, a 1,2-phenylene group, 1 , 3—Phenylene group, 1,4—Phenylene group, 3, 3, 1 Biphenylylene group, 3, 4, 1 Phiphenylylene group, 4, 4, 1 Biphenylylene group, 3, 3 "— m—Evening Phenylylene group, 4, 4 "1 p-Evening phenylylene group, 1, 4 1-naphthylene group, 2, 6-naphthylene group, 2, 7-naphthylene group, 2, 6-anthrylene group, 9, 10-anthrylene group, 2, 4 One flanged group, 3, 4—Flangedyl group, 2, 5—Flangedyl group, 2, 4—Tiofensyl group, 3, 4—Tiofensyl group, 2, 5—Tiofensyl group, 2, 4—Pyrrolzyl
  • One or more hydrogen atoms contained in these groups are substituted with a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom; Selected from the group consisting of an alkoxyl group having 1 to 6 carbon atoms; an aryl group that may be substituted with a halogen atom; and an aryloxy group having 6 to 14 carbon atoms that may be substituted with a halogen atom. Mention may be made of groups obtained by substitution with at least one group.
  • S 1 is a divalent group or a single bond force represented by the above formula (S-3), and S 2 is a 2 in the above formula (S-1).
  • S 1 is a divalent group or a single bond force represented by the above formula (S-3)
  • S 2 is a 2 in the above formula (S-1).
  • a divalent group in which b is 1 or a single bond is preferred.
  • Y is a monovalent organic group, preferably an alkyl group having 5 or more carbon atoms, a monovalent group having 5 or more carbon atoms having an alicyclic structure, or a haloalkyl group having 1 or more carbon atoms, and more preferably.
  • Z is a trivalent organic group, preferably a trivalent aromatic group having 5 to 20 carbon atoms.
  • phenyl, tolyl, xylyl, mesityl, cumenyl bif Examples of groups obtained by removing two hydrogen atoms from a benzene ring of a monovalent group having 6 to 20 carbon atoms having a benzene ring such as an benzyl group, a naphthyl group, a benzyl group, a phenethyl group, or a benzoyl group be able to. Of these, a group obtained by removing two hydrogen atoms on the benzene ring of a phenyl group or a benzyl group is preferable.
  • D 1 and D 2 are each independently an oxygen atom, a sulfur atom or one NR- (wherein, R is a hydrogen atom or an alkyl group), preferably an oxygen atom or - NH-, particularly preferably oxygen Is an atom.
  • diamine (1) used in the present invention include, for example, the following formulas (la) to (20 a;), (lb) to (20 b), (1 c) to (20 c) and (1 Examples thereof include compounds represented by d) to (20d).
  • the compound represented by the above formula (2) is synthesized by reacting the reaction product with the reaction product, and reacting the reaction product with alcohol, phenol, octahalogenated alkyl, halogenated aryl, amine or carboxylic acid chloride. Then, it can be produced by a method of reducing it.
  • Compounds represented by the above formula (C_l) include, for example, halocatenoic acid, halocatenoic acid lide, 41- (4-halophenyl) keihynoic acid and alcohol, phenol, halogenated alkyl, octalogated aryl Alternatively, it can be obtained by reacting with an amine.
  • Examples of the compound represented by the above formula (A-1) include acrylic acid, acrylic acid chloride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyhexyl acrylate. It can be obtained by reacting a compound such as a rate with a compound such as an alcohol having two nitro groups, phenol, alkyl halide, halogenated aryl, or carboxylic acid chloride.
  • acrylic acid derivatives such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate , Hexyl acrylate, lauryl acrylate, stearyl acrylate, 2 (perfluorooctyl) ethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name “F A_ 1 0 8”), etc.
  • the compound represented by the above formula (C-2) includes, for example, octalohynoic acid, halochenoyl chloride, 4- (4-halophenyl) kehinoic acid, an alcohol having two ditro groups, phenol It can be obtained by reacting with a compound such as an alkyl halide, a halogenated aryl, or a carboxylic acid chloride.
  • Diamine (1) can be obtained, for example, by reducing the compound represented by the above formula (2) obtained through the Heck reaction as described above.
  • a milder reagent as much as possible.
  • mild reaction reagents include tin (I I) chloride or metal zinc, or a combination thereof with hydrogen chloride or ammonium chloride. Of these, tin chloride (I I) is particularly preferred because of its mild reactivity.
  • Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid used in the liquid crystal aligning agent of the present invention include, for example, butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic Acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetraforce sulfonic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetra-force sulfonic acid 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, dicyclohe
  • R 1 and R 3 each represent a divalent organic group having an aromatic ring
  • R 2 and R 4 each represent a hydrogen atom or . an alkyl group
  • aromatic tetracarboxylic dianhydrides such as compounds represented by the above. These may be used alone or in combination of two or more.
  • the benzene ring of the aromatic dianhydride may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).
  • the diamine used in synthesizing the polyamic acid used in the liquid crystal aligning agent of the present invention contains the above-mentioned diamine (1).
  • diamine (1) in synthesizing the above polyamic acid, other diamines can be used together with diamine (1) as diamine.
  • the proportion of diamine (1) in the total diamine used here is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and more preferably 20 to 50 mol%. That power S is particularly preferable.
  • An aromatic diamine such as a compound represented by:
  • R 5 is -0, 1 COO-, 10C 0, -NHCO-
  • R 6 is a monovalent organic group having a skeleton or a group selected from steroid skeleton, trifluoromethylphenyl group, and fluorophenyl group. or an alkyl group with carbon number. 6 to 30, R 7 is an alkyl group having 1 to 4 carbon atoms, a 1 is an integer of 0 to 3.
  • R 8 is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X 1 is a divalent organic group.
  • R 9 is an alkyl group having 1 to 4 carbon atoms, and & 2 is an integer of 0 to 3.
  • R 1 is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and R 1 1 is each Carbon number;!
  • a 3 is an integer of 0 to 4 respectively
  • X 2 is a divalent organic group, a plurality of a 3 and X 2 are Each may be the same or different.
  • Diamines having two primary amino groups in the molecule and nitrogen atoms other than these primary amino groups (excluding those corresponding to the compounds represented by the above formula (D—I)) .);
  • R 12 is each a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 12 may be the same or different, and p is each ,:! ⁇ Is an integer of 3 and q is an integer of 1 ⁇ 20.
  • diaminoorganosiloxanes such as compounds represented by the formula: These diamines can be used alone or in combination of two or more.
  • the benzene ring of the aromatic diamine may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).
  • R 7 , R 9 and R 11 in the above formulas (D_I), (D-II) and (D-III) are each preferably a methyl group, and al, a 2 and a 3 are each 0 or 1 is preferable, and 0 is more preferable.
  • R 6 having a steroid skeleton include, for example, cholestane-1-yl group, cholester-5-ene-3-yl group, cholester 24 _en-1-yl group, cholester-5 , 24-Gen 3-yl group, Lanostane 3-yl group, and the like.
  • dodecanoxy-1,2,4-diaminobenzene pentadecanoxy-1,2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-1 , 5-Diaminobenzene, Dodecanoxy-1, 2, 5-Diaminobenzene, Pentadecanoxy-2, 5-Diaminobenzene, Hexadecanoxy-1, 2,5-Diaminobenzene, Octadecanoxy 2, 5-Diaminobenzene and the following formula (D-8) (D—1
  • the proportion of tetracarboxylic dianhydride and diamine used in the synthesis reaction of the polyamic acid that can be used in the liquid crystal aligning agent of the present invention is such that the tetracarboxylic dianhydride is equivalent to 1 equivalent of the amino group contained in the diamine.
  • the ratio of the anhydride acid anhydride group to 0.2 to 2 equivalents is preferred, and the ratio to 0.3 to 1.2 equivalents is more preferred.
  • the polyamic acid synthesis reaction is preferably carried out in an organic solvent, preferably-
  • the reaction is carried out at a temperature of 20 to 15 ° C, more preferably 0 to 100 ° C, and preferably 0.5 to 500 hours, more preferably 5 to 200 hours.
  • the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid.
  • Non-proline polar solvents such as n-butyrolactone, tetramethylurea and hexamethylphosphoric triamide
  • phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol.
  • the amount of organic solvent used (a: when organic solvent is used in combination with the poor solvent described later, this means the total amount used).
  • organic solvent alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc., which are generally believed to be poor solvents for polyamic acid, should be used in combination as long as the polyamic acid to be produced does not precipitate. Can do.
  • Such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4 monobutanediol, triethylene glycol, ethylene glycol mono Methyl ether, lactyl acetate, butyl lactyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, cetyl oxalate Jetyl malonate, Jetyl ether, Ethylene glycol methyl ether, Ethylene glycol ethyl ether, Ethylene glycol mono-n-propyl ether, Ethylene glycol-i monopropyl ether, Ethi Lenglycol
  • the proportion of the polyamic acid generated can be appropriately set within the range where it does not precipitate. It is 70% by weight or less, and more preferably 50% by weight or less.
  • a reaction solution obtained by dissolving polyamic acid is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, and after the polyamic acid contained in the reaction solution is isolated, it may be used for the preparation of the liquid crystal aligning agent, or the isolated polyamic acid is purified. In addition, you may use for preparation of a liquid crystal aligning agent.
  • Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. Can be performed.
  • the polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of evaporating under reduced pressure with an evaporator once or several times.
  • the imidized polyamic acid (imidized polymer) that can be used in the present invention can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid as described above.
  • the tetracarboxylic dianhydride used for synthesizing the polymer is a tetracarboxylic dianhydride containing alicyclic tetracarboxylic dianhydride.
  • Carboxylic dianhydrides are preferred, especially 2, 3, 5 1,3,3 a, 4,5,9b—Hexahydro-5- (tetrahydro-1,2,5-doxo-3-furanyl) mononaphtho [1, 2— c ] Furan 1,3-dione, 1, 3, 3 a, 4, 5, 9b—Hexahydro 8-Methyl 1 5- (Tetrahydro 1,5-dioxo 3-furanyl) One naphtho [1, 2—c] furan-1,3-dione, 3-oxabicyclo [3. 2.
  • octane-1,4-dione 6 spiro 1 ′ (tetrahydrofuran-2 ′, 5′—dione), 5— (2,5-Dioxotetrahydro-3-furanyl) 1-Methyl-3-cyclohexene 1,2-Dicarboxylic anhydride, 3, 5,6 1-trioxyloxy 2_Carpoxymethylnorpolnan — 2: 3, 5: 6-dianhydrous and 4,9-dioxatricyclo [5. 3. 1. 0 2 ' 6 ] undecane group 3, 5, 8, 10-tetraone A tetracarboxylic dianhydride containing at least one selected from is preferred.
  • the ratio of the alicyclic tetracarboxylic dianhydride in the total tetracarboxylic dianhydride is preferably 50 mol% or more, more preferably 90 mol% or more.
  • the diamine used for synthesizing this is the same as described above for the polyamic acid.
  • Dehydration and ring closure of polyamic acid can be accomplished by (i) heating the polyamic acid, or (ii) dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure catalyst to this solution, and heating as necessary. By the method.
  • the reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 200 ° C., more preferably 60 to 170. When the reaction temperature is less than 50 ° C, the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C, the molecular weight of the resulting imidized polymer may decrease.
  • the reaction time in the method of heating the polyamic acid is preferably 0.5 to 200 hours, more preferably 10 to 100 hours.
  • a dehydrating agent and a dehydrating ring-closing catalyst are added to the polyamic acid solution (ii).
  • the dehydrating agent for example, an acid anhydride such as acetic anhydride, propionic anhydride, or anhydrous trifluoroacetic acid can be used.
  • the amount of the dehydrating agent used is preferably 0.01 to 20 moles per mole of the structural unit of the amic acid.
  • tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. However, it is not limited to these.
  • the amount of the dehydrating ring-closing catalyst used is preferably from 0.01 to 10 mol per 1 mol of the dehydrating agent used.
  • the organic solvent used for the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid.
  • the reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 50 hours, more preferably 1 ⁇ 10 hours.
  • the reaction solution thus obtained may be directly used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution.
  • the imidized polymer may be isolated and then used for preparing a liquid crystal aligning agent, or the isolated imidized polymer may be purified and then used for preparing a liquid crystal aligning agent.
  • a method such as solvent replacement can be applied. Isolation and purification of the imidized polymer can be performed by performing the same operations as in the isolation and purification method of polyamic acid.
  • the imidized polymer used in the present invention may have a low imidization ratio in which only a part of the amic acid structure is dehydrated and cyclized.
  • the imidization ratio of the imidized polymer used in the present invention is preferably 20% or more, more preferably 40% or more.
  • the “imidation ratio” is a percentage of the number of imide rings to the total number of amic acid units and imide rings in the polymer. At this time, a part of the imide ring may be an isoimide ring.
  • the imidization rate is determined by dissolving 1 imide polymer in a suitable solvent such as deuterated dimethyl sulfoxide, measuring 1 H—NMR at room temperature using tetramethylsilane as a reference substance, and using the following formula (1): It can be determined by the formula shown.
  • Imidization rate (%) (1— A 1 / A 2 X) X 1 0 0 • (1)
  • a 1 is the peak area derived from the protons of the NH group found at 10 ppm
  • a 2 is the peak area derived from other protons
  • ⁇ is the polyamic acid before the dehydration ring closure reaction. Is the ratio of the number of other protons to one proton of ⁇ group in
  • the polyamic acid and imidized polymer may be of a terminal-modified type with a controlled molecular weight.
  • a terminal-modified polymer is synthesized by adding a molecular weight regulator such as acid monoanhydride, monoamine compound, or monoisocyanate compound to the reaction system when synthesizing the polyamic acid. Can do.
  • the acid monoanhydride for example, maleic anhydride, fuuric anhydride, itaconic anhydride, ⁇ -decylsuccinic acid anhydride, ⁇ -dodecylsuccinic acid anhydride, ⁇ -tetradecylsuccinic acid Anhydride, ⁇ -hexadecyl succinic anhydride, etc. can be mentioned.
  • Examples of the monoamine compound include aniline, hexylamine, ⁇ -butylamine, 11-pentylamine, ⁇ -hexylamine, ⁇ -heptamine, ⁇ -talylamine, ⁇ -nonylamine, ⁇ -decylamine, ⁇ -undecylamine, ⁇ -dodecylamine, ⁇ -tridecylamine, ⁇ -tetradecylamine, ⁇ -pendecylamine, ⁇ -hexadecylamine, ⁇ -heptadecylamine, ⁇ -aged decadecamine, ⁇ -eicosylamine .
  • Examples of monoisocyanate compounds include phenyl isocyanate and naphthyl isocyanate.
  • the amount of these molecular weight regulators used is preferably 0.2 mol or less, more preferably 0.1 mol or less, based on 1 mol of diamine used in the synthesis of the polyamic acid.
  • the polyamic acid or imidized polymer thereof contained in the liquid crystal aligning agent of the present invention has a concentration of 20 to 80 mPa when dissolved in N-methylpyrrolidone to give a solution having a concentration of 10% by weight. ⁇ It is preferable that it exhibits a viscosity of s, and it is more preferable that it exhibits a viscosity of 30 to 50 Om Pa * s.
  • the solution viscosity (m P a ′ s) is a value measured at 25 ° C. using an E-type rotational viscometer.
  • the liquid crystal aligning agent of the present invention has a group strength composed of the above polyamic acid and imidized product thereof, a force containing at least one selected from the above as an essential component, and other components as long as the effects of the present invention are not impaired. Can be contained.
  • other components include polymers other than the above polyamic acid and imidized products thereof (hereinafter referred to as “other polymers”) compounds having at least one epoxy group in the molecule (hereinafter simply referred to as “epoxy compounds”). )), And functional silane compounds.
  • Said other polymer can be used in order to improve the solution characteristic of the liquid crystal aligning agent of this invention, and the electrical property of the liquid crystal aligning film obtained.
  • examples of such other polymers include polyamic acids other than the above polyamic acids, imidized products thereof, polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene monophenyl maleimide) derivatives, Examples include poly (meth) acrylate.
  • the use ratio is the total of the polymers (the total of the above polyamic acid and its imidized product and other polymers. The same applies hereinafter. )) Is preferably 90% by weight or less, and more preferably 80% by weight or less.
  • the said epoxy compound can be used in order to improve the adhesiveness with respect to the substrate surface of the liquid crystal aligning film obtained. Examples of the epoxy compound include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether. 4 hours
  • the percentage of usage of the functionally functional cisilarane compound is as follows, with respect to the total weight of the total weight of the polymerized polymer. However, it is less than 44 parts by weight or less. . Gugu liquid crystal alignment agent >>
  • the liquid crystal alignment agent according to the present invention is from the group consisting of the above-described polypolyamimic acid and its imidized compound. There are at least 11 different polymer combinations and other components that can be optionally added to the polymer. If desired, the composition may be dissolved or dissolved in an organic solvent solvent medium. .
  • organic solvent solvent that constitutes the liquid crystal crystal alignment agent of the present invention a synthetic reaction of polypolyamimic acid can be used.
  • the solvent solvent shown as an example as an example of what can be used for the reaction can be separated from here. .
  • Concentration of solid-solid fraction in the liquid crystal crystal alignment agent of the present invention (components other than the solvent solvent of the liquid crystal crystal alignment agent) This is the ratio of the total weight of the liquid to the total weight of the liquid crystal alignment agent.)) Is the viscosity It is selected in consideration of volatility and volatility. . The preferred range is from 11 to 1100 weight percent%. . Susuna no Wachi, the invention of the present invention
  • 2200 Night-night crystal orientation aligning agent is coated on the surface of the base substrate plate and forms a coating film that forms a liquid crystal crystal orientation film. If it is formed, but the solid content concentration concentration is less than 11% by weight%, the coating film here The film thickness of the film is too small and small, and it is difficult to obtain a good and favorable liquid crystal crystal orientation film, and the solid-solid fraction concentration concentration is In the case where the weight exceeds 1100% by weight%, the film thickness of the coating film becomes excessively large. It is difficult to obtain a good and favorable liquid crystal crystal alignment film, and the viscosity of the liquid crystal crystal alignment agent is increased and increased. The special characteristics of the coated fabric are inferior. .
  • the range of solid solid content concentration that can be particularly preferred is the range of liquid crystal alignment agent on the base substrate. It depends on the method used for the method. . For example, in the case according to the Spipin Nana method, the range of 11 to 55% to 44 to 55% by weight %% Leave it. . In the case of the printing method, the solid / solid content concentration is set within the range of 33 to 99% by weight%, and According to this, it is particularly preferable to set the viscosity of the solution solution within the range of 11 22 to 55 OO mmPP aa ⁇ ss. Good.
  • the solid content concentration is in the range of 1 to 5% by weight, and the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
  • Particularly preferable organic solvents used in the liquid crystal aligning agent of the present invention include, for example, N-methyl-2-pyrrolidone, r-butyrolactone, tert-butylactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4 -Hydroxy-4 1 Methyl-2-Pen Yunone, Ethylene glycol monomethyl ether, Butyl lactate, Ptyl acetate, Methyl methoxypropionate, Ethyl ethoxypropionate, Ethylene glycol methyl ether, Ethylene glycol ether ether, Ethylene glycol N-propyl ether, ethylene glycol i-propyl ether, ethylene glycol i-propyl ether, ethylene glycol
  • the liquid crystal alignment film of the present invention is formed from the liquid crystal alignment film of the present invention as described above.
  • the liquid crystal alignment film of the present invention can be produced, for example, by the following method. First, the liquid crystal aligning agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film, for example, a roll coating method, a spinner method, a printing method, an ink jet method or the like. Then, the coated surface is preferably heated to form a coating film.
  • a patterned transparent conductive film for example, a roll coating method, a spinner method, a printing method, an ink jet method or the like.
  • the substrate for example, glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyethersulfur Transparent substrates made of synthetic resins such as phon, polycarbonate, and poly (alicyclic olefins) can be used.
  • the transparent conductive film provided on one surface of a substrate NESA film made of tin oxide (Sn_ ⁇ 2) (US PPG registered trademark), oxidation in Jiumu tin monoxide (ln 2 0 3 - Sn_ ⁇ 2) consisting of I A TO film or the like can be used.
  • a method using photo-etching or a method using a mask when forming the transparent conductive film is used.
  • a silane coupling agent, titanate compound or the like may be applied to the surface of the substrate in advance. Good.
  • preheating is preferably performed for the purpose of removing the solvent contained in the liquid crystal aligning agent to prevent dripping.
  • the pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C.
  • a baking (post-bake) process is performed for the purpose of completely removing the solvent.
  • the calcination (post-bake) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
  • the liquid crystal aligning agent of the present invention thus forms a coating film that becomes a liquid crystal aligning film by removing the organic solvent after coating, but the liquid crystal aligning agent of the present invention contains a polymer having an amic acid structure.
  • the film can be further heated to promote dehydration and cyclization to form a more imidized coating film.
  • the film thickness of the coating film to be formed is preferably 0.001 to 1 m, more preferably 0.005 to 0.5 m.
  • the coating film is irradiated with linearly polarized light, partially polarized radiation or non-polarized radiation, and in some cases, further heated at a temperature of 150 to 250 ° C. to give liquid crystal alignment ability.
  • An alignment film can be formed.
  • ultraviolet rays having a wavelength of 150 nm to 800 nm and ultraviolet rays having a wavelength of 300 nm to 400 nm capable of using visible light rays are preferable.
  • the irradiation dose is preferably 50 to 5,000 J / m 2 , more preferably 200 to 2 , OOOJ / m 2 .
  • the liquid crystal aligning agent of the present invention has a ratio Even when radiation having a relatively long wavelength, for example, radiation having a wavelength of about 3650 nm to 400 nm including ultraviolet light having a wavelength of 36.5 nm, which is used for general purposes, a small radiation dose, for example, 10 , 0 0 0 0 J Zm 2 or less, and further 5 or 0 0 0 0 J / m 2 or less, it has an advantage that a liquid crystal alignment film showing good liquid crystal alignment performance can be obtained.
  • irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or these may be applied. You may go in combination.
  • the direction of irradiation needs to be oblique.
  • low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, YAG lasers, excimer lasers, argon lasers, and semiconductor lasers should be used as radiation sources.
  • the ultraviolet rays in the preferred wavelength region can be obtained by means of using a filter, a diffraction grating, or the like together with a light source, for example.
  • various laser single light sources as the light source it may be irradiated with a wavelength of 1/2, 1/3, or 1 Z4 times by combining this with a nonlinear optical crystal.
  • the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed as described above.
  • the liquid crystal display element of the present invention can be produced, for example, by the following method. As described above, two substrates (one pair) on which the liquid crystal alignment film of the present invention was formed were prepared, and the two substrates were formed so that the radiation directions of the respective liquid crystal alignment films were orthogonal or antiparallel. Are placed opposite to each other with a gap (cell gap) between them, and the peripheral parts of the two substrates are bonded together using a sealing agent, and liquid crystal is injected and filled into the cell gap partitioned by the substrate surface and the sealing agent. The holes are sealed to form a liquid crystal cell. And a liquid crystal display element can be obtained by arrange
  • the sealing agent for example, an epoxy resin containing aluminum oxide aluminum spheres as a curing agent and a spacer can be used.
  • the liquid crystal include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable.
  • a Schiff base liquid crystal, an azoxy liquid crystal, a phenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, A tert-phenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, and a cubane liquid crystal can be used.
  • cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate; trade names “C-15” and “CB-15” (Merck) It may be used by adding a ferroelectric liquid crystal such as p-decyloxybenzylidene p-amino-2-methylbutyl cinnamate.
  • the polarizing plate to be bonded to the outer surface of the liquid crystal cell is a polarizing plate in which a polarizing film called “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films or H
  • a polarizing plate made of the film itself is a polarizing plate made of the film itself.
  • Imidization ratio of imidized polymers in the following synthesis examples were sufficiently dried under reduced pressure imidized polymer at room temperature, deuterated dimethyl sulfoxide as a solvent, at room temperature 1 H- NMR of tetramethyl Rushiran as reference substance Using each peak area of the chart obtained by measurement, it was obtained by the above formula (1).
  • 3,5-Dinito mouth benzoate was suspended in 200 mL of pyridine. This While the suspension was cooled with ice, a solution of 29.4 g of (iii) dissolved in 10 OmL of pyridine was slowly added. The mixture was stirred at 0 ° C. for 15 minutes and then reacted at room temperature for an additional hour. This reaction mixture was poured into 2.4 kg of hydrochloric acid acidic ice water, and the resulting precipitate was recovered by filtration. The recovered precipitate was heated and refluxed twice in ethanol to remove unreacted components, whereby 35 g (yield 85%) of (iv) white powder was obtained.
  • TCA 2, 3, 5-Tri-force loxycyclopentyl acetic acid dianhydride
  • CBDA 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride
  • the liquid crystal aligning agent was prepared by diluting to a solution with a solid content concentration of 2.5% by weight and further filtering this solution through a filter having a pore size of 1 m.
  • the liquid crystal aligning agent prepared above was applied onto the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner and heated at 180 ° C. for 1 hour to obtain a film thickness of 0.06.
  • a coating film was formed.
  • the surface of the coating film was irradiated with polarized ultraviolet light containing 313 nm and 365 nm emission lines using a Hg-Xe lamp and Grande Taylor prism for 50 seconds from a direction inclined 45 ° from the substrate normal, thereby improving the liquid crystal alignment ability.
  • a liquid crystal alignment film was thus formed.
  • the illuminances at wavelengths of 313 nm and 365 nm on the irradiated surface were 2 mWZ cm 2 and 5 mW / cm 2 , respectively.
  • the same operation was repeated to create two (one pair) substrates that were irradiated with polarized UV light.
  • an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 zm was applied to the outer periphery of the surface on which the liquid crystal alignment film was formed by screen printing.
  • the substrates were stacked and pressure-bonded so that the irradiation directions of polarized ultraviolet rays were antiparallel to each substrate, and the adhesive was heat-cured at 150 ° C for 1 hour.
  • a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled into the gap between the liquid crystal inlet and the substrate, and the liquid crystal inlet was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated at 150 and then gradually cooled to room temperature.
  • a polarizing plate was bonded to both the outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other and at an angle of 45 ° with the polarization direction of the liquid crystal alignment film, thereby producing a liquid crystal display element.
  • the liquid crystal display device manufactured as described above is based on the method described in Non-Patent Document 2 (TJ Scheffer. A 1. J. Ap p 1. Phys. V o. 19, p. 201 3 (1980)).
  • the pretilt angle was 89 ° as determined from the tilt angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using He—Ne laser light.
  • Example 1 instead of the solution containing the imidized polymer (B-17), the solutions containing the polyamic acid or imidized polymer synthesized in the above Synthesis Examples 18 to 39 are shown in Table 3.
  • a liquid crystal aligning agent was prepared in the same manner as in Example 1 except that each of these was used, and a liquid crystal display element was produced and evaluated. The evaluation results are shown in Table 3.
  • Example 2 4
  • Example 1 a liquid crystal display was used in the same manner as in Example 1 except that the emission line with a wavelength of 3 13 nm was cut using a mouth-cut filter at the time of irradiation with polarized ultraviolet light and the irradiation time was set to 100 seconds.
  • the pretilt angle was 89 ° and the liquid crystal alignment was good. Comparative Example 1
  • Example 24 except that the solution containing polyamic acid (a-1) synthesized in Comparative Synthesis Example 1 was used instead of the solution containing imidized polymer (B-17).
  • a liquid crystal aligning agent was prepared in the same manner as described above, and a liquid crystal display device was produced and evaluated. The evaluation results are shown in Table 3.
  • the liquid crystal aligning agent of the present invention uses a light source in a long wavelength region where a high-intensity light source can be easily obtained, for example, UV light having a wavelength of 365 nm, which is used for general purposes. Even in such a case, a liquid crystal alignment film can be formed by a photo-alignment method with a small radiation dose. Therefore, this liquid crystal alignment film is applied to liquid crystal display elements. In this case, the liquid crystal display element can be manufactured at a lower cost than before.
  • the liquid crystal display element having the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be effectively applied to various apparatuses, for example, a desk calculator, a wristwatch, a table clock, a counting display board, a word processor, a personal computer. 1. It can be suitably used for devices such as liquid crystal televisions.

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Abstract

L'invention porte sur un agent d'alignement de cristaux liquides contenant au moins un polymère choisi dans le groupe constitué par des acides polyamiques obtenus à l'aide de diamines représentés par la formule (1) ci-dessous et des produits imidés de tels acides polyamiques. (Dans la formule (1), Ar représente un groupe aromatique divalent; S1 et S2 représentent indépendamment un groupe de liaison divalent ou une liaison simple; Y représente un groupe organique monovalent; Z représente un groupe organique trivalent; et D1 et D2 représentent indépendamment un atome d'oxygène, un atome de soufre ou -NR-, R représentant un atome d'hydrogène ou un groupe alkyle.)
PCT/JP2008/069821 2007-10-26 2008-10-24 Agent d'alignement de cristaux liquides, procédé de formation de film d'alignement de cristaux liquides et dispositif d'affichage à cristaux liquides WO2009054545A1 (fr)

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JP2011018022A (ja) * 2009-06-11 2011-01-27 Jsr Corp 液晶配向剤および液晶表示素子
CN102031122A (zh) * 2009-10-06 2011-04-27 Jsr株式会社 液晶取向剂、液晶显示元件、聚酰胺酸、聚酰亚胺和化合物
WO2012046608A1 (fr) * 2010-10-07 2012-04-12 シャープ株式会社 Dispositif d'affichage à cristaux liquides
CN103097946A (zh) * 2010-07-05 2013-05-08 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及使用其的液晶显示元件
JP2014532104A (ja) * 2011-10-03 2014-12-04 ロリク アーゲーＲｏｌｉｃ Ａｇ 光アライニング材料
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KR20100132906A (ko) * 2009-06-10 2010-12-20 제이에스알 가부시끼가이샤 1위 치환 3,5―디아미노벤젠의 제조 방법 및, 이에 사용되는 화합물, 그의 제조 방법 및 용도
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JP2011018022A (ja) * 2009-06-11 2011-01-27 Jsr Corp 液晶配向剤および液晶表示素子
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CN102031122B (zh) * 2009-10-06 2014-06-18 Jsr株式会社 液晶取向剂、液晶显示元件、聚酰胺酸、聚酰亚胺和化合物
KR101625539B1 (ko) 2009-10-06 2016-05-30 제이에스알 가부시끼가이샤 액정 배향제, 액정 표시 소자 및 관련 화합물
CN102031122A (zh) * 2009-10-06 2011-04-27 Jsr株式会社 液晶取向剂、液晶显示元件、聚酰胺酸、聚酰亚胺和化合物
CN103097946A (zh) * 2010-07-05 2013-05-08 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及使用其的液晶显示元件
CN103097946B (zh) * 2010-07-05 2015-09-30 日产化学工业株式会社 液晶取向处理剂、液晶取向膜及使用其的液晶显示元件
US8999465B2 (en) 2010-10-07 2015-04-07 Sharp Kabushiki Kaisha Liquid crystal display device
WO2012046608A1 (fr) * 2010-10-07 2012-04-12 シャープ株式会社 Dispositif d'affichage à cristaux liquides
US9207495B2 (en) 2011-03-09 2015-12-08 Sharp Kabushiki Kaisha Liquid crystal display device
JP2014532104A (ja) * 2011-10-03 2014-12-04 ロリク アーゲーＲｏｌｉｃ Ａｇ 光アライニング材料

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CN101836155B (zh) 2012-01-25
KR101169862B1 (ko) 2012-07-31
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