WO2009051207A1 - Agent d'alignement de cristaux liquides, et procédé de production d'un film d'alignement pour cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, et procédé de production d'un film d'alignement pour cristaux liquides Download PDF

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Publication number
WO2009051207A1
WO2009051207A1 PCT/JP2008/068807 JP2008068807W WO2009051207A1 WO 2009051207 A1 WO2009051207 A1 WO 2009051207A1 JP 2008068807 W JP2008068807 W JP 2008068807W WO 2009051207 A1 WO2009051207 A1 WO 2009051207A1
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WIPO (PCT)
Prior art keywords
liquid crystal
group
dianhydride
aligning agent
polyamic acid
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PCT/JP2008/068807
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English (en)
Japanese (ja)
Inventor
Toshiyuki Akiike
Tsutomu Kumagai
Satoshi Fukuma
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Jsr Corporation
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Application filed by Jsr Corporation filed Critical Jsr Corporation
Priority to JP2009538152A priority Critical patent/JP5477572B2/ja
Priority to CN200880108389A priority patent/CN101809066A/zh
Priority to KR1020107008301A priority patent/KR101193350B1/ko
Publication of WO2009051207A1 publication Critical patent/WO2009051207A1/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
    • C08G73/1075—Partially aromatic polyimides
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • G02F1/133788—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 light irradiation, e.g. linearly polarised light photo-polymerisation

Definitions

  • the present invention provides a liquid crystal aligning agent that gives a liquid crystal alignment film having a good liquid crystal alignment ability and excellent image sticking properties even with a small exposure amount by irradiation with polarized or non-polarized radiation without rubbing treatment, and the bright liquid crystal alignment film. It relates to a manufacturing method.
  • a nematic liquid crystal with positive dielectric anisotropy is made into a sandwich structure with a substrate with a transparent electrode having a liquid crystal alignment film, and if necessary, the long axial force of liquid crystal molecules between S substrates
  • a liquid crystal display element having the above liquid crystal cell is known (Japanese Patent Laid-Open No. 56-91277 and Japanese Patent Laid-Open No. 11-12528).
  • the liquid crystal alignment film is usually provided with a liquid crystal alignment ability 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.
  • a method rubbing method
  • dust and static electricity are likely to be generated in the process, so there is a problem that dust adheres to the alignment film surface and causes display defects.
  • the circuit damage of the TFT element is caused by the generated static electricity, resulting in a decrease in yield.
  • liquid crystal display elements with higher definition in the future will inevitably have irregularities on the substrate surface as the pixel density increases, making uniform rubbing treatment difficult.
  • liquid crystal alignment ability is imparted by irradiating a radiation sensitive thin film such as polyvinyl cinnamate, polyimide, and azobenzene derivative formed on the substrate surface with polarized or non-polarized radiation.
  • a radiation sensitive thin film such as polyvinyl cinnamate, polyimide, and azobenzene derivative formed on the substrate surface with polarized or non-polarized radiation.
  • the photo-alignment method is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (JP-A-6-287453, JP-A-10-251646, JP-A-11-2815).
  • JP-A-11-152475 JP-A-2000-144136, JP-A-2000-31951, JP-A-2000-281724, JP-A-9-297313, JP-A-2003-307736 JP-A-2004-163646 and JP-A-2002-250924).
  • the liquid crystal alignment film tilts the liquid crystal molecules at a predetermined angle with respect to the substrate surface.
  • the pretilt angle developability is usually imparted by tilting the incident direction of the irradiated radiation to the substrate surface from the substrate normal.
  • a vertical (homeotope pick) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known.
  • this mode of operation when a voltage is applied between the substrates to tilt the liquid crystal molecules in a direction parallel to the substrate, the liquid crystal molecules are tilted from the substrate normal direction to one direction in the substrate plane.
  • a method of providing protrusions on the substrate surface for example, a method of providing stripes on the transparent electrode, and using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface.
  • tilting pre-tilting
  • 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 expression by a photo-alignment method. 8068807
  • the liquid crystal alignment film produced by the photo-alignment method can be effectively applied to various liquid crystal display elements.
  • the conventional photo-alignment film has a problem that a large amount of radiation is required to obtain a large pretilt angle.
  • a liquid crystal alignment ability is imparted to a thin film containing an azobenzene derivative by the photo-alignment method
  • radiation whose optical axis is tilted from the substrate normal is 10,000 J / m
  • two or more irradiations have to be performed (JP 2002-250924 A, JP 2004-83810 A, and J. oft he S ID 11/3, 2003, p 579).
  • the present invention has been made in view of the above circumstances.
  • An object of the present invention is to provide a liquid crystal aligning agent that gives a liquid crystal alignment film having good liquid crystal alignment ability and excellent image sticking properties even with a small amount of exposure by irradiation with polarized or non-polarized light without rubbing treatment, and the liquid crystal An object of the present invention is to provide a method for forming an alignment film.
  • Tetracarboxylic dianhydride and the following formula (1) PT / JP2008 / 068807
  • R 1 is an alkyl group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms, and some or all of the hydrogen atoms of these alkyl groups or alicyclic groups are R 2 , R 4, and R 5 may each independently be a single bond, 101, —S—, 1 COO—, 10C ⁇ One, One CONH—, One NHCO—, One COS—, One SCO—, — O— CO— O—, One NH— COO— or — O— CO— NH—, R 3 has 6 to 20 carbon atoms A divalent aromatic group, a divalent alicyclic group having 5 to 30 carbon atoms, a divalent group having a condensed ring having 6 to 30 carbon atoms, or a divalent heterocyclic group having 5 to 30 carbon atoms.
  • R s is a fluorine atom, methylation group or Shiano group
  • a is an integer of 0 to 3
  • b is an integer from 0 to 20
  • c is an integer of 0 to 4
  • d is 0 It is an integer of ⁇ 4.
  • liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyamic acid obtained by reacting with a diamine compound containing a compound represented by formula (I) and a polyimide formed by imidizing the polyamic acid.
  • the liquid crystal aligning agent is applied on the substrate to form a coating film, and the coating film is irradiated with radiation.
  • the liquid crystal aligning agent of the present invention comprises a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound containing a compound represented by the above formula (1), and a polyimide formed by imidizing the polyamic acid.
  • a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound containing a compound represented by the above formula (1), and a polyimide formed by imidizing the polyamic acid.
  • tetra-force sulfonic acid dianhydride used in the production of the polyamic acid in the present invention include 2,3,5-tri- force loxycyclopentyl acetic acid dianhydride, butanetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic acid dianhydride, 1, 3 one dimethyl ⁇ , 2, 3, 4-cyclobutane tetracarboxylic acid dianhydride, 1, 2, 3, 4 Shikuropen evening down dianhydride 3, 5, 6-tricarpoxynorporanone 2-acetic acid dianhydride, 2, 3, 4, 5-tetrahydrofurantetracarboxylic dianhydride, 1, 3, 3 a, 4, 5, 9 b—Hexahydro-5— (tetrahydro-2,5-dioxo-3-furanyl) 1 naphtho
  • An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above.
  • tetra-force sulfonic acid dianhydride used in the production of polyamic acid in the present invention is 1, 3, 3 a, 4, 5, 9 b-hexahydro-5- (tetrahydrone 1,2-5-oxo. 1-Frael) 1-naphtho [1, 2-c] 1-furan 1-, 3-dione, 1, 3, 3a, 4, 5, 9b-Hexahydro-5- (tetrahydro D 8068807, on
  • the diamine compound used for synthesizing the polyamic acid in the present invention includes a compound represented by the above formula (1).
  • R 1 in the above formula (1) is preferably an alkyl group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms. A part of hydrogen atoms of this alkyl group or alicyclic group may be substituted with a fluorine atom.
  • R 1 is more preferably an alkyl group having 1 to 20 carbon atoms, a cholestenyl group or a cholestanyl group. A part of the hydrogen atoms of the alkyl group, cholesteryl group, or cholestenyl group may be substituted with a fluorine atom.
  • R 1 examples include, for example, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl.
  • R 2 and R 4 are each independently a single bond, preferably 1 O—, 1 COO— or 1 O CO—force S.
  • R3 include, for example, 1,4-diphenylene group, 1,3-phenylene group, 1,4-cyclohexylene group, 1,3-cyclohexylene group, pyridine-1,2,5-diyl group A pyrimidine 1, 2, 5-diyl group, 2, 5-thiophenzyl group, 2, 5-furanylene group or CH group optionally substituted by a nitrogen atom 1, 4 mononaphthylene group or 2, 6-naphthylene group Can be mentioned. Of these, 1,4 monophenylene groups are preferred.
  • R 5 when b is 0 is preferably one COO— *, one CONH— *, —NHCO one *, one COS— * or one NHCOO— *, more preferably one COO— * (however, In the above, the bond marked with “*” is one (CH 2 ) c- side.)
  • R 5 when b is an integer of 1 to 20 is preferably 1 O—, 1 C001 or 1 O CO—.
  • a is preferably 0 or 1 force.
  • b is preferably an integer of 1 to 10.
  • c is preferably 0, 1 or 2.
  • the bonding positions of the two amino groups are in the 2,5-position or 3,5-position.
  • Preferred examples of the diamine compound of the present invention include the following formulas (1-1) to (1 1 1 2)
  • R 1 b and c have the same meanings as in the above formula (1).
  • R 1 in the above formulas (1-1) to (1-12) is preferably an alkyl group having 1 to 20 carbon atoms, a cholesteryl group or a cholestanyl group.
  • a part or all of the hydrogen atoms of the alkyl group, cholesteryl group, or cholestanyl group of R 1 are fluorine atoms.
  • b is preferably 2 to 10.
  • c is preferably 0, 1 or 2.
  • the compound represented by the above formula (1) may be used as the diamine compound, or the compound represented by the above formula (1) and other compounds may be used. You may use together with a diamine compound.
  • Aromatic diamines such as compounds represented by each of
  • Aromatic diamines having heteroatoms such as diaminotetraphenylthiophene; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclo Hexane, Isophoronediamine, Tetrahydrodicyclopentagenylenediamine, Hexahydro-4,7-methanoindanylenediethylenediamine, Tricyclo cT / JP2008 / 068807
  • aliphatic or cycloaliphatic diamines such as undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine);
  • Examples include diaminoorganosiloxanes such as diaminohexamethyldisiloxane.
  • the diamine compound used in the production of the polyamic acid in the present invention contains the compound represented by the above formula (1)
  • 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.
  • a ratio of 0.2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
  • the synthetic reaction of the polyamic acid is carried out in an organic solvent, preferably at a temperature of 120 to 150 ° C, more preferably at a temperature of 0 to 100 ° C, preferably 0.5 to 24 hours. More preferably, it is performed for 2 to 10 hours.
  • 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, N,
  • Non-proline polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, thiopropylolactone, tetramethylurea, hexamethylphosphortriamide; phenols such as m-cresol, xylenol, phenol, halogenated phenol Mention may be made of system solvents.
  • the amount of organic solvent used (a: the total amount of these used when an organic solvent and a poor solvent described later are used together) is the total amount of tetracarboxylic dianhydride and diamine compound (b) Is preferably from 0.1 to 50% by weight, more preferably from 5 to 30% by weight, based on the total amount of the reaction solution (a + b).
  • organic solvent alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents for polyamic acid
  • organic solvent alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like, which are poor solvents for polyamic acid
  • poor solvents include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4 monobutanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactylate, butyric lactate Acetone, Methyl butyl ketone, Methyl isobutyl ketone, Cyclohexanone, Methyl acetate, Ethyl acetate, Butyl acetate, Methyl methoxypropionate, Ethyl ethoxypropionate, Jetyl oxalate, Jetyl malon
  • Ether ethylene glycol methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monodimethyl ether, ethylene glycol ether ether Acetate, diethyl glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, jetylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Terrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, black benzene o- dichloro port benzene, hexane, can heptane, octane, benzene, Torr E emissions, and the like xylene.
  • the use ratio can be appropriately set within the range in which the produced polyamic acid does not precipitate. 0% by weight or less.
  • the reaction solution strength S obtained by dissolving the polyamic acid is obtained.
  • This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or 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 may be purified. In addition, you may use for preparation of a liquid crystal aligning agent.
  • Polyamic acid is isolated by pouring the reaction solution into a large amount of a 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. be able to.
  • polyamic acid can be purified by a method of dissolving this 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 polyimide in the present invention can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above to imidization. At this time, the entire amic acid structure may be dehydrated and cyclized to be completely imidized. ⁇ € ⁇ / ⁇ 2008 / 068807
  • the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist.
  • the polyimide contained in the liquid crystal aligning agent of the present invention preferably has an imidation ratio of 30% or more, more preferably 40 to 90%.
  • polyamic acid for example, (i) the method of heating polyamic acid or (ii) polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring closure catalyst are added during this dissolution night. Depending on the method, heating can be performed.
  • the reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 20 ° C., more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C, the dehydration and ring-closing reaction force does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting polyimide may decrease.
  • the reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.
  • the dehydrating agent for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do.
  • the amount of the dehydrating agent used is preferably 0.1 to 20 mol per 1 mol of the amic acid structural unit.
  • 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 closure reaction include the 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 ° C, more preferably 10 to 150 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably ;! ⁇ 8 hours.
  • the polyimide obtained in the above method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or after purifying the obtained polyimide, the liquid crystal aligning agent. You may use for preparation of.
  • a reaction solution containing polyimide is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, 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. It may be used for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after purifying the isolated polyimide.
  • the liquid crystal aligning agent of the present invention contains at least one polymer selected from the group consisting of the above polyamic acid and polyimide as an essential component, and is preferably prepared as a solution.
  • the liquid crystal aligning agent of the present invention may contain other components as required in addition to at least one polymer selected from the group consisting of the above polyamic acid and polyimide.
  • examples of such other components include polymers other than the above polyamic acid or polyimide (hereinafter referred to as “other polymers”), heat-sensitive crosslinking agents, and functional silane compounds. These other polymers can be used to improve solution and electrical properties.
  • examples of such other polymer include polyamic acid obtained by reacting teracarboxylic dianhydride and a diamine compound not containing the compound represented by the above formula (1) (hereinafter referred to as “other polyamic acid”).
  • a polyimide obtained by imidizing the other polyamic acid (hereinafter referred to as “other polyimide”), polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly ( Styrene monophenylmaleimide) derivatives, poly (meth) acrylates, etc. From the viewpoint of electrical characteristics, other polyamic acids are preferred.
  • the content ratio is obtained by reacting tetracarboxylic dianhydride with a diamine compound containing the compound represented by the above formula (1).
  • the total amount of the polyamic acid to be obtained and the polyimide formed by imidizing the polyamic acid is preferably 5.00 parts by weight or less, and preferably 100 to 2 parts by weight. More preferably, it is more preferably 300 to 1,000 parts by weight.
  • the heat-sensitive crosslinking agent can be used for stabilizing the pretilt angle and improving the coating film strength.
  • a polyfunctional epoxy compound is effective as the heat-sensitive cross-linking agent.
  • Bisphenol ⁇ type epoxy resin Bisphenol ⁇ type epoxy resin, phenol enopolak type epoxy resin, cresol linnopolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester epoxy Resins, glycidyldiamin epoxy resins, heterocyclic epoxy resins, acrylic resins having an epoxy group, and the like can be used.
  • these commercially available products include Epolite 4 00 E, 3 00 2 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicoat 8 2 8, 1 52, and Epoxy Nopolac 1 80 S (Japan) Epoxy resin (manufactured by Co., Ltd.).
  • a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination for the purpose of efficiently causing a crosslinking reaction.
  • the functional silane compound can be used for the purpose of improving the adhesion of the obtained liquid crystal alignment film to the substrate.
  • Examples of functional silane compounds include 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, 2-7 minoprovir trimethoxysilane, 2-aminopropyltriethoxysilane, N 1 (2— Aminoethyl) 1-Aminopropyltrimethoxysilane, N— (2-Aminoethyl) 1-Aminopropylmethyldimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyltriethoxysilane, N— Ethoxycarbonyl 3-Aminopropyltrimethoxysilane, N-ethoxycal Ponyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane,
  • Solvents used in preparing the liquid crystal aligning agent of the present invention in a solution state include dissolving at least one polymer selected from the group consisting of the above polyamic acid and polyimide, and other components optionally contained therein. However, there is no particular limitation as long as the organic solvent does not react with these. Examples of such a solvent include the organic solvents exemplified above as those used for the synthesis of polyamic acid. At this time, you may use together the poor solvent illustrated as what is used for the synthesis
  • a preferable solvent used for preparing the liquid crystal aligning agent of the present invention is obtained by combining one or more of the above organic solvents, and is contained in the liquid crystal aligning agent at the following preferable solid content concentration. Each component does not precipitate, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 4 O mNZm.
  • Solid content concentration of the liquid crystal aligning agent of the present invention that is, all components other than the solvent in the liquid crystal aligning agent.
  • the proportion of the total weight of the liquid crystal aligning agent in the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10% by weight.
  • the liquid crystal aligning agent of the present invention is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is less than 1% by weight, the film thickness of this coating film is too small. Thus, it may be difficult to obtain a good liquid crystal alignment film.
  • the particularly preferable range of the solid concentration varies depending on the method employed when applying the liquid crystal aligning agent. For example, in the case of the spinner method, a range force of 1.5 to 4.5% by weight S In the case of the particularly preferred printing method, the solid content concentration is in the range of 3 to 9% by weight, thereby The viscosity is particularly preferably in the range of 12 to 5 O mPa ⁇ s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and accordingly the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
  • the temperature at which the liquid crystal aligning agent of the present invention is prepared is preferably 0 ° C. to 200 ° C., more preferably 20 ° C. to 60 ° C. Forming method of liquid crystal alignment film>
  • the liquid crystal aligning agent of this invention can be used conveniently in order to form a liquid crystal aligning film.
  • a method for forming a liquid crystal alignment film for example, the liquid crystal aligning agent of the present invention is applied onto a substrate to form a coating film, and then the coating film is irradiated with radiation to impart liquid crystal alignment ability to the coating film. The method of doing can be mentioned.
  • the liquid crystal aligning agent of the present invention is appropriately applied to the transparent conductive film side of the substrate provided with the patterned transparent conductive film, for example, a roll coating method, a spinner method, a printing method, an ink jet method, or the like. Apply by the method.
  • preheating is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent.
  • the pre-bake temperature is preferably 30 to 200, more preferably 40 to 15 ° C, and particularly preferably 40 to 100 ° C.
  • the pre-bake time is preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes. Then complete the solvent PC leakage 68807
  • a firing (post-bake) process is carried out for the purpose of complete removal.
  • This post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 25 ° C.
  • the post-bake time is preferably 1 to 300 minutes, more preferably 2 to 120 minutes.
  • the film thickness of the coating film formed here is preferably from 0.001 to Lm, more preferably from 0.005 to 0.5 m.
  • the 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 polysulfone can be used.
  • Examples of the transparent conductive film NESA film made of S N_ ⁇ 2, I n 2 0 3 - or the like can be used consisting of S N_ ⁇ 2 I TO film.
  • a photo-etching method or a method using a mask when forming the transparent conductive film is used.
  • a functional silane compound, a titanate compound, or the like is applied on the substrate and the transparent conductive film in advance. You may keep it.
  • the coating film is irradiated with radiation, and optionally subjected to heat treatment at a temperature of 150 to 250 ° C., preferably for 1 to 120 minutes, to impart liquid crystal alignment ability.
  • the radiation can be linearly or partially polarized radiation or unpolarized radiation.
  • the type of radiation for example, ultraviolet rays including light having a wavelength of 150 nm to 80 nm and visible light can be used, and ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable.
  • irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. May be.
  • the direction of irradiation needs to be oblique.
  • Examples of light sources used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal octaride lamps, argon resonance lamps, xenon lamps, and excimer lamps. -You can use the one.
  • the ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
  • the radiation dose is preferably 1 J / m 2 or more and less than 1 0, 0 0 0 J Zm 2 , more preferably 1 0 to 3, 0 0 0 J Zm 2 .
  • a radiation dose of 10 0, 0 00 J Zm 2 or more was necessary.
  • the radiation dose at the time of photo-alignment method is 1 0 0 0 0 J Zm 2 less than further 3, 0 0 0 J Zm 2 or less, in particular 1, 0 0 0 Even if it is not more than J 2 / m 2 , especially 80 0 J 2 / m 2 or less, it can give good liquid crystal orientation and contribute to a reduction in manufacturing cost of the liquid crystal display element.
  • the “pretilt angle” in the present invention represents the angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.
  • the liquid crystal display element formed using the liquid crystal aligning agent of this invention can be manufactured as follows, for example.
  • a polarizing plate is bonded on both surfaces so that the polarization direction forms a predetermined angle with the orientation axis of the liquid crystal alignment film of the substrate, thereby obtaining a liquid crystal display element.
  • the angle between the polarization directions of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate must be adjusted on the two substrates on which the liquid crystal alignment film is formed.
  • a liquid crystal display element can be obtained.
  • the cell when the liquid crystal alignment film is vertically aligned, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, and a polarizing plate is By laminating such that the polarization direction forms an angle of 45 ° with the easy alignment axis, a liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained.
  • sealing agent for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.
  • liquid crystal for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used.
  • a nematic liquid crystal having positive dielectric anisotropy is preferable.
  • biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, Biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, and cubane liquid crystal are used.
  • cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral products such as those sold under the trade names “C-1 5 J” and “CB-1 5 J (Merck)” Agent: Ferroelectric liquid crystal such as P-decyloxybenzylidene p-amino-2-methylbutylcinnamate may be further added.
  • a nematic type liquid crystal having negative dielectric anisotropy is preferable.
  • a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, Xanthine liquid crystals are used.
  • a polarizing film As a polarizing plate used outside the liquid crystal cell, a polarizing film called a “H film” in which polyvinyl alcohol is stretched and absorbed while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
  • the polarizing plate which consists of can be mentioned.
  • Compound (1-3-1) was synthesized according to the above.
  • a 1 L eggplant-shaped flask was charged with 82.2 g of methyl 4-hydroxybenzoate, 165.9 g of potassium carbonate and 40 OmL of N, N-dimethylacetamide, stirred for 1 hour at room temperature, The reaction was carried out by adding 95.1 g of Yodo 4, 4, 4 and 4 trifluorobenzene and stirring for 5 hours. After completion of the reaction, reprecipitation was carried out with water, and 32 g of sodium hydroxide and 40 OmL of water were added to the resulting precipitate and refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, neutralize with hydrochloric acid, and precipitate formed with ethanol. By recrystallization, 80.4 g of white crystals of the compound (1-3-1-1) were obtained.
  • a 50-mL three-necked flask was charged with 36.1 g of hydroxycinnamic acid, 55.2 g of potassium carbonate, 2.41 g of tetraptyl ammonium bromide, 20 OmL of tetrahydrofuran and 40 OmL of water.
  • This aqueous solution was ice-cooled, and a tetrahydrofuran solution containing a reaction product of the above compound (11-3-1-1) and thionyl chloride was slowly added dropwise, followed by further stirring for 2 hours for reaction.
  • This solution was filtered through a filter having a pore size of 1 ⁇ m to prepare liquid crystal aligning agent 3.
  • Example 6 Manufacturing of vertical alignment type liquid crystal display elements>
  • the liquid crystal aligning agent 1 prepared above was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner, and pre-baked on an 80 ° C hot plate for 1 minute.
  • a film with a thickness of 0.1 m was formed by post-baking at 180 ° C for 1 hour.
  • the surface of this coating film is irradiated with polarized ultraviolet light (1,000 J / m 2) containing a 313 nm emission line from a direction tilted 40 ° from the normal of the substrate, using a Hg-Xe lamp and a Dalanterra prism.
  • polarized ultraviolet light 1,000 J / m 2
  • a polarizing plate is attached to both sides of the substrate so that the polarization directions are orthogonal to each other and form an angle of 45 ° with the polarization direction of ultraviolet rays irradiated to the liquid crystal alignment film.
  • a liquid crystal display device was manufactured.
  • This liquid crystal display element was evaluated as follows. The results are shown in Table 1.
  • the liquid crystal display device manufactured above was observed with a microscope for the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V was turned ON / OFF (applied 'released). .
  • the pretilt angle was measured by a crystal rotation method using He—Ne laser light. A case where the pretilt angle was 89.5 to 85 ° was judged as “good”.
  • a voltage of 5 V was applied to the liquid crystal display device manufactured as described above for 60 microseconds with a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the application release was measured.
  • the measuring device used was “VHR-1” manufactured by Toyo Corporation. A case where the voltage holding ratio was 90% or more was judged as “good”.
  • Example 6 vertical alignment liquid crystal display elements were produced and evaluated in the same manner as in Example 6 except that the liquid crystal aligning agents listed in Table 1 were used. The results are shown in Table 1. table 1
  • the liquid crystal aligning agent of the present invention is a light with a small exposure amount.
  • a liquid crystal alignment film having good liquid crystal alignment ability, good pretilt angle characteristics and excellent image sticking characteristics can be formed by the alignment method, and a liquid crystal display element exhibiting excellent liquid crystal alignment characteristics and high display characteristics is obtained. be able to. The invention's effect
  • the liquid crystal aligning agent of the present invention is superior in alignment performance and excellent in the photo-alignment method with a smaller radiation dose as compared with the conventionally known liquid crystal aligning agent that can obtain a liquid crystal alignment film by the photo-alignment method.
  • a liquid crystal alignment film exhibiting image sticking characteristics is provided. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, a liquid crystal display element having better display performance and electrical characteristics than before can be manufactured at a lower cost.
  • a liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be effectively applied to various devices, such as a desk calculator, a wristwatch, a table clock, a counting display board, a word processor, a personal computer, a liquid crystal television, etc. It is suitably used for the above devices.

Abstract

Cette invention concerne un agent d'alignement de cristaux liquides comprenant au moins un polymère choisi dans le groupe constitué par un acide polyamique produit par réaction d'un dianhydride d'acide tétracarboxylique avec un composé de diamine comprenant des composés spécifiques représentés typiquement par un composé répondant à la formule (1-1), et un polyimide produit par imidation de l'acide polyamique. Où R1 représente un groupe alkyle ayant de 1 à 20 atomes de carbone ou un groupe alicyclique ayant de 5 à 50 atomes de carbone; et b représente un nombre entier de 0 à 20. L'agent d'alignement de cristaux liquides permet de produire un film d'alignement pour cristaux liquides ayant de bonnes propriétés d'alignement et d'excellentes propriétés d'ancrage grâce à un procédé de photo-alignement à plus bas niveau d'irradiance.
PCT/JP2008/068807 2007-10-19 2008-10-09 Agent d'alignement de cristaux liquides, et procédé de production d'un film d'alignement pour cristaux liquides WO2009051207A1 (fr)

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JP2009538152A JP5477572B2 (ja) 2007-10-19 2008-10-09 液晶配向剤および液晶配向膜の形成方法
CN200880108389A CN101809066A (zh) 2007-10-19 2008-10-09 液晶取向剂和液晶取向膜的形成方法
KR1020107008301A KR101193350B1 (ko) 2007-10-19 2008-10-09 액정 배향제 및 액정 배향막의 형성 방법

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CN101921598A (zh) * 2009-06-11 2010-12-22 Jsr株式会社 液晶取向剂和液晶显示元件
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
JP2011158835A (ja) * 2010-02-03 2011-08-18 Jsr Corp 液晶配向剤
WO2013026691A1 (fr) 2011-08-25 2013-02-28 Rolic Ag Composés photoréactifs
CN103443697A (zh) * 2011-01-28 2013-12-11 日产化学工业株式会社 含有聚酰胺酸酯和聚酰胺酸的液晶取向剂
JP2015135464A (ja) * 2013-10-07 2015-07-27 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
WO2018173648A1 (fr) * 2017-03-23 2018-09-27 Jsr株式会社 Procédé de fabrication d'un film d'alignement de cristaux liquides et élément à cristaux liquides
KR20190039148A (ko) * 2016-08-03 2019-04-10 닛산 가가쿠 가부시키가이샤 박리층 형성용 조성물

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CN102559205B (zh) 2010-12-29 2014-07-30 第一毛织株式会社 液晶取向剂、使用其制造的液晶取向膜和液晶显示器
KR101333709B1 (ko) 2011-01-24 2013-11-27 제일모직주식회사 액정 배향제, 이를 이용하여 제조한 액정 배향막 및 상기 액정 배향막을 포함하는 액정표시소자
CN103718093B (zh) * 2011-08-04 2016-11-23 日产化学工业株式会社 光取向处理法用的液晶取向剂、及使用该液晶取向剂的液晶取向膜
KR101444190B1 (ko) 2011-12-19 2014-09-26 제일모직 주식회사 액정 배향제, 이를 이용한 액정 배향막 및 상기 액정 배향막을 포함하는 액정표시소자
JP6347917B2 (ja) * 2013-05-27 2018-06-27 株式会社ジャパンディスプレイ 液晶表示装置およびその製造方法
KR20200088846A (ko) * 2017-11-30 2020-07-23 닛산 가가쿠 가부시키가이샤 액정 배향제, 액정 배향막 및 액정 표시 소자

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JP2006220676A (ja) * 2004-03-01 2006-08-24 Chisso Corp 液晶配向膜用組成物、液晶配向膜、液晶挟持基板及び液晶表示素子
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CN101921598B (zh) * 2009-06-11 2014-01-08 Jsr株式会社 液晶取向剂和液晶显示元件
CN101921598A (zh) * 2009-06-11 2010-12-22 Jsr株式会社 液晶取向剂和液晶显示元件
KR101625539B1 (ko) 2009-10-06 2016-05-30 제이에스알 가부시끼가이샤 액정 배향제, 액정 표시 소자 및 관련 화합물
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
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
JP2011158835A (ja) * 2010-02-03 2011-08-18 Jsr Corp 液晶配向剤
CN103443697A (zh) * 2011-01-28 2013-12-11 日产化学工业株式会社 含有聚酰胺酸酯和聚酰胺酸的液晶取向剂
CN103443697B (zh) * 2011-01-28 2016-02-24 日产化学工业株式会社 含有聚酰胺酸酯和聚酰胺酸的液晶取向剂
WO2013026691A1 (fr) 2011-08-25 2013-02-28 Rolic Ag Composés photoréactifs
US9366906B2 (en) 2011-08-25 2016-06-14 Rolic Ag Photoreactive compounds
JP2015135464A (ja) * 2013-10-07 2015-07-27 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
KR20190039148A (ko) * 2016-08-03 2019-04-10 닛산 가가쿠 가부시키가이샤 박리층 형성용 조성물
KR102410266B1 (ko) 2016-08-03 2022-06-17 닛산 가가쿠 가부시키가이샤 박리층 형성용 조성물
WO2018173648A1 (fr) * 2017-03-23 2018-09-27 Jsr株式会社 Procédé de fabrication d'un film d'alignement de cristaux liquides et élément à cristaux liquides

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TW200922974A (en) 2009-06-01
JPWO2009051207A1 (ja) 2011-03-03
CN101809066A (zh) 2010-08-18

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