Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4042—Imines; Imides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
  • G02F1/133788—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 relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, a liquid crystal aligning agent that can be applied to a small amount of exposure when forming a liquid crystal alignment film by irradiation with polarized or non-polarized radiation without rubbing treatment, shows uniform liquid crystal alignment ability and excellent electrical properties
• the present invention relates to a liquid crystal alignment film and a liquid crystal display element that exhibits high-quality display performance and is excellent in reliability. Background art
• a nematic liquid crystal having positive dielectric anisotropy has a sandwich structure with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of liquid crystal molecules is continuously twisted between 0 and 360 ° between the substrates as necessary.
• Liquid crystal display elements having liquid crystal cells such as TN (Twisted Nematic), STN (Super Twisted Nematic), and IPS (In Plane Switching) types are known. (See JP 56-91277 and JP 1 12 0528).
• 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. If the liquid crystal alignment film is formed by rubbing treatment, dust and static electricity are likely to be generated in the process, which may cause display defects due to dust adhering to the alignment film surface.
• a substrate having a TFT (Thin Film Transistor) element there is a problem that 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 will As the density of pixels increases, irregularities are inevitably generated on the substrate surface, making uniform rubbing more difficult.
• the liquid crystal alignment ability is imparted by irradiating the 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 is a pretilt that tilts liquid crystal molecules at a predetermined angle with respect to the substrate surface. It must have angular 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 when a voltage is applied can be uniformly controlled by using a vertical alignment film imparted with alignment regulating ability and pretilt angle characteristics by a photo-alignment method.
• 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 require a large amount of radiation irradiation to obtain a large pretilt angle.
• radiation whose optical axis is tilted from the substrate normal is 10,000 J Zm 2 It has been reported that irradiation has to be carried out above (see JP 2002-250924 A, JP 2004-83810 A and J. oft he SID 1 1/3, 200 3, p 579). Disclosure of the invention
• An object of the present invention is to provide a liquid crystal aligning agent that can be applied to a small amount of exposure when forming a liquid crystal alignment film by irradiation with polarized or non-polarized radiation without rubbing treatment, uniform liquid crystal aligning ability and excellent
• An object is to provide a liquid crystal alignment film exhibiting electrical characteristics and a liquid crystal display element exhibiting high quality display performance and excellent reliability.
• R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alicyclic group having 5 to 50 carbon atoms, and a part of hydrogen atoms of these alkyl groups or alicyclic groups or All may be substituted with a fluorine atom, a cyano group or an aryl group
• R 2 and R 4 are each independently a single bond, — ⁇ —, —S—, — C ⁇ 001, — ⁇ C ⁇ ⁇ , 1 CONH—, 1 NHCO—, 1 COS—, 1 SCO—, 1 O— CO— 0 1, 1 NH-COO—, 10 — CO— NH— or —C 0 1
• R 3 is carbon Number 6 ⁇ 20 divalent aromatic groups, divalent alicyclic groups having 5 to 30 carbon atoms, divalent groups having a fused ring having 6 to 30 carbon atoms or divalent heterocyclic groups having 5 to 30 carbon atoms R 3 divalent aromatic group, divalent aromatic group,
• R 8 is a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
• R 9 is a single bond, 101, —S— , 1 CO 0, 1 CO—, _C 0 NH—, 1 NHCO—, 1 COS—, 1 SCO—, ⁇ 0 1 CO— 0 1, 1 NH—C 0 1, 1 1 CO_NH— or 1 CO—
• e is an integer from 0 to 4, except that the bond marked with “*” in formula (2) binds to the base (CH 2 ) b —.
• R 6 is selected from a fluorine atom, a methyl group or a cyano group, Z is a hydroxyl group or a carboxyl group, a is an integer of 0 to 3, and R 5 is the above formula
• b is an integer from 0 to 20
• R 5 is a single bond, 1 O—, — S—, — C001, 10C ⁇ 1 or — NR 7 — (wherein R 7 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms), and b is 1 to 20
• c is an integer from 0 to 4
• d is an integer from 0 to 4.
• the above object of the present invention is achieved by a method for forming a liquid crystal alignment film in which the above liquid crystal aligning agent is applied onto a substrate to form a coating film, and the coating film is irradiated with radiation. Further, the above object of the present invention is achieved thirdly by a liquid crystal alignment film formed from the above liquid crystal aligning agent, and fourthly by a liquid crystal display element having the liquid crystal alignment film.
• the liquid crystal aligning agent of the present invention comprises: (A) a compound represented by the above formula (1) (hereinafter referred to as “compound
• (B) epoxy compound a compound having two or more epoxy groups in one molecule (hereinafter, also referred to as “(B) epoxy compound”)
• polymer (C) A polymer containing at least one selected from the group consisting of polyamic acid and polyimide (hereinafter also referred to as “polymer (C)”).
• polymer (C) A polymer containing at least one selected from the group consisting of polyamic acid and polyimide (hereinafter also referred to as “polymer (C)”).
• the compound (A) used in the present invention is a compound represented by the above formula (1).
• R 1 in the above formula (1) is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, or an alicyclic group having 17 to 30 carbon atoms. Specific examples thereof include an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptylylene group. , N-year-old cutyl group, etc .;
• fluoroalkyl group having 1 to 6 carbon atoms examples include 4, 4, 4-trifluorofluoro group, 3, 3, 4, 4, 4-pentafluorobutyl group, 4, 4, 5, 5, 5, 5-pentafluoropentyl group 4, 4, 5, 5, 6, 6, 6—Heppu Such as a syl group;
• Examples of the alicyclic group having 17 to 30 carbon atoms include a cholestenyl group and a cholesynyl group.
• R 2 and R 4 are preferably each independently a single bond, — ⁇ 1, one COO— or — ⁇ C ⁇ 1.
• R 3 include, for example, 1,4-phenylene group, 1,3-phenylene group, 1,4-cyclohexylene group, 1,3-cyclohexylene group, pyridine 1,2,5 —Diyl group, pyrimidine-1,2,5-diyl group, 2,5-thiophenzyl group, 2,5-furanylene group, CH group 1,4 1-naphthylene group or 2,6- A naphthylene group can be mentioned. Of these, 1,4-diphenylene groups are preferred.
• R 5 is a divalent group represented by the above formula (2), 0 or 1 is preferable.
• R 5 may be a single bond, _ ⁇ _, or 1, 4_phenylene group among the divalent groups represented by the above formula (2), the following formula (2-1), (2-2) or (2-3)
• a divalent basic force represented by R 6 is preferably a fluorine atom.
• a is preferably 0 or 1 force s.
• R 5 is a single bond or a divalent group represented by the above formula (2)
• b is preferably an integer of 0 to 10;
• R 5 is 101, 1 S—, 1 COO—, In the case of 10C ⁇ 1 or — NR 7 — (wherein R 7 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms), b is 1 to An integer of 10 is preferred.
• c is preferably 0 or 1 force S.
• d is preferably 0 or 1 force.
• Z is a hydroxyl group or a carboxyl group, but when c is 0, Z is preferably a hydroxyl group.
• Preferred examples of the compound (A) used in the present invention include, for example, the following formulas (1 1) to (1 26)
• the method for synthesizing the compound represented by the above formula (1) is not particularly limited, and can be appropriately performed by a conventional method of organic chemistry.
• examples of the synthesis method will be described for some of the compounds represented by the above formula (1), but the synthesis method is not limited thereto.
• the compound represented by the above formula (1-2) is, for example, hydroxycinnamic acid and a compound (wherein R 1 has the same meaning as in the above formula (1), and X is a halogen atom. .)
• a base for example, potassium carbonate
• an alkali metal compound for example, sodium hydroxide
• the halogen atom for X is preferably an iodine atom, a bromine atom or a chlorine atom.
• the compound represented by the above formula (11-14) can be synthesized, for example, by the following reaction route. That is, first, methyl hydroxybenzoate and a compound I ⁇ X (R 1 and X have the same meaning as described above) are reacted in the presence of a base (for example, potassium carbonate), and then an alkali metal compound (for example, By hydrolysis in the presence of sodium hydroxide, etc. (1 1 4 1 a)
• R 1 has the same meaning as in the above formula (1-4).
• the compound represented by the above formula (1-25) is synthesized by using acetyl phenol instead of acetyl benzoic acid in the synthesis of the compound represented by the above formula (1 1 2 4). be able to.
• the compound represented by the above formula (11 26) is prepared by reacting the compound represented by the above formula (1-25) with succinic anhydride in the presence of an organic base (for example, triedylamine). Can be synthesized.
• an organic base for example, triedylamine
• the (B) epoxy compound used in the present invention is a compound having two or more epoxy groups in one molecule, and has a function of performing a crosslinking reaction by heating.
• epoxy compounds include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol nopolac type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, and glycidyl diamine type epoxy resins. And heterocyclic epoxy resins and acrylic resins having an epoxy group.
• examples of these commercially available products include Epolite 400 E, 300 R2 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicourt 8 28, 1552, Epoxy Nopolac 18 OS (Japan Epoxy Resin Co., Ltd.) For example).
• daricidyldiamin-based epoxy resin strength S is preferred, and more preferably the following formula (3)
• R is a divalent organic group having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms, provided that the group R contains an oxygen atom or sulfur nuclear S. Good.
• the epoxy compound may be used in combination with a base catalyst for the purpose of efficiently causing a crosslinking reaction.
• a base catalyst for example, 1-benzil 2-methylimidazole can be mentioned.
• the polymer (C) used in the present invention contains at least one selected from the group consisting of polyamic acid and polyimide.
• the polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine compound, preferably in an organic solvent.
• An aromatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by each of the above.
• diamine compounds used in the synthesis of polyamic acid include p-phenylene diamine, m-phenylene diamine, 4,4'-diaminodiphenyl diamine, 4, 4'-diaminodiphenylethane, 4, 4 ' --Diaminodiphenylsulfide, 4, 4 '—Diaminodiphenyl sulfone, 3,3'—Dimethyl-1,4'—Diaminobiphenyl, 4, 4 '—Diaminobenzanilide, 4, 4' — Diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) — 1,3,3-trimethylindane, 6-amino 1- (4, 1-aminophenol) 1, 1, 3, 3_trimethylindane, 6-amino 1- (4, 1-aminophenol) 1, 1, 3, 3_trimethylindane
• An aromatic diamine such as a diamine compound represented by each of the following:
• Aromatic diamines having heteroatoms such as diaminotetraphenylthiophene; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenedia Mine, Octamethylenediamine, Nonamethylenediamine, 1,4-Diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentengenylenediamine, Hexahydro-4,7-Mindanediethylenemethylene Jiamin, Tricyclo [6. 2. 1. 0 2 ' 7 ] —aliphatic or cycloaliphatic diamines such as undecylenedimethyl diamine, 4,4, -methylene bis (cyclohexylamine);
• Examples include diaminoorganosiloxanes such as diaminohexamethyldisoxyhexane.
• diamine compounds can be used alone or in combination of two or more.
• the proportion of tetracarboxylic dianhydride and diamine compound used in the polyamic acid synthesis reaction is such that the acid anhydride group of tetracarboxylic dianhydride is equivalent to 1 equivalent of 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 polyamic acid is preferably synthesized in an organic solvent, preferably at a temperature of 20 to 150, more preferably at a temperature of 0 to 100. Is carried out for 0.5 to 24 hours, more preferably 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, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethylsulfoxide, aptilolactone, tetramethylurea, hexamethylphosphortriamide; m-cresol, xylenol, phenol, halogenated phenol Examples thereof include phenol solvents.
• the amount of organic solvent used (a: However, when an organic solvent is used in combination with a poor solvent described later, the total amount of these used) is the total amount of tetracarboxylic dianhydride and diamine compound ( The amount b) is preferably 0.1 to 50% by weight, more preferably 5 to 30% by weight, based on the total amount of the reaction solution (a + b).
• alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc. which are poor solvents for polyamic acid, can be used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate.
• poor solvents include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, lactic acid ethyl, butyl lactate, acetone, Methyl ethyl ketone, Methyl isobutyl ketone, Cyclohexanone, Methyl acetate, Ethyl acetate, Ptyl acetate, Methyl methoxypropionate, Ethyl ethoxypropionate, Jetyl oxalate, Jetyl malonate, Jetyl ether,
• the proportion of the polyamic acid generated can be appropriately set within the range where it does not precipitate. 50% by weight or less.
• 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, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid may be purified.
• Polyamic acid is 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 in which the polyamic acid is dissolved again in an organic solvent and then precipitated in a poor solvent, or a method in which the step of evaporating under reduced pressure in an evaporator is performed 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 as described above. At this time, all of the amic acid structure may be dehydrated and cyclized to completely imidize, or only a part of the amic acid structure may be dehydrated and cyclized to partially combine the amic acid structure and the imide structure. It may be a compound.
• Dehydration and ring closure of polyamic acid can be accomplished by U)) heating the polyamic acid or (ii) dissolving polyamic acid in an organic solvent and adding a dehydrating agent and dehydration ring closure catalyst to this solution and heating as necessary. Is done.
• the reaction temperature in the above method for heating the polyamic acid of U) is preferably 50 to 200, more preferably 60 to 170. If the reaction temperature is less than 50, the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200, it is obtained. 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.
• an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent.
• the dehydrating agent is preferably used in an amount of 0.01 to 20 mol per 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.
• Examples of 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 cyclization reaction is preferably 0 to 180, more preferably 10 to 150, 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 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 purifying the obtained polyimide.
• a reaction solution containing polyimide is obtained. This reaction solution may be used as it is 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, and the polyimide was isolated. It may be used for preparing a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after purifying the isolated polyimide.
• the isolation and purification of the polyimide can be performed by performing the same operations as described above as the isolation and purification method of the polyamic acid.
• the polymer (C) in the present invention contains the polyamic acid and the poly It may consist of at least one selected from the group consisting of, and may contain other polymers in addition to at least one selected from the group consisting of polyamic acid and polyimide.
• Other polymers can be used to improve solution and electrical properties, for example, polyamic acid esters, polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (Styrene monophenylmaleimide) derivatives, poly (methyl) acrylate and the like.
• the content ratio is preferably 50% by weight or less with respect to the total amount of the polymer (C). Most preferably, the polymer (C) in the present invention does not contain other polymers.
• the liquid crystal aligning agent of the present invention contains the compound (A), (B) epoxy compound and polymer (C) as essential components, and is preferably prepared as a solution.
• the liquid crystal aligning agent of this invention can contain another component other than the said (A)-(C) component as needed.
• examples of such other components include a radiation-sensitive crosslinking agent and a sensitive silane compound.
• examples of the radiation-sensitive crosslinking agent include a reaction product of the compound represented by the above formula (1) and the glycidyl diamine epoxy resin.
• the ratio of both used in the reaction of the compound represented by the above formula (1) and the glycidyl diamine epoxy resin is expressed by the above formula (1) with respect to 1 equivalent of the daricidyl diamine epoxy resin.
• the amount of the compound is preferably 0.1 to 10 equivalents, more preferably 0.2 to 2 equivalents.
• the reaction temperature is preferably 20 to 2500, more preferably 50 to 180, and the reaction time is preferably 0.5 to 200 hours, more preferably 1 to 10 hours. .
• an appropriate base catalyst may be added to promote the reaction. It is preferable to carry out the reaction in an organic solvent.
• the organic solvent that can be used here is preferably an aprotic organic solvent, and specific examples thereof include 1-methyl-2-pyrrolidone.
• the ratio (solid content concentration) of the total weight of the compound represented by the above formula (1) and the glycidyldiammine epoxy resin to the total amount of the reaction solution is preferably 1 % By weight or more, more preferably 5 to 50% by weight.
• 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-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-amino Ethyl) 1-Aminopropyl trimethoxysilane, N— (2-Aminoethyl) 1 3-Aminopropylmethyldimethoxysilane, 3-ureidopropyl piltrimethoxysilane, 3-ureidopropyltriethoxysilane, N— Ethoxycarbonoluene 3-Aminopropyl trimethoxysilane, N-Ethoxycarbonyl- 3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylene-triamine, N--trimethoxysilylpropyltriethylene-triamine , 1 0-trimethoxysily
• the usage ratio of each component contained in the liquid crystal aligning agent of the present invention is as follows.
• the proportion of compound (A) used is based on 100 parts by weight of the total polymer (the total of polymer (C), that is, the total of polyamic acid, polyimide and other polymers; the same shall apply hereinafter).
• the amount is preferably 1 to 100 parts by weight, more preferably 10 to 50 parts by weight.
• the proportion of the epoxy compound used is preferably 1 to 100 parts by weight, more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the total polymer.
• the use ratio of the base catalyst is preferably 50 parts by weight or less, more preferably 20 parts by weight with respect to 100 parts by weight of the epoxy compound. It is as follows.
• the use ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight with respect to 100 parts by weight of the total of the polymers. Less than parts by weight.
• the use ratio thereof is preferably 50 parts by weight or less, more preferably 20 parts by weight based on 100 parts by weight of the total polymer. Less than parts by weight.
• the use ratio thereof is preferably 50 parts by weight or less, more preferably 2 parts by weight based on 100 parts by weight of the total polymer. 0 parts by weight or less.
• the solvent used when preparing the liquid crystal aligning agent of the present invention in a solution state the components (A) to (C) described above and other components optionally contained are dissolved and do not react with them. If it is an organic solvent, there will be no restriction
• a preferred solvent used in the preparation of 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.
• the liquid crystal aligning agent has a surface tension of 25 to 4 OmNZm.
• the solid content concentration of the liquid crystal aligning agent of the present invention that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc. Preferably, it is in the range of 1 to 10% by weight.
• the liquid crystal aligning agent of the present invention is applied to the substrate surface, and the force 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 the coating film becomes too small. It may be difficult to obtain a good liquid crystal alignment film.
• the particularly preferable range of the solid content concentration varies depending on the method employed when applying the liquid crystal aligning agent to the substrate. For example, in the case of the spinner method, a range force S of 1.5 to 4.5% by weight S is particularly preferable. In the case of the printing method, it is particularly preferred that the solid content concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is 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 thus 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 to 200, and more preferably 20 T: to 60.
• 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, a method of applying a liquid crystal alignment agent of the present invention on a substrate to form a coating film, and then irradiating the coating film with radiation to impart a liquid crystal alignment capability is given. be able to.
• the liquid crystal aligning agent is applied by an appropriate application method such as a roll coating method, a spinner method, a printing method, an ink jet method, or the like.
• 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 150, and particularly preferably 40 to 100.
• the pre-bake time is preferably 0.:! To 10 minutes, and more preferably 0.5 to 5 minutes. After that, a firing (post-bake) process is carried out for the purpose of completely removing the solvent.
• This post-bake temperature is preferably 80 to 300, and more preferably 120 to 25.
• the post-bake time is preferably 1 to 300 minutes, more preferably 2 to 120 minutes.
• the thickness of the coating film formed here is preferably from 0.001 to 1 m, more preferably from 0.005 to 0.5 zm, after removal of the solvent.
• a glass such as float glass or soda glass
• a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used.
• Examples of the transparent conductive film NESA film made of S N_ ⁇ 2, I n 2 ⁇ 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, titanate, or the like is previously applied onto the substrate and the transparent conductive film. You may keep it.
• the coating film is irradiated with linearly polarized light or partially polarized radiation or non-polarized radiation, and in some cases, a heat treatment is preferably performed at a temperature of 150 to 250, preferably for 1 to 120 minutes.
• a heat treatment is preferably performed at a temperature of 150 to 250, preferably for 1 to 120 minutes.
• the radiation for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 80 nm can be used, but light having a wavelength of 300 nm to 400 nm is included.
• irradiation may be performed from a direction perpendicular to the substrate surface or from an oblique direction to give a pretilt angle. May be.
• the direction of irradiation needs to be oblique.
• a light source to be used for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used.
• the ultraviolet rays in the preferred wavelength region can be obtained by means of using the light source together with, for example, a filter, a diffraction grating, or the like.
• the radiation dose is preferably 1 J Zm 2 or more and less than 10 and 0 0 0 J Zm 2 , more preferably 10 to 3 and OOOJ 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 less than J Zm 2 , especially 80 0 J Zm 2 , good liquid crystal orientation can be imparted, which contributes 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 having a TN type or S TN type liquid crystal cell 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 A liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained by bonding so that the polarization direction forms an angle of 45 ° with the easy alignment axis.
• 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, bicycloquine 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-15” and “CB-15” (manufactured by Merck) Agent: Ferroelectric liquid crystal such as p-decyloxybenzylidene mono-p-amino-2-methylbutylcinnamate can be further added and used.
• a nematic type liquid crystal having negative dielectric anisotropy is preferable, for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane. Hexane liquid crystals are used.
• 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.
• polymer 1 b Take 15 g of polymer 1 a synthesized in Synthesis Example 5 above, add 60 g of N-methyl-2-pyrrolidone, 1.8 g of pyridine and 2.31 g of acetic anhydride, and add 120 g for 4 hours. An imidization reaction was performed. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, the precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 12 g of polyimide (hereinafter referred to as “polymer 1 b”). The imidization ratio of the polymer 1b was 50%.
• polymer 1 b The imidization ratio of the polymer 1b was 50%.
• Liquid crystal aligning agent 1 was prepared by filtering through a filter having a pore size of 1 zm.
• the liquid crystal aligning agent 1 prepared above is applied to a glass substrate with a transparent electrode made of an ITO film. Apply to the transparent electrode surface using a spinner, pre-bake on a hot plate at 80 for 1 minute, and then post-bake at 200 for 1 hour to form a coating film with a film thickness of 0.1 lm did.
• a Hg_Xe lamp and a Grand Taylor prism to irradiate the surface of this coating film with polarized ultraviolet rays (1.00 J / m 2) containing a 313 nm emission line from a direction inclined by 40 ° from the substrate normal, A liquid crystal alignment film was formed by imparting alignment ability.
• An epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5. nm is applied by screen printing to the periphery of each surface of the pair of substrates on which the liquid crystal alignment film is formed.
• the substrates were stacked and pressure-bonded, and heated at 150 for 1 hour to thermally cure the adhesive.
• a positive nematic liquid crystal (MLC, MLC-6221, containing a chiral agent) was injected and filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment during liquid crystal injection, this was heated at 150 for 10 minutes and then slowly cooled to room temperature.
• a TN-type liquid crystal display element is manufactured by laminating polarizing plates on both outer surfaces of the substrate so that the polarization directions thereof are orthogonal to each other and parallel to the polarization direction of the liquid crystal alignment film. did.
• the liquid crystal display device manufactured above was observed with an optical microscope for the presence or absence of abnormal domains in the change in brightness when a voltage of 5 V was turned on and off (applied / released). .
• 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”. Examples 2-10
• Example 1 except that the types of the compound (A :), (B) epoxy compound and polymer (C) were as shown in Table 1, respectively, the liquid crystal alignment agents 2 to; I 0 was synthesized respectively.
• a liquid crystal display device was produced in the same manner as in Example 1 using each of the above and evaluated. The results are shown in Table 2.
• a liquid crystal display device was produced in the same manner as in Example 1 except that the liquid crystal aligning agents 1 to 10 prepared in Examples 1 to 10 were used, and I 0 was used, and the irradiation amount of polarized ultraviolet rays was set to 200 J Zm 2. , evaluated.
• Example 1 (1-2-1) (3-2) Polymer 1a Liquid crystal aligning agent 1
• Example 2 Polymer 1a Liquid crystal aligning agent 2
• Example 3 (3-14) Polymer 1a Liquid crystal aligning agent 3
• Example 4 (3-14) Polymer 1a Liquid crystal aligning agent 4
• Example 5 (1-2-2) (3-14) Polymer lb Liquid crystal aligning agent 5
• Example 6 (3-2) Polymer 1a Liquid Crystal Alignment Agent 6
• Example 7 Polymer 1 a Liquid Crystal Alignment Agent 7
• Example 8 (3-14) Polymer 1 a Liquid Crystal Alignment Agent 8
• Example 9 (3-14) Polymer 1 a Liquid Crystal Alignment Agent 9
• Example 10 (3-14) Polymer 1 b Liquid crystal alignment agent 10 Table 2
• the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having good liquid crystal aligning properties and electrical characteristics by a photo-alignment method with a small amount of radiation irradiation. It can be suitably applied to the liquid crystal display element.
• the liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention has extremely excellent liquid crystal alignment, it can be applied to a liquid crystal coating type retardation film. The invention's effect
• the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which shows favorable and uniform alignment performance with the photo-alignment method of a small amount of radiation irradiation compared with the conventionally known liquid crystal aligning agent. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element, the liquid crystal display element can be manufactured at an extremely low cost.
• the liquid crystal display element comprising the 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. It is suitably used for such devices.
• the liquid crystal aligning agent of the present invention can exert its advantageous effects to the maximum when applied to a TN type liquid crystal display element.

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