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WO2011115077A1 - Agent d'alignement de cristaux liquides contenant un ester d'acide polyamique à extrémité modifiée et film d'alignement de cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides contenant un ester d'acide polyamique à extrémité modifiée et film d'alignement de cristaux liquides Download PDF

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Publication number
WO2011115077A1
WO2011115077A1 PCT/JP2011/055972 JP2011055972W WO2011115077A1 WO 2011115077 A1 WO2011115077 A1 WO 2011115077A1 JP 2011055972 W JP2011055972 W JP 2011055972W WO 2011115077 A1 WO2011115077 A1 WO 2011115077A1
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Prior art keywords
polyamic acid
liquid crystal
acid ester
group
added
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PCT/JP2011/055972
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English (en)
Japanese (ja)
Inventor
直樹 作本
隆夫 堀
洋介 飯沼
勇歩 野口
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2012505684A priority Critical patent/JP5708636B2/ja
Priority to CN201180024029.8A priority patent/CN102893206B/zh
Priority to KR1020127026263A priority patent/KR101816940B1/ko
Publication of WO2011115077A1 publication Critical patent/WO2011115077A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a liquid crystal aligning agent containing a polyamic acid ester having a terminal modified and a polyamic acid, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element.
  • liquid crystal alignment film for controlling the alignment state of liquid crystals is usually provided in the element.
  • a liquid crystal alignment film a polyimide liquid crystal alignment film obtained by applying a liquid crystal alignment agent mainly composed of a polyimide precursor such as polyamic acid (polyamic acid) or a solution of soluble polyimide to a glass substrate or the like and baking it is mainly used. It is used.
  • liquid crystal alignment films have high liquid crystal alignment characteristics and stable pretilt angles in addition to the demands for suppressing the decrease in contrast and reducing the afterimage phenomenon. Characteristics such as a voltage holding ratio, suppression of an afterimage generated by AC driving, a small residual charge when a DC voltage is applied, and / or an early relaxation of a residual charge accumulated by a DC voltage are becoming increasingly important.
  • polyamic acid and its imidized polymer contains one carboxylic acid group in the molecule as a liquid crystal alignment film with a high voltage holding ratio and a short time until the afterimage generated by direct current voltage disappears.
  • a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amino group in the molecule ( For example, see Patent Document 3).
  • a liquid crystal alignment agent containing a polyamic acid obtained from a dianhydride and a specific diamine compound or an imidized polymer thereof for example, see Patent Document 4
  • a method of suppressing an afterimage caused by alternating current driving in a liquid crystal display element of a lateral electric field driving method a method of using a specific liquid crystal alignment film that has good liquid crystal alignment and large interaction with liquid crystal molecules (patent) Document 5) has been proposed.
  • liquid crystal televisions with large screens and high-definition are mainly used, and the demand for afterimages has become more severe, and characteristics that can withstand long-term use in harsh usage environments are required.
  • liquid crystal alignment films to be used are required to have higher reliability than conventional liquid crystal alignment films. Not only the initial characteristics of the liquid crystal alignment films are good, but also, for example, they are longer at high temperatures. There is a need to maintain good properties even after time exposure.
  • polyamic acid ester is highly reliable, and heat treatment when imidizing it does not cause a decrease in molecular weight. It has been reported that it is excellent in reliability (see Patent Document 6).
  • polyamic acid esters generally have problems such as high volume resistivity and a large amount of residual charge when a DC voltage is applied, but the characteristics of polyimide liquid crystal aligning agents containing such polyamic acid esters are improved. How to do is not yet known.
  • the present invention paid attention to a liquid crystal aligning agent obtained by blending a polyamic acid ester and a polyamic acid excellent in electrical characteristics as a method for improving the characteristics of the liquid crystal aligning agent containing the polyamic acid ester.
  • a liquid crystal alignment film obtained from a liquid crystal aligning agent obtained by blending such a polyamic acid ester and a polyamic acid is not satisfactory in terms of both liquid crystal alignment properties and electrical characteristics.
  • a liquid crystal alignment film obtained from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid causes white turbidity, a decrease in voltage holding ratio when the film is used at a high temperature, and direct current Problems such as generation of afterimages due to voltage accumulation and generation of afterimages due to AC driving occur.
  • the present invention relates to a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid, in which both the liquid crystal alignment property and the electrical characteristics are good, and a liquid crystal alignment film having transparency without white turbidity is obtained.
  • An object is to provide an alignment agent.
  • the present inventor when a liquid crystal alignment film formed from a liquid crystal aligning agent containing a polyamic acid ester and a polyamic acid was analyzed, it was confirmed that fine irregularities were generated on the film surface.
  • the present inventor has modified the terminals so that the fine irregularities generated on the film surface have a specific structure as described below at least part of the terminal amino group of the polyamic acid ester. It is found that the use of a polyamic acid ester can significantly suppress the above, and when the fine unevenness generated on the film surface is reduced, the above-mentioned difficulties of the liquid crystal aligning agent containing the polyamic acid ester and the polyamic acid Has been found to be resolved.
  • the polyamic acid ester having a modified end is improved in solubility in an organic solvent even when it has a high molecular weight, and the polyamic acid ester having a modified end and a polyamic acid are added.
  • the liquid crystal aligning agent to be contained can be a liquid crystal aligning agent having a relatively low viscosity even when contained in a high concentration in an organic solvent, which makes it easy to produce a liquid crystal aligning film by, for example, an inkjet method, It has also been found that it is easy to produce a liquid crystal alignment film having a large thickness.
  • R 1 is an alkyl group having 1 to 5 carbon atoms
  • a 1 to A 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group, or An alkynyl group
  • X 1 and X 2 are tetravalent organic groups
  • Y 1 and Y 2 are divalent organic groups.
  • R 2 and R 3 each independently represents an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. Group, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group or heterocyclic group which may have a substituent.
  • the polyamic acid ester, the polyamic acid, and an organic solvent wherein the total amount of the polyamic acid ester and the polyamic acid is 0.5% by mass to 15% by mass with respect to the organic solvent.
  • the liquid crystal aligning agent according to any one of the above 1 to 3, which is an ester.
  • X 1 and X 2 in Formula (1) and Formula (2) are each independently at least one selected from the group consisting of structures represented by the following formulas: Liquid crystal aligning agent.
  • Y 1 is at least one selected from the group consisting of structures represented by the following formula.
  • the present invention fine irregularities on the surface can be reduced, the interface characteristics of the liquid crystal alignment film such as an afterimage caused by alternating current drive can be improved, and electrical characteristics such as voltage holding ratio, ion density, and residual DC voltage can be obtained.
  • the liquid crystal aligning agent which improved the physical characteristic and improved reliability is provided.
  • a polyamic acid ester whose terminal amino group is modified to have a specific structure as described below, it is possible to reduce the fine irregularities generated on the surface of the film and reduce the polyamic acid.
  • the polyamic acid ester having a surface free energy lower than that of the polyamic acid is unevenly distributed on the surface.
  • the polyamic acid ester and the polyamic acid undergo phase separation, an aggregate of polyamic acid is formed in the polyamic acid ester phase, and / or an aggregate of polyamic acid ester in the polyamic acid phase Therefore, a film having a large number of fine irregularities on the film surface is formed.
  • the solvent is removed from the liquid crystal aligning agent to form a liquid crystal aligning film.
  • Phase separation between the polyamic acid ester and the polyamic acid is promoted, the polyamic acid ester is present near the film surface without being mixed with the polyamic acid, and the polyamic acid is mixed with the polyamic acid ester inside the film and at the substrate interface. Will exist without. Therefore, the surface of the obtained liquid crystal alignment film is smooth because unevenness due to phase separation of the polyamic acid ester and the polyamic acid is not formed.
  • a liquid crystal alignment film having a smooth surface without unevenness is formed by a polyamic acid ester having excellent orientation stability and reliability covering the surface of the film, and a polyamic acid having excellent electrical characteristics is formed inside the film. And at the electrode interface, it is considered to have excellent characteristics.
  • the liquid crystal alignment film having a smooth surface also reduces the cloudiness of the film due to the occurrence of unevenness.
  • the polyamic acid ester and polyamic acid used in the present invention are polyimide precursors for obtaining a polyimide, and are polymers having sites capable of undergoing an imidation reaction shown below by heating.
  • the polyamic acid ester and polyamic acid contained in the liquid crystal aligning agent of the present invention have the following formula (1) and the following formula (2), respectively.
  • R 1 is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.
  • R 1 is particularly preferably a methyl group from the viewpoint of ease of imidization by heat.
  • a 1 and A 2 are each independently a hydrogen atom or an alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms that may have a substituent.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a bicyclohexyl group.
  • alkenyl group examples include those in which one or more CH 2 —CH 2 structures existing in the above alkyl group are replaced with a CH ⁇ CH structure, and more specifically, vinyl groups, allyl groups, 1- Examples include propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group and the like.
  • Alkynyl groups include those in which one or more CH 2 —CH 2 structures present in the alkyl group are replaced with C ⁇ C structures, and more specifically, ethynyl groups, 1-propynyl groups, 2 -Propynyl group and the like.
  • the above alkyl group, alkenyl group, and alkynyl group may have a substituent as long as it has 1 to 10 carbon atoms as a whole, and may further form a ring structure by the substituent. Note that forming a ring structure with a substituent means that the substituents or a substituent and a part of the mother skeleton are bonded to form a ring structure.
  • substituents are halogen groups, hydroxyl groups, thiol groups, nitro groups, aryl groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, alkyls.
  • the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the aryl group as a substituent include a phenyl group. This aryl group may be further substituted with the other substituent described above.
  • the organooxy group which is a substituent can have a structure represented by OR.
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above. Specific examples of the alkyloxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
  • the organothio group as a substituent can have a structure represented by —S—R.
  • R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.
  • the organosilyl group as a substituent can have a structure represented by —Si— (R) 3 .
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group.
  • the acyl group as a substituent can have a structure represented by —C (O) —R. Examples of R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
  • Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
  • ester group which is a substituent a structure represented by —C (O) O—R or —OC (O) —R can be shown.
  • R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • the thioester group which is a substituent can have a structure represented by —C (S) O—R or —OC (S) —R.
  • R include the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group, and the like. These Rs may be further substituted with the substituent described above.
  • the phosphate group which is a substituent can have a structure represented by —OP (O) — (OR) 2 .
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the substituent amide group include —C (O) NH 2 , —C (O) NHR, —NHC (O) R, —C (O) N (R) 2 , —NRC (O) R.
  • the structure represented by can be shown.
  • the R may be the same or different, and examples thereof include the alkyl group, alkenyl group, alkynyl group, and aryl group described above. These Rs may be further substituted with the substituent described above.
  • Examples of the aryl group as a substituent include the same aryl groups as described above. This aryl group may be further substituted with the other substituent described above.
  • Examples of the alkyl group as a substituent include the same alkyl groups as described above. This alkyl group may be further substituted with the other substituent described above.
  • Examples of the alkenyl group as a substituent include the same alkenyl groups as described above. This alkenyl group may be further substituted with the other substituent described above.
  • Examples of the alkynyl group that is a substituent include the same alkynyl groups as described above. This alkynyl group may be further substituted with the other substituent described above.
  • a 1 and A 2 a hydrogen atom or a carbon atom that may have a substituent is 1
  • An alkyl group of 1 to 5 is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.
  • X 1 and X 2 are tetravalent organic groups and are not particularly limited. Two or more kinds of X 1 and X 2 may be mixed in the polyimide precursor. If specific examples of X 1 and X 2 are shown, X-1 to X-46 shown below can be mentioned independently.
  • X 1 and X 2 are each independently X-1, X-2, X-3, X-4, X-5, X-6, X-8, X from the availability of monomers. -16, X-19, X-21, X-25, X-26, X-27, X-28 or X-32 are preferred.
  • the amount of tetracarboxylic dianhydride having these preferable X 1 and X 2 is preferably 20 to 100 mol%, more preferably 40 to 100 mol% of the total tetracarboxylic dianhydride.
  • Y 1 and Y 2 are each independently a divalent organic group and are not particularly limited. Specific examples of Y 1 and Y 2 include the following Y-1 to Y-103. As Y 1 and Y 2 , two or more kinds may be mixed independently.
  • Y 1 is represented by Y-7, Y-10, Y-11, Y-12, Y -13, Y-21, Y-22, Y-23, Y-25, Y-26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46
  • Diamines having Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, or Y-98 are preferred.
  • the amount of these diamines preferably used as Y 1 is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
  • Y 1 is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y- 86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96, or Y-97 are more preferred.
  • Such Y 1 is preferably at least one selected from the group consisting of structures represented by the following formulae.
  • Y 2 is Y-19, Y-23, Y-25, Y-26, Y-27, Y-30, Y-31, Y-32, Y-33, Y-34, Y-35, Y- 36, Y-40, Y-41 Y-42, Y-44, Y-45, Y-49, Y-50, Y-51, or Y-61 are more preferred, and Y-31 or Y-40 diamine Is preferred.
  • the amount of these diamines preferably used as Y 2 is preferably 1 to 100 mol%, more preferably 50 to 100 mol% of the total diamine.
  • the phase separation between the polyamic acid ester and the polyamic acid is further promoted, and the surface of the liquid crystal alignment film obtained by coating and baking becomes smoother. It is preferable to introduce a diamine containing a primary amino group, a hydroxyl group, an amide group, a ureido group, or a carboxyl group into the polyamic acid.
  • Y- 2 is more preferably Y-19, Y-31, Y-40, Y-45, Y-98, or Y-99, particularly Y-98 or Y-99 containing a carboxyl group.
  • Y 2 is preferably at least one selected from structures represented by the following formula.
  • the polyamic acid ester represented by the above formula (1) is obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (6) to (8) with the diamine compound represented by the formula (9). be able to.
  • the polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above monomer.
  • a polyamic acid ester can be manufactured by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine.
  • the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • an organic solvent ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • the esterifying agent those that can be easily removed by purification are preferable.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.
  • the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or ⁇ -butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more. .
  • the concentration at the time of production is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be produced by reacting.
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the concentration of the polymer during production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight polymer is easily obtained.
  • the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
  • Polyamic acid ester can be produced by polycondensation of tetracarboxylic acid diester and diamine. Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base, and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. It can be produced by reacting.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
  • the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
  • the base tertiary amines such as pyridine and triethylamine can be used.
  • the addition amount of the base is preferably 2 to 4 moles relative to the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • the Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times mol with respect to the diamine component.
  • the production method of (1) or (2) is particularly preferable.
  • the polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid represented by the above formula (2) can be obtained by a reaction between a tetracarboxylic dianhydride represented by the following formula (10) and a diamine compound represented by the formula (11).
  • tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C. for 30 minutes to 24 hours, preferably 1 to 12 hours.
  • the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These are used alone or in combination. May be.
  • the concentration of the produced polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
  • the polyamic acid ester whose terminal is modified is obtained by reacting the polyamic acid ester having an amino group at the terminal obtained as described above with a chlorocarbonyl compound represented by the following formula (12).
  • A is a single bond, —O—, —S—, or —NR 3 —.
  • R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkynyl group, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group which may have a substituent, It is a heterocyclic group.
  • alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a vinyl group, a 1-propenyl group, and an isopropenyl group.
  • a short alkyl group having 1 to 3 carbon atoms is preferable, and a linear alkyl group is preferable to a branched group.
  • the cycloalkyl group having 3 to 6 carbon atoms is preferably a cyclopropyl group or a cyclobutyl group.
  • aryl group a phenyl group and a naphthyl group are preferable.
  • chlorocarbonyl compound of the present invention examples include, but are not limited to, the following (C-1) to (C-36) chlorocarbonyl compounds.
  • chlorocarbonyl compound the smaller the number of carbon atoms, the smaller the interaction between the ends, and the aggregation of the polyamic acid ester can be suppressed. Therefore, as the chlorocarbonyl compound, C-1, C-2, C-3, C-16, C-17, C-19, C-20, C-21, C-27, or C-29 is more preferred. Preferably, C-1, C-2, C-3, C-16, or C-17 is more preferable.
  • the terminal of the polyamic acid ester having a repeating unit of the formula (1) having an amino group at the terminal is modified so that the amino group has the structure of the formula (3).
  • This terminal-modified polyamic acid ester can be obtained by several methods, but after dissolving the polyamic acid ester powder having an amino group at the terminal in an organic solvent, a chlorocarbonyl compound is added in the presence of a base.
  • the molar ratio of the diamine component to the tetracarboxylic acid dialkyl ester derivative is preferably 1: 0.7 to 1: 1, and more preferably 1: 0.8 to 1: 1.
  • a method of adding a chlorocarbonyl compound to the above reaction system a method of adding a tetracarboxylic acid dialkyl ester derivative and reacting with a diamine, a reaction of a tetracarboxylic acid dialkyl ester derivative and a diamine sufficiently, There is a method of adding a chlorocarbonyl compound after producing a polyamic acid ester in which is an amino group. The latter method is more preferable because the molecular weight of the polymer can be easily controlled.
  • the reaction between the polyamic acid ester having an amino group at the terminal and the chlorocarbonyl compound is carried out at ⁇ 20 to 150 ° C., preferably 0 to 50 ° C. in the presence of a base and an organic solvent. 30 minutes to 24 hours, preferably 30 minutes to 4 hours.
  • the addition amount of the chlorocarbonyl compound is preferably 0.5 to 60 mol%, more preferably 1 to 40 mol%, based on one repeating unit of the polyamic acid ester having an amino group at the end. When the addition amount is large, unreacted chlorocarbonyl compound remains and is difficult to remove, so that it is more preferably 1 to 20 mol%.
  • pyridine triethylamine, and 4-dimethylaminopyridine can be preferably used, but pyridine is preferable because the reaction proceeds gently. If the amount of the base is too large, removal is difficult, and if it is too small, the molecular weight is small. Therefore, the amount is preferably 2 to 4 times the mol of the chlorocarbonyl compound.
  • the organic solvent used for the production of the terminal polyamic acid ester is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer. These may be used alone or in combination of two or more. Also good. If the concentration at the time of production is too high, polymer precipitation is likely to occur, and if it is too low, the molecular weight does not increase, so 1 to 30% by mass is preferable, and 5 to 20% by mass is more preferable.
  • the polyamic acid ester modified in the terminal has a total amount of the polyamic acid ester contained in the liquid crystal aligning agent. It is not necessarily required to be modified, but it is preferably 15% or more, more preferably 40% or more, particularly preferably 60% or more, based on the total amount of polyamic acid ester contained. .
  • the content of the terminal amino group-modified polyamic acid ester is small, it is not preferable because sufficient effects aimed at in the present invention cannot be obtained.
  • the liquid crystal aligning agent of this invention has the form of the solution by which the polyamic acid ester and polyamic acid which modified the said terminal were melt
  • the molecular weight of the terminal polyamic acid ester is preferably 2,000 to 500,000, more preferably 5,000 to 300,000 in terms of its weight average molecular weight even when the terminal amino group is not modified. More preferably, it is 10,000 to 100,000.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the weight average molecular weight of the polyamic acid is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the difference in weight average molecular weight between the terminal polyamic acid ester and the polyamic acid is preferably 1,000 to 1200,000, more preferably 3,000 to 80,000, and 5,000 to 60,000. Is particularly preferred.
  • the mass ratio of the polyamic acid ester to the polyamic acid (polyamic acid ester / polyamic acid) contained in the liquid crystal aligning agent of the present invention is preferably 1/9 to 9/1.
  • the ratio is more preferably 2/8, and particularly preferably 3/7 to 7/3. By setting the ratio within this range, it is possible to provide a liquid crystal aligning agent having good liquid crystal alignment properties and electrical characteristics.
  • the liquid crystal aligning agent of this invention has the form of the solution in which the polyamic acid ester and polyamic acid which modified the terminal were melt
  • a method of mixing a polyamic acid ester and a polyamic acid powder and dissolving in an organic solvent a method of mixing a polyamic acid ester powder and a polyamic acid solution, a method of mixing a polyamic acid ester solution and a polyamic acid powder, There is a method of mixing a polyamic acid ester solution and a polyamic acid solution.
  • the reaction solution obtained may be used, or the reaction solution may be diluted with an appropriate solvent. There may be.
  • the polyamic acid ester which modified the terminal is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
  • the polymer concentration is preferably 10 to 30% by mass, particularly preferably 10 to 15% by mass.
  • the heating temperature is preferably 20 to 150 ° C, particularly preferably 20 to 80 ° C.
  • the content (concentration) of the end-modified polyamic acid ester in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film to be formed, but it is uniform and has no defect. From the viewpoint of forming a film, it is preferably 0.5% by mass or more with respect to the organic solvent, and from the viewpoint of storage stability of the solution, it is preferably 15% by mass or less, particularly preferably 1 to 10% by mass.
  • the other liquid crystal aligning agent which is a compound which has liquid crystal aligning property other than the polyamic acid ester which modified the terminal may contain.
  • liquid crystal aligning agents examples include various types such as a polyamic acid ester whose terminal amino group is not modified, a soluble polyimide, and / or a liquid crystal aligning agent containing polyamic acid.
  • the polyamic acid ester whose end is modified has a high solubility in an organic solvent, so it has excellent alignment characteristics and electrical characteristics, but has a low solubility in an organic solvent, for example, a liquid crystal aligning agent containing polyamic acid or soluble polyimide. It is particularly useful when it is contained.
  • the said organic solvent contained in the liquid crystal aligning agent of this invention will not be specifically limited if the polymer component of the amic acid ester and polyamic acid which modified at least one part of the terminal amino group melt
  • Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like.
  • the silane coupling agent when adding a silane coupling agent to the liquid crystal aligning agent of the present invention, before mixing the polyamic acid ester solution and the polyamic acid solution, the polyamic acid ester solution, the polyamic acid solution, or the polyamic acid ester solution And polyamic acid solution.
  • the silane coupling agent can be added to the polyamic acid ester-polyamic acid mixed solution. Since the silane coupling agent is added for the purpose of improving the adhesion between the polymer and the substrate, as a method for adding the silane coupling agent, the silane coupling agent is added to a polyamic acid solution that can be unevenly distributed in the film and the substrate interface, and the polymer is added.
  • a method in which the silane coupling agent is sufficiently reacted with the polyamic acid ester solution is more preferable. If the addition amount of the silane coupling agent is too large, unreacted ones may adversely affect the liquid crystal orientation. If the addition amount is too small, the effect on the adhesion does not appear.
  • the content is preferably from 01 to 5.0% by mass, and more preferably from 0.1 to 1.0% by mass.
  • the liquid crystal aligning agent of this invention may contain the solvent for improving the coating-film uniformity at the time of apply
  • a solvent a solvent having a surface tension lower than that of the organic solvent is generally used.
  • ethyl cellosolve examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, di Propylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactic acid Isoamyl ester, and the like.
  • the liquid crystal aligning agent of this invention may contain various additives, such as a silane coupling agent and a crosslinking agent.
  • a silane coupling agent or a crosslinking agent in order to prevent polymer precipitation, it is preferable to add a poor solvent before adding a poor solvent to the liquid crystal aligning agent.
  • silane coupling agent that can be used in the liquid crystal aligning agent of the present invention is not limited thereto.
  • the addition amount of the silane coupling agent is 0.01 to 5.0% by mass with respect to the polymer component from the viewpoint that the unreacted agent does not adversely affect the liquid crystal orientation and the effect of adhesion appears. Preferably, 0.1 to 1.0% by mass is more preferable.
  • a silane coupling agent in order to prevent polymer precipitation, it is preferable to add before adding the solvent for improving the above-mentioned coating film uniformity.
  • Specific examples of the imidization accelerator for polyamic acid ester are given below, but the imidization accelerator that can be used in the liquid crystal aligning agent of the present invention is not limited thereto.
  • D in the above formulas (B-1) to (B-17) is each independently a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.
  • (B-14) to (B-17) there are a plurality of D's in one formula, but these may be the same or different.
  • the content of the imidization accelerator is not particularly limited as long as the effect of promoting thermal imidation of the polyamic acid ester is obtained. If the lower limit is deliberately shown, it is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably with respect to 1 mol of the amic acid ester moiety of the following formula (13) contained in the polyamic acid ester. 0.1 mol or more is mentioned.
  • the upper limit of the polyamic acid ester of the present invention can be determined.
  • the imidization accelerator is 2 mol or less, more preferably 1 mol or less, and still more preferably 0.5 mol or less with respect to 1 mol of the amic acid ester moiety of the following formula (13) contained.
  • the liquid crystal alignment film of the present invention is a coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking, and if necessary, this coating film surface is rubbed or the like. Alignment treatment is performed.
  • the substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed.
  • an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the organic solvent contained, the film is dried at 50 to 120 ° C. for 1 to 10 minutes, and then baked at 150 to 300 ° C. for 5 to 120 minutes.
  • the thickness of the coating film after baking is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, and therefore it is 5 to 300 nm, preferably 10 to 200 nm.
  • Examples of the method for aligning the coating film include a rubbing method and a photo-alignment method, but the liquid crystal aligning agent of the present invention is particularly useful when used in the photo-alignment method.
  • the photo-alignment treatment method there is a method in which the surface of the coating film is irradiated with radiation polarized in a certain direction, and in some cases, a heat treatment is further performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
  • the radiation ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used.
  • ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable.
  • radiation may be irradiated while heating the coated substrate at 50 to 250 ° C. Dose of the radiation is preferably in the range of 1 ⁇ 10,000mJ / cm 2, and particularly preferably in the range of 100 ⁇ 5,000mJ / cm 2.
  • the liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.
  • the molecular weight of the polyamic acid ester is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and is a number average molecular weight (hereinafter also referred to as Mn) and a weight average molecular weight (hereinafter also referred to as Mw) as polyethylene glycol and polyethylene oxide equivalent values. ) was calculated.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran) (THF) is 10 ml / L) Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) of about 12,000, 4,000, 1,000). In order to avoid the overlapping of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000
  • the coating film of the liquid crystal aligning agent obtained by spin coating is dried for 5 minutes on a hot plate at a temperature of 80 ° C. and baked for 1 hour in a hot air circulation oven at a temperature of 250 ° C. to form a coating film having a film thickness of 100 nm. Obtained.
  • the film surface of this coating film was observed with an atomic force microscope (AFM), the center line average roughness (Ra) of the film surface was measured, and the flatness of the film surface was evaluated.
  • AFM atomic force microscope
  • Measuring device L-trace probe microscope (manufactured by SII Technology) [Voltage holding ratio]
  • a liquid crystal aligning agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and baked for 60 minutes in a hot air circulation oven at 250 ° C. to be imidized with a film thickness of 100 nm.
  • a membrane was obtained.
  • the coating surface was irradiated with 100 mJ / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
  • Two substrates with such a liquid crystal alignment film are prepared, and a 6 ⁇ m spacer is sprayed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment is antiparallel.
  • the periphery was sealed and the empty cell having a cell gap of 6 ⁇ m was produced.
  • Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the inlet was sealed to obtain a liquid crystal cell.
  • the voltage holding ratio of the liquid crystal cell was measured as follows. By applying a voltage of 4 V for 60 ⁇ s and measuring the voltage after 16.67 ms, the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 23 ° C., 60 ° C., and 90 ° C., and the measurement was performed at each temperature.
  • the measurement of the ion density of the liquid crystal cell was performed as follows. Measurement was performed using a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Technica. A triangular wave of 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C. and 60 ° C., and the measurement was performed at each temperature. [AC drive burn-in of FFS drive liquid crystal cell] On a glass substrate, a 50 nm thick ITO electrode having the shape shown in FIG.
  • Comb-shaped ITO electrodes (electrode width: 3 ⁇ m, electrode spacing: 6 ⁇ m, electrode height: 50 nm) shown in FIG. 3 as electrodes in the layer are fringe field switching (hereinafter referred to as FFS) driving electrodes.
  • the liquid crystal aligning agent was apply
  • the coating surface was irradiated with 100 mJ / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
  • a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed.
  • the two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added.
  • An empty cell was produced by curing.
  • Liquid crystal MLC-2041 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell.
  • VT characteristic voltage-transmittance characteristic
  • a rectangular wave of ⁇ 4 V / 120 Hz was applied for 4 hours.
  • the voltage was turned off and left at a temperature of 58 ° C. for 60 minutes, and then the VT characteristics were measured again, and the difference in voltage at which the transmittance before and after the rectangular wave application was 50% was calculated.
  • this crystal was found to be compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (1,3-DM -CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).
  • 1 H NMR (CDCl 3 , ⁇ ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).
  • the obtained end-modified polyamic acid ester resin powder (3.3076 g) was placed in a 50 ml Erlenmeyer flask, NMP (30.4854 g) was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-1).
  • the viscosity of this polyamic acid solution at a temperature of 25 ° C. was 14550 mPa ⁇ s.
  • the obtained polyamic acid ester resin powder 14.8252 was placed in a 200 ml Erlenmeyer flask, NMP 99.3048 g was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-5).
  • Example 1 In a 20 ml sample tube containing a stirrer, 1.5016 g of the polyamic acid ester solution (PAE-1) obtained in Production Example 1 and 1.0469 g of the polyamic acid solution (PAA-1) obtained in Production Example 5 were triangular. It took to the flask, NMP1.4916g and BCS1.0249g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (I).
  • PAE-1 polyamic acid ester solution
  • Example 2 In a 20 ml sample tube containing a stirrer, 1.5050 g of the polyamic acid ester solution (PAE-2) obtained in Production Example 2 and 0.9091 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. Into the flask, 1.6291 g of NMP and 1.0032 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (II).
  • Example 3 In a 20 ml sample tube containing a stirrer, 1.5138 g of the polyamic acid ester solution (PAE-3) obtained in Production Example 3 and 0.8932 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. It took to the flask, NMP1.6438g and BCS1.0231g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (III).
  • Example 4 In a 20 ml sample tube containing a stir bar, 1.5097 g of the polyamic acid ester solution (PAE-4) obtained in Production Example 4 and 0.8953 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were triangular. It took to the flask, NMP1.6372g and BCS1.0101g were added, and it stirred for 30 minutes with the magnetic stirrer, and obtained liquid crystal aligning agent (IV).
  • Example 5 The liquid crystal aligning agent (I) obtained in Example 1 was filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and a temperature of 250 An imidized film having a film thickness of 100 nm was obtained after baking for 60 minutes in a hot air circulating oven at 0 ° C. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later. (Example 6) An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (II) obtained in Example 2 was used.
  • Example 7 An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (III) obtained in Example 3 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
  • Example 8 An imidized film was produced in the same manner as in Example 5 except that the liquid crystal aligning agent (IV) obtained in Example 4 was used. The centerline average roughness (Ra) of this film was measured. About a measurement result, it shows in Table 1 mentioned later.
  • Example 9 The liquid crystal aligning agent (I) obtained in Example 1 was filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and a temperature of 250 An imidized film having a film thickness of 100 nm was obtained after baking for 60 minutes in a hot air circulating oven at 0 ° C.
  • the coating surface was irradiated with 100 mJ / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
  • Two substrates with such a liquid crystal alignment film are prepared, and a 6 ⁇ m spacer is sprayed on the liquid crystal alignment film surface of one of the substrates, and then the two substrates are combined so that the alignment is antiparallel.
  • the periphery was sealed and the empty cell having a cell gap of 6 ⁇ m was produced.
  • Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this empty cell at room temperature, and the inlet was sealed to obtain a liquid crystal cell.
  • Example 7 A liquid crystal cell was produced in the same manner as in Example 9 except that the liquid crystal aligning agent (a) obtained in Comparative Example 1 was used. For this liquid crystal cell, the voltage holding ratio was measured, and then the ion density was measured. The measurement results of the voltage holding ratio and the ion density are shown in Table 2 described later.
  • Example 9 From the results of Example 9 and Comparative Example 7, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention was a highly reliable liquid crystal alignment film.
  • Example 10 After filtering the liquid crystal aligning agent (I) obtained in Example 1 with a 1.0 ⁇ m filter, an ITO electrode having a film thickness of 50 nm as a first layer and an insulating film as a second layer on a glass substrate.
  • a silicon nitride film having a thickness of 500 nm is used as a third layer of a fringe field switching (hereinafter referred to as FFS) having comb-shaped ITO electrodes (electrode width: 3 ⁇ m, electrode interval: 6 ⁇ m, electrode height: 50 nm). ) It was applied by spin coating to a glass substrate on which driving electrodes were formed. After drying on an 80 ° C.
  • FFS fringe field switching
  • a coating film having a thickness of 130 nm.
  • the coating surface was irradiated with 100 mJ / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
  • a coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which no electrode was formed as a counter substrate, and an orientation treatment was performed. The two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added.
  • Example 10 and Comparative Example 8 From the results of Example 10 and Comparative Example 8, it was confirmed that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can obtain a liquid crystal alignment film having a small degree of AC drive burn-in and a small residual voltage.
  • the obtained polyamic acid ester solution was poured into 498 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 226 g of ethanol once, 452 g of water twice, and 453 g of ethanol 1 This was washed 3 times with 113 g of ethanol and dried to obtain 4.4587 g of white polyamic acid ester resin powder.
  • the yield was 98.53%.
  • the obtained polyamic acid ester solution was poured into 500 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 455 g of water twice, and 455 g of ethanol 1 This was washed 3 times with 114 g of ethanol and dried to obtain 4.2721 g of white polyamic acid ester resin powder.
  • the yield was 93.91%.
  • the yield was 96.99%.
  • 2.2172 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 19.9964 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-10).
  • the obtained polyamic acid ester solution was poured into 491 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 223 g of ethanol once, 446 g of water twice, and 446 g of ethanol 1 This was washed 3 times with 111 g of ethanol and dried to obtain 3.74 g of white polyamic acid ester resin powder.
  • the yield was 83.86%.
  • the obtained polyamic acid ester solution was poured into 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.7689 g of white polyamic acid ester resin powder. The yield was 83.0%.
  • the obtained polyamic acid ester solution was poured into 499 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 454 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 4.2667 g of white polyamic acid ester resin powder. The yield was 95.7%.
  • the obtained polyamic acid ester solution was added to 552 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 460 g of water twice, and 228 g of ethanol 1 This was washed three times with 115 g of ethanol and dried to obtain 4.24 g of white polyamic acid ester resin powder.
  • the yield was 92.2%.
  • the obtained polyamic acid ester solution was added to 545 g of ethanol while stirring, and the precipitated white precipitate was collected by filtration, followed by 227 g of ethanol once, 454 g of water twice, and 227 g of ethanol once. This was washed 3 times with 114 g of ethanol and dried to obtain 3.89 g of white polyamic acid ester resin powder. The yield was 85.7%.
  • the obtained polyamic acid ester solution was added to 1224 g of methanol while stirring, and the deposited precipitate was collected by filtration, then washed with 408 g of methanol four times and dried to obtain a polyamic acid ester resin powder. It was.
  • 1.0172 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 9.4167 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-32).
  • the obtained polyamic acid ester solution was poured into 1018 g of 2-propanol with stirring, and the deposited precipitate was collected by filtration, then washed with 504 g of 2-propanol five times and dried to obtain a polyamic acid ester.
  • a resin powder was obtained.
  • 1.8932 g of the obtained polyamic acid ester resin powder was placed in a 50 ml Erlenmeyer flask, 17.0436 g of ⁇ -BL was added, and the mixture was stirred and dissolved at room temperature for 24 hours to obtain a polyamic acid ester solution (PAE-33).
  • Example 11 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4106 g of the polyamic acid ester solution (PAE-7) obtained in Production Example 7 and 1.6477 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. Then, 2.3811 g of NMP and 1.5934 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-1).
  • PAE-7 polyamic acid ester solution obtained in Production Example 7
  • 2.3811 g of NMP and 1.5934 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-1).
  • Example 12 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3986 g of the polyamic acid ester solution (PAE-10) obtained in Production Example 10 and 1.6926 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3700 g) and BCS (1.6042 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-2).
  • Example 13 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4102 g of the polyamic acid ester solution (PAE-11) obtained in Production Example 11 and 1.6552 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3643 g) and BCS (1.6339 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-3).
  • Example 14 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4153 g of the polyamic acid ester solution (PAE-12) obtained in Production Example 12 and 1.6606 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3594 g) and BCS (1.6607 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-4).
  • PAE-12 polyamic acid ester solution obtained in Production Example 12
  • NMP (2.3594 g) and BCS (1.6607 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-4).
  • Example 15 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4079 g of the polyamic acid ester solution (PAE-13) obtained in Production Example 13 and 1.6504 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3762 g) and BCS (1.6062 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-5).
  • PAE-13 polyamic acid ester solution obtained in Production Example 13
  • NMP (2.3762 g) and BCS (1.6062 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-5).
  • Example 16 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3990 g of the polyamic acid ester solution (PAE-9) obtained in Production Example 9 and 1.6445 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3564 g) and BCS (1.6084 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-6).
  • PAE-9 polyamic acid ester solution obtained in Production Example 9
  • NMP (2.3564 g) and BCS (1.6084 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-6).
  • Example 17 A stir bar was placed in a 50 ml Erlenmeyer flask, and 2.3984 g of the polyamic acid ester solution (PAE-14) obtained in Production Example 14 and 1.663 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3651 g) and BCS (1.6102 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-7).
  • PAE-14 polyamic acid ester solution obtained in Production Example 14
  • NMP (2.3651 g) and BCS (1.6102 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-7).
  • Example 18 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.3983 g of the polyamic acid ester solution (PAE-21) obtained in Production Example 21 and 1.6284 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 were taken. NMP (2.3625 g) and BCS (1.5973 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-8).
  • PAE-21 polyamic acid ester solution obtained in Production Example 21
  • NMP (2.3625 g) and BCS (1.5973 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-8).
  • Example 19 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4288 g of the polyamic acid ester solution (PAE-22) obtained in Production Example 22 was taken, and 1.6277 g of the polyamic acid solution (PAA-3) obtained in Production Example 30 was taken. NMP (2.3674 g) and BCS (1.6044 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (V-9).
  • Example 20 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4073 g of the polyamic acid ester solution (PAE-15) obtained in Production Example 15 and 1.4266 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5623 g of NMP and 1.6037 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-1).
  • PAE-15 polyamic acid ester solution
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 21 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4315 g of the polyamic acid ester solution (PAE-8) obtained in Production Example 8 and 1.4539 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5771 g of NMP and 1.6047 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-2).
  • PAE-8 polyamic acid ester solution obtained in Production Example 8
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 22 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4080 g of the polyamic acid ester solution (PAE-16) obtained in Production Example 16 was taken, and 1.5842 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 was taken. 2.5699 g of NMP and 1.6067 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-3).
  • PAE-16 polyamic acid ester solution obtained in Production Example 16
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 23 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4016 g of the polyamic acid ester solution (PAE-20) obtained in Production Example 20 and 1.5320 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5650 g of NMP and 1.5970 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-4).
  • PAE-20 polyamic acid ester solution obtained in Production Example 20
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 24 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4105 g of the polyamic acid ester solution (PAE-19) obtained in Production Example 19 and 1.4186 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5900 g of NMP and 1.6034 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-5).
  • PAE-19 polyamic acid ester solution obtained in Production Example 19
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 25 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4208 g of the polyamic acid ester solution (PAE-17) obtained in Production Example 17 and 1.4416 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5948 g of NMP and 1.6192 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-6).
  • PAE-17 polyamic acid ester solution obtained in Production Example 17
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 26 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4128 g of the polyamic acid ester solution (PAE-18) obtained in Production Example 18 and 1.4003 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5658 g of NMP and 1.6040 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-7).
  • PAE-18 polyamic acid ester solution obtained in Production Example 18
  • PAA-2 polyamic acid solution obtained in Production Example 6
  • Example 27 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4003 g of the polyamic acid ester solution (PAE-23) obtained in Production Example 23 and 1.4214 g of the polyamic acid solution (PAA-2) obtained in Production Example 6 were taken. Then, 2.5769 g of NMP and 1.6258 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VI-8).
  • Example 28 A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4970 g of the polyamic acid ester solution (PAE-14) obtained in Production Example 14 and 0.6867 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 were taken. Then, 1.8321 g of NMP and 0.9933 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-1).
  • Example 29 A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4939 g of the polyamic acid ester solution (PAE-20) obtained in Production Example 20 was taken, and 0.6778 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 was taken. Then, 1.8243 g of NMP and 0.9970 g of BCS were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-2).
  • Example 30 A stirrer was placed in a 50 ml Erlenmeyer flask, and 1.4923 g of the polyamic acid ester solution (PAE-17) obtained in Production Example 17 and 0.6527 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 were taken. Further, 1.8424 g of NMP and 1.0093 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VII-3).
  • Example 31 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4514 g of the polyamic acid ester solution (PAE-24) obtained in Production Example 24 was taken, and 2.6079 g of the polyamic acid solution (PAA-4) obtained in Production Example 31 was taken. Then, N294 (3.2294 g), BCS (2.0193 g), 4- (t-butoxycarbonylamino) pyridine (hereinafter abbreviated as Boc-AP) as an imidization accelerator (0.0745 g) were added, and a magnetic stirrer was added. The mixture was stirred for a minute to obtain a liquid crystal aligning agent (VIII-1).
  • Example 32 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4389 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 was taken, and 2.0025 g of the polyamic acid solution (PAA-6) obtained in Production Example 33 was taken.
  • NMP (3.8213 g), BCS (2.0747 g), and N- ⁇ - (9-fluorenylmethoxycarbonyl) -Nt-butoxycarbonyl-L-histidine (hereinafter referred to as Fmoc-His) as an imidization accelerator.
  • Example 33 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4317 g of the polyamic acid ester solution (PAE-26) obtained in Production Example 26 and 2.4209 g of the polyamic acid solution (PAA-7) obtained in Production Example 34 were taken. Further, 3.2161 g of NMP, 2.0138 g of BCS, and 0.0443 g of Fmoc-His as an imidization accelerator were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-3).
  • Example 34 A stir bar was placed in a 50 ml Erlenmeyer flask, and 2.44033 g of the polyamic acid ester solution (PAE-24) obtained in Production Example 24 and 1.8146 g of the polyamic acid solution (PAA-5) obtained in Production Example 32 were taken. NMP (3.8062 g) and BCS (2.0598 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-4).
  • Example 35 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4133 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 2.4596 g of the polyamic acid solution (PAA-8) obtained in Production Example 35 were taken. NMP (3.2232 g) and BCS (2.0172 g) were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-5).
  • Example 36 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4188 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 1.8056 g of the polyamic acid solution (PAA-9) obtained in Production Example 36 were taken. 3.8213 g of NMP and 2.0016 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-6).
  • Example 37 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4086 g of the polyamic acid ester solution (PAE-25) obtained in Production Example 25 and 2.0296 g of the polyamic acid solution (PAA-10) obtained in Production Example 37 were taken. NMP (3.6425 g) and BCS (2.0192 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-7).
  • Example 38 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4038 g of the polyamic acid ester solution (PAE-26) obtained in Production Example 26 and 2.4958 g of the polyamic acid solution (PAA-11) obtained in Production Example 38 were taken. NMP (3.2333 g) and BCS (2.0473 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-8).
  • Example 39 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4592 g of the polyamic acid ester solution (PAE-27) obtained in Production Example 27 and 2.3451 g of the polyamic acid solution (PAA-12) obtained in Production Example 39 were taken. In addition, 0.3698 g of NMP, 3.0082 g of ⁇ -BL, and 2.0164 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-9).
  • PAE-27 polyamic acid ester solution obtained in Production Example 27
  • 0.3698 g of NMP, 3.0082 g of ⁇ -BL, and 2.0164 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-9).
  • Example 40 A stirrer was placed in a 50 ml Erlenmeyer flask, and 2.4180 g of the polyamic acid ester solution (PAE-28) obtained in Production Example 28 and 2.2640 g of the polyamic acid solution (PAA-12) obtained in Production Example 39 were taken. , N912 (0.3912 g), ⁇ -BL (2.9920 g) and BCS (2.0276 g) were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-10).
  • PAE-28 polyamic acid ester solution obtained in Production Example 28
  • PAA-12 polyamic acid solution obtained in Production Example 39
  • Example 41 A stirrer was placed in a 50 ml Erlenmeyer flask and 2.4290 g of the polyamic acid ester solution (PAE-29) obtained in Production Example 29 was taken, and 2.1331 g of the polyamic acid solution (PAA-13) obtained in Production Example 40 was taken. 1.1458 g of NMP, 2.4939 g of ⁇ -BL, and 2.0804 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (VIII-11).
  • Example 42 The liquid crystal aligning agent (V-1) obtained in Example 11 was filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at a temperature of 80 ° C. for 5 minutes. An imidized film having a film thickness of 100 nm was obtained after baking for 20 minutes in a warm air circulating oven at 230 ° C. The centerline average roughness (Ra) of this imidized film was measured. About a measurement result, it shows in Table 4 mentioned later.
  • Example 43 to 69 and Comparative Examples 17 to 24 Each coating film was formed in the same manner as in Example 42 except that the respective liquid crystal aligning agents obtained in Examples 12 to 34, 38 to 41, and Comparative Examples 9 to 16 were used. The film surface of each coating film was observed with AFM. Further, the center line average roughness (Ra) was measured for each coating film. These measurement results are shown in Table 4 described later.
  • the surface irregularities of the liquid crystal and the liquid crystal alignment film such as the reduction of fine irregularities on the surface and the reduction of the afterimage due to alternating current drive, are improved, and the voltage holding ratio, the ion density, the residual DC voltage, etc.
  • the electrical characteristics of the are also improved.
  • the present invention is widely useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.

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Abstract

La présente invention concerne un agent d'alignement de cristaux liquides qui peut réduire les irrégularités microscopiques sur la surface de films d'alignement de cristaux liquides, améliore les propriétés d'alignement des cristaux liquides et présente des caractéristiques électriques améliorées telles que la relaxation de la tension CC résiduelle et la densité VHR/ion. L'agent d'alignement des cristaux liquides est caractérisé en ce qu'il contient: un ester d'acide polyamique ayant une unité structurale représentée par la formule générale (1) et ayant une extrémité modifiée de sorte qu'un groupe amino sur l'extrémité ait une structure spécifique représentée par la formule générale (3); un acide polyamique ayant une unité structurale représentée par la formule générale (2); et un solvant organique. (R1 représente un groupe alkyle C1-5, A1 et A2 représentent indépendamment un atome d'hydrogène ou un groupe alcényle, un groupe alcynyle ou un groupe alkyle C1-10 facultativement substitué, X1 et X2 représentent un groupe organique tétravalent, et Y1 et Y2 représentent un groupe divalent.) (dans la formule générale (3), A représente une liaison simple, -O-, -S-, ou -NR3-, et R2 et R3 représentent indépendamment un groupe méthyle, un groupe éthyle, un groupe vinyle, un groupe 1-propényle, un groupe isopropényle, un groupe cycloalkyle C3-6, un groupe phényle, un groupe naphtyle ou un anneau hétérocyclique.)
PCT/JP2011/055972 2010-03-15 2011-03-14 Agent d'alignement de cristaux liquides contenant un ester d'acide polyamique à extrémité modifiée et film d'alignement de cristaux liquides Ceased WO2011115077A1 (fr)

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CN201180024029.8A CN102893206B (zh) 2010-03-15 2011-03-14 包含对末端进行了修饰的聚酰胺酸酯的液晶取向剂及液晶取向膜
KR1020127026263A KR101816940B1 (ko) 2010-03-15 2011-03-14 말단을 수식한 폴리아믹산에스테르 함유 액정 배향제, 및 액정 배향막

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TWI568773B (zh) 2017-02-01
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