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WO2011149071A1 - Agent d'alignement de cristaux liquides qui comprend un composé contenant un groupe clivable thermiquement, et film d'alignement de cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides qui comprend un composé contenant un groupe clivable thermiquement, et film d'alignement de cristaux liquides Download PDF

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Publication number
WO2011149071A1
WO2011149071A1 PCT/JP2011/062258 JP2011062258W WO2011149071A1 WO 2011149071 A1 WO2011149071 A1 WO 2011149071A1 JP 2011062258 W JP2011062258 W JP 2011062258W WO 2011149071 A1 WO2011149071 A1 WO 2011149071A1
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group
liquid crystal
compound
aligning agent
crystal aligning
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English (en)
Japanese (ja)
Inventor
直樹 作本
祐樹 高山
隆夫 堀
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to KR1020127033890A priority Critical patent/KR101823712B1/ko
Priority to CN201180035610.XA priority patent/CN103003741B/zh
Priority to JP2012517340A priority patent/JP5761183B2/ja
Publication of WO2011149071A1 publication Critical patent/WO2011149071A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • 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

Definitions

  • the present invention has high mechanical strength, excellent resistance to rubbing treatment, liquid crystal orientation, particularly excellent electrical characteristics such as voltage holding ratio and ion density at high temperature, and a reliability that provides a high pretilt angle.
  • the present invention relates to a liquid crystal aligning agent that can form a liquid crystal aligning film having high properties, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element.
  • Liquid crystal display elements used for liquid crystal televisions, liquid crystal displays, and the like are usually provided with a liquid crystal alignment film for controlling the alignment state of the liquid crystals.
  • a liquid crystal alignment film a polyimide-based 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.
  • a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic anhydride group in the molecule, and 1 in the molecule A liquid crystal aligning agent containing a very small amount of a compound selected from compounds containing three tertiary amino groups (see Patent Document 3), a tetracarboxylic dianhydride having a specific structure and a tetracarboxylic dianhydride having cyclobutane
  • Patent Document 4 A liquid crystal aligning agent containing a polyamic acid obtained from the diamine compound or an imidized polymer thereof (see Patent Document 4) is known.
  • liquid crystal aligning agent containing an imide group-containing monomer having a specific structure or an amic acid site-containing monomer, together with polyamic acid or polyimide, polyamic acid and an imidized polymer of polyamic acid.
  • a liquid crystal aligning agent (see Patent Document 6) containing one kind of polymer and at least one compound selected from an amic acid compound and an imide compound has been proposed.
  • the present invention provides a liquid crystal alignment film having a large mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, particularly electrical characteristics such as voltage holding ratio and ion density at high temperatures,
  • An object of the present invention is to provide a liquid crystal aligning agent capable of forming a highly reliable liquid crystal aligning film that gives a high pretilt angle.
  • the present inventor has intensively studied to achieve the above object, and as a result, a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, which are components of a conventional liquid crystal aligning agent, and / or Or a compound having an amino group protected by a heat-releasable group that replaces hydrogen by heating and having an amic acid or an amic acid ester structure (hereinafter referred to as “thermal desorption”). It was also found that the above-mentioned object can be achieved by a liquid crystal aligning agent containing a release group-containing compound.
  • a compound having an amino group protected by a heat-releasable group that replaces hydrogen by heating added to the liquid crystal aligning agent and having an amic acid or amic acid ester structure (hereinafter referred to as a heat-releasable group-containing compound) Is a novel compound not yet published in the literature before the filing of the present application, but when such a heat-releasable group-containing compound is added to the liquid crystal aligning agent, the film has high mechanical strength and resistance to rubbing treatment. It was found that a liquid crystal alignment film having excellent reliability and excellent electrical properties such as liquid crystal alignment properties, in particular, voltage holding ratio and ion density at high temperatures, and giving a high pretilt angle can be formed. .
  • the present invention has the following gist. 1. Protected by a polyimide precursor obtained by reacting a diamine compound and a tetracarboxylic acid derivative, and / or a polyimide imidized with the polyimide precursor, and a thermally desorbable group that replaces hydrogen by heating at 80 to 300 ° C.
  • a liquid crystal aligning agent comprising a compound having an amino group-containing amic acid or amic acid ester structure.
  • the liquid crystal aligning agent according to 1 above, wherein the polyimide precursor has a repeating unit represented by the following formula (7).
  • X 1 is a tetravalent organic group
  • Y 1 is a divalent organic group
  • R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • a 1 and A 2 are respectively Independently a hydrogen atom or an optionally substituted alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms.
  • the polyimide precursor and the polyimide are contained in a total amount of 0.5 to 15% by mass in the liquid crystal aligning agent, and an amic acid or an amic acid having an amino group protected by a thermally detachable group that replaces hydrogen by heating.
  • the compound having an acid ester structure is 0.5 to 50 mol% based on one unit of the polyimide precursor having a repeating unit represented by the above formula (7) and the repeating unit of the imidized polymer of the polyimide precursor.
  • X is a tetravalent organic group
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z is a structure represented by the following formula (2).
  • Z 1 is a single bond or a divalent organic group having 1 to 30 carbon atoms.
  • R 2 and R 3 are each independently a hydrogen atom or a carbon number which may have a substituent.
  • An alkyl group having 1 to 30 alkyl groups, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, which may form a ring structure, and R 4 may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms.
  • D 1 is a thermally leaving group.
  • liquid crystal aligning agent according to any one of 1 to 4 above, wherein the thermally leaving group is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group. 6). 6. The liquid crystal aligning agent according to any one of 1 to 5, wherein X is any one selected from the group consisting of a structure represented by the following formula.
  • X is a tetravalent organic group
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z is a structure represented by the following formula (2).
  • Z 1 is a single bond or a divalent organic group having 1 to 30 carbon atoms.
  • R 2 and R 3 are each independently a hydrogen atom or a carbon number which may have a substituent.
  • An alkyl group having 1 to 30 alkyl groups, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof, which may form a ring structure, and R 4 may have a hydrogen atom or a substituent and may have 1 to 30 carbon atoms.
  • D 1 is a thermally leaving group.
  • a bischlorocarbonyl compound represented by the following formula (3) and a monoamine compound represented by the following formula (4) have a molar ratio of (chlorocarbonyl compound / monoamine) of 1/2 to 1/3. 11.
  • a tetracarboxylic dianhydride represented by the following formula (6) and a monoamine compound represented by the above formula (4) have a molar ratio of (tetracarboxylic dianhydride / monoamine) of 1/2 to 1/3. 11. The compound according to the above 10, obtained by reacting.
  • the obtained liquid crystal alignment film has high mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, in particular, electrical characteristics such as voltage holding ratio and ion density at high temperatures,
  • a liquid crystal alignment agent capable of forming a highly reliable liquid crystal alignment film giving a high pretilt angle is provided.
  • the liquid crystal aligning agent of the present invention can form a liquid crystal aligning film having the above-mentioned excellent characteristics and is excellent in long-term storage stability when stored before using the liquid crystal aligning agent.
  • a compound having an amino group protected by a thermally desorbable group contained in the liquid crystal aligning agent of the present invention and having an amic acid or an amic acid ester structure is a novel compound, and such a novel compound is also provided. Is done.
  • liquid crystal aligning agent of the present invention has excellent characteristics as described above is not necessarily clear, but is estimated as follows.
  • the thermally desorbable group-containing compound contained in the liquid crystal aligning agent of the present invention has a heat desorbing property at a temperature during the firing process when the liquid crystal aligning agent is applied to the substrate surface and baked to form a liquid crystal alignment film.
  • the group is decomposed and a highly reactive primary or secondary amine is generated.
  • the generated primary or secondary amine accelerates the imidization reaction of the polyimide precursor and / or the polymer of the polyimide, which is the main component contained in the liquid crystal aligning agent, and brings about a high imidization ratio.
  • This causes a cross-linking reaction and gives a large mechanical strength to the liquid crystal alignment film obtained from the liquid crystal aligning agent.
  • the increase in mechanical strength results in improved rubbing resistance and stability of liquid crystal characteristics at high temperatures.
  • the thermally detachable group-containing compound has the same amic acid or amic acid ester structure as the polyimide precursor and / or polyimide polymer, which is the main component contained in the liquid crystal aligning agent, When this is added to the liquid crystal aligning agent, the liquid crystal alignment is improved rather than inhibiting the liquid crystal alignment, and as a result, the liquid crystal characteristics such as voltage holding ratio, ion density, and pretilt angle are improved. Furthermore, since the thermally detachable group-containing compound does not decompose until a high temperature is applied, it has no adverse effect on the storage stability of the liquid crystal aligning agent containing the compound. None give.
  • the obtained liquid crystal alignment film has high mechanical strength, excellent resistance to rubbing treatment, and excellent liquid crystal alignment properties, in particular, electrical characteristics such as voltage holding ratio and ion density at high temperatures,
  • a liquid crystal alignment agent capable of forming a highly reliable liquid crystal alignment film giving a high pretilt angle is provided.
  • the thermally detachable group-containing compound added to the liquid crystal aligning agent in the present invention is a compound having an amino group protected by a thermally detachable group and having an amic acid or an amic acid ester structure,
  • the temperature is 80 to 300 ° C., preferably 100 to 250 ° C., particularly preferably 150 to 230 ° C.
  • the thermally desorbable group is decomposed and replaced with a hydrogen atom.
  • the liquid crystal aligning agent is applied to the substrate of the liquid crystal display element, and the thermally desorbable group is desorbed and replaced with hydrogen at a normal temperature of 150 to 300 ° C. when firing.
  • the thermal leaving group-containing compound used in the present invention is preferably represented by the following general formula (1).
  • X is a tetravalent organic group
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • Z has a structure represented by the following formula (2).
  • Z 1 is a single bond or a divalent organic group having 1 to 30 carbon atoms
  • R 2 and R 3 are each independently a hydrogen atom or a carbon atom that may have a substituent.
  • R 4 may have a hydrogen atom or a substituent and has 1 to 30 carbon atoms.
  • D 1 is an amino-protecting group that replaces a hydrogen atom by heating.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 1 has a bulky structure, when used as a liquid crystal alignment film, there is a possibility that the alignment of the liquid crystal may be inhibited. Therefore, R 1 is more preferably a hydrogen atom, a methyl group, or an ethyl group, An atom or a methyl group is particularly preferred.
  • X is a tetravalent organic group, and its structure is not particularly limited. Specific examples of X include X-1 to X-46 shown below. Among them, X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26 X-27, X-28 or X-32 is preferred.
  • R 2 and R 3 each independently represent a hydrogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group having 1 to 30 carbon atoms which may have a substituent, or And may form a ring structure.
  • 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 obtained by replacing one or more CH—CH structures present in the above alkyl group with C ⁇ C structures, and more specifically, vinyl groups, allyl groups, 1-propenyl groups.
  • 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.
  • aryl group examples include a phenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1 -Phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
  • the above alkyl group, alkenyl group, alkynyl group, and aryl group may have a substituent as long as the whole has 1 to 20 carbon atoms, and may further form a ring structure by the substituent.
  • 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 examples include halogen groups, hydroxyl groups, thiol groups, nitro groups, organooxy groups, organothio groups, organosilyl groups, acyl groups, ester groups, thioester groups, phosphate ester groups, amide groups, aryl groups, alkyls.
  • the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the organooxy group can have a structure represented by —O—R such as an alkoxy group, an alkenyloxy group, and an aryloxy group.
  • 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 alkyloxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, and a lauryloxy group.
  • the organothio group as a substituent can have a structure represented by —SR, such as an alkylthio group, an alkenylthio group, and an arylthio group.
  • R include the above-described alkyl group, alkenyl group, and aryl group. These Rs may be further substituted with the substituent described above.
  • alkylthio group examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group, a nonylthio group, a decylthio group, and a laurylthio 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 groups and aryl groups described above. These Rs may be further substituted with the substituent described above.
  • Specific examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, Examples include decyldimethylsilyl group.
  • the acyl group as a substituent can have a structure represented by —C (O) —R.
  • 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.
  • As the ester group which is a substituent a structure represented by —C (O) O—R or —OC (O) —R can be shown. Examples of R include the above-described alkyl group, alkenyl group, and aryl group.
  • the thioester group which is a substituent can have a structure represented by —C (S) O—R or —OC (S) —R.
  • R examples include the above-described alkyl group, alkenyl group, and aryl group.
  • 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 groups and aryl groups 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 groups and aryl groups 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.
  • R 4 is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms which may have a substituent. Specific examples of the alkyl group and the substituent include the same alkyl groups and substituents as described above.
  • Z 1 is a single bond or a divalent organic group having 1 to 30 carbon atoms. When Z 1 is a divalent organic group having 1 to 30 carbon atoms, it is preferably a divalent organic group represented by the following formula (8).
  • B 1 and B 2 are each independently a single bond or a divalent linking group, provided that at least one of B 1 and B 2 is a divalent linking group.
  • R 8 and R 9 are each independently a single bond or an optionally substituted alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof. Specific examples of the B 1 and B 2 are shown below, but is not limited thereto.
  • B-10, B-11, R 10 and R 11 are a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aryl group which may have a substituent, or a group thereof. It is a combination and may form a ring structure.
  • Specific examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and substituent include the same ones as described above.
  • R 10 and R 11 have a bulky structure such as an aromatic ring or an alicyclic structure
  • the liquid crystal alignment may be lowered. Therefore, methyl group, ethyl group, propyl group , An alkyl group such as a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
  • R 8 and R 9 are an alkylene group having 1 to 20 carbon atoms, an alkenylene group, an alkynylene group, an arylene group, or a combination thereof, specific examples thereof are listed below. It is not limited to.
  • alkylene group examples include a structure in which one hydrogen atom is removed from an alkyl group. More specifically, a methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-butylene group 1,2-pentylene group, 1,2-hexylene group, 1,2-nonylene group, 1,2-dodecylene group, 2,3-butylene group, 2,4-pentylene group, 1,2-cyclopropylene Group, 1,2-cyclobutylene group, 1,3-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1,2-cyclononylene group, 1,2-cyclododecylene, etc.
  • the alkenylene group includes a structure in which one hydrogen atom is removed from an alkenyl group. More specifically, 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1- Ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1, Examples include 4-butylene group, 1,2-ethenylene-1,2-butylene group, 1,2-ethenylene-1,2-heptylene group, 1,2-ethenylene-1,2-decylene group and the like.
  • the alkynylene group includes a structure in which one hydrogen atom is removed from the alkynyl group. More specifically, an ethynylene group, an ethynylene methylene group, an ethynylene-1,1-ethylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene-1,3-propylene group, Examples include ethynylene-1,4-butylene group, ethynylene-1,2-butylene group, ethynylene-1,2-heptylene group, ethynylene-1,2-decylene group and the like.
  • the arylene group includes a structure in which one hydrogen atom is removed from an aryl group. More specifically, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2, Examples thereof include a 3-naphthylene group, a 2,6-naphthylene group, a 3-phenyl-1,2-phenylene group, and a 2,2′-diphenylene group.
  • the alkylene group, alkenylene group, alkynylene group, arylene group, and a combination thereof may have a substituent as long as the number of carbon atoms is 1 to 20 as a whole, and a ring structure depending on the substituent. May be formed.
  • 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. Examples of this substituent include the same ones as described above.
  • R 8 and R 9 have a small number of carbon atoms, the liquid crystal orientation is improved when used as a liquid crystal alignment film. Therefore, an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 1 to 5 carbon atoms, a carbon number 1-5 alkynylene groups are preferred. Moreover, it is preferable that both or one of R 8 and R 9 is a single bond.
  • D 1 is an amino-protecting group, and its structure is not particularly limited as long as it is a functional group that can be replaced by a hydrogen atom by heating.
  • this protecting group D 1 is preferably not desorbed at room temperature, preferably a protecting group that is deprotected by heat of 80 ° C. or more, more preferably 100 It is a protecting group that is deprotected by heat at a temperature of at least ° C.
  • it is preferably a protective group that is deprotected with heat of 300 ° C.
  • the protecting group is deprotected with the following heat, and more preferably the protecting group is deprotected with a heat of 200 ° C. or less.
  • an ester group represented by the following formula is preferable.
  • R 11 is a hydrocarbon having 1 to 22 carbon atoms.
  • ester group represented by the above formula (9) examples include methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert- Examples include butoxycarbonyl group, sec-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, 9-fluorenylmethoxycarbonyl group and the like.
  • a structure in which the elimination reaction efficiently proceeds at a baking temperature of 150 ° C. to 300 ° C. when obtaining the liquid crystal alignment film is preferable, and a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group is more preferable.
  • a tert-butoxycarbonyl group is particularly preferred.
  • the compounds of the present invention can include the following structures, but are not limited thereto.
  • the compound of the present invention is a bischlorocarbonyl compound represented by the following formula (3), a tetracarboxylic acid derivative represented by the following formula (5), or a tetracarboxylic dianhydride represented by the following formula (6).
  • a monoamine compound represented by the following formula (4) as a raw material and can be synthesized by various methods. Specific examples include the methods (i) to (iii), but are not limited thereto.
  • the bischlorocarbonyl compound of the above formula (3) is obtained by reacting, for example, a tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R 5 OH to form a tetracarboxylic acid dialkyl ester, It can be obtained by converting a carboxyl group into a chlorocarbonyl group with an agent.
  • the tetracarboxylic acid derivative of the above formula (5) can be obtained, for example, by reacting the tetracarboxylic dianhydride of the above formula (6) with an alcohol represented by R 5 OH.
  • the monoamine compound of the above formula (4) is obtained by reacting a compound having a primary or secondary amino group represented by the following formula with di-tert-butyl dicarbonate in the presence of a base, or a primary or secondary Although it can be obtained by a method in which a compound having an amino group is reacted with chloroformic acid-9-fluorenylmethyl in the presence of a base, it is not particularly limited as long as it is a known method.
  • the synthesis method of the compound of the present invention includes the following methods (i) to (iii), but is not limited thereto.
  • the compound of the present invention is obtained by reacting the biscarbonyl compound represented by the above formula (3) with the monoamine compound represented by the above formula (4).
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently.
  • the amount of the base added is preferably 2 to 4 moles relative to the bischlorocarbonyl compound from the viewpoint of easy removal.
  • (Ii) Method of synthesizing from tetracarboxylic acid derivative and monoamine compound
  • the compound of the present invention is obtained by dehydrating condensation of a tetracarboxylic acid derivative represented by the above formula (5) and a monoamine compound represented by the above formula (4).
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • 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 amount of the condensing agent added is preferably 2 to 3 moles compared to the tetracarboxylic acid derivative.
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base added is preferably 2 to 4 moles relative to the diamine component from the viewpoint of easy removal.
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • 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 the mol of the monoamine compound.
  • the compound of the present invention comprises a tetracarboxylic dianhydride represented by the above formula (6) and a monoamine compound represented by the above formula (4). It can be synthesized by reacting. Specifically, the tetracarboxylic dianhydride and the monoamine compound are used in the presence of an organic solvent at ⁇ 20 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. It can be synthesized by reacting.
  • the solvents used in the above reaction are N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide because of the solubility of tetracarboxylic dianhydride, monoamine compound, and product. , Tetrahydrofuran, chloroform, and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, or tetrahydrofuran is preferable, and these may be used alone or in combination.
  • the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
  • R 1 in the above formula (1) is an alkyl group having 1 to 5 carbon atoms
  • various esterifying agents are added to a reaction solution of tetracarboxylic dianhydride and a monoamine compound. And can be synthesized by esterification of the carboxyl group.
  • the tetracarboxylic dianhydride, monoamine compound, and esterifying agent in the presence of an organic solvent at ⁇ 20 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably It can be synthesized by reacting for 1 to 4 hours.
  • the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per mole of tetracarboxylic dianhydride.
  • Solvents used in the above reactions (i) to (iii) are N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N— because of the solubility of monomers and products used in the synthesis.
  • Examples thereof include dimethylacetamide, tetrahydrofuran, chloroform, and the like, and N-methyl-2-pyrrolidone, N, N-dimethylformamide, or tetrahydrofuran is preferable, and these may be used alone or in combination.
  • the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.
  • the reaction solution obtained by the reactions (i) to (iii) can be used as it is as the composition of the present invention.
  • the compound of the present invention in which R 1 in formula (1) is a hydrogen atom is obtained by the above method (iii)
  • it is a reaction between an acid anhydride and an amine, and therefore reaction by-products and removal are necessary.
  • the compound of the present invention can be precipitated by pouring the reaction solution obtained by the reactions (i) to (iii) above into a poor solvent while thoroughly stirring. Precipitation is carried out several times, washed with a poor solvent, and then purified at room temperature or by heating and drying to obtain a powder of the compound of the present invention.
  • a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, etc. are mentioned.
  • purification by various methods is preferable. Examples of the purification method include silica gel column chromatography, recrystallization, and washing with an organic solvent.
  • Recrystallization is more preferable from the viewpoint of simplicity of operation and high purification efficiency.
  • the organic solvent used for recrystallization is an organic solvent which can recrystallize the compound of this invention, it may select the kind and may recrystallize with 2 or more types of mixed solvents.
  • the polyimide precursor contained in the liquid crystal aligning agent of this invention is a polymer which has the site
  • the polyimide precursor used in the present invention has a structure represented by the following formula (7).
  • R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms.
  • a 1 and A 2 are each independently a hydrogen atom or an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms which may have a substituent.
  • Specific examples of the alkyl group 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.
  • the above alkyl group may have a substituent, and may further form a ring structure with the substituent.
  • 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.
  • a 1 and A 2 have a hydrogen atom or a substituent. More preferred is an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom, a methyl group or an ethyl group.
  • X 1 is a tetravalent organic group
  • Y 1 is a divalent organic group.
  • Two or more kinds of X 1 may be mixed in the polyimide precursor.
  • X-1 to X-46 which are the same as those exemplified as X, are Can be mentioned.
  • Y 1 is a divalent organic group and is not particularly limited.
  • two or more types of Y 1 may be mixed. Specific examples of Y 1 include the following Y-1 to Y-97.
  • Y 1 is 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- More preferred are diamines of 45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75, Y-98. .
  • a diamine having a long chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination of these in the side chain may be introduced into the polyimide precursor or polyimide.
  • Y 1 is preferably Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y-86.
  • any pretilt angle can be expressed.
  • examples of the polyimide precursor include polyamic acid esters and polyamic acids.
  • the polyamic acid ester can be obtained by reaction of any of the tetracarboxylic acid derivatives represented by the following formulas (10) to (12) with the diamine compound represented by the formula (13).
  • the polyamic acid ester represented by the above formula (1) can be synthesized by the following methods (1) to (3) using the above monomer.
  • Polyamic acid ester can be synthesized by esterifying 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.
  • the esterifying agent is preferably one that can be easily removed by purification, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • 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. Good.
  • the concentration at the time of synthesis 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 synthesized by reacting.
  • 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 polymer concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
  • the solvent used for the synthesis 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.
  • 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 synthesized by reacting.
  • condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
  • 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.
  • 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.
  • 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 method (1) or the method (2) is particularly preferable.
  • the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above 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 weight average molecular weight of the polyamic acid ester is preferably 5,000 to 300,000, and more preferably 10,000 to 200,000.
  • the number average molecular weight is preferably 2,500 to 150,000, and more preferably 5,000 to 100,000.
  • the polyamic acid when the polyimide precursor is a polyamic acid, the polyamic acid can be obtained by a reaction between a tetracarboxylic dianhydride represented by the following formula (12) and a diamine compound represented by the formula (13).
  • X 1 , Y 1 , A 1 and A 2 are the same as defined in the above formula (7).
  • 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.
  • 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. It may be used.
  • the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation hardly occurs and a high molecular weight body 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 weight average molecular weight of the polyamic acid is preferably 10,000 to 300,000, more preferably 20,000 to 200,000.
  • the number average molecular weight is preferably 2,500 to 15,000, and more preferably 5,000 to 100,000.
  • the imidization reaction for dehydrating and cyclizing the polyimide precursor is generally thermal imidization or chemical imidation, but chemical imidation in which the imidization reaction proceeds at a relatively low temperature may reduce the molecular weight of the resulting polyimide. Less likely to occur.
  • Chemical imidation can be performed by stirring the polyimide precursor in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the reaction temperature at this time is ⁇ 20 to 250 ° C., preferably 0 to 180 ° C., and the reaction time can be 1 to 100 hours.
  • the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the polyimide precursor, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the polyimide precursor. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction.
  • Examples of the basic catalyst used for imidization include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
  • examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
  • an organic solvent the solvent used at the time of the polyamic acid polymerization reaction mentioned above can be used.
  • the imidation rate by chemical imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
  • the added catalyst remains in the solution. Therefore, in order to use it for the liquid crystal aligning agent of the present invention, this polyimide solution is put into a poor solvent which is being stirred. It is preferable to use the polyimide after precipitation. Although it does not specifically limit as a poor solvent used for precipitation collection
  • the polyimide precipitated by adding it to a poor solvent can be recovered by filtration, washing and drying at room temperature or under reduced pressure at normal temperature or by heating. By further dissolving the powder in a good solvent and reprecipitating it 2 to 10 times, the polyimide can be purified. When impurities cannot be completely removed by a single precipitation recovery operation, it is preferable to repeat this purification step. Mixing or sequentially using, for example, three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons as the poor solvent in the repeated purification step is preferable because the purification efficiency is further increased.
  • poor solvents such as alcohols, ketones, and hydrocarbons
  • the imidation ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited. What is necessary is just to set to arbitrary values in consideration of the solubility of a polyimide.
  • the molecular weight of the polyimide contained in the liquid crystal aligning agent of the present invention is not particularly limited, but if the molecular weight of the polyimide is too small, the strength of the resulting coating film may be insufficient, and conversely, the molecular weight of the polyimide is too large. And the viscosity of the liquid crystal aligning agent manufactured may become high too much, and the workability
  • the liquid crystal aligning agent of this invention is a form of the solution which said polyimide precursor and / or polyimide melt
  • a polyimide precursor such as polyamic acid ester and / or polyamic acid
  • the resulting reaction solution itself may be used. It may be diluted with a solvent.
  • a polyimide precursor and / or a polyimide is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
  • the content (concentration) of the polyimide precursor and / or polyimide (hereinafter also referred to as polymer) in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed.
  • the polymer content is preferably 0.5% by mass or more with respect to the organic solvent, and preferably 15% by mass or less from the viewpoint of storage stability of the solution. More preferably, it is 1 to 10% by mass.
  • the above-described heat-leaving group-containing compound is added to the liquid crystal aligning agent of the present invention.
  • the thermally desorbable group-containing compound is preferably added in an amount of 0.5 to 50 mol% with respect to 1 unit of the repeating unit of the polyimide precursor and the imidized polymer of the polyimide precursor.
  • the content of the heat-leaving group-containing compound is more preferably 1 to 30 mol%, particularly preferably 5 to 20 mol%. When the content is excessively small, the imidization reaction or crosslinking reaction of the polyimide precursor becomes insufficient, and when it is excessively large, the liquid crystal orientation may be adversely affected. It is not preferable.
  • the organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer is uniformly dissolved.
  • 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-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt
  • the liquid crystal aligning agent of the present invention may contain a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer.
  • a solvent for improving the uniformity of the coating film when the liquid crystal aligning agent is applied to the substrate, in addition to the organic solvent for dissolving the polymer.
  • 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, butyl cellosolve acetate, 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, 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. Two types of these
  • the liquid crystal aligning agent of the present invention may contain various additives such as a silane coupling agent and a crosslinking agent.
  • the silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is applied and the liquid crystal alignment film formed thereon.
  • a silane coupling agent is given to the following, it is not limited to this.
  • the amount of the silane coupling agent added is too large, unreacted ones may adversely affect the liquid crystal orientation, and if too small, the effect on adhesion will not appear, so the amount of the silane coupling agent is 0 with respect to the solid content of the polymer. 0.01 to 5.0% by weight is preferable, and 0.1 to 1.0% by weight is more preferable.
  • An imidization accelerator may be added to efficiently advance imidization of the polyamic acid ester when the coating film is baked.
  • the liquid crystal aligning agent of the present invention has the purpose of changing the electrical properties such as the polymer other than the polymer and the dielectric constant and conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired.
  • a dielectric or conductive material, and further a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
  • the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation, or without alignment treatment in vertical alignment applications.
  • the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used, and an ITO electrode for driving a liquid crystal is formed. It is preferable to use a prepared substrate from the viewpoint of simplification of the process.
  • an opaque substance such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used.
  • the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
  • the substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C.
  • the polyimide precursor contained in the liquid crystal aligning agent changes in conversion ratio to polyimide depending on the baking temperature, but the liquid crystal aligning agent does not necessarily need to be 100% imidized.
  • the firing time can be set to an arbitrary time, but if the firing time is too short, display failure may occur due to the influence of the residual solvent. Therefore, the firing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes.
  • the thermally detachable group-containing compound contained in the liquid crystal aligning agent of the present invention decomposes the thermally detachable group, resulting in a highly reactive primary or secondary amine.
  • the generated primary or secondary amine accelerates the imidization reaction of the polyimide precursor and / or the polymer of the polyimide, which is the main component contained in the liquid crystal aligning agent, and brings about a high imidization ratio. This causes a cross-linking reaction and gives a large mechanical strength to the liquid crystal alignment film obtained from the liquid crystal aligning agent. An increase in mechanical strength results in improved rubbing resistance and stability of liquid crystal properties at high temperatures.
  • the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm.
  • the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
  • the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.
  • liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
  • Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
  • the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
  • 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).
  • Mw weight average molecular weight
  • Mp peak top molecular weight
  • 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 at a temperature of 230 ° C. for 20 minutes to form an imidized film having a thickness of 100 nm. After this coating film was rubbed, the surface state of the film was observed to evaluate the presence or absence of rubbing scratches, the presence or absence of scraped film, and the presence or absence of film peeling.
  • a liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried for 5 minutes on a hot plate at a temperature of 80 ° C, and baked for 20 minutes in a hot air circulation oven at 230 ° C to form a coating film having a thickness of 100 nm. I let you.
  • the coating surface was rubbed or photo-aligned 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 liquid crystal alignment was observed with a polarizing microscope, and the liquid crystal alignment was evaluated according to the following criteria. ⁇ Evaluation criteria> ⁇ : No flow alignment is observed, and no light leakage occurs under crossed Nicols. ⁇ : Some flow alignment is observed, and light leakage is observed under crossed Nicols. X: Flow orientation is observed throughout the 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. [Ion density] 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.
  • the temperature of the liquid crystal cell was 23 ° C. and 60 ° C., and the measurement was performed at each temperature.
  • Pretilt angle measurement The pretilt angle of the liquid crystal cell was measured using an AxoScan manufactured by Axometrics.
  • the diamine compound (DA-1) was synthesized by the following four-step route.
  • Second step Synthesis of compound (A6)
  • N-propargylaminoacetic acid t-butyl 12.0 g, 70.9 mmol
  • dichloromethane 600 mL
  • di-t-butyl dicarbonate 15.5 g, A solution of 70.9 mmol
  • dichloromethane 100 mL
  • the reaction solution was brought to room temperature and stirred for 20 hours.
  • the reaction solution was washed with 300 mL of saturated brine and dried over magnesium sulfate.
  • the activated carbon was filtered, the organic solvent was distilled off under reduced pressure, and the remaining oil was dried under reduced pressure to obtain a diamine compound (DA-1).
  • the yield was 19.8 g, and the yield was 96%.
  • the diamine compound (DA-1) was confirmed by 1 H NMR.
  • 1,3-DM 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • 1,3-DM 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride
  • -CBDA abbreviated 220 g (0.981 mol)
  • methanol 2200 g 6.87 mol, 10 wt times with respect to 1,3-DM-CBDA
  • the mixture was stirred as it was at 75 ° C. for 1 hour and 30 minutes, and then the solvent was distilled off with an evaporator until the internal volume reached 924.42 g in a water bath at 40 ° C. This was heated to 60 ° C., the crystals precipitated when the solvent was distilled off were dissolved, the insoluble matter was filtered by performing hot filtration at 60 ° C., and then the filtrate was heated to 25 ° C. at a rate of 1 ° C. for 10 minutes. It was cooled with. After stirring for 30 minutes at 25 ° C., the precipitated white crystals were taken out by filtration, and the crystals were washed with 264.21 g of n-heptane. This was dried under reduced pressure to obtain 226.09 g of white crystals.
  • this crystal was found to be compound (3-1), that is, dimethyl-1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate (hereinafter referred to as 1,3 -DM-CBDE-C1) (HPLC relative area 99.5%) (yield 77.2%).
  • 1H NMR (CDCl3, ⁇ ppm): 3.78 (s, 6H), 3.72 (s, 2H), 1.69 (s, 6H).
  • Second step Synthesis of precursor (1-a2)
  • 20.90 g (78.49 mmol) of the precursor (1-a1) was placed, and 200 ml of tetrahydrofuran was added.
  • the reaction vessel was purged with nitrogen
  • 2.09 g of palladium carbon was added and purged with nitrogen.
  • the reaction vessel was purged with hydrogen and stirred at 20 ° C. for 19 hours.
  • palladium carbon was removed by Celite filtration, and the solvent was removed from the filtrate to obtain a white solid.
  • the obtained solid was dissolved in 20 ml of acetic ester, and 140 ml of hexane was added for recrystallization.
  • This monoamine solution was transferred to a dropping funnel, and the monoamine solution was dropped into a four-necked flask over 15 minutes. After dropping, the mixture was stirred for 20 hours. After 20 hours, the reaction solution was poured into 200 ml of water, and extracted with 100 ml of chloroform. The obtained organic layer was washed twice with pure water and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a white solid. The obtained solid was dissolved in 30 ml of tetrahydrofuran, and recrystallized by adding 100 ml of diisopropyl ether. The precipitated solid was collected by suction filtration and dried under reduced pressure.
  • First step synthesis of precursor (1-b1)
  • 4-bromonitrobenzene 8.95 g (44.30 mmol) of 4-bromonitrobenzene, 0.311 g (0.44 mmol) of bis (triphenylphosphine) palladium (II) dichloride, and 0.1% of copper iodide were added.
  • 169 g (0.89 mmol) and 5.38 g (53.16 mmol) of triethylamine were added, 30 ml of tetrahydrofuran was added, and the mixture was stirred at room temperature (20 ° C.) for 10 minutes.
  • Second step Synthesis of precursor (1-c2) Add 40.00 g (0.168 mol) of precursor (1-c1) and 32.86 g (0.238 mol) of potassium carbonate to a 1 L four-necked flask, add 481 g of DMF, and heat and stir at 60 ° C. for 7 hours. did. After 7 hours, the obtained reaction solution was poured into 3 L of pure water with stirring, and 1 L of acetate was added for extraction. The obtained organic layer was washed twice with pure water with 500 ml of 1M aqueous sodium hydroxide solution and dried over anhydrous magnesium sulfate. After removing the desiccant, the solvent was distilled off to obtain a yellow solid.
  • the obtained solid was dissolved in 200 ml of acetic ester, and 1 L of hexane was added with stirring to precipitate a solid.
  • the obtained solid was collected by suction filtration and dried under reduced pressure.
  • the yellow solid obtained from 1 HNMR was confirmed to be the precursor (1-c2).
  • the yield was 35.49 g, and the yield was 71.3%.
  • the obtained reaction solution was poured into 1800 g of water with stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 1800 g of water, once with 1800 g of ethanol, and three times with 540 g of ethanol.
  • a white solid was obtained.
  • the obtained white solid was dissolved in ethyl acetate, and hexane was added for recrystallization.
  • the precipitated solid was collected by suction filtration and dried under reduced pressure.
  • the yellow solid obtained from 1 HNMR was confirmed to be the precursor (1-c).
  • the yield was 15.23 g, and the yield was 84.4%.
  • Example 4 Synthesis of Compound (1-d) A 300 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, and 1.87 g (6.63 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 1.10 g (13.9 mmol) of pyridine were added thereto. Was added and heated to reflux. To this solution, 1.54 g (12.9 mmol) of thionyl chloride was added and heated under reflux for 1 hour. After 1 hour, 3.13 g (19.56 mmol) of the precursor (1-a2) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours.
  • the obtained reaction solution was poured into 500 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 500 g of water, once with 500 g of methanol, and three times with 240 g of methanol.
  • a white solid was obtained.
  • the obtained white solid was put into a 200 ml eggplant type flask, 100 ml of ethyl acetate was added, and the mixture was heated and stirred. The remaining solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the white solid obtained from 1 HNMR was the compound (1-d). The yield was 1.97 g, and the yield was 41.4%.
  • Example 5 Synthesis of Compound (1-j) A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.04 g (4.42 mmol) of the precursor (1-a2) was added, 20 g of NMP, and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred. And dissolved. Next, while stirring this monoamine solution, 0.658 g (2.22 mol) of CBDE-Cl was added and reacted for 2 hours under water cooling.
  • the obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol.
  • a white solid was obtained.
  • the obtained white solid was put into a 50 ml eggplant type flask, 30 ml of ethyl acetate was added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. After 30 minutes, the remaining solid was filtered off with suction and dried under reduced pressure. It was confirmed that the white solid obtained by 1 HNMR was the precursor (1-j). The yield was 0.42 g, and the yield was 27.3%.
  • Example 6 Synthesis of Compound (1-k) A 30 ml four-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 1.06 g (3.99 mmol) of the precursor (1-c3) was added, 20 g of NMP, and 0.58 g (7.43 mmol) of pyridine as a base were added and stirred. And dissolved. Next, while stirring this monoamine solution, 0.658 g (1.99 mol) of CBDE-Cl was added and reacted for 2 hours under water cooling.
  • the obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 200 g of water, once with 200 g of ethanol, and three times with 100 g of ethanol.
  • a white solid was obtained.
  • the obtained white solid was put into a 50 ml eggplant type flask, 30 ml of ethyl acetate was added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. After 30 minutes, the remaining solid was filtered off with suction and dried under reduced pressure. It was confirmed that the white solid obtained by 1 HNMR was the precursor (1-k). The yield was 0.58 g, and the yield was 38.4%.
  • Example 7 Synthesis of Compound (1-i) A 50 ml two-necked flask equipped with a stirrer was placed in a nitrogen atmosphere, 0.62 g (2.20 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid and 0.38 g (4.80 mmol) of pyridine were added, and dehydrated tetrahydrofuran was added. 20 ml was added and heated to reflux. To this solution, 0.55 g (4.62 mmol) of thionyl chloride was added and heated to reflux for 1 hour. After 1 hour, 1.23 g (4.62 mmol) of the precursor (1-c3) was added to the reaction solution, and the mixture was further heated to reflux for 2 hours.
  • the obtained reaction solution was poured into 200 g of water while stirring, and the precipitated white precipitate was collected by filtration, and then washed once with 100 g of water, once with 100 g of ethanol, and three times with 50 g of ethanol. To obtain a pale yellow solid.
  • the obtained pale yellow solid was put into a 50 ml eggplant type flask, 20 ml of ethyl acetate was added, and the mixture was heated and stirred. The remaining solid was collected by suction filtration and dried under reduced pressure. It was confirmed that the white solid obtained from 1 HNMR was the compound (1-i). The yield was 0.57 g, and the yield was 33.1%.
  • Example 8 Preparation of a solution containing compound (1-e) 2.37 g (10.03 mmol) of the precursor (1-a2) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 9.40 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 0.98 g (5.00 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to obtain the compound (1-e). A containing solution was obtained.
  • Example 9 Preparation of Compound (1-f) -Containing Solution 2.37 g (10.03 mmol) of the precursor (1-a2) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and then 9.62 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 1.09 g (5.00 mmol) of PMDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-f). A containing solution was obtained.
  • Example 10 Preparation of Compound (1-g) -Containing Solution 2.66 g (9.99 mmol) of the precursor (1-c3) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 10.19 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 1.09 g (5.00 mmol) of CBDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-g). A containing solution was obtained.
  • Example 11 Preparation of Compound (1-h) -Containing Solution 3.99 g (15.0 mmol) of the precursor (1-c3) was placed in a 50 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, and then 16.91 g of NMP was added and stirred while feeding nitrogen. A monoamine solution was obtained. While stirring this monoamine solution, 1.64 g (7.52 mmol) of PMDA was added, NMP was further added so that the solid content concentration was 20% by mass, and the mixture was stirred at room temperature for 24 hours to give compound (1-h) A containing solution was obtained.
  • Example 12 In a 100 ml Erlenmeyer flask, 44.3382 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3 was added, and then 19.6930 g of GBL and 16.0839 g of BCS were added, and a diluted polyamic acid ester solution was added. Obtained. In a 20 ml sample tube containing a stir bar, 5.02 g of the above solution was added, and then 0.0645 g of the compound (1-a) obtained in Example 1 (0.005 g per mol of the polyamic acid ester repeating unit). 1 mol equivalent) was added, and the mixture was stirred at room temperature for 30 minutes to completely dissolve the compound (1-a) to obtain a liquid crystal aligning agent (A1-1).
  • PAE-1 polyamic acid ester solution obtained in Synthesis Example 3
  • Example 13 The same procedure as in Example 12 except that 0.1 mol equivalent of the compound (1-c) obtained in Example 3 was used in place of compound (1-a) with respect to 1 mol of the polyamic acid ester repeating unit. Thus, a liquid crystal aligning agent (A1-2) was obtained.
  • Example 14 instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added in an amount of 0.1 molar equivalent with respect to 1 mole of the polyamic acid ester repeating unit of the compound (1-e).
  • a liquid crystal aligning agent (A1-3) was obtained in the same manner as in Example 12 except that it was added so that
  • Example 15 instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added in an amount of 0.1 molar equivalent based on 1 mol of the polyamic acid ester repeating unit of the compound (1-f).
  • a liquid crystal aligning agent (A1-4) was obtained in the same manner as in Example 12 except that it was added so that
  • Example 16 instead of the compound (1-a), the compound (1-g) -containing solution obtained in Example 10 was added in an amount of 0.1 molar equivalent relative to 1 mole of the polyamic acid ester repeating unit of the compound (1-g).
  • a liquid crystal aligning agent (A1-5) was obtained in the same manner as in Example 12 except that it was added so that
  • Example 17 instead of the compound (1-a), the compound (1-h) -containing solution obtained in Example 11 was added in an amount of 0.1 molar equivalent based on 1 mol of the polyamic acid ester repeating unit of the compound (1-h).
  • a liquid crystal aligning agent (A1-6) was obtained in the same manner as in Example 12 except that it was added so that
  • Example 18 Into a 20-ml sample tube containing a stir bar, 4.4560 g of the polyamic acid ester solution (PAE-2) obtained in Synthesis Example 4 was added, and then 1.8437 g of NMP and 1.5021 g of BCS were added, and further implementation was performed. Add 0.1023 g of compound (1-a) obtained in Example 1 (0.2 molar equivalent to 1 mol of polyamic acid ester repeating unit) and stir at room temperature for 30 minutes to give compound (1-a). By completely dissolving, a liquid crystal aligning agent (A2-1) was obtained.
  • PAE-2 polyamic acid ester solution obtained in Synthesis Example 4
  • Example 19 The same procedure as in Example 18 except that 0.2 mol equivalent of the compound (1-d) obtained in Example 4 was used in place of compound (1-a) with respect to 1 mol of the polyamic acid ester repeating unit. Thus, a liquid crystal aligning agent (A2-2) was obtained.
  • Example 20 instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was added in an amount of 0.2 molar equivalent based on 1 mol of the polyamic acid ester repeating unit of the compound (1-e).
  • a liquid crystal aligning agent (A2-3) was obtained in the same manner as in Example 18 except that it was added so that
  • Example 21 instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was added in an amount of 0.2 molar equivalent based on 1 mol of the polyamic acid ester repeating unit of the compound (1-f).
  • a liquid crystal aligning agent (A2-4) was obtained in the same manner as in Example 18 except that it was added so that
  • Example 22 Into a 20 ml sample tube containing a stir bar, 4.4156 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 5 was added, and then 1.3409 g of NMP and 1.4426 g of BCS were added. The compound (1-a) obtained in 1 was added in an amount of 0.2113 g (0.2 molar equivalent based on 1 mol of the polyamic acid repeating unit) and stirred at room temperature for 30 minutes to completely dissolve the compound (1-a). By dissolving, a liquid crystal aligning agent (A3-1) was obtained.
  • PAA-1 polyamic acid solution obtained in Synthesis Example 5
  • Example 23 instead of compound (1-a), compound (1-d) obtained in Example 4 was used in the same manner as in Example 22 except that 0.2 molar equivalent was used per 1 mol of the polyamic acid repeating unit. As a result, a liquid crystal aligning agent (A3-2) was obtained.
  • Example 24 instead of the compound (1-a), the compound (1-e) -containing solution obtained in Example 8 was prepared so that the compound (1-e) was 0.2 molar equivalent with respect to 1 mole of the polyamic acid repeating unit.
  • a liquid crystal aligning agent (A3-3) was obtained in the same manner as in Example 22 except that it was added as described above.
  • Example 25 instead of the compound (1-a), the compound (1-f) -containing solution obtained in Example 9 was used in such a manner that the compound (1-f) was 0.2 molar equivalent with respect to 1 mol of the polyamic acid repeating unit.
  • a liquid crystal aligning agent (A3-4) was obtained in the same manner as in Example 22 except that it was added as described above.
  • Example 26 The liquid crystal aligning agent (A1-1) obtained in Example 12 was filtered through a 1.0 ⁇ m membrane filter, spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, and then 230 The film was baked at 10 ° C. for 10 minutes to obtain an imidized film having a thickness of 100 nm. This coating film was shaved off and the FT-IR spectrum was measured by the ATR method to calculate the imidization rate. The results are shown in Table 1.
  • Example 27 to 31 Using the liquid crystal aligning agents (A1-2) to (A1-6) obtained in Examples 13 to 17, an imidized film was produced in the same manner as in Example 26, and an FT-IR spectrum was measured. The imidization rate was calculated. The results are shown in Table 1.
  • Comparative Example 6 Using the liquid crystal aligning agent (B1-1) obtained in Comparative Example 1, an imidized film was produced in the same manner as in Example 26, and an FT-IR spectrum was measured to calculate an imidization ratio. The results are shown in Table 1.
  • Example 32 The liquid crystal aligning agent (A2-1) obtained in Example 18 was filtered through a 1.0 ⁇ m membrane filter, spin-coated on a glass substrate, dried on a hot plate at a temperature of 80 ° C. for 5 minutes, then 20 The film was baked at 10 ° C. for 10 minutes to obtain an imidized film having a thickness of 100 nm. This coating film was shaved off and the FT-IR spectrum was measured by the ATR method to calculate the imidization rate. The results are shown in Table 2.
  • Example 33 to 35 Using the liquid crystal aligning agents (A2-2) to (A2-4) of the present invention obtained in Examples 19 to 21, imidized films were prepared in the same manner as in Example 32, and FT-IR spectra were measured. And the imidization ratio was calculated. The results are shown in Table 2.
  • Example 36 The liquid crystal aligning agent (A3-1) obtained in Example 22 was filtered through a 1.0 ⁇ m membrane filter, spin-coated on a glass substrate with a transparent electrode, and placed on a hot plate at a temperature of 80 ° C. for 5 minutes. After being dried, the film was baked at 230 ° C. for 20 minutes to obtain an imidized film having a film thickness of 100 nm. The polyimide film was rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), and then the surface state of the polyimide film was observed. No debris or peeling of the polyimide film was observed.
  • Example 37 A polyimide film was produced and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
  • Example 38 A polyimide film was produced and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-3) obtained in Example 24 was used. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
  • Example 39 A polyimide film was produced and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (A3-4) obtained in Example 25 was used. When the surface state of the polyimide film was observed, scratches due to rubbing, scraping of the polyimide film, and peeling of the polyimide film were not observed.
  • Comparative Example 9 A polyimide film was prepared and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed.
  • Example 10 A polyimide film was prepared and rubbed in the same manner as in Example 36 except that the liquid crystal aligning agent (B3-2) obtained in Comparative Example 5 was used. When the surface state of the polyimide film was observed, scratches due to rubbing and scraped scraps of the polyimide film were observed. From the results of Examples 36 to 39 and Comparative Example 9, it is possible to obtain an imidized film excellent in mechanical strength that is hard to be damaged by rubbing by applying and baking a polyamic acid solution to which the compound of the present invention is added. confirmed. In addition, the results of Examples 38 and 39 and Comparative Example 10 confirm that the reaction product of tetracarboxylic dianhydride and precursor (1-a2) improves the mechanical strength of the resulting imidized film. It was done.
  • Example 40 The liquid crystal aligning agent (A2-1) obtained in Example 18 was filtered through a 1.0 ⁇ m membrane filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After the baking for 20 minutes at a temperature of 230 ° C., an imidized film having a film thickness of 100 nm was formed.
  • This coating film is rubbed with a rayon cloth (roll diameter: 120 mm, rotation speed: 300 rpm, moving speed: 20 mm / sec, indentation amount: 0.4 mm), cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and air blown After removing the water droplets at, the substrate was dried at 80 ° C. for 10 minutes 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 combined so that the rubbing directions of the two substrates are 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 liquid crystal cell with the injection port sealed was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. Went. The results are shown in Tables 3 and 4 below.
  • Example 41 A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A2-2) obtained in Example 19 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4 below.
  • Example 42 A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-1) obtained in Example 22 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.
  • Example 43 A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.
  • Example 11 A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (B2-1) obtained in Comparative Example 2 was used and the firing time was 1 hour. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.
  • Example 12 A liquid crystal cell was produced in the same manner as in Example 40 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Tables 3 and 4.
  • Example 44 The liquid crystal aligning agent (A3-1) obtained in Example 22 was filtered through a 1.0 ⁇ m membrane filter, spin-coated on a glass substrate with a transparent electrode, and dried for 5 minutes on a hot plate at a temperature of 80 ° C. After the baking for 20 minutes at a temperature of 230 ° C., an imidized film having a film thickness of 100 nm was formed. The coating surface was irradiated with 1 J / cm 2 of 254 nm ultraviolet light through a polarizing plate to obtain a substrate with a liquid crystal alignment film.
  • Example 45 A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (A3-2) obtained in Example 23 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Table 5.
  • Example 13 A liquid crystal cell was produced in the same manner as in Example 44 except that the liquid crystal aligning agent (B3-1) obtained in Comparative Example 4 was used. The liquid crystal cell was observed for liquid crystal orientation, pretilt angle measurement, voltage holding ratio measurement, and ion density measurement. The results are shown in Table 5.
  • the mechanical strength is large, the resistance to rubbing treatment is excellent, and the liquid crystal alignment property, in particular, the electrical characteristics such as voltage holding ratio and ion density at high temperature, A highly reliable liquid crystal alignment film giving a high pretilt angle can be formed.
  • 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 permettant d'obtenir un film d'alignement de cristaux liquides qui présente une grande résistance mécanique et donc une excellente résistance au frottement. Le film d'alignement de cristaux liquides est extrêmement fiable et présente d'excellentes propriétés d'alignement de cristaux liquides ainsi que d'excellentes caractéristiques électriques, telles que le rapport de maintien de tension à des températures élevées et la densité ionique, et il offre également un grand angle préincliné. La présente invention concerne en particulier un agent d'alignement de cristaux liquides qui est caractérisé en ce qu'il contient : un précurseur de polyimide obtenu par la mise en réaction d'un constituant diamine avec un dérivé d'acide tétracarboxylique, et/ou un polyimide obtenu par imidisation du précurseur de polyimide ; et un composé contenant un groupe amino protégé par un groupe clivable thermiquement, qui est remplacé par de l'hydrogène lorsqu'il est chauffé à une température comprise entre 80 et 300 ˚C, et présentant une structure d'acide amique ou d'ester d'acide amique.
PCT/JP2011/062258 2010-05-28 2011-05-27 Agent d'alignement de cristaux liquides qui comprend un composé contenant un groupe clivable thermiquement, et film d'alignement de cristaux liquides Ceased WO2011149071A1 (fr)

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KR1020127033890A KR101823712B1 (ko) 2010-05-28 2011-05-27 열탈리성기 함유 화합물을 함유하는 액정 배향제 및 액정 배향막
CN201180035610.XA CN103003741B (zh) 2010-05-28 2011-05-27 包含含热脱离性基团的化合物的液晶取向剂及液晶取向膜
JP2012517340A JP5761183B2 (ja) 2010-05-28 2011-05-27 熱脱離性基含有化合物を含有する液晶配向剤、及び液晶配向膜

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JP2015135393A (ja) * 2014-01-17 2015-07-27 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子、位相差フィルム及び位相差フィルムの製造方法
KR20160115685A (ko) * 2015-03-27 2016-10-06 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 액정 표시 소자, 위상차 필름 및 그의 제조 방법, 중합체 그리고 화합물
JP2017049576A (ja) * 2015-09-02 2017-03-09 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子、並びにこれらの製造方法
JP2018507930A (ja) * 2015-09-08 2018-03-22 エルジー・ケム・リミテッド 液晶配向剤用重合体
JP2018523164A (ja) * 2016-03-28 2018-08-16 エルジー・ケム・リミテッド 液晶配向剤、これを含む液晶配向膜および液晶配向膜の製造方法
JP2021516365A (ja) * 2019-01-17 2021-07-01 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、これを用いた液晶配向膜および液晶表示素子
JP2021516368A (ja) * 2019-01-21 2021-07-01 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜および液晶表示素子
JP2022071804A (ja) * 2020-10-28 2022-05-16 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
US11512255B2 (en) 2018-11-20 2022-11-29 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
WO2023068085A1 (fr) * 2021-10-18 2023-04-27 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé
US11667844B2 (en) 2018-11-20 2023-06-06 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
WO2025164545A1 (fr) * 2024-01-31 2025-08-07 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

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KR102278975B1 (ko) * 2013-11-28 2021-07-16 닛산 가가쿠 가부시키가이샤 액정 배향제 및 그것을 사용한 액정 표시 소자
CN106415380B (zh) * 2014-04-03 2019-08-02 日产化学工业株式会社 含有聚酰胺酸酯-聚酰胺酸共聚物的液晶取向剂、以及使用了其的液晶取向膜
KR20150118527A (ko) * 2014-04-14 2015-10-22 제이엔씨 주식회사 액정 배향제, 액정 배향막 및 액정 표시 소자
KR102512603B1 (ko) * 2014-09-26 2023-03-21 닛산 가가쿠 가부시키가이샤 액정 배향 처리제, 액정 배향막 및 액정 표시 소자
JP6888241B2 (ja) * 2015-04-08 2021-06-16 Jsr株式会社 液晶配向剤、液晶配向膜、液晶配向膜の製造方法、液晶素子及び液晶素子の製造方法
KR101835746B1 (ko) * 2015-09-08 2018-03-07 주식회사 엘지화학 액정 배향제용 중합체
KR102202053B1 (ko) * 2018-01-17 2021-01-11 주식회사 엘지화학 액정 배향제 조성물, 이를 이용한 액정 배향막의 제조 방법, 및 이를 이용한 액정 배향막
JP7347410B2 (ja) * 2018-03-30 2023-09-20 日産化学株式会社 新規な液晶配向剤、液晶配向膜及び液晶表示素子
KR102238704B1 (ko) 2018-12-21 2021-04-08 주식회사 엘지화학 가교제 화합물, 이를 포함하는 감광성 조성물, 및 이를 이용한 감광 재료
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JP2015135393A (ja) * 2014-01-17 2015-07-27 Jsr株式会社 液晶配向剤、液晶配向膜、液晶表示素子、位相差フィルム及び位相差フィルムの製造方法
KR20160115685A (ko) * 2015-03-27 2016-10-06 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 액정 표시 소자, 위상차 필름 및 그의 제조 방법, 중합체 그리고 화합물
JP2016186568A (ja) * 2015-03-27 2016-10-27 Jsr株式会社 液晶配向剤、液晶配向膜及びその製造方法、液晶表示素子、位相差フィルム及びその製造方法、重合体並びに化合物
KR102390792B1 (ko) 2015-03-27 2022-04-25 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 그의 제조 방법, 액정 표시 소자, 위상차 필름 및 그의 제조 방법, 중합체 그리고 화합물
KR102563014B1 (ko) * 2015-09-02 2023-08-02 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 소자, 그리고 이들의 제조 방법
KR20170027665A (ko) * 2015-09-02 2017-03-10 제이에스알 가부시끼가이샤 액정 배향제, 액정 배향막 및 액정 소자, 그리고 이들의 제조 방법
JP2017049576A (ja) * 2015-09-02 2017-03-09 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子、並びにこれらの製造方法
JP2018507930A (ja) * 2015-09-08 2018-03-22 エルジー・ケム・リミテッド 液晶配向剤用重合体
JP2018523164A (ja) * 2016-03-28 2018-08-16 エルジー・ケム・リミテッド 液晶配向剤、これを含む液晶配向膜および液晶配向膜の製造方法
US10526540B2 (en) 2016-03-28 2020-01-07 Lg Chem, Ltd. Liquid crystal aligning agent, liquid crystal alignment layer comprising the same and method for preparing liquid crystal alignment layer
US11667844B2 (en) 2018-11-20 2023-06-06 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
US11512255B2 (en) 2018-11-20 2022-11-29 Lg Chem, Ltd. Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
JP2021516365A (ja) * 2019-01-17 2021-07-01 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、これを用いた液晶配向膜および液晶表示素子
US11667843B2 (en) 2019-01-17 2023-06-06 Lg Chem, Ltd. Liquid crystal alignment agent composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film, and liquid crystal display using the same
JP7102537B2 (ja) 2019-01-17 2022-07-19 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜の製造方法、これを用いた液晶配向膜および液晶表示素子
JP6992242B2 (ja) 2019-01-21 2022-01-13 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜および液晶表示素子
US11561438B2 (en) 2019-01-21 2023-01-24 Lg Chem, Ltd. Liquid crystal alignment agent composition, and liquid crystal alignment film, and liquid crystal display using the same
JP2021516368A (ja) * 2019-01-21 2021-07-01 エルジー・ケム・リミテッド 液晶配向剤組成物、これを用いた液晶配向膜および液晶表示素子
JP2022071804A (ja) * 2020-10-28 2022-05-16 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
JP7517208B2 (ja) 2020-10-28 2024-07-17 Jsr株式会社 液晶配向剤、液晶配向膜、液晶素子及び液晶素子の製造方法
WO2023068085A1 (fr) * 2021-10-18 2023-04-27 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, élément d'affichage à cristaux liquides, et composé
WO2025164545A1 (fr) * 2024-01-31 2025-08-07 日産化学株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides les utilisant

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JP5761183B2 (ja) 2015-08-12
TW201209078A (en) 2012-03-01
KR101823712B1 (ko) 2018-01-30
CN103003741A (zh) 2013-03-27
TWI522390B (zh) 2016-02-21
JPWO2011149071A1 (ja) 2013-07-25
KR20130109018A (ko) 2013-10-07
CN103003741B (zh) 2015-05-13

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