WO2012157982A2 - Composé de diamine, son procédé de préparation, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides - Google Patents

Composé de diamine, son procédé de préparation, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides Download PDF

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WO2012157982A2
WO2012157982A2 PCT/KR2012/003910 KR2012003910W WO2012157982A2 WO 2012157982 A2 WO2012157982 A2 WO 2012157982A2 KR 2012003910 W KR2012003910 W KR 2012003910W WO 2012157982 A2 WO2012157982 A2 WO 2012157982A2
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liquid crystal
formula
bis
diamino
carbon atoms
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PCT/KR2012/003910
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WO2012157982A3 (fr
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이성규
최진욱
안용호
소상완
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주식회사 동진쎄미켐
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Priority to CN201280035787.4A priority Critical patent/CN103748068B/zh
Publication of WO2012157982A2 publication Critical patent/WO2012157982A2/fr
Publication of WO2012157982A3 publication Critical patent/WO2012157982A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Definitions

  • Diamine compound its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element
  • This invention relates to a diamine compound, its manufacturing method, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element. More specifically, the present invention relates to a diamine compound having a novel structure that can be used as a photoalignment agent, a method for preparing the same, a liquid crystal aligning agent, a liquid crystal alignment layer, and a liquid crystal display device.
  • the liquid crystal alignment layer is in contact with the liquid crystal molecules and plays a role of uniformly aligning the liquid crystal molecules.
  • the liquid crystal alignment layer is a key material for driving the liquid crystal to uniformly align the liquid crystal in one direction so that the liquid crystal can perform the role of a polarizer of the light.
  • the liquid crystal alignment characteristic of the liquid crystal alignment layer and the electrical characteristics as a thin film are the characteristics of the liquid crystal display. It influences the display quality.
  • Representative methods for forming the liquid crystal alignment film include inorganic vapor deposition, Langmuir-Blodgett (LB) method, polymer stretching method, rubbing method, and the like, and photo-alignment method and ion beam irradiation method. It is proposed.
  • the most commonly used method is rubbing, which rubs the surface of the substrate with a cloth.
  • the rubbing method is a method in which a glass substrate is rubbed in a predetermined direction with paper, and the long axes of the liquid crystal molecules are aligned and aligned along the rubbing direction.
  • This rubbing method is an orientation method that is most commonly used industrially because it has an advantage of easy orientation processing, which is suitable for mass production, stable orientation, and easy control of pretilt angle.
  • polyimide As the material of the alignment film, polyimide having low dielectric constant, high thermal stability, excellent mechanical strength, and excellent process capability is most used.
  • various problems or disadvantages have been pointed out in using polyimide as an alignment film material.
  • the present invention uses a photo-alignment technology that is a method for aligning the liquid crystal molecules without rubbing to solve the problems of the conventional liquid crystal alignment method, the thermal stability is excellent even after the formation of the alignment film, high orientation and stability even after ultraviolet irradiation It aims at providing the diamine compound for liquid crystal aligning agent manufacture which can be done.
  • the present invention is to provide a method for producing the diamine compound in the neck "enemy.
  • an object of this invention is to provide the liquid crystal aligning agent containing the polyamic acid or polyimide obtained by reacting tetracarboxylic dianhydride to the diamine component containing the said diamine compound. Moreover, an object of this invention is to provide the liquid crystal aligning film formed from the said liquid crystal aligning agent.
  • an object of this invention is to provide the liquid crystal display element provided with the said liquid crystal aligning film.
  • the present invention provides a diamine compound represented by the following formula (10). [Formula 10]
  • the present invention is a diamine compound represented by the following formula (23).
  • n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the present invention provides a liquid crystal alignment comprising a polyamic acid or a polyimide obtained by reacting a tetraamine dianhydride with a diamine component represented by the formula (10) or a diamine component containing the diamine compound represented by the formula (23). Offer
  • this invention provides the liquid crystal aligning film formed from the said liquid crystal aligning agent.
  • this invention provides the liquid crystal display element provided with the said liquid crystal aligning film.
  • the present invention comprises the steps of preparing a compound represented by the following formula (9) and a compound represented by the following formula (8) by reacting the compound represented by the formula (8);
  • n is an integer of 1 to 20;
  • R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
  • PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.
  • the present invention comprises the steps of preparing a compound represented by the formula (22) by reacting a compound represented by the formula (12) and a compound represented by the following formula (21);
  • It provides a method for producing a diamine compound represented by the formula (23) comprising the step of removing the protecting group PG of the compound represented by the formula (22).
  • n is an integer of 1 to 20;
  • R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
  • PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.
  • liquid crystal aligning agent comprising a polyamic acid or a polyimide prepared using the diamine compound of the present invention
  • optical alignment technology which is a method for aligning the liquid crystal molecules without rubbing
  • the diamine compound of this invention is mixed with the other diamine compound for liquid crystal aligning film manufacture, the whole mixture can be photo-aligned. Therefore, other compounds that cannot apply the photoalignment can also perform photoalignment, so that the range of the photoalignment can be widened and the alignment effect can be enhanced.
  • the liquid crystal aligning agent manufactured from the diamine compound of this invention can manufacture a liquid crystal aligning film using the photo-alignment technique which irradiates a polarized ultraviolet-ray (UV) to a polymer film, without a rubbing process.
  • UV polarized ultraviolet-ray
  • Photo-alignment technology uses the principle of generating optical reaction and generating optical anisotropy in the film. Therefore, in order to use the photo-alignment control technology of the liquid crystal, it is necessary to use the light having a linear polarization directional, the photoreaction process of the polymer film such as photoisomerization, photopolymerization or photolysis is required, the polarization of the light irradiated with the direction of the liquid crystal molecules Various conditions are required, such as being able to be controlled by direction.
  • Photoisomerization reaction has the disadvantages of inverse reaction and contamination of liquid crystal layer due to decomposition products in photolysis reaction.
  • the initial polyvinyl cinnamate polymer was investigated. Because of the short wavelength, there is a problem in mass production such as the general purpose large exposure apparatus being difficult to use.
  • the diamine compound of the present invention is a monomer that can be used as a chalcone-based photopolymerization alignment agent, as well as excellent in the pretilt angle, voltage retention and orientation properties as well as photoalignment It is an excellent photopolymerization alignment agent monomer which makes photo-alignment possible even if it is mixed with a difficult thermal polymerization alignment agent monomer.
  • polyimide resins that have been widely used as photo-alignment agents refer to high heat-resistant resins prepared by condensation of an aromatic tetracarboxylic acid or a derivative thereof and an aromatic diamine or an aromatic diisocyanate, followed by imidization.
  • the polyimide resin may have various molecular structures depending on the type of monomer used. Generally, pyromellitic dianhydride (PMDA) or nonphthalic anhydride (BPDA) is used as the aromatic tetracarboxylic acid component, and para-phenylenediamine (p-PDA) and meta-phenylenediamine (m) are used as the aromatic diamine component. -PDA), 4,4'-oxydianiline (ODA), 4,4'-methylenedianiline (MDA), 2,2'- bisaminophenylnuclear fullopropane (HFDA),
  • PMDA pyromellitic dianhydride
  • BPDA nonphthalic anhydride
  • p-PDA para-phenylenediamine
  • m meta-phenylenediamine
  • -PDA 4,4'-oxydianiline
  • MDA 4,4'-methylenedianiline
  • HFDA 2,2'- bisaminophenylnuclear
  • Parabisaminophenoxydiphenylsulfone p-BAPS
  • 1,4-bisaminophenoxybenzene TPE-Q
  • 1,3-bisaminophenoxybenzene TPE-R
  • BAPP 2,2'-bisamino Phenoxyphenyl propane
  • HFBAPP 2,2'-bisaminophenoxyphenyl nucleofluoropropane
  • the alignment of the liquid crystal molecules in the liquid crystal display device using such a photo-alignment technology to provide a compound for producing a liquid crystal alignment film that was able to form a pretilt only by UV exposure after the formation of the alignment film.
  • the diamine compound of the present invention may be represented by the following formula (10) or formula (23).
  • n is an integer of 1 to 20; R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • n is an integer of 1 to 5
  • R1 to R8 are the same or different from each other, and each independently, may be H or an alkyl group having 1 to 10 carbon atoms.
  • ⁇ may be 1, and R1 to R8 may be ⁇ .
  • the diamine compound represented by Formula 10 may include the steps of preparing a compound represented by the following Formula 9, and a compound represented by the following Formula 6; And it may be prepared by the step of removing the protecting group PG of the compound represented by the formula (9).
  • n is an integer of 1 to 20;
  • R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , a halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
  • PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- methoxybenzyl), DM PM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl) is a protecting group selected from the group consisting of.
  • the diamine compound represented by Chemical Formula 10 may be prepared by performing the following reactions I, II, III, IV and V stepwise.
  • the compound represented by the formula (23) is a compound represented by the following formula (12), and the compound represented by the following formula 21 to produce a compound represented by the following formula (22); And it may be prepared by the step of removing the protecting group PG of the compound represented by the formula (22).
  • n is an integer of 1 to 20;
  • R1 to R8 are the same as or different from each other, and independently of each other, H, CN, NO 2 , CF 3 , halogen, an alkyl group having 1 to 10 carbon atoms, or having 1 to 10 carbon atoms.
  • PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), BOC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn (benzyl), Carbamate, PMB (p- It is a protecting group selected from the group consisting of methoxybenzyl), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl).
  • the diamine compound represented by Formula 23 may be prepared by performing the following semi-formulas VI, VII, and VII step by step.
  • n is an integer of 1 to 20
  • R1 to R8 are the same or different from each other, and each independently, H, CN, N0 2 , CF 3 , halogen, an alkyl group having 1 to 10 carbon atoms or carbon number Alkoxy group of 1 to 10,
  • PG is Cbz (carbobenzyloxy), Moz (p-Methoxybenzyl carbonyl), B OC (tert-butyloxycarbonyl), FMOC (9-fluorenylmethyloxycarbonyl), Ac (acetyl), Bz (benzoyl), Bn ( benzyl), Carbamate, pB-methoxybenzyl (PMB), DMPM (3,4-dimethoxybenzyl), PMP (p-methoxypheyl), Ts (tosyl), and Ns (nosyl). .
  • the diamine compound represented by Chemical Formula 10, or the diamine compound represented by Chemical Formula 23 may include a chalcone structure and react with tetracarboxylic dianhydride to prepare polyamic acid or polyimide.
  • Liquid crystal aligning agent Liquid crystal aligning agent
  • the present invention provides a liquid crystal aligning agent containing a polyamic acid or polyimide obtained by reacting tetracarboxylic dianhydride to a diamine component containing a diamine compound represented by the following general formula (10). Moreover, this invention provides the liquid crystal aligning agent containing the polyamic acid or polyimide obtained by making tetracarboxylic dianhydride react with the diamine component containing the diamine compound represented by following General formula (23).
  • n is an integer of 1 to 20;
  • R1 to R8 are the same as or different from each other, and are each independently H, CN, NO 2 , CF 3 , halogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the "diamine component" includes at least one diamine compound of the present invention represented by the above formula (10) or formula (23), and refers to further including another diamine compound.
  • the diamine compound represented by the formula (10) or (23) of the present invention can give a photo-orientation by forming a polyamic acid or polyimide by mixing with other diamine compound having no photoactivity. Therefore, the vertical alignment of the liquid crystal can be stabilized.
  • diamine compound which can be used with the diamine compound represented by the said Formula (10) or (23), for example, P-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4, 4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5 -Amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane
  • tetracarboxylic dianhydride used for synthesize combining polyamic acid or polyimide in the liquid crystal aligning agent of this invention
  • alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride Water is available.
  • the said alicyclic tetracarboxylic dianhydride is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4- cyclobutane tetracarr, for example.
  • Acid dianhydrides 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-tetramethyl-1,2,3,4 ⁇ cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclonucleic acid tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclonuxyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene 1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3
  • aromatic tetracarboxylic dianhydride a pyromellitic dianhydride, 4,4'- nonphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3, for example , 3 ', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 3,3 ', 4,4'-biphenyl tertetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenyl silanetetracarboxylic dianhydride, 1,2,3,4-furtetracarboxylic dianhydride,
  • a polyamic acid can be obtained by making the said tetracarboxylic dianhydride react with the diamine component containing the amine compound represented by the said Formula (10), or the amine compound represented by the said Formula (23).
  • the use ratio of the said tetracarboxylic dianhydride and the said diamine component used for the synthesis reaction of the said polyamic acid is about 0.2 to about 2 the acid anhydride group of the said tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the said diamine component.
  • the ratio which becomes equivalent is preferable, More preferably, it is the ratio which becomes about 0.7 to about 1.2 equivalent.
  • Synthetic reaction of the polyamic acid is preferably in an organic solvent, under temperature conditions of about -20 to about 150 ° C, more preferably about 0 to about 100 ° C, preferably about 1 to about 72 hours, more preferably Preferably for about 3 to about 48 hours.
  • the organic solvent is not particularly limited as long as it can dissolve the polyamic acid produced.
  • N_methyl_2-pyridone, ⁇ , ⁇ - dimethylacetamide, ⁇ , ⁇ -dimethyl Amide compounds such as formamide, 3-butoxy- ⁇ , ⁇ -dimethylpropanamide, 3-methoxy- ⁇ , ⁇ -dimethylpropanamide, 3-nuxyloxy- ⁇ , ⁇ -dimethylpropanamide, dimethyl sulfoxide aprotic compounds such as ⁇ -butyrolactone, tetramethylurea and nuxamethylphosphortriamide;
  • Phenolic compounds, such as m-cresol, xylenol, a phenol, a halogenated phenol, etc. can be illustrated.
  • organic solvent alcohol, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used in combination without causing precipitation of polyamic acid.
  • such a poor solvent for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclonucleool, ethylene glycol, propylene glycol, 1,4-butanedi, triethylene glycol, ethylene glycol monomethyl Tere, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclonucleanone, methyl acetate, ethyl acetate, butyl acetate, Methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol -n-propyl ether, ethylene glycol -i-propyl Ether, ethylene glycol -n-butyl
  • a reaction solution obtained by dissolving the polyamic acid is obtained.
  • the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure or the reaction solution is distilled off under reduced pressure with an evaporator to obtain a polyamic acid.
  • the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent, followed by a step of precipitating with a poor solvent or distilling off under reduced pressure with an evaporator once or several times.
  • the polyimide can be obtained by imidating by dehydrating and closing the obtained polyamic acid.
  • the dehydration ring closure of the polyamic acid is preferably carried out by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to the solution as necessary. It is performed by the method of heating.
  • the reaction temperature in the method of heating the polyamic acid of (i) is preferably about 50 to about 200 ° C., more preferably about 60 to about 170 ° C.
  • the reaction time is preferably about 1 to about 8 hours, more preferably about 3 to about 5 hours.
  • reaction temperature is less than 5 (rc, the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may be lowered.
  • acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used.
  • the amount of the dehydrating agent used varies depending on the target imidation ratio, but it is preferable that the amount of the dehydrating agent be about 0.01 to about 20 moles per 1 mole of the amic acid structure of the polyamic acid.
  • the dehydration ring closure catalyst tertiary amines such as pyridine, collidine, rutidine and triethylamine can be used, for example. However, it is not limited to this. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be about 0.01 to about 10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be made higher as the usage-amount of said dehydrating agent and dehydrating ring closure agent increases.
  • an organic solvent used for dehydration ring reaction the organic solvent illustrated as what is used for the synthesis
  • the reaction temperature of the dehydration ring closure reaction is preferably about 0 to about 18 CTC, more preferably about 10 to about 150 ° C.
  • the reaction time is preferably about 1 to about 8 hours, more preferably about 3 to about 5 hours.
  • the polyimide obtained by the said method (i) may be used for manufacture of a liquid crystal aligning agent as it is, or the polyimide obtained may be used for manufacture of a liquid crystal aligning agent after a restriction
  • the reaction solution containing a polyimide is obtained.
  • This reaction solution may be used as it is to manufacture a liquid crystal aligning agent as it is, or may be used to prepare a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, and after isolating the polyimide, the liquid crystal aligning agent. It may be used for the production of or may be used for the production of a liquid crystal aligning agent after purifying the isolated polyimide.
  • methods, such as solvent substitution can be applied, for example.
  • the liquid crystal aligning agent of this invention contains the said polyamic acid or the polyimide which dehydrated and closed the polyamic acid, and the additive mix
  • the said polymer and additive are preferably melt
  • the solid content (components other than the solvent of the liquid crystal aligning agent) concentration in the liquid crystal aligning agent of the present invention is appropriately selected in consideration of viscosity, volatility, and the like, but is preferably about 1 to about 10 with respect to the median of the entire liquid crystal aligning agent. It may range from 0 wt. / 0.
  • liquid crystal aligning agent When the solid content concentration is less than 1% by weight, the film thickness formed by applying the liquid crystal aligning agent is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the thickness becomes too large. A favorable liquid crystal aligning film cannot be obtained, the viscosity of a liquid crystal aligning agent will increase, and coating property will fall. Liquid crystal alignment film
  • An alignment film can be formed by apply
  • the liquid crystal aligning agent can be applied, for example, by a method such as a coater method, a spinner method, a printing method, or an inkjet method, and then a liquid crystal alignment film is formed by heating the coated surface.
  • preliminary heating may be preferably performed for the purpose of preventing liquid flow of the applied aligning agent.
  • the prebaking temperature is preferably : about 30 to about 300 ° C, more preferably about 40 to about 200 ° C, particularly preferably about 50 to about 150 ° C.
  • the solvent may be completely removed, and a firing (post-baking) process may be performed for the purpose of thermally imidizing the polyamic acid.
  • This firing (post-baking) temperature is preferably about 80 to about 300 ° C., more preferably about 120 to about 25 CTC.
  • the liquid crystal aligning agent containing a polyamic acid is apply
  • the film thickness of the liquid crystal alignment film formed is preferably about 0.001 to about 1 um, more preferably about 0.005 to about 0.5 um.
  • the dried coating surface may be subjected to an alignment treatment by irradiating ultraviolet rays in a wavelength range of about 150 to about 450 nm.
  • the intensity of the exposure may be irradiated with energy of about 50 mJ / cm 2 to about 10 J / cm 2 , preferably about 500 mJ / cm 2 to about 5 J / cm 2 .
  • liquid crystal alignment film having an excellent alignment stability and excellent thermal stability can be obtained.
  • This invention provides the liquid crystal display element containing the said liquid crystal aligning film.
  • the liquid crystal display device may be manufactured according to conventional methods known in the art. For example, one of the two substrates on which the liquid crystal alignment layer according to the present invention is formed is coated with an adhesive containing a ball spacer at the end of the substrate, and then One substrate is bonded together to bond cells. Thereafter, the liquid crystal cell may be completed by injecting a liquid crystal into the completed cell and performing heat treatment.
  • the liquid crystal display element of this invention provided with the said liquid crystal aligning film shows the excellent orientation state, and is excellent in the thermal stability of a liquid crystal alignment state.
  • the compound of formula 9 (129 g, 0.18 mol) was dissolved in 1.7 L of Methylene Chloride, and 520 mL of TFA was added at 0 ° C for 1 hour. Then banung and at room temperature for 4 hours, the solvent was removed under reduced pressure, the novel halo hyangje monomer of the invention (E) - 2, 4 -diaminophenethyl 4- (3-oxo-3- (4- (4, 4,4-trifluorobutoxy) phenyl) prop-l-enyl) benzoate (Formula 10) was prepared.
  • Compound 20 was purified using silica gel column chromatography [EtOAc / MC (1: 1 ⁇ 3: 1)]. 4-formylbenzoic acid (91.1 g, 0.61 mol), EDCI (167 g, 0.81 mol), DMAP (12.4 g, 0.11 mol), in a solution of the compound of formula 20 (98.4 g, 0.20 mol) in acetonitrile (1.5 L), DIPEA (87.0 mL, 0.50 mol) was added thereto and reacted at 10 ° C. or below to prepare a compound of Formula 21 (80.0 g, 53%).
  • a compound of formula 12 prepared in Scheme VII (82.3 g, 0.22 mol) was dissolved in DMF (650 mL), 60% NaH (8.95 g, 0.23 mol) was dispersed in DMF (520 mL), and reacted for 24 hours. Turned on. A solution of a compound of Formula 21 (64.5 g, 86.0 mmol) in DMF (650 mL) was mixed and reacted at room temperature for 14 hours to prepare a compound of Formula 22 (6 g, 1 g, 65%). Compound 22 was purified using column chromatography [Hexane / EtOAc (2: 1)].
  • NMP N-methyl-2-pyridone
  • TCAAH 3,5-tricarboxy cyclopentyl acetic anhydride
  • G _ W butyronitrile was added to the impregnated lactone (GBL) 32.7 g was banung for 24 hours. After reaction, 36.4 g of g-butyrolactone (GBL), 2.73 g of N-methyl-2-pyrrolidone (NMP), and 51.8 g of butyl cellosolve (BC) were added to obtain a 5 wt% liquid crystal aligning agent A. . (Viscosity 13 cP, 25 ° C.) Example 2
  • NMP N-methyl-2-pyridone
  • TCAAH tricarboxy cyclopentyl acetic anhydride
  • NMP N-methyl-2-pyridone
  • TCAAH 2,3,5-tricarboxy cyclopentyl acetic anhydride
  • the liquid crystal aligning agents A-G obtained by the said method were filtered using the filter of 1 micrometer of pore diameters.
  • This liquid crystal aligning agent A to G using a spinner on a transparent conductive film containing an ITO film provided on one surface of a glass substrate using a spinner, rotation time 10 rpm, rotation time 1800 rpm, rotation time 20 seconds It was applied in two steps, and 60 seconds of pre cure at 180 ° C, the main cure for 20 minutes at 210 ° C to remove the solvent, to form a coating film.
  • the substrate was exposed for 30 seconds at an intensity of 300 mJ / cm 2 and 10 mW using an exposure machine to prepare two (pair) substrates having a liquid crystal alignment film.
  • an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 4 um was applied to each of the outer edges of the substrate having the liquid crystal alignment film of the substrate having the pair of liquid crystal alignment films, and then overlapped and pressed so that the liquid crystal alignment film faces each other.
  • the adhesive was cured.
  • the liquid crystal injection hole was sealed with an acrylic photocuring adhesive to manufacture a liquid crystal display device.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un composé d'amine, son procédé de préparation, et un agent d'alignement de cristaux liquides, un film d'alignement de cristaux liquides et un dispositif d'affichage à cristaux liquides le contenant. L'agent d'alignement de cristaux liquides contenant un acide polyamique ou un polyimide préparé à l'aide du composé d'amine selon l'invention permet d'obtenir un film d'alignement de cristaux liquides et un dispositif d'affichage à cristaux liquides ayant une excellente stabilité thermique même après formation du film d'alignement de cristaux liquides, et exprimant un alignement et une stabilité élevés même après exposition à des rayons ultraviolets.
PCT/KR2012/003910 2011-05-18 2012-05-17 Composé de diamine, son procédé de préparation, agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides, et dispositif d'affichage à cristaux liquides WO2012157982A2 (fr)

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TWI494347B (zh) * 2012-12-25 2015-08-01 Taiwan Textile Res Inst 二硝單體、二胺單體、聚醯亞胺以及經改質的聚醯亞胺
JP6627595B2 (ja) * 2015-06-11 2020-01-08 Jnc株式会社 光配向用液晶配向膜を形成するための液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子
CN112457866B (zh) * 2020-10-29 2021-07-27 深圳清荷科技有限公司 一种液晶取向剂、液晶取向膜以及液晶显示元件
CN112403513A (zh) * 2020-11-03 2021-02-26 桂林理工大学 一种三乙烯二胺衍生物手性催化剂及其合成方法

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KR20050030219A (ko) * 2002-07-30 2005-03-29 롤리크 아게 광활성 물질
KR100837788B1 (ko) * 2007-06-13 2008-06-13 한국화학연구원 광반응형 방향족 고리 측쇄기를 갖는 폴리아믹산광배향막의 제조방법 및 이를 이용한 액정 셀
WO2008145225A2 (fr) * 2007-05-25 2008-12-04 Rolic Ag Matières photoréticulables comprenant un groupe alicyclique
WO2011010619A1 (fr) * 2009-07-21 2011-01-27 日産化学工業株式会社 Composé de diamine, acide polyamique, polyimide et agent d'alignement des cristaux liquides

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JPH11160712A (ja) * 1997-09-18 1999-06-18 Canon Inc 液晶素子
KR101587125B1 (ko) * 2008-08-21 2016-02-03 삼성디스플레이 주식회사 광반응성 화합물 및 그것을 이용한 액정 표시 소자

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KR20050030219A (ko) * 2002-07-30 2005-03-29 롤리크 아게 광활성 물질
WO2008145225A2 (fr) * 2007-05-25 2008-12-04 Rolic Ag Matières photoréticulables comprenant un groupe alicyclique
KR100837788B1 (ko) * 2007-06-13 2008-06-13 한국화학연구원 광반응형 방향족 고리 측쇄기를 갖는 폴리아믹산광배향막의 제조방법 및 이를 이용한 액정 셀
WO2011010619A1 (fr) * 2009-07-21 2011-01-27 日産化学工業株式会社 Composé de diamine, acide polyamique, polyimide et agent d'alignement des cristaux liquides

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CN103748068A (zh) 2014-04-23
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KR101990302B1 (ko) 2019-06-18
CN103748068B (zh) 2015-08-05
KR20130004069A (ko) 2013-01-09

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