WO2015182925A1 - Synthèse nouvelle de diamine et agent d'alignement de cristaux liquides l'utilisant - Google Patents

Synthèse nouvelle de diamine et agent d'alignement de cristaux liquides l'utilisant Download PDF

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WO2015182925A1
WO2015182925A1 PCT/KR2015/005131 KR2015005131W WO2015182925A1 WO 2015182925 A1 WO2015182925 A1 WO 2015182925A1 KR 2015005131 W KR2015005131 W KR 2015005131W WO 2015182925 A1 WO2015182925 A1 WO 2015182925A1
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bis
dianhydride
mmol
liquid crystal
acid
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Korean (ko)
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최진욱
윤성일
강소희
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Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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Priority claimed from KR1020150069598A external-priority patent/KR102420541B1/ko
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Publication of WO2015182925A1 publication Critical patent/WO2015182925A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two 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
    • 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

Definitions

  • the present invention relates to a polyimide resin for a liquid crystal aligning agent and a process for producing the same, and is a process for producing a diamine compound which can be used as a raw material for a polyimide alignment film which is easy to control the angle of pretilt angle and exhibits excellent liquid crystal aligning property and a polyamic acid Or a polyimide and a liquid crystal aligning agent containing the same.
  • the driving method of a liquid crystal display device is a twist nematic (TN) mode in which nematic liquid crystal molecules are arranged between two transparent electrode substrates coated with an alignment film on a transparent electrode, a super twist nematic twist nematic (hereinafter abbreviated as "STN") mode, an infinite switching (IPS) mode, a vertical alignment (VA) mode, and a thin film transistor Quot; TFT type ").
  • TN twist nematic
  • IPS infinite switching
  • VA vertical alignment
  • TFT type thin film transistor Quot
  • Typical examples of the most frequently used polymer compounds include polymer compositions such as polyamic acid-based and soluble polyimide-based polymers that are imidized with polyamic acid. They are widely used industrially as an aligning agent for orienting a liquid crystal with excellent heat resistance and chemical resistance.
  • these macromolecular compounds are formed by polymerization of diamine and tetracarboxylic acid anhydride, and the structure of the monomers causes the material properties of the polymer compound to be exhibited.
  • the basic requirement of the alignment film is control of the pretilt angle. It is known that the pretilt angle of the liquid crystal molecules is greatly influenced by the shape of the surface of the alignment film and the length of the side chains.
  • a diamine or a tetracarboxylic acid is introduced into the anhydride.
  • a diamine which is easy to introduce a side chain group is used.
  • JP-A-64-25126 and JP-A-5-27244 have proposed a liquid crystal aligning agent comprising a polyamic acid or polyimide having a diamine having a long chain alkyl group as a raw material.
  • a polyimide liquid crystal aligning agent using an aliphatic side chain type diamine having a linear alkoxy group, an alkyl ester group, or a fluorinated alkyl group as a side chain is generally known.
  • the characteristics of various alignment films differ depending on the aromatic system and the aliphatic system.
  • Aromatic components act as hard cores in the polymer chain, resulting in low solubility in organic solvents and poor processability in industry.
  • an alignment layer containing a large amount of an aliphatic or alicyclic group can improve the above disadvantages.
  • the aliphatic polyamic acid-based alignment agent is inferior in orientation of the liquid crystal, and the aliphatic soluble polyimide has poor adhesiveness to the substrate, and peeling of the coating film tends to occur even in weak rubbing.
  • a polyimide and a polyamic acid are mixed with each other but they are separated by heat.
  • a liquid crystal aligning agent produced by a block copolymerization method of polyimide and polyamic acid has problems .
  • the diamine having side chains proposed in the prior art has a problem in that the efficiency of controlling the pretilt angle with respect to the amount of introduction and the reactivity at the time of polymerization are low.
  • the reactivity of the diamine is low, polymerization of the polymer compound takes time, and in some cases, polymerization hardly proceeds. If polymerization takes time, there is a problem in industrial production, and if the degree of polymerization of the polymer compound is insufficient, it becomes a problem from the viewpoint of durability as a liquid crystal alignment film.
  • the present invention relates to a novel diamine compound having a large effect of adjusting the angle of incidence and excellent in polymerization reactivity even with a small amount of introduction, and a polyamic acid or polyimide synthesized as a part of the diamine, and a liquid crystal alignment And the like.
  • the present invention provides a diamine compound represented by the following formula (1), which can be used as a starting material for a polyimide alignment film which is easy to control the angle of pretilt angle and exhibits excellent liquid crystal alignability, and a process for producing the same.
  • X 2 is -O- or -COO-, -OCO-, -CH 2 O - a linking group selected from, Z -, - OCH 2 - , -CF 2 O-, -OCF 2 -, -CH 2 CH 2 1 and Z < 2 > are independently a single bond,
  • Y 1 , Y 2 , Y 3 and Y 4 are independently H or F,
  • Z 3 can be selected from alkyl, fluorine, alkoxy, fluoroalkyl, fluoroalkoxy, and a has a value between 0 and 5.
  • the present invention relates to a diamine compound which can be used as a raw material of a polyimide alignment film which is easy to control a pretilt angle and exhibits excellent liquid crystal alignment properties, a process for producing the same, a polyamic acid or polyimide for a liquid crystal aligner using the same, and a process for producing the same.
  • the present invention provides a diamine benzene derivative represented by the following formula (1) and a process for producing the same.
  • X 2 is -O- or -COO-, -OCO-, -CH 2 O - a linking group selected from, -, - OCH 2 -, -CF 2 O-, -OCF 2 -, -CH 2 CH 2
  • Z 1 and Z 2 are independently a single bond, or Y 1 , Y 2 , Y 3 and Y 4 are independently H or F,
  • Z 3 can be selected from alkyl, fluorine, alkoxy, fluoroalkyl, fluoroalkoxy, and a has a value between 0 and 5.
  • Examples of the alicyclic acid dianhydrides of formula (2) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1
  • aromatic acid dianhydrides of Formula 2 include pyromellitic dianhydride, 4,4'-biphthalic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3 ', 4,4'-biphenylether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ', 4,4'- 4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dian
  • the diamine represented by the formula (3) is specifically exemplified by p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, Aminodiphenylsulfide, 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) - trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'- di
  • A is a divalent organic group constituting a tetracarboxylic acid and R 2 is a divalent organic group having no side chain group.
  • the present invention also provides a liquid crystal display element comprising the liquid crystal alignment layer.
  • the liquid crystal alignment material of the present invention comprises two benzene rings each substituted with one amino group and one amino group substituted with a methyl group
  • the liquid crystal is more uniformly oriented, and the solubility and transparency with respect to the organic solvent can be remarkably improved.
  • the side chain is characterized by having an alkyl chain group, an aromatic group, and a fatty ring group as shown in Formula 1 so as to facilitate the adjustment of the angle of the preliminary crystal.
  • these side chains are designed to achieve the object of the present invention.
  • the alkyl chain located at the end of the side chain lowers the surface tension and increases the solubility by making space for the organic solvent to penetrate between the polymer chains.
  • the aliphatic ring not only supports the liquid crystal molecule, but also the solid core group and the terminal alkyl group are connected in the form of a rod like a liquid crystal, and when the liquid crystal is placed around the side chain, the liquid crystal orientation can be increased by interaction with the side of the liquid crystal.
  • the length of the diamine side chain and the length of the side chain spacing are determined depending on the average length of the long axis of the liquid crystal molecule and the required size of the preliminary crystal.
  • the solvent in step (a) may be at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), dimethylacetamide, Chloro-4-hydroxytoluene, dioxane, tetrahydrofuran (THF), tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, ), And cyclohexanone, which is an inert solvent.
  • NMP N-methyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • DMSO dimethylsulfoxide
  • dimethylacetamide Chloro-4-hydroxytoluene
  • dioxane tetrahydrofuran
  • THF tetrahydrofuran
  • tetrahydrofuran tetrahydrofuran
  • tetrahydrofuran tetrahydrofur
  • the polyimide resin produced by the production method of the present invention is a polyimide resin for a liquid crystal aligning agent of a liquid crystal display device having a weight average molecular weight of 1,000 to 200,000.
  • the side chain length of the polyamide resin is 0.8 to 1.5 times the length of the long axis of the liquid crystal molecule, and the length between side chains is 1.5 to 3.5 times the length of the long axis of the liquid crystal molecule.
  • the present invention also provides a liquid crystal alignment film produced using the polyimide resin for a liquid crystal aligning agent of the liquid crystal display, and a liquid crystal display device including the same.
  • the diamine compound of Formula 1 may be prepared by a method similar to Reaction Scheme 1 or Reaction Scheme 2.
  • the connecting portion X 2 is a bonding group such as an ether bond (-O-) or an ester bond (-COO-), and these bonding groups can be formed by a common organic synthesis method.
  • this is a method of reacting a hydroxyl group derivative containing an ether, and the corresponding X 3 is a halogen-substituted benzene derivative or a halogen-substituted alkyl derivative of X 3 and X 2 in the connecting ester under the presence of an alkali in general.
  • an ether bond is formed by dissolving di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1- phenylene) -dicarbamate in DMF, The reaction is carried out at room temperature, and the halogen-substituted compound to be connected is dissolved in DMF and reacted. (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene)) -dicarbamate was dissolved in Methylene Chloride, DCC (3.68 g, 17.86 mmol) and DMAP (0.22 g, 1.79 mmol) at room temperature.
  • the method for reducing the dinitro compound there is no particular limitation on the method for reducing the dinitro compound, and there is no particular limitation on the method for reducing the dinitro compound, and it is possible to use a catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium- Dioxane, or an alcohol-based solvent with hydrogen gas, hydrazine, hydrogen chloride, or the like.
  • a catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium- Dioxane, or an alcohol-based solvent with hydrogen gas, hydrazine, hydrogen chloride, or the like.
  • A is a tetravalent organic group constituting a tetracarboxylic acid and B is a divalent organic group constituting a diamine of the general formulas (1) and (3).
  • the tetracarboxylic dianhydride of Formula 2 may be slowly reacted with the reaction solution of the side chain-type diamine compound of Formula 1 and the diamine of Formula 3 in N-methyl-2-pyrrolidone at 5 ° C, After the addition, the mixture is stirred at room temperature for 6 hours to prepare a polyamic acid-based block copolymer.
  • the viscosity can be controlled by using a cellosolve solvent such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether and the like.
  • the polyamic acid block copolymer of the present invention can be thermally treated at 100 to 250 ° C for 30 minutes to 2 hours to convert it into a polyimide by a dehydration ring-closure reaction.
  • polyamic acid can be converted to polyimide by chemical imidization reaction by stirring at 0 to 180 ° C for 1 to 100 hours in the presence of a basic catalyst and acid anhydride.
  • the polyimide solution thus obtained is preferably precipitated and recovered as mentioned above in the synthesis of polyamic acid.
  • the solvent used for the production of the polyamic acid is not particularly limited as long as the polyamic acid is soluble, but specific examples thereof include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) But are not limited to, sulfoxide (DMSO), dimethylacetamide, gamma -butyrolactone, hexamethylphosphoramide, hexamethylphosphoramide, tetramethylene sulfone, tetramethylurea, p-chlorophenol, -4-hydroxytoluene, dioxane, tetrahydrofuran (THF), cyclohexanone, and the like.
  • NMP N-methyl-2-pyrrolidone
  • DMF N-dimethylformamide
  • DMSO sulfoxide
  • dimethylacetamide gamma -butyrolactone
  • hexamethylphosphoramide hexamethylphosphoramide
  • the solvent does not dissolve the polyamic acid, it may be mixed with the solvent in such a range that the produced polyamic acid is not precipitated. Furthermore, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the produced polyamic acid, it is preferable to use an organic solvent that is dehydrated and dried if possible.
  • a in the tetracarboxylic acid dianhydride in the production step of polyamic acid is a tetravalent organic group.
  • Specific examples thereof include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3', 4,4'-biphenyltetracarboxylic acid (BPDA), 1,2,4,5-benzenetetracarboxylic dianhydride (PMDA), cyclobutanetetracarboxylic dianhydride (CBDA) and 4- (2,5-ditoxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-carboxylic acid dianhydride (TDA).
  • BTDA 4,4'-benzophenonetetracarboxylic dianhydride
  • ODPA 4,4'-oxydiphthalic anhydride
  • BPDA
  • the diamine having a nitrogen atom of the above formula (4) or (5) is a divalent organic group constituting the above formula (1).
  • the benzyl group derivatives linked by the methylene group located at the terminal of the side chain of the diamine can exhibit liquid crystal aligning property.
  • the main chain, the side chain diamine and the tetracarboxylic acid dianhydride containing a large amount of aromatic can increase the surface polarity and decrease the surface tension of the orientation film. It affects the control of the angle of incidence.
  • the benzyl group to which the amine is linked may increase the solubility by creating a space through which the organic solvent can permeate through the chains.
  • the diamine compound having nitrogen atom in the above formula (4) or (5) may be a divalent organic group derived from the formula (3) (diamine compound having no side substituent).
  • specific examples thereof include 4,4'-diaminodiphenyl ether (ODA), 4,4'-methylenebiscyclohexylamine (PACM), 4,4'-methylene-2-methylcyclohexylamine (ANCAMINE) (MDA), 4.4'-hexafluoroisopropyldiphenyldiamine (6FDA), p-phenylenediamine (p-PDA) and the like .
  • the temperature is usually 5 to 100 ° C. Note that higher temperatures will terminate the polymerization sooner, but the molecular weight of the polymer can be too high.
  • the reaction concentration is 5 to 30% by weight, and uniform stirring is carried out to obtain a required molecular weight.
  • the obtained polyamic acid may be used by diluting the reaction solution and may be used by redissolution through precipitation.
  • Examples of the poor solvent used for the precipitation recovery include, but are not limited to, methanol, ethanol, hexane, acetone, butyl cellosolve, methyl ethyl ketone, toluene, benzene and diethyl ether.
  • the polyamic acid precipitate obtained by charging into a poor solvent may be recovered as a solid by filtration, washing and recovery, and then dried at room temperature or under reduced pressure or by heating and drying.
  • the side chain type divalent organic group R 2 is used for imparting the functionality of a polyimide such as liquid crystal aligning property, solubility and membrane permeability, and in the case of a divalent organic group R 2 having no side chain, Is used to determine the distribution of groups.
  • n is an integer of 1 to 10, more preferably 2 to 4.
  • the side chain length of the branched-chain divalent organic group R 2 is preferably adjusted so that the ratio of the average length of the long axis of the liquid crystal molecules is 0.8 to 1.5 times, and the length of the side chain groups is 1.5 to 3.5 times longer than the length of the long axis of the liquid crystal molecules. It is preferable to determine the type and amount of the divalent organic group R 2 having no group. In this way, it is possible to produce a polyimide resin having a specific structure that exhibits excellent orientation properties in polyimide and excellent properties in terms of solubility, membrane permeability, and chemical stability.
  • the weight average molecular weight of the polyimide resin is 1,000 to 200,000.
  • the present invention provides a liquid crystal alignment layer using the polyimide resin, wherein the liquid crystal alignment layer can be obtained by coating an alignment liquid containing the polyimide compound on a patterned substrate and then firing the liquid.
  • the solvent used for the alignment solution is not particularly limited as long as it is usually used in a liquid crystal alignment solution and can dissolve the polyimide compound.
  • the alignment solution contains 1 to 30% by weight of the polyimide compound .
  • the liquid crystal alignment layer of the present invention is excellent in liquid crystal alignment and rubbing resistance, has a high voltage maintaining ratio and high contrast, can control the pretilt angle of a liquid crystal which can reduce charge accumulation, By maximizing the interaction effect between the side chains of the mid layer and having a 90 ⁇ angle square, uniform and stable orientation can be obtained.
  • 4- (4,4,4-trifluorobutoxy) benzoate (7 g, 9.5 mmol) was added to a solution of 4- (2,2-bis (4 - ((tert-butoxycarbonyl) amino) (4 g, 78%) of 4- (2,2-bis (4-aminophenyl) ethyl) phenyl 4- (4,4,4-trifluorobutoxy) benzoate was obtained by reacting the mixture at 0 ° C for 1 hour .
  • the reaction vessel was charged with di-tert-butyl ((2- (4-hydroxyphenyl) ethane-1,1-diyl) bis (4,1-phenylene) -dicarbamate (9 g, 17.86 mmol) in Methylene Chloride (3.83 g, 17.86 mmol), DCC (3.68 g, 17.86 mmol), DMAP (0.22 g, 1.79 mmol), 2,3 ', 4', 5'-tetrafluoro- [1,1'- biphenyl] -4- mmol) was added and reacted at room temperature for 12 hours to obtain 4- (2,2-bis (4 - ((tert-butoxycarbonyl) amino) phenyl) ethyl) phenyl 2,3 ', 4', 5'-tetrafluoro- [ , 1'-biphenyl] -4-carboxylate (9 g, 67%).
  • Phenyl) ethyl] phenyl 2,3 ', 4', 5'-tetrafluoro- [1,1'-biphenyl] -4-carboxylate prepared by reacting 4- (2,2- (4-aminophenyl) ethyl) phenyl 2,3 ', 4', 5'-tetramethyluronium tetrafluoroborate was prepared by adding TFA (50 ml) at 0 ° C and reacting for 1 hour.
  • tetrafluoro- [1,1'-biphenyl] -4-carboxylate (5 g, 74%).
  • 1,1-diyl) bis (4,1-phenylene)) dicarbamate (6g, 8.02mmol) was added to a mixture of di-tert- butyl ((2- (4- TFA (30 ml) was added at 0 ° C and the reaction was carried out for 1 hour to give 3 g of 4,4 '- (2- (4- (4- (4-pentylcyclohexyl) phenoxy) phenyl) ethane-1,1-diyl) dianiline , 77%).
  • Phenylenediamine (0.81 g, 7.5 mmol) and the dianiline (2.00 g, 3.7 mmol) obtained in Synthesis Example 1 were dissolved in N-methyl-2 -Pyrolidone (29.02 g) was added to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.83 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) was dissolved in ⁇ -butyrolactone (17.26 g) slowly dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.81 g, 7.5 mmol) and the dianiline (2.00 g, 3.7 mmol) obtained in Synthesis Example 1 were dissolved in N-methyl-2 (2.10 g, 9.4 mmol) and pyromellitic dianhydride (2.04 g, 9.4 mmol) were dissolved in pyrrolidone (29.02 g) at room temperature, Is slowly added dropwise to the reaction solution in ⁇ -butyrolactone (17.82 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.78 g, 7.2 mmol) and the dianiline (2.00 g, 3.6 mmol) obtained in Synthesis Example 2 were dissolved in N-methyl-2 (1.76 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (28.15 g) 9.0 mmol) was dissolved in? -Butyrolactone (16.75 g) and slowly added dropwise to the reaction solution for 2 hours, followed by reaction for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.78 g, 7.2 mmol) and the dianiline (2.00 g, 3.6 mmol) obtained in Synthesis Example 2 were dissolved in N-methyl-2 (2.01 g, 9.0 mmol) and pyromellitic dianhydride (1.96 g, 9.0 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (28.15 g) Is slowly added dropwise to the reaction solution which is dissolved in? -Butyrolactone (17.28 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.82 g, 7.6 mmol) and the dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 4 were dissolved in N-methyl-2 (1.86 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (29.27 g) 9.5 mmol) was dissolved in ⁇ -butyrolactone (17.41 g) slowly dropwise over 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.82 g, 7.6 mmol) and the dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 4 were dissolved in N-methyl-2 (2.12 g, 9.5 mmol) and pyromellitic dianhydride (2.06 g, 9.5 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (29.27 g) Is slowly added dropwise to the reaction solution in which ⁇ -butyrolactone (17.97 g) dissolves for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.81 g, 7.5 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 5 were dissolved in N-methyl-2 -Pyrolidone (29.09 g) was added to a solution of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (1.84 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) was dissolved in ⁇ -butyrolactone (17.31 g) and slowly added dropwise to the reaction solution for 2 hours. The reaction mixture was reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (0.81 g, 7.5 mmol) and dianiline (2.00 g, 3.8 mmol) obtained in Synthesis Example 5 were dissolved in N-methyl-2 (2.10 g, 9.4 mmol) and pyromellitic dianhydride (2.05 g, 9.4 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (29.09 g) Is slowly added dropwise to the reaction solution in ⁇ -butyrolactone (17.86 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (1.04 g, 9.6 mmol) and the dianiline (2.00 g, 4.8 mmol) obtained in Synthesis Example 6 were dissolved in N-methyl-2 (2.35 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (35.22 g) 12.0 mmol) was dissolved in? -Butyrolactone (20.95 g) and slowly added dropwise to the reaction solution for 2 hours, followed by reaction for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (1.04 g, 9.6 mmol) and the dianiline (2.00 g, 4.8 mmol) obtained in Synthesis Example 6 were dissolved in N-methyl-2 (2.69 g, 12.0 mmol) and pyromellitic dianhydride (2.62 g, 12.0 mmol) were added to the reaction solution, which was dissolved in pyridine (35.22 g) Is slowly added dropwise to the reaction solution which is dissolved in? -Butyrolactone (21.67 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (1.02 g, 9.5 mmol) and the dianiline (2.00 g, 4.7 mmol) obtained in Synthesis Example 7 were dissolved in N-methyl-2 (2.32 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were added to the reaction solution, which was dissolved in tetrahydrofuran-pyrrolidone (34.82 g) 11.8 mmol) was slowly added dropwise to the reaction solution in 20.71 g of? -Butyrolactone for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • Phenylenediamine (1.02 g, 9.5 mmol) and the dianiline (2.00 g, 4.7 mmol) obtained in Synthesis Example 7 were dissolved in N-methyl-2 (2.65 g, 11.8 mmol) and pyromellitic dianhydride (2.58 g, 11.8 mmol) were added to the reaction solution, which was dissolved in pyrrolidone (36.00 g) (21.41 g) dissolved in ⁇ -butyrolactone (21.41 g) for 2 hours and reacted for 6 hours to obtain a polyamic acid solution.
  • the polyamic acid solution obtained in Examples 1 to 28 was dissolved in a solvent in which? -Butyrolactone and butyl cellosolve were mixed to prepare a solution having a concentration of 5% by weight, and the solution was filtered with a filter of 0.1 ⁇ ⁇ to prepare a polyimide liquid crystal aligning agent .
  • liquid crystal aligning agents were prepared in the same manner as in the production of the polyamic acid solutions obtained in Comparative Examples 1 and 2,
  • liquid crystal aligning agents obtained in Examples 29 to 56 and Comparative Examples 3 and 4 were applied to a glass substrate on which a transparent conductive film was patterned by a spinner method. After the application, the substrate was prebaked at 100 ⁇ for 30 minutes and then baked at 250 ⁇ for 1 hour to obtain a substrate on which a polyimide alignment film having a thickness of 700 ⁇ was formed.
  • the two substrates were opposed to each other with a certain gap (cell gap) without rubbing the orientation film surface of the two substrates on which the liquid crystal alignment film was formed as described above, and the two peripheral portions of the substrate were bonded using a sealing agent, Liquid crystal was injected and filled in the cell gap defined by the liquid crystal cell, and the injection hole was sealed to fabricate the liquid crystal cell. Then, a polarizing plate was bonded to the outer surface of the liquid crystal cell, that is, the other surface of each substrate constituting the liquid crystal cell so that the direction of the polarization axis thereof was orthogonal to obtain a liquid crystal display element.
  • the sealing agent a thermosetting resin and an epoxy resin containing aluminum oxide as a spacer were used.
  • the properties of the liquid crystal aligning agent using the polyimide resin prepared in the present invention such as (1) squareness of the pretilt angle and (2) orientation, were evaluated by the following methods, and the results are shown in Table 1.
  • Examples 29 to 32 of the polyimide resins using the diamine of Synthesis Example 2 in the above Examples are suitable for the TN mode (4 to 5 ⁇ ), and the polyimide resins Examples 37 to 40 2 °) is suitable for the IPS mode.
  • the polyamic acid except for the examples 29 to 32 and 37 to 40 according to the present invention exhibited a VA mode (89 to 90 °) It is possible to confirm that a high pretilt angle is formed at a desired angle.
  • a liquid crystal aligning agent capable of maximizing the interaction effect between the liquid crystal molecules and the side chains of the polyimide by using the diamine compound, have.
  • a liquid crystal alignment film formed using the alignment agent and a liquid crystal display element having the liquid crystal alignment film formed using the alignment agent and a liquid crystal display element having the liquid crystal alignment film.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

La présente invention concerne une résine polyimide pour un agent d'alignement vertical et un procédé pour préparer celui-ci. L'invention concerne un procédé de préparation d'un composé diamine polyimide à chaîne latérale, qui présente un angle de pré-inclinaison élevé et uniforme et peut par conséquent être utilisé en tant que matériau pour une couche d'alignement en polyimide, et une résine de polyimide pour un agent d'alignement vertical, qui présente une orientation uniforme et stable et qui est susceptible de présenter un angle de pré-inclinaison de 90° à l'aide du procédé, et un procédé de fabrication de celui-ci. A cet effet, la présente invention concerne un dérivé de diaminobenzène représenté par la formule chimique 1.
PCT/KR2015/005131 2014-05-29 2015-05-22 Synthèse nouvelle de diamine et agent d'alignement de cristaux liquides l'utilisant Ceased WO2015182925A1 (fr)

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CN119912344A (zh) * 2025-01-10 2025-05-02 株洲时代新材料科技股份有限公司 用于动态橡胶的臭氧防护助剂及其制备方法、应用以及一种橡胶

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JP7351294B2 (ja) * 2018-03-30 2023-09-27 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
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