CN104073261A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- CN104073261A CN104073261A CN201410110716.7A CN201410110716A CN104073261A CN 104073261 A CN104073261 A CN 104073261A CN 201410110716 A CN201410110716 A CN 201410110716A CN 104073261 A CN104073261 A CN 104073261A
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- aligning agent
- polyamic acid
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 55
- 239000013078 crystal Substances 0.000 claims description 38
- 150000004985 diamines Chemical class 0.000 claims description 25
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 17
- 125000000962 organic group Chemical group 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000004642 Polyimide Substances 0.000 claims description 4
- 238000005755 formation reaction Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000001680 brushing effect Effects 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 12
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- 239000007787 solid Substances 0.000 description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical group OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
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- 238000010189 synthetic method Methods 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 Cc1ccc(C(O)O*)cc1 Chemical compound Cc1ccc(C(O)O*)cc1 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 239000003643 water by type Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HJIYHOVBJRVELV-UHFFFAOYSA-N C(C)OCC(=S)OCCO Chemical compound C(C)OCC(=S)OCCO HJIYHOVBJRVELV-UHFFFAOYSA-N 0.000 description 1
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N Nc1ccc(Cc(cc2)ccc2N)cc1 Chemical compound Nc1ccc(Cc(cc2)ccc2N)cc1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
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- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A liquid crystal alignment agent comprises a polyamic acid derivative , and a liquid crystal alignment film prepared by the liquid crystal alignment agent has a stable pretilt angle and excellent film brushing performance.
Description
Technical field
The present invention relates to a kind of crystal aligning agent and made liquid crystal orienting film and liquid crystal display device thereof.
Prior art
For promoting the image quality of liquid crystal display device, liquid crystal orienting film should have following character: the electrical specification that (1) is good: do not produce ghost, voltage retention is high.(2) stable tilt angle: liquid crystal molecule and an angle of the necessary inclination in liquid crystal orienting film surface, make liquid crystal molecule be subject to can rotate towards fixed-direction after electric field driven, to reach homogeneous orientation effect, the angle of aforementioned inclination is tilt angle (Pretilt Angle), the stability of tilt angle can affect reaction times and the orientation homogeneity of liquid crystal display device, and then affects image quality.(3) good brush film: do not produce friction brush mark and cutting chip when liquid crystal orienting film is coated on substrate.
Along with popularizing of liquid crystal display device, human consumer day by day promotes for the requirement of liquid crystal display device image quality, how further to improve the image quality of liquid crystal display device, is the target that relevant dealer makes great efforts.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of crystal aligning agent, utilize the made liquid crystal orienting film of this crystal aligning agent that stable tilt angle can be provided, contribute to shorten the reaction times of liquid crystal display device and promote its orientation homogeneity, and then improving its image quality.
Another object of the present invention is to provide a kind of crystal aligning agent, and it has good brush film.
Be to provide a kind of crystal aligning agent according to the embodiment of an aspect of of the present present invention, comprise polyamic acid derivative (A), its structure is suc as formula shown in (I), in formula (I), A1 and A2 are respectively quadrivalent organic radical group independently, and A3 and A4 are respectively divalent organic group independently, and R is any monovalent organic radical group, k+p=1, and 0.01≤k:
According to aforesaid crystal aligning agent, can also comprise polyimide, polyamic acid or imide-amido acid multipolymer.
According to aforesaid crystal aligning agent, wherein R can be the organic group shown in formula (III), formula (IV) or formula (V):
Formula (III) is to formula (V), and it is that 1 to 20 alkyl, carbon number are the organic group shown in 4 to 22 alicyclic, formula (VI) or the organic group shown in formula (VII) that R1 can be carbon number:
In formula (VI) and formula (VII), R2 can be benzene, hexanaphthene, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic, R3 be hydrogen, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic.
According to aforesaid crystal aligning agent, the reactant in the formation reaction of polyamic acid derivative (A) can comprise tetracarboxylic dianhydride (a-1), diamines (a-2) and monoamine (a-3).
Be to provide a kind of crystal aligning agent according to another embodiment of the present invention, comprise polyamic acid derivative (B), its structure is suc as formula shown in (II), and in formula (II), A1 and A2 are respectively quadrivalent organic radical group independently, A3 and A4 are respectively divalent organic group independently, R is any monovalent organic radical group, k+m1+m2=1,0≤m1,0<m2, and 0.01≤k:
Be to provide a kind of liquid crystal orienting film according to the embodiment of another aspect of the present invention, it uses the crystal aligning agent of aforementioned any one to form.
Be to provide a kind of liquid crystal display device according to the embodiment of another aspect of the present invention, it comprises aforesaid liquid crystal orienting film.
By the liquid crystal orienting film of this crystal aligning agent institute shape, stable tilt angle and good brush film can be provided, thereby utilize the made liquid crystal display device of this liquid crystal orienting film can meet the demand in market.
Embodiment
Polyamic acid derivative (A)
Polyamic acid derivative (A), its structure is suc as formula shown in (I):
In formula (I), A1 and A2 are respectively quadrivalent organic radical group independently, and A3 and A4 are respectively divalent organic group independently, and R is any monovalent organic radical group, k+p=1, and 0.01≤k.Preferably, 0.05≤k≤0.7; More preferably, 0.05≤k≤0.4.
Wherein R can be the organic group shown in formula (III), formula (IV) or formula (V):
Formula (III) is to formula (V), and it is that 1 to 20 alkyl, carbon number are the organic group shown in 4 to 22 alicyclic, formula (VI) or the organic group shown in formula (VII) that R1 can be carbon number:
In formula (VI) and formula (VII), R2 can be benzene, hexanaphthene, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic, R3 be hydrogen, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic.
The formation reaction of polyamic acid derivative (A), can tetracarboxylic dianhydride (a-1), diamines (a-2) and monoamine (a-3) be as reactant, carries out polyreaction and obtain in organic solvent.
Polyamic acid derivative (B)
Polyamic acid derivative (B), its structure is suc as formula shown in (II), in formula (II), A1 and A2 are respectively quadrivalent organic radical group independently, and A3 and A4 are respectively divalent organic group independently, and R is any monovalent organic radical group, k+m1+m2=1,0≤m1,0<m2, and 0.01≤k; Preferably, 0.05≤k≤0.7; More preferably, 0.05≤k≤0.4:
Can be by polyamic acid derivative (A) be carried out to dehydration closed-loop reaction, to obtain polyamic acid derivative (B), work as m1>0, represent polyamic acid derivative (A) to carry out partial dehydration ring-closure reaction, work as m1=0, represent polyamic acid derivative (A) to carry out complete dehydration closed-loop reaction.
Tetracarboxylic dianhydride (a-1)
Tetracarboxylic dianhydride (a-1) can be but is not limited to the structure shown in formula (a-1-1), formula (a-1-2) or formula (a-1-3):
Above-mentioned tetracarboxylic dianhydride (a-1) can be used alone, and also can use two or more simultaneously.Do not affecting under the condition of LCD alignment film properties, tetracarboxylic dianhydride (a-1) also can use together with other tetracarboxylic dianhydrides.
Diamines (a-2)
Diamines (a-2) can be but is not limited to the structure shown in formula (a-2-1) or formula (a-2-2):
Above-mentioned diamines (a-2) can be used alone, and also can use simultaneously.Do not affecting under the condition of LCD alignment film properties, diamines (a-2) also can use together with other diamines.
Monoamine (a-3)
Monoamine (a-3) can be but is not limited to the structure shown in formula (a-3-1) or formula (a-3-2):
Above-mentioned monoamine (a-3) can be used alone, and also can use simultaneously.Do not affecting under the condition of LCD alignment film properties, monoamine (a-3) also can use together with other monoamines.
The synthetic method of polyamic acid derivative (A)
Using tetracarboxylic dianhydride (a-1), diamines (a-2) and monoamine (a-3) as reactant, in organic solvent (a-4), carry out polyreaction, with the solution that obtains comprising polyamic acid derivative (A).
Particularly, first in organic solvent (a-4), carrying out the first stage with monoamine (a-3) with tetracarboxylic dianhydride (a-1) reacts, temperature with room temperature to 100 DEG C is carried out 1 to 5 hour, in this elementary reaction, the equivalence ratio of the amido of monoamine (a-3) and tetracarboxylic dianhydride's (a-1) anhydride group can be 1:1 to 3:1, preferably, can be 1:1.
Afterwards, in the product of first stage reaction, add chlorizating agent if thionyl chloride (thionyl chloride) is to carry out subordinate phase reaction (being chlorination reaction), carry out 1 to 5 hour with room temperature, in this elementary reaction, the equivalence ratio of chlorizating agent and tetracarboxylic dianhydride's (a-1) anhydride group can be 1:1 to 3:1, preferably, can be 1:1.
Then, in the product of subordinate phase reaction, adding diamines (a-2) carries out the phase III with tetracarboxylic dianhydride (a-1) and reacts, temperature with room temperature to 60 DEG C is carried out 1 to 10 hour, with the solution that obtains comprising polyamic acid derivative (A), in this elementary reaction, the equivalence ratio of the amido of diamines (a-2) and tetracarboxylic dianhydride's (a-1) anhydride group can be 0.5:1 to 2:1, preferably, can be 0.7:1 to 1.5:1.
Finally, the aforementioned solution that includes polyamic acid derivative (A) is poured in the poor solvent of a large amount of solubleness and separated out, to be precipitated thing, this throw out is dried with reduced pressure after cleaning again, can obtain polyamic acid derivative (A).The polyamic acid derivative (A) of gained can carry out one or many purifying, purification step is as follows: polyamic acid derivative (A) is dissolved in to (a-4) in organic solvent, and separate out with the poor solvent of solubleness, to be precipitated thing, and will after sediment undergoes washing, under reduced pressure, be dried.
Aforementioned organic solvent (a-4), comprises the preferably poor organic solvent (a-4-2) of organic solvent (a-4-1) and solubleness of polyamic acid derivative (A) solubleness.Wherein solubleness preferably organic solvent (a-4-1) including but not limited to METHYLPYRROLIDONE (a-4-1-1), N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethyl-urea, hexamethylphosphoramide, gamma-butyrolactone, pyridine, above solubleness preferably organic solvent (a-4-1) can be used alone, and also can mix two or more uses simultaneously.
The poor organic solvent (a-4-2) of solubleness also can with aforementioned solubleness preferably organic solvent (a-4-1) mix use, be unlikely to be precipitated but prerequisite is polyamic acid derivative (A).Solubleness poor organic solvent (a-4-2) is including but not limited to methyl alcohol, ethanol, Virahol, propyl carbinol, hexalin, ethylene glycol, Ethylene Glycol Methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, Anaesthetie Ether, acetone, methyl ethyl ketone, pimelinketone, methyl acetate, ethyl acetate, tetrahydrofuran (THF), methylene dichloride, trichloromethane, 1,2-ethylene dichloride, benzene,toluene,xylene, normal hexane, normal heptane, octane.
The synthetic method of polyamic acid derivative (B)
In the synthetic method of aforementioned polyamic acid derivative (A), the solution that comprises polyamic acid derivative (A) that is reacted to gained the phase III reacts through dehydration closed-loop, can obtain the solution that comprises polyamic acid derivative (B), reaction conditions and extracting process obtain polyimide with conventional polyamic acid dehydration closed-loop, do not repeat them here.
Crystal aligning agent
Crystal aligning agent of the present invention comprises polyamic acid derivative (A) or polyamic acid derivative (B), organic solvent (C), and optionally comprises additive (D).
Crystal aligning agent of the present invention, can also comprise polyimide (E), polyamic acid (F) or imide-amido acid multipolymer (G), to improve the character of crystal aligning agent.
Polyamic acid derivative (A) or polyamic acid derivative (B) are dissolved in to organic solvent (C), can form crystal aligning agent.The temperature of preparing crystal aligning agent is preferably 0 DEG C to 150 DEG C, more preferably 20 DEG C to 50 DEG C.
Crystal aligning agent can be adjusted the solids content that it comprises according to viscosity and volatility, is preferably the solids content that comprises 1wt%～10wt%.Solids content if solids content lower than 1wt%, can make the thickness of liquid crystal orienting film after coating too thin, and reduces its regiospecific, if during higher than 10wt%, can affect coating quality.
Aforementioned organic solvent (C) is including but not limited to METHYLPYRROLIDONE, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N-methyl caprolactam, dimethyl sulfoxide (DMSO), gamma-butyrolactone, butyrolactam, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol monobutyl ether etc., above organic solvent (C) can use in two or more mixing.Except above-mentioned cited organic solvent (C), as long as solubilized polyamic acid derivative (A) or polyamic acid derivative (B) all can be used as organic solvent (C).
Aforementioned additive (D) can be organosilicon (oxygen) hydride compounds (D-1) or epoxy compounds (D-2).
Liquid crystal orienting film
The method that forms liquid crystal orienting film comprises following steps:
First, crystal aligning agent of the present invention is coated on the glass substrate with patterning nesa coating to form coat, coating process is including but not limited to roller coating method, method of spin coating and print process, and coating process is conventional, does not repeat them here.
Secondly, coat is carried out to heated baking, make coat form liquid crystal orienting film.The object of heated baking is the organic solvent (C) removing in crystal aligning agent, can impel polyamic acid derivative (A) or polyamic acid derivative (B) to carry out dehydration closed-loop reaction simultaneously.The temperature of heated baking can be 80 DEG C～300 DEG C, more preferably 100 DEG C～240 DEG C.The thickness of the liquid crystal orienting film forming is taking 0.005～0.5 micron as good.
Finally, with the cylinder that is wound with nylon or cotton fiber cloth, liquid crystal orienting film is carried out to rubbing, make liquid crystal orienting film there is regiospecific to liquid crystal molecule.
Liquid crystal display device
The method that forms liquid crystal display device comprises following steps:
First, have on the glass substrate of foregoing liquid crystal alignment film and be coated with frame glue in one, and spray separation material on another has the glass substrate of foregoing liquid crystal alignment film.
Secondly, the aforementioned two sheet glass substrates with liquid crystal orienting film are combined to brush each other film direction mode orthogonal or parallel to each other.
Finally, in the gap of two glass substrates, inject liquid crystal, and sealing injection hole, liquid crystal display device can be formed.
The evaluation assessment of liquid crystal display device
(1) tilt angle stability: will inject the liquid crystal display device of liquid crystal (ZLI-4792), measure tilt angle by crystallization rotational method, and calculate the degree of variation of tilt angle according to measuring result.Particularly, first obtain the tilt angle observed value of nine points in liquid crystal display device with crystallization rotational method, degree of variation using the difference of maximum value in nine tilt angle observed values and minimum value as tilt angle again, the degree of variation of tilt angle is less, represents that the stability of tilt angle is higher.When the degree of variation of tilt angle is less than 0.1, judge that the stability of tilt angle is as excellent, when the degree of variation of tilt angle is 0.1～0.2, the stability of judging tilt angle as in, when the degree of variation of tilt angle is greater than 0.2, judge that the stability of tilt angle is as poor.Aforementioned crystallization rotational method is the method for the measurement tilt angle commonly used, does not repeat them here.
(2) High Temperature Pre inclination angle variation: crystal aligning agent is coated on substrate, carried out heated baking with 210 DEG C, 220 DEG C with 230 DEG C respectively, be finally combined into liquid crystal display device; Measure the tilt angle at three temperature with crystallization rotational method, each liquid crystal display device measures 10 points in addition average, gets the difference of maximum value and minimum value as the standard of the amount of commenting, and the less representation property of numerical value is better.
(3) brush film: crystal aligning agent is applied on tin indium oxide (ITO) substrate with method of spin coating, and toast with baking oven, continuous carry out orientation with 0.4 micron of 1000 revs/min of rotating speed, platform movement speed 60 mm/second, the amount of being pressed into and brush film 3 times, with the surface of the liquid crystal orienting film after polarizing microscope visual observation brush film, be judged to be excellently without observing brush mark and cutting swarf, observe brush mark and cutting swarf and be judged to be bad.
(4)
1h-NMR: sample thief is positioned in NMR test tube, with tritium for chloroform by sample dissolution, use Brooker company (Brucker Corporation) manufacture NMR analyser measure (model is: Waters2487).
(5) polymer molecule amount measurement: use gel permeation chromatography (GPC) device that Waters (Waters Corporation) manufactures to measure (model is: Bruker AVANCE400MHz), at 35 DEG C of tubing string temperature, using the dimethyl formamide that contains lithiumbromide and phosphoric acid (DMF) as washing fluid, draw weight average molecular weight and number molecular-weight average via conversion by the time of polystyrene.
Embodiment
(1) synthetic monoamine (a-3-1), polyamic acid derivative (A-1)～(A-6) and imide-amido acid multipolymer (G-1):
Synthesis example 1: monoamine (a-3-1) synthetic:
The reaction formula of synthetic monoamine (a-3-1) is as follows, first synthetic mesophase product (w), then synthesize monoamine (a-3-1) by intermediate product (w):
First, in the reaction flask of 2 liters, add 4-nitrobenzoyl chloride (4-nitrobenzoyl chloride) 102 grams of (550 mmole), 1200 grams of toluene (Toluene) and 75.9 grams, salt of wormwood (Potassium carbonate) (550 mmole), under room temperature, stir 5 minutes.Separately 4-(4 '-amyl group)-dicyclo hexanol (4-(4 '-pentyl)-dicyclohexylanol) 126 grams (500 mmole) is dissolved in 200 grams of toluene, and slowly splash in previous reaction bottle, after dripping off totally, under room temperature, stir again 4 hours, add pure water extraction 3 times, and with dried over mgso organic layer, filter and collect filtrate, and dry with concentrating under reduced pressure, can obtain 188.5 grams of intermediate products (w) (470 mmole), productive rate 94%.The spectroscopic data of intermediate product (w) is:
1h NMR (400MHz, CDCl3) δ 8.30～8.23 (2H), 8.15～8.20 (2H), 5.24～5.36 (0.6H), 4.85～4.95 (0.4H), 0.8～2.1 (30H) ppm.
Afterwards, in another reaction flask of 2 liters, add 188.5 grams of intermediate products (w) (470 mmole), 1000 grams of toluene, 10 grams of 10% palladium-carbon catalysts (10%Palladium-on-carbon), stir 10 minutes.In previous reaction bottle, slowly splash into again 50 milliliters of 80% hydrazine hydrates (80%Hydrazine hydrate), drip off totally and stir again 4 hours.Room temperature falls back in question response temperature, and air exhaust filtering is collected filtrate, and removed solvent with concentrating under reduced pressure, gets final product to obtain 174 grams of monoamines (a-3-1) (470 mmole), productive rate 100%.The spectroscopic data of monoamine (a-3-1):
1h NMR (400MHz, CDCl3) δ 7.80～7.86 (2H), 6.58～6.65 (2H), 5.15～5.20 (0.6H), 4.75～4.85 (0.4H), 3.96～4.06 (2H), 0.8～2.1 (30H) ppm.
Synthesis example 2: polyamic acid derivative (A-1) synthetic:
In a reaction flask, 1.49 grams of monoamines (a-3-1) (4 mmole) and tetracarboxylic dianhydride (a-1-1) 0.39 gram (2 mmole) are added in the METHYLPYRROLIDONE (a-4-1-1) of 30 grams, at room temperature stir 2 hours, then the product in reaction flask is carried out to the chlorination reaction of 2 hours, add again 7.37 grams of diamines (a-2-1) (20 mmole) to stir 2 hours, finally add 3.53 grams of tetracarboxylic dianhydrides (a-1-1) (18 mmole) and under room temperature, stir again 3 hours.Reaction soln is poured in deionized water and made polyamic acid derivative (A-1) separate out rear collection, with after washed with methanol several, under the vacuum condition of 60～70 DEG C, dry.The number molecular-weight average (Mn) of the polyamic acid derivative (A-1) generating is 12000, and weight average molecular weight is 31000(Mw).
Synthesis example 3～7: polyamic acid derivative (A-2)～(A-6) synthetic:
Polyamic acid derivative (A-2)～(A-6), in the time that each stage synthesis material and synthesis example 2 have replacing, is listed below table one, and all the other synthesis steps and condition are with synthesis example 2.
Table one
Synthesis example 8: imide-amido acid multipolymer (G-1) synthetic:
In a reaction flask, sequentially 4.90 grams of tetracarboxylic dianhydrides (a-1-1) (25 mmole), tetracarboxylic dianhydride (a-1-2) 13.51 grams (45 mmole), tetracarboxylic dianhydride (a-1-3) 5.45 grams (25 mmole) and diamines (a-2-1) 36.84 grams (100 mmole) are made an addition in the METHYLPYRROLIDONE (a-4-1-1) of 243 grams, the solution that preparation solids content is 20wt%, and at the temperature of 40 DEG C to 50 DEG C, react 4 hours to 5 hours, can obtain including the solution of polyamic acid.Add 8 grams of 14 grams of pyridines and acetic anhydride in aforesaid polyamic acid solution, at 100 DEG C to 110 DEG C, carry out dehydration closed-loop reaction 3 to 4 hours.Obtained solution is poured in methyl alcohol and is separated out, to obtain imide-amido acid multipolymer (G-1), last, by imide-amido acid multipolymer (G-1) to be dried under reduced pressure after washed with methanol.The number molecular-weight average of the imide-amido acid multipolymer (G-1) generating is 22000, and weight average molecular weight is 62000.
(2) preparation of the crystal aligning agent of embodiment 1～embodiment 12 and experimental technique:
By polymkeric substance such as polyamic acid derivative (A-1)～(A-6) and imide-amido acid multipolymers (G-1), be dissolved in gamma-butyrolactone and METHYLPYRROLIDONE mixed solvent according to the ratio shown in table two, be prepared into the solution that solids content is 6wt%, and filter with the strainer of 0.45 micron of diameter, collected filtrate is the embodiment 1～embodiment 12 of crystal aligning agent of the present invention.
The crystal aligning agent of aforementioned each embodiment is coated on glass substrate by roller printing press, and be dried 20 minutes with the hot-plate of 200 DEG C, formation thickness is the film of 0.08 micron.This film carries out rubbing with 0.4 micron of 1000 revs/min of roller rotating speed, platform movement speed 60 mm/second, the amount of being pressed into.
On the glass substrate with foregoing liquid crystal alignment film, be coated with again frame glue, on the glass substrate of another tool foregoing liquid crystal alignment film, spray separation material, again the two sheet glass substrates with liquid crystal orienting film are combined to brush each other the mutually perpendicular mode of film direction, and in the gap of two glass substrates, inject liquid crystal (ZLI-4792), and sealing injection hole, form liquid crystal display device.
The liquid crystal display device of gained is carried out to the assessment of tilt angle, tilt angle stability and brush film.Assessment result as shown in Table 2.
Table two
As shown in Table 2, more than during the tilt angle stability of embodiment 1 to embodiment 12 is all, High Temperature Pre inclination angle variation maximum is only 0.24, brush film is all excellent, hence one can see that, the present invention, by add polyamic acid derivative (A) in crystal aligning agent, can make made liquid crystal orienting film have stable tilt angle and good brush film.
In table two, except during embodiment 6 with the tilt angle stability of embodiment 10 is, the tilt angle stability of other embodiment is all excellent.Thin sight, the content of the polyamic acid derivative (A) of embodiment 1～5, embodiment 7～9, embodiment 11～12 is all high with the content of embodiment 10 compared with embodiment 6, and meaning is the stability that polyamic acid derivative (A) can improve the tilt angle of liquid crystal orienting film.
From above-mentioned embodiment, the present invention by adding polyamic acid derivative (A) or polyamic acid derivative (B) in crystal aligning agent, make the made liquid crystal orienting film of crystal aligning agent there is stable tilt angle and good brush film, and can improve the image quality of liquid crystal display device, to meet the need of market.
Although the present invention discloses as above with embodiment; so it is not in order to limit the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, therefore protection scope of the present invention is when being as the criterion depending on the accompanying claim person of defining.
Claims (10)
1. a crystal aligning agent, comprises:
Polyamic acid derivative (A), its structure is suc as formula shown in (I):
In formula (I), A1 and A2 are respectively quadrivalent organic radical group independently, and A3 and A4 are respectively divalent organic group independently, and R is any monovalent organic radical group, k+p=1, and 0.01≤k.
2. crystal aligning agent as claimed in claim 1, also comprises:
Polyimide, polyamic acid or imide-amido acid multipolymer.
3. crystal aligning agent as claimed in claim 1, wherein this R is the organic group shown in formula (III), formula (IV) or formula (V):
Formula (III) is to formula (V), and R1 is that carbon number is that 1 to 20 alkyl, carbon number are the organic group shown in 4 to 22 alicyclic, formula (VI) or the organic group shown in formula (VII):
In formula (VI) and formula (VII), R2 be benzene, hexanaphthene, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic, R3 be hydrogen, carbon number be 1 to 20 alkyl or carbon number be 4 to 22 alicyclic.
4. crystal aligning agent as claimed in claim 1, wherein the reactant in the formation reaction of this polyamic acid derivative (A) comprises tetracarboxylic dianhydride (a-1), diamines (a-2) and monoamine (a-3).
5. crystal aligning agent as claimed in claim 4, the wherein structure shown in this tetracarboxylic dianhydride (a-1) contained (a-1-1), formula (a-1-2) or formula (a-1-3):
6. crystal aligning agent as claimed in claim 4, the wherein structure shown in this diamines (a-2) contained (a-2-1) or formula (a-2-2):
7. crystal aligning agent as claimed in claim 4, the wherein structure shown in this monoamine (a-3) contained (a-3-1) or formula (a-3-2):
8. a crystal aligning agent, comprises:
Polyamic acid derivative (B), its structure is suc as formula shown in (II):
In formula (II), A1 and A2 are respectively quadrivalent organic radical group independently, and A3 and A4 are respectively divalent organic group independently, and R is any monovalent organic radical group, k+m1+m2=1,0≤m1,0<m2, and 0.01≤k.
9. a liquid crystal orienting film, it is by being formed as claim 1 to the crystal aligning agent of claim 8 any one.
10. a liquid crystal display device, comprises liquid crystal orienting film as claimed in claim 9.
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| CN108885375B (en) | 2016-11-28 | 2021-05-18 | 株式会社Lg化学 | Liquid crystal alignment film, method for preparing the same, and liquid crystal display device using the same |
| KR102065718B1 (en) | 2017-10-17 | 2020-02-11 | 주식회사 엘지화학 | Liquid crystal alignment film and liquid crystal display using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749777A (en) * | 1986-06-18 | 1988-06-07 | Nissan Chemical Industries Ltd. | Liquid crystal aligning agent from tetracarboxylic acid dianhydride, diamine and monoamine |
| JPH01180518A (en) * | 1988-01-12 | 1989-07-18 | Nissan Chem Ind Ltd | Orientation treating agent |
| CN1685282A (en) * | 2002-09-25 | 2005-10-19 | 日产化学工业株式会社 | Aligning agent for liquid crystal and liquid-crystal display element |
| CN1922540A (en) * | 2004-02-26 | 2007-02-28 | 日产化学工业株式会社 | Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same |
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| TWI395769B (en) * | 2006-03-22 | 2013-05-11 | Jsr Corp | Liquid crystal alignment agent and method for forming liquid crystal alignment film |
| KR100913605B1 (en) * | 2007-12-07 | 2009-08-26 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
| TWI591097B (en) * | 2011-10-25 | 2017-07-11 | 達興材料股份有限公司 | Liquid crystal alignment agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749777A (en) * | 1986-06-18 | 1988-06-07 | Nissan Chemical Industries Ltd. | Liquid crystal aligning agent from tetracarboxylic acid dianhydride, diamine and monoamine |
| JPH01180518A (en) * | 1988-01-12 | 1989-07-18 | Nissan Chem Ind Ltd | Orientation treating agent |
| CN1685282A (en) * | 2002-09-25 | 2005-10-19 | 日产化学工业株式会社 | Aligning agent for liquid crystal and liquid-crystal display element |
| CN1922540A (en) * | 2004-02-26 | 2007-02-28 | 日产化学工业株式会社 | Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same |
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