CN1128384C - Aligning agent for liquid crystal - Google Patents
Aligning agent for liquid crystal Download PDFInfo
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- CN1128384C CN1128384C CN 98805234 CN98805234A CN1128384C CN 1128384 C CN1128384 C CN 1128384C CN 98805234 CN98805234 CN 98805234 CN 98805234 A CN98805234 A CN 98805234A CN 1128384 C CN1128384 C CN 1128384C
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- liquid crystal
- aligning agent
- polyimide precursor
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Abstract
The present invention provides a liquid crystal orientation agent. A resinous component comprises a polyimide precursor, and a chemical structure of the polyimide precursor is represented as a general formula (1). The present invention also provides a liquid crystal orientation agent of the polyimide precursor, a main component of the liquid crystal orientation agent comprises the polyimide precursor, and the liquid crystal orientation agent is represented by a general formula (2). In the formula, Y is a tetravalent aliphatic radical group, Z is a divalent aromatic radical group, and R is H or alkyl.
Description
The present invention relates to be used to produce the aligning agent for liquid crystal (aligning agent) of liquid crystal indicator.More particularly, the present invention relates to provide high and stablize the aligning agent for liquid crystal of the liquid crystal indicator of tilt angle (pretilt angle).
Liquid crystal indicator is widely used in thin-type display device recently.The general liquid crystal indicator that uses is stable twisted nematic (TN) and STN Super TN type (STN).In producing these liquid crystal indicators, as disclosed in JP-B-62-38689, can be inserted between two transparency electrode coated articles for making liquid crystal, be special direction with respect to coated article and come into line, need a fine setting layer.In the liquid crystal indicator of TN type and STN type, liquid crystal also needs to tilt to come into line, and promptly is tilt angle with the coated article surface, and this just need finish with aligning agent for liquid crystal.For example, tilt angle requires to 4-8 ° in the STN type.The aligning agent for liquid crystal that can reach high like this tilt angle has the polyimide precursor solution of mentioning and discusses in JP-A-3-261915 in JP-A-1-177514 soluble polyimide solution.Yet, in the liquid crystal indicator of producing with this aligning agent for liquid crystal, have some problems, promptly the tilt angle instability, tilt angle reduces under 80 ℃ or higher hot environment, display quality is bad etc.
As a diverse ways that reaches high tilt angle of discussing in JP-A-3-164714 is to introduce siloxane structure.Yet, in this method, introduce siloxane structure and make the liquid crystal fine setting bad to certain altitude, therefore, in some cases, siloxane can not be introduced and obtain must measuring of enough tilt angles.
In recent years, liquid crystal indicator need improve performance, requires the material of fine setting layer to have than the past more property.Particularly, as mentioned above, the material of fine setting layer must have stable tilt angle, and good electrical properties, must demonstrate homogeneous film mouldability, burnish resistance etc. in producing liquid crystal indicator.And, used low temperature because produce liquid crystal indicator in recent years, so the fine setting layer material above-mentioned performance that must demonstrate will be equal to or higher than level in the past, even when using heating-up temperature to be lower than 200 ℃.
The aligning agent for liquid crystal that the present invention relates to has overcome the problems referred to above of traditional aligning agent for liquid crystal, and the liquid crystal indicator with high and stable tilt angle can be provided.
That is, aligning agent for liquid crystal provided by the invention comprises the polyimide precursor for polyamic acid or poly amic acid ester as resinous principle, and its chemical constitution is following general formula (1):
That is to say, by the polyimide precursor of following general formula (3) expression,
Wherein X is a trivalent organic group, and A is a divalent organic group, and R is H or alkyl, and n is 1 or with higher number, and m is 0 or above number.
It is to comprise above-mentioned polyimide precursor and with the aligning agent for liquid crystal of the polyimide precursor of following general formula (2) expression that the present invention also provides principal ingredient:
(in the formula, Y is the tetravalence aliphatic group, and Z is two valency aromatic groups, and R is H or alkyl)
The principal ingredient of aligning agent for liquid crystal of the present invention comprises the polyimide precursor that contains general formula (3) expression, and this aligning agent for liquid crystal can make the liquid crystal fine setting good, and can obtain high tilt angle.
Being used in the polyimide precursor by general formula (3) expression of the present invention can be by 1, and two (the 3-aminopropyl dimetylsilyl) benzene of 4-wait to react in polar solvent with the tetracarboxylic dianhydride and obtain.When using the tetracarboxylic dianhydride, can obtain polyamic acid.When polyamic acid during through esterification or when above-mentioned reaction is carried out with the tetrabasic carboxylic acid diester, can obtain poly amic acid ester.
Tetracarboxylic dianhydride's example is 1,2,4,5-benzenetetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, cyclo-butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, two rings [2,2,2] suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxy tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic acid dianhydride.But the tetracarboxylic dianhydride is not limited to these examples.
Poly amic acid ester can generate the tetrabasic carboxylic acid diester with alcohol (for example methyl alcohol, ethanol, 1-propyl alcohol or 2-propyl alcohol) reaction by the tetracarboxylic dianhydride, makes diester with the diamines dehydrating condensation, or makes polyamic acid with the dehydration of alcohols condensation.
Be used for the polyimide precursor by general formula (1) expression of the present invention in production, can use and remove 1, the outer diamines of two (the 3-aminopropyl dimetylsilyl) benzene of 4-is not as long as this use hinders the effect by the structure of general formula (1) expression.The example of diamines is a p-phenylenediamine, between-phenylenediamine, 2, the 5-diaminotoluene, 3, the 5-diaminotoluene, 2, the 5-diamido is right-dimethylbenzene, 3,3 '-methyl biphenyl amine, 3,4 '-the diamido phenylate, 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 1,3-(3-amino-benzene oxygen) benzene, 1,3-(4-amino-benzene oxygen) benzene, 1,4-(3-amino-benzene oxygen) benzene, 1,4-(4-amino-benzene oxygen) benzene, 4,4 '-(4-amino-benzene oxygen) biphenyl, 2,2-pair [4,4 '-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4,4 '-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-pair [4,4 '-(4-amino-benzene oxygen) phenyl] sulfone, 1, two (4-amino-benzene oxygen) propane of 3-, 1, two (4-amino-benzene oxygen) butane of 4-, ethylenediamine, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1,5-diamido pentane, 1, the 6-diamino hexane, 1,7-diamido heptane, 1,8-diamido octane, 1, the 10-diamino decane, 1,12-diamido dodecane, 1,4-diamino-cyclohexane and 4,4 '-diamino-dicyclohexyl methane.Diamines is not limited to these examples.
In the present invention, the resinous principle of aligning agent for liquid crystal had both contained the polyimide precursor by general formula (1) expression, when containing the polyimide precursor of being represented by general formula (2) again, obtained good electrical properties.
Being used for the polyimide precursor by general formula (2) expression of the present invention can be equal to aromatic diamine by aliphatic tetracarboxylic dianhydride and obtain in the polar solvent reaction.When using aliphatic tetracarboxylic dianhydride, can obtain polyamic acid.When polyamic acid can obtain poly amic acid ester through esterification or when using aliphatic tetrabasic carboxylic acid diester in above-mentioned reaction.
The example by the aliphatic tetracarboxylic dianhydride of the polyimide precursor of general formula (2) expression that is used for making the present invention is butane tetracarboxylic acid dianhydride, cyclo-butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, two rings [2,2,2] suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxy tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride and 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic acid dianhydride.But aliphatic tetracarboxylic dianhydride is not limited to these examples.
The example by the aromatic diamine of the polyimide precursor of general formula (2) expression that is used for obtaining the present invention is a p-phenylenediamine, between-phenylenediamine, 2, the 5-diaminotoluene, 3, the 5-diaminotoluene, 2,5-diamido-right-dimethylbenzene, 3,3 '-dimethylbenzidine, 3,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl ether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 1,3-(3-amino-benzene oxygen) benzene, 1,3-(4-amino-benzene oxygen) benzene, 1,4-(3-amino-benzene oxygen) benzene, 1,4-(4-amino-benzene oxygen) benzene, 4,4 '-(4-phenoxy group) biphenyl, 2,2-two [4,4 '-(4-amino-benzene oxygen) phenyl] propane, 2,2-pair [4,4 '-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two [4,4 '-(4-amino-benzene oxygen) phenyl] sulfone, 1, two (4-the amino-benzene oxygen)-propane and 1 of 3-, two (4-amino-benzene oxygen) butane of 4-.But aromatic diamine is not limited to these examples.
Being used for polymerization is N-methyl-pyrrolidone, dimethyl formamide and diethylformamide with the example of the polar organic solvent of any polyimide precursor of obtaining the present invention and using.But polar organic solvent is not limited to these examples.
Aligning agent for liquid crystal of the present invention comprises resinous principle and solvent composition.The example that is used for the solvent composition of aligning agent for liquid crystal of the present invention is the mixed solvent of mixed solvent, NMP and PGDA of mixed solvent, NMP and propylene glycol list n-butyl ether of N-N-methyl-2-2-pyrrolidone N-, (NMP) and butyl cellulose and the mixed solvent of diethylformamide and butyl cellulose.But solvent composition is not limited to these examples.Aligning agent for liquid crystal of the present invention also can comprise very a spot of silane coupling agent or be used to improve bonding with coated article based on the coupling agent of titanium.
Go through the present invention below by embodiment.But the present invention never is subjected to the restriction of these embodiment.
(synthetic embodiment 1)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 1,2,4 of 21.81 grams (0.10 mole), 5-benzenetetracarboxylic acid dianhydride is scattered in the 300 gram N-N-methyl-2-2-pyrrolidone N-s (NMP).In tap funnel, with 1 of 12.62 grams (0.05 mole), two (3-aminopropyl dimetylsilyl) the benzene uniform dissolution of 4-splash into the whole solution that obtains in the tap funnel and can divide in the flask in the NMP of 100 grams, and the content in the flask is stirring in nitrogen stream under 10 ℃ simultaneously.Then, stirring was carried out 3 hours.Remove tap funnel, add 2 of 20.53 grams (0.05 mole) can dividing in the flask, 2-two [4,4 '-(4-amino-benzene oxygen) phenyl] propane stirs the potpourri that obtains 5 hours down at 10 ℃.System is returned room temperature, obtain the nmp solution of polyamic acid.With NMP and butyl cellulose dilution, make the concentration of resinous principle become 5% this solution, the ratio of NMP and butyl cellulose becomes 8: 2, obtains aligning agent for liquid crystal (1) like this.
(synthetic embodiment 2)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 3,3 of 29.42 grams (0.10 mole) ', 4,4 '-biphenyl tetracarboxylic dianhydride is scattered in 300 grams N-N-methyl-2-2-pyrrolidone N-s (NMP).In tap funnel, with 1 of 25.24 grams (0.10 mole), two (3-aminopropyl dimetylsilyl) the benzene uniform dissolution of 4-splash into the whole solution that obtains in the tap funnel and can divide in the flask in the NMP of 100 grams, and the content in the flask is stirring in nitrogen stream under 10 ℃ simultaneously.Then, stirring was carried out 8 hours.System is returned room temperature, obtain the nmp solution of polyamic acid.With NMP and butyl cellulose dilution, make the concentration of resinous principle become 5% this solution, the ratio of NMP and butyl cellulose becomes 8: 2, obtains aligning agent for liquid crystal (2) like this.
(synthetic embodiment 3)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 1,2,4 of 21.81 grams (0.10 mole), 5-benzenetetracarboxylic acid dianhydride is scattered in the 300 gram N-N-methyl-2-2-pyrrolidone N-s (NMP).System in the stirring, is splashed into from the pyridines of tap funnel with 15.82 grams (0.20 mole) in nitrogen stream at 20 ℃.After this, stirring was carried out 3 hours.Splash into 6.41 gram (0.20 mole) methyl alcohol from tap funnel then, stir and carried out 5 hours.System is as cold as 10 ℃, splashes into the solution that 41.27 dicyclohexylcarbodiimides that restrain (0.20 mole) are dissolved in 100 gram NMP, then stirred 30 minutes from tap funnel.With 1 of 12.62 grams (0.05 mole), 4,4 of two (3-aminopropyl dimetylsilyl) benzene of 4-and 10.01 grams (0.05 mole) '-benzidine ether, stirred 8 hours.The suspending liquid that obtains splashed in 20 times 1: 1 the water and methanol mixture.The solid filtering that obtains is collected and obtained poly amic acid ester in 48 hours 25 ℃ of vacuum drying.5 gram poly amic acid esters are dissolved in the mixed solvent of 8: 2 gamma-butyrolacton of 95 grams and butyl cellulose.Obtain aligning agent for liquid crystal (3).
(synthetic embodiment 4)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 19.83 the gram (0.10 mole) 4,4 '-diaminodiphenyl-methane be scattered in 300 the gram NMP in.Under 10 ℃ and when nitrogen flows down system's stirring, add 19.81 gram (0.10 mole) butane tetracarboxylic acid dianhydrides.The potpourri that obtains stirred 5 hours at 10 ℃.System is returned room temperature, obtain the nmp solution of polyamic acid.With NMP and butyl cellulose dilution, make the concentration of resinous principle become 5% this solution, the ratio of NMP and butyl cellulose becomes 8: 2.The solution that 70 grams are obtained mixes with 30 gram alignment agents (3), obtains aligning agent for liquid crystal (4).
(embodiment 1)
The aligning agent for liquid crystal (1) that synthetic embodiment 1 is obtained was spun on the glass coated article with ito transparent electrode, with the coated article of coating in 170 ℃ of clean stoves dry 120 minutes.The friction coated article, and form the Xiao Chi in 50 microns in antiparallel gap with it.Liquid crystal (ZLI-2293, the product of Merck) is poured into into Xiao Chi.The liquid crystal Xiao Chi that obtains is heated to 100 ℃, and is as cold as room temperature at leisure.Observe with polarizing microscope, point out the good fine setting of liquid crystal.It is 6.0 ° that the tilt angle of liquid crystal is measured by crystal rotation method.With liquid crystal Xiao Chi place 90 ℃ 1,000 hour, measure tilt angle then, be 6.0 °.Produced the liquid crystal Xiao Chi in 7 microns in gap with identical method, and place 90 ℃ 1,000 hour.Sinusoidal wave 33Hz ± 5 volt is granted Xiao Chi before and after leave standstill, and the mensuration current value.As a result, be to put preceding 1.3 times placing 90 ℃ of 1,000 hour after-current values.
(embodiment 2)
The aligning agent for liquid crystal (2) that obtains with synthetic embodiment 2 repeats the operation of embodiment 1.Liquid crystal fine setting is good, is 6.4 ° at the tilt angle that is statically placed in 90 ℃ of liquid crystal before 1,000 hour, and leaving standstill after 1,000 hour is 6.2 °, and the current value of increase is 1.2 times.
(embodiment 3)
Be used in the operation that aligning agent for liquid crystal (3) that synthetic embodiment 3 obtains repeats embodiment 1.Liquid crystal fine setting is good, is 5.0 ° at the tilt angle that is statically placed in 90 ℃ of liquid crystal before 1,000 hour, and leaving standstill after 1,000 hour is 5.0 °, and the current value of increase is 1.3 times.
(embodiment 4)
Be used in the operation that aligning agent for liquid crystal (4) that synthetic embodiment 4 obtains repeats embodiment 1.Liquid crystal fine setting is good, is 6.0 ° at the tilt angle that is statically placed in 90 ℃ of liquid crystal before about 1,000 hour, and leaving standstill after 1,000 hour is 6.0 °, and the current value of increase is 1.0 times.
(comparative example 1)
Can divide in the flask at four necks that thermometer, stirrer, feed(raw material)inlet and dried nitrogen draft tube are housed, with 1,2,4 of 21.81 grams (0.10 mole), 5-benzenetetracarboxylic acid dianhydride is scattered among the 300 gram NMP.With system 10 ℃ in nitrogen stream, stir in, with 2 of 20.53 grams (0.05 mole), 2-two [4,4 '-(4-amino-benzene oxygen) phenyl] propane adds from the feed(raw material)inlet.The potpourri that obtains was stirred 5 hours down at 10 ℃.System is turned back to the nmp solution that room temperature obtains polyamic acid.With NMP and butyl cellulose dilution, make the concentration of resinous principle become 5% this solution, the ratio of NMP and butyl cellulose becomes 8: 2, obtains aligning agent for liquid crystal (5).
Repeat the operation of embodiment 1 with aligning agent for liquid crystal (5).Liquid crystal fine setting is good, is 2.5 ° at the tilt angle that is statically placed in 90 ℃ of liquid crystal before about 1,000 hour, and leaving standstill after 1,000 hour is 2.5 °, and the electric current added value is 2.1 times.
(comparative example 2)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 29.42 the gram (0.10 mole) 3,3 ', 4,4 '-BPDA be scattered in 300 the gram NMP in.In tap funnel, with 24.85 gram (0.10 moles) 1, two (3-aminopropyl) the tetramethyl disiloxane uniform dissolution of 3-splash into the whole solution in the tap funnel and can divide in the flask in 100 gram NMP, simultaneously under 10 ℃ at nitrogen stream stirred flask content.Stir then and carried out 8 hours.System is turned back to the nmp solution that room temperature obtains polyamic acid.With NMP and butyl cellulose dilution, make the concentration of resinous principle become 5% this solution, the ratio of NMP and butyl cellulose becomes 8: 2, obtains aligning agent for liquid crystal (6).
Repeat the operation of embodiment 1 with aligning agent for liquid crystal (6).The liquid crystal fine setting is bad.
(comparative example 3)
Can divide in the flask at four necks that thermometer, stirrer, tap funnel and dried nitrogen draft tube are housed, with 1,2,4 of 21.81 grams (0.10 mole), 5-benzenetetracarboxylic acid dianhydride is scattered among the 300 gram NMP.When in nitrogen stream, system being stirred under 20 ℃, splash into 15.82 gram (0.20 mole) pyridines by tap funnel.After this stirred 3 hours.Splash into 6.41 gram (0.20 mole) methyl alcohol by tap funnel then, and stirred 5 hours.System is as cold as 10 ℃, splashes into 41.27 gram (0.20 mole) dicyclohexylcarbodiimides by tap funnel and be dissolved in 100 solution that restrain among the NMP, then stirred 30 minutes.To wherein adding 1 of 24.85 grams (0.10 mole), two (3-aminopropyl) tetramethyl disiloxanes of 3-, and stirred 8 hours.The suspending liquid that obtains splashed in 20 times 1: 1 the water and methanol mixture.Filter and collect the solid that obtains, and carried out vacuum drying 48 hours, obtain poly amic acid ester at 25 ℃.5 gram poly amic acid esters are dissolved in 8: 2 the gamma-butyrolacton and butyl cellulose mixed solvent of 95 grams, obtain aligning agent for liquid crystal (7).
Repeat the operation of embodiment 1 with aligning agent for liquid crystal (7).The liquid crystal fine setting is bad.
In any one of embodiment 1-4, obtain good liquid crystal fine setting and the high tilt angle of 5.0-7.0.90 ℃ leave standstill 1,000 hour after, it is very little that tilt angle changes, and having good stability of tilt angle is described.The current value increase is very little, has only 1.3 times or still less, particularly current value does not increase in embodiment 4, only 1.0 times and fine.
In comparative example 1, be not used as aligning agent for liquid crystal because do not contain the polyamic acid of the chemical constitution of general formula (1) expression, tilt angle is low to moderate 2.5, and current value is greatly to 2.1 times.
In comparative example 2, because the polyamic acid that contains the silica alkyl structure that uses, and siloxane is not the chemical constitution by general formula (1) expression, so the liquid crystal fine setting is bad.
The poly amic acid ester that contains the silica alkyl structure for using in comparative example 3, and siloxane is not the chemical constitution by general formula (1) expression, so the liquid crystal fine setting is bad.
Therefore, aligning agent for liquid crystal of the present invention can obtain good liquid crystal fine setting, and has high and stable liquid crystal pretilt angle, and the liquid crystal indicator of good visual performance and high reliability can be provided.
Commercial Application
The present invention relates to be used in the aligning agent for liquid crystal of producing liquid crystal indicator. More particularly, originally Invention relates to the liquid crystal aligning with high and stable tilt angle that liquid crystal indicator can be provided Agent. Therefore, the present invention can be used in the various industrial departments that use liquid crystal.
Claims (2)
1. aligning agent for liquid crystal, the polyimide precursor that it comprises the polyamic acid of following general formula (3) expression or poly amic acid ester are as resinous principle:
Wherein X is a trivalent organic group, and A is a divalent organic group, and R is H or alkyl, and n is 1 or a higher number, and m is 0 or a higher number.
2. aligning agent for liquid crystal, its principal ingredient comprise the polyimide precursor of claim 1 and by the polyimide precursor of following general formula (2) expression:
In the formula, Y is the tetravalence aliphatic group, and Z is two valency aromatic groups, and R is H or alkyl.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98805234 | 1998-03-19 |
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| Publication Number | Publication Date |
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| CN1257587A CN1257587A (en) | 2000-06-21 |
| CN1128384C true CN1128384C (en) | 2003-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 98805234 Expired - Fee Related CN1128384C (en) | 1998-03-19 | 1998-03-19 | Aligning agent for liquid crystal |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011115118A1 (en) * | 2010-03-15 | 2011-09-22 | 日産化学工業株式会社 | Liquid crystal alignment agent containing polyamic acid ester, and liquid crystal alignment film |
| KR101864914B1 (en) * | 2011-03-31 | 2018-06-05 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent and liquid crystal alignment film using same |
| TWI622621B (en) * | 2013-03-25 | 2018-05-01 | Nissan Chemical Ind Ltd | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN106769886A (en) * | 2017-01-12 | 2017-05-31 | 薛永富 | A kind of liquid transparency fully-automated synthesis method |
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