Polyimide precursor, and liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element having the same
A technology of polyimide precursor and liquid crystal alignment agent, which is applied in liquid crystal materials, organic chemistry, instruments, etc., and can solve the problems of lower reliability, precipitation, and lower reliability of liquid crystal display components
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[0301] The present invention will be further specifically described below using examples, but the present invention is not limited by these examples.
[0302] In addition, the abbreviations and structures of the following compounds, and the measuring method of each characteristic are as follows.
[0303] (solvent)
[0304] DMF: N,N-Dimethylformamide
[0305] THF: Tetrahydrofuran
[0306] NMP: N-methyl-2-pyrrolidone
[0307] BCS: Butyl Cellosolve
[0308] (diamine)
[0309] DA-A: 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropan-1-one
[0310] DA-1: 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropan-1-one
[0311] DA-2: 4-(4-(4-heptylcyclohexyl)phenoxy)benzene-1,3-diamine
[0312] 3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide
[0313] (acid dianhydride)
[0314] BODA: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride
[0315] CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride
[0316] (additive)
[0317] 3AMP: 3-pyri...
Synthetic example 1
[0353] Aromatic diamine compound (DA-A): 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-methoxy-2-methylpropane- Synthesis of 1-keto
[0354] The aromatic diamine compound (DA-A) was synthesized according to the 5-step route shown below. In addition, an aromatic diamine compound (DA-A) corresponds to the said specific diamine compound.
[0355] Step 1: 2-Hydroxy-2-methyl-1-(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)propan-1-one Synthesis of (DA-A-1)
[0356]
[0357] Dissolve IRGACURE 2959 (2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 50.0 g, 223 mmol) in THF (200 g), add p-toluenesulfonate Acid monohydrate (0.424g, 2.23mmol) was added dropwise to 3,4-dihydro-2H-pyran (23.4g, 279mmol) over 10 minutes, and reacted at room temperature for 3 hours. Then, the reaction solution was filtered, and the filtrate was concentrated to obtain 2-hydroxy-2-methyl-1-(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy yl)phenyl)propan-1-one as a crude product (green liqu...
Embodiment 1 and 2
[0376]
[0377] BODA (10.01g, 40.0mmol), 3AMPDA (4.85g, 20.0mmol), DA-A (13.78g, 40.0mmol), DA-2 (15.22g, 40.0mmol) were dissolved in NMP (166.2g), in After reacting at 60 degreeC for 5 hours, CBDA (11.57g, 59.0mmol) and NMP (55.4g) were added, it was made to react at 40 degreeC for 10 hours, and the polyamic-acid solution was obtained.
[0378] After adding NMP to this polyamic-acid solution (250g) and diluting to 6.5 mass %, the acetic anhydride (45.9g) and pyridine (14.2g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 3 hours. This reaction solution was poured into methanol (3300 ml), and the obtained precipitate was collected by filtration. This deposit was wash|cleaned with methanol, it dried under reduced pressure at 100 degreeC, and the polyimide powder (A) was obtained. The imidization rate of this polyimide was 72%, the number average molecular weight was 14000, and the weight average molecular weight was 38000.
[0379] NMP (44.0...
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