US 4,749,777 AGrant
Liquid Crystal Aligning Agent From Tetracarboxylic Acid Dianhydride, Diamine and Monoamine
Issue Date:1988-06-07
•11 Claims
Abstract
A liquid crystal aligning agent consisting essentially of a polyimide resin obtained by the polymerization of a diamine, a tetracarboxylic acid dianhydride and a monoamine of the formula: wherein R.sup.1 is a divalent organic group, R.sup.2 is an alkyl group having from 6 to 20 carbon atoms, and n is 0 or 1.
Metadata
Assignee
- Nissan Chemical Industries Ltd.
Inventors
- Noriaki Kohtoh
- Toyohiko Abe
- Hiroyoshi Fukuro
Application Information
Application Number:US 0605158
Filing Date:1987-06-11
Priority Date:1987-06-11
Art Unit:153
Classifications
IPC:
C08G 7310C08G 6904
Field of Search:
528351;182;126;352;353
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLE 1
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2.96 g (0.016 mol) of n-dodecylamine and 15.69 g (0.08 mol) of cyclobutanetetracarboxylic acid dianhydride are reacted in 433 g of N-methyl-2-pyrrolidone (hereinafter referred to simply as NMP) at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polymeric acid intermediate thus obtained was 0.69 dl/g (0.5 wt % NMP solution, 30.degree. C.).
This solution was diluted with NMP to a total solid content of 2% by weight, and then spin-coated at 3,500 rpm on a glass substrate provided with a transparent electrode, and then heat-treated at 170.degree. C. for 60 minutes to form a polyimide resin film having a thickness of from 1,000 to 1,500 .ANG.. The coated film was rubbed with a cloth.
A pair of such substrates were assembled with a spacer of 50 .mu.m interposed therebetween so that the coated films faced to each other with the respective rubbing directions arranged in an antiparallel relationship to each other. Then, liquid crystals (ZLI-2293, manufactured by Merk Company) were injected to obtain a homogeneous alignment cell.
This cell was rotated in a cross nikol, whereby brightness and darkness were distinctly observed, and excellent alignment in the direction of rubbing was confirmed.
With respect to this cell, the pretilt angle was measured by a magnet capacitance null method and was found to be 10.degree..
Example 2
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3.85 g (0.016 mol) of n-hexadecylamine and 15.69 g (0.08 mol) of cyclobutanetetracarboxylic acid dianhydride were reacted in 422 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.52 dl/g (0.5 wt % NMP solution, 30.degree. C.).
This solution was diluted with NMP to a total solid content of 2% by weight, and then a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 19.degree., and the alignment was excellent.
Example 3
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2.06 g (0.016 mol) of n-octylamine and 15.69 g (0.08 mol) of cyclobutanetetracarboxylic acid dianhydride was reacted in 422 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.62 dl/g (0.5 wt % NMP solution, 30.degree. C.).
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 4.5.degree., and the alignment was excellent.
Example 4
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4.18 g (0.016 mol) of 1-(p-aminophenyl)dodecane and 15.69 g (0.08 mol) of cyclobutanetetracarboxylic acid dianhydride was reacted in 445 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.51 dl/g (0.5 wt % NMP solution, 30.degree. C.)
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 10.5.degree., and the alignment was excellent.
Example 5
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 15.69 g (0.08 mol) of cyclobutane tetracarboxylic acid dianhydride was reacted in 445 g of NMP at room temperature for 4 hours, and then 4.62 g (0.016 mol) of 1-(p-aminophenyl)tetradecane was added thereto, and the mixture was stirred for further 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.47 dl/g (0.5 wt % NMP solution, 30.degree. C. )
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 12.5.degree. and the alignment was excellent.
Example 6
14.26 g (0.072 mol) of diaminodiphenylmethane, 3.85 g (0.016 mol) of n-hexadecylamine and 17.44 g (0.08 mol) of pyromellitic acid anhydride were reacted in 320 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.55 dl/g (0.5 wt % NMP solution, 30.degree. C.)
This solution was diluted with NMP to a total solid content of 2% by weight and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 7.6.degree., and the alignment was excellent.
Example 7
16.70 g (0.072 mol) of 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 3.85 g (0.016 mol) of n-hexadecylamine and 15.69 g (0.08 mol) of cyclobutane tetracarboxylic acid dianhydride were reacted in 326 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.48 dl/g (0.5 wt % NMP solution, 30.degree. C.)
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal melecules was 14.5.degree., and the alignment was excellent.
Comparative Example 1
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 15.69 g (0.08 mol) of cyclobutanetetracarboxylic acid dianhydride were reacted in 433 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.38 dl/g (0.5 wt % NMP solution, 30.degree. C.)
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1
The pretilt angle of the liquid crystal molecules was 2.7.degree..
Comparative Example 2
29.52 g (0.072 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 15.22 g (0.0776 mol) of cyclobutanetetracarboxylic acid dianhydride were reacted in 402.7 g of NMP at room temperature for 4 hours to obtain a polyamic acid intermediate solution.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.68 dl/g (0.5 wt % NMP solution, 30.degree. C.).
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 2.4.degree..
Comparative Example 3
A polyamic acid intermediate solution was prepared in the same manner as in Example 1 except that 1.17 g (0.016 mol) of n-butylamine was used instead of n-dodecylamine and 417 g of NMP was used as the solvent.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.46 dl/g (0.5 wt % NMP solution, 30.degree. C.).
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 2.9.degree..
Comparative Example 4
A polyamic acid intermediate solution was prepared in the same manner as in Example 1 except that 1.49 g (0.016 mol) of aniline was used instead of n-dodecylamine and 420 g of NMP was used as the solvent.
The reduced viscosity .eta.sp/c of the polyamic acid intermediate thus obtained was 0.64 dl/g (0.5 wt % NMP solution, 30.degree. C.)
This solution was diluted with NMP to a total solid content of 2% by weight, and a cell was prepared in the same manner as in Example 1.
The pretilt angle of the liquid crystal molecules was 2.9.degree..
Claims
We claim:
1. A liquid crystal aligning agent consisting essentially of a polyimide resin obtained by the polymerization of a diamine, a tetracarboxylic acid dianhydride and a monoamine of the formula: wherein R.sup.1 is a divalent organic group, R.sup.2 is an alkyl group having from 6 to 20 carbon atoms, and n is 0 or 1.
2. The liquid crystal aligning agent according to claim 1 wherein the polyimide resin is obtained by polymerizing a mol of a diamine, b mol of a tetracarboxylic dianhydride and c mol of a monoamine of the formula I in a relation to satisfy the following formulas:
3. The liquid crystal aligning agent according to claim 2, wherein the polymerization is conducted at a temperature of from -20.degree. to 400.degree. C.
4. The liquid crystal aligning agent according to claim 1, wherein the diamine is an aromatic diamine selected from the group consisting of p-phenylene diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, 2,2-diaminodiphenylpropane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-di(4-aminophenoxy)diphenylsulfone and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
5. The liquid crystal aligning agent according to claim 1, wherein the diamine is an alicyclic diamine selected from the group consisting of 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodicyclohexylsulfone and 4,4'-diaminodicyclohexyl ether.
6. The liquid crystal aligning agent according to claim 1, wherein the diamine is an aliphatic diamine selected from the group consisting of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane.
7. The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic acid dianhydride is an aromatic tetracarboxylic acid dianhydride selected from the group consisting of pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride and biphenyltetracarboxylic acid dianhydride.
8. The liquid cyrstal aligning agent according to claim 1, wherein the tetracarboxylic acid dianhydride is an alicyclic tetracarboxylic acid dianhydride selected from the group consisting of cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride and cyclohexanetetracarboxylic acid dianhydride.
9. The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic acid dianhydride is a butanetetracarboxylic acid dianhydride.
10. The liquid crystal aligning agent according to claim 1, wherein the monoamine is an aliphatic amine selected from the group consisting of n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-hexadecylamine, 1,3-dimethylbutylamine, 1,5-dimethylhexylamine and 2-ethylhexylamine.
11. The liquid crystal aligning agent according to claim 1, wherein the monoamine is an aromatic amine selected from the group consisting of p-aminophenylhexane, p-aminophenyloctane, p-aminophenyldodecane, p-aminophenyltetradecane, p-aminophenylhexadecane, p-aminophenoxyoctane, p-aminophenoxydodecane and p-aminophenoxyhexadecane.
Patent Citations (1)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3994567 | 1976-11-01 | Matsuo et al. |
Non-Patent Literature (1)
- Chemical Abstracts, vol. 99, 1983, p. 550, abstract no. 203665n, Columbus, Ohio, U.S.; & JP-A-57 133 432 (Canon K.K.) Aug. 18, 1982.