Process and materials for inducing pre-tilt in liquid crystals and liquid crystal displays

• US 5,817,743 A
• Filed: 05/14/1996
• Issued: 10/06/1998
• Est. Priority Date: 03/29/1996
• Status: Expired due to Fees

• Current Assignee: Elsicon Incorporated
• Original Assignee: Alliant Techsystems Incorporated (Northrop Grumman Corporation)
• Inventors: Gibbons, Wayne M., Shannon, Paul J., Sun, Shao-Tang
• Primary Examiner(s): HAMPTON HIGHTOWER, PATRICIA
• Application Number:
  US08/645,824
• Time in Patent Office: 875 Days
• Field of Search: 528/353, 428/1, 428/473.5, 350/341, 350/349, 350/350 S, 350/351, 350/346, 350/345, 350/350 R, 359/44.9
• US Class Current: 528/353
• CPC Class Codes: C08G 73/10 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08G 73/1039 comprising halogen-containing substituents
• CPC Class Codes: C08G 73/1085 Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
• CPC Class Codes: C09K 2323/031 Polarizer or dye
• CPC Class Codes: G02F 1/133723 Polyimide, polyamide-imide
• CPC Class Codes: G02F 1/133788 by light irradiation, e.g. linearly polarised light photo-polymerisation
• CPC Class Codes: Y10T 428/31721 Of polyimide

Abstract

A process for inducing pre-tilt in alignment of a liquid crystal medium comprising exposing at least one optical alignment layer, comprising anisotropically absorbing molecules and hydrophobic moieties, to polarized light; the polarized light having a wavelength within the absorption band of said anisotropically absorbing molecules; wherein the exposed anisotropically absorbing molecules induce alignment of the liquid crystal medium at an angle + and -θ with respect to the direction of the polarization of the incident light beam and along the surface of the optical alignment layer, and induce a pre-tilt at an angle Φ with respect to the surface of the optical alignment layer and applying a liquid crystal medium to said optical alignment layer, is described. The invention also is directed to liquid crystal display elements made by the process of the invention and to novel polyimide compositions that are useful as optical alignment layers in the invention.

Claims

1. A process for inducing pre-tilt in alignment of a liquid crystal medium adjacent to a surface of an optical alignment layer comprising;

(a) exposing at least one optical alignment layer, comprising anisotropically absorbing molecules and hydrophobic moieties, to polarized light, the polarized light having a wavelength within the absorption band of said anisotropically absorbing molecules;

wherein the exposed anisotropically absorbing molecules induce alignment of the liquid crystal medium at an angle + and -θ

with respect to the direction of the polarization of the incident light beam and along the surface of the optical alignment layer, and induce a pre-tilt at an angle Φ

with respect to the surface of the optical alignment layer;

(b) applying the liquid crystal medium to the optical alignment layer, the medium having an isotropic point; and

thereafter

(c) heating the liquid crystal medium above its isotropic point; and

(d) cooling the liquid crystal medium below its isotropic point.

2. A process of claim 1 wherein the exposing comprises at least two exposures to polarized light.

3. A process of claim 1 comprising exposing at least one optical alignment layer to polarized light at an oblique angle of incidence.

4. A process of claim 3 further comprising exposing the optical alignment layer to polarized light at a second angle of incidence.

5. A process of claim 4 wherein the polarized light used in the exposure at an oblique angle of incidence and a second angle of incidence has different directions of polarization.

6. A process of claim 1 wherein the liquid crystal medium is heated at a temperature about from 0.01°

to 60°

C. above the isotropic point of the liquid crystal medium.

7. A process of claim 6 comprising heating the liquid crystal medium for about from 1 second to 8 hours.

8. A process of claim 6 comprising cooling tile liquid crystal medium at a rate of about from 1000°

to 0.01°

C./min.

9. A process of claim 8 comprising cooling the liquid crystal medium for a period of about from 1 second to 8 hours.

10. A process of claim 1 wherein the anisotropically absorbing molecules and hydrophobic moieties are covalently bonded to a polymer.

11. A process of claim 1 wherein the anisotropically absorbing molecules are nonbonded solutes dissolved in a hydrophobic polymer.

12. A process of claim 10 wherein the polymer comprises a polyimide polymer.

13. A process of claim 12 wherein the polyimide polymer is a reaction product of at least one tetracarboxylic dianhydride and at least one hydrophobic diamine, which comprises at least one structural element of the formula I ##STR43## wherein Y is a divalent radical selected from the formulas II and III ##STR44## wherein Z is selected from tile group consisting of --S--, --O--, --SO₂ --, --CH₂ --, --C(CF₃)₂ --, --C(O)--, --CH₂ CH₂ --, --NR-- and a covalent bond wherein R is a C₁ -C₄ hydrocarbon chain;

X is independently selected from R₁, --O--R₁, --S--R₁, --N(R₂)--R₁ ;

wherein R₁ is independently selected from C₄ -C₂₀ perfluorinated alkyl chain, C₄ -C₂₀ partially fluorinated alkyl chain, and C₁₀ -C₂₀ hydrocarbon chain;

X₁ is independently selected from X and H;

R₂ is independently selected from H, C₁ -C₉ hydrocarbon chain and R₁ ; and

wherein M is a tetravalent organic radical derived from said tetracarboxylic dianhydride containing at least two carbon atoms, no more than two carbonyl groups of the dianhydride being attached to any one carbon atom of the tetravalent radical.

14. A process of claim 13 wherein the polyimide polymer is a copolyimide which additionally comprises at least one structural element of formula Ia ##STR45## wherein Y₁ is a divalent organic radical having at least two carbon atoms other than Y;

M is as defined in claim 13, and wherein the ratio of structural elements of formula I and Ia are 1;

99 to 99;

1.

15. A process of claim 13 wherein the tetracarboxylic dianhydride is a diaryl ketone tetracarboxylic dianhydride and said structural element of the formula I is formula IV ##STR46## wherein X₂ is independently selected from the group consisting of H, CL, F, Br, R₃ and R₃ O--, wherein R₃ is independently selected from C₁ -C₃ perflourinated alkyl chain, C₁ -C₃ partially flourinated alkyl chain and C₁ -C₈ hydrocarbon chain;

m is 1 or 0; and

Z and Y are as defined in claim 13.

16. A process of claim 13 wherein at least one tetracarboxylic dianhydride is an alicyclic tetracarboxylic dianhydride.

17. A process of claim 15 wherein the polyimide polymer is a copolymer, and additionally includes an alicyclic tetracarboxylic dianhydride, which further comprises the structural element of formula V ##STR47## wherein P is a tetravalent organic radical derived from said alicyclic tetracarboxylic dianhydride containing at least four carbon atoms, no more than one carbonyl group of the dianhydride being attached to any one carbon atom of the tetravalent radical;

Y is as defined in claim 13.

18. A process of claim 17 wherein the copolymer comprises a ratio of structural elements of formulas IV and V of 1:

10 to 99;

1.

19. A process of claim 17 wherein the alicyclic tetracarboxylic dianhydride is selected from 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxycyclopentaneacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride and cyclobutanetetracarboxylic acid dianhydride.

20. A process of claim 15 wherein the diaryl ketone tetracarboxylic anhydride is 3,3'"'"',4,4'"'"'-benzophenonetetracarboxylic dianhydride.

21. A process of claim 13 wherein the polyimide polymer is a copolyimide which additionally comprises at least one structural element of formula VI ##STR48## wherein X₂ is independently selected from the group consisting of H, CL, F, Br, R₃ and R₃ O--, wherein R₃ is independently selected from C₁ -C₃ perflourinated alkyl chain, C₁ -C₃ partially flourinated alkyl chain and C₁ -C₈ hydrocarbon chain;

and M is as described in claim 13.

22. A process of claim 13 wherein the hydrophobic diamine is selected from the group consisting of 4-(1H,1H-pentadecafluoro-1-octyloxy)-1,3-benzenediamine, 4-(1H,1H,11H-eicosafluoro-1-undecyloxy)-1,3-benzenediamine, 4-(1-octadecyloxy)-1,3-benzenediamine, 4-(1-hexadecyl)-1,3-benzenediamine and 2-(1-octadecyloxy)-1,4-benzenediamine.

23. A process of claim 1 wherein the anisotropically absorbing molecules are selected from the group arylazo, poly(arylazo), stilbene and diaryl ketone derivatives.

24. A process of claim 1 wherein the anisotropically absorbing molecules are selected from the group arylazo, stilbene and diaryl ketone derivatives having absorbance maxima between 150 and 400 nm.

25. A process of claim 1 wherein the anisotropically absorbing molecules are selected from the group consisting of 4,4'"'"'-diaminostilbene, the 2,4-diaminophenylhydrazones of benzophenone, 4,4'"'"'-diaminobenzophenone, and 3,3'"'"'-bis(trifluoromethyl)benzophenone and diazodiamine A.

26. A process of claim 1 wherein the anisotropically absorbing molecules are selected from the group consisting of benzophenone, 4,4'"'"'-bis(trifluoromethyl)benzophenone, 3,4'"'"'-bis(trifluoromethyl)benzophenone, 3,3'"'"'-bis(trifluoromethyl)benzophenone;

and phenylhydrazones of benzophenone, 4,4'"'"'-bis(trifluoromethyl)benzophenone, 3,4'"'"'-bis(trifluoromethyl)benzophenone; and

3,3'"'"'-bis(trifluoromethyl)benzophenone.

27. A process of claim 1 wherein the polarized light is from a laser.

28. A process of claim 1 wherein the polarized light is from a source selected from the group:

mercury arc, xenon deuterium, and quartz tungsten halogen lamp, and black lights;

in combination with a polarizer.

29. A process of claim 1 wherein the polarized light is unpolarized at its source and that is incident upon the optical alignment layer at an oblique angle of incidence.

30. A process of claim 1 wherein the exposing is performed in a scanning mode.

31. A process of claim 1 wherein the exposing comprises delivery of 0.001 to 2000 J/cm², within the absorption band of the anisotropically absorbing molecules, to said optical alignment layer.

32. A process of claim 1 wherein the exposing is a two step process of:

exposing at least one optical alignment layer to polarized light at a normal incidence, and

exposing said optical alignment layer to polarized light at an oblique incidence.

33. A process of claim 1 wherein said exposing is a two step process of:

exposing said optical alignment layer to polarized light of a first direction of linear polarization of the incident light, and

exposing said optical alignment layer to polarized light of a second direction of linear polarization of the incident light.

34. A process of claim 1 wherein the exposing is a two step process of:

exposing said optical alignment layer to polarized light of a first direction of linear polarization of the incident light, and

exposing said optical alignment layer to polarized light of second direction of linear polarization of the incident light, at an oblique incidence.

35. A process of claim 1 wherein the polarized light has one or more wavelengths of about from 150 to 800 nm.

36. A process of claim 1 wherein the polarized light has one or more wavelengths of about from 150 to 400 nm.

37. A process of claim 1 wherein the polarized light has one or more wavelengths of about from 300 to 400 nm.

38. A process of claim 1 wherein the applying a liquid crystal medium comprises capillary filling a cell.

39. A process of claim 1 wherein the applying a liquid crystal to medium comprises casting of said liquid crystal medium onto an optical alignment layer.

40. A process of claim 1 wherein the liquid crystal medium is selected from the group consisting of nematic liquid crystals, ferroelectric liquid crystals, polymerizable nematic liquid crystals and nematic liquid crystalline polymers.

41. A process of claim 1 wherein the liquid crystal medium is selected from the group consisting of nematic liquid crystals and polymerizable nematic liquid crystals.

42. A process of claim 41 wherein the nematic liquid crystals are selected from the group consisting of 4-cyano-4'"'"'-alkylbiphenyls, 4-alkyl-(4'"'"'-cyanophenyl)cyclohexanes and superflourinated liquid crystal mixtures.

43. A process of claim 1 wherein the alignment of the liquid crystal medium is at an angle + and -θ

, wherein θ

is equal to 90°

.

44. A process of claim 1 wherein the pre-tilt at an angle Φ

is about from 1°

to 30°

.

45. A process of claim 1 wherein the pre-tilt at an angle Φ

is about from 2°

to 15°

.

46. A liquid crystal display element derived from the process of claim 1.

47. A process of claim 2 wherein the exposures are simultaneous.

48. A process of claim 2 wherein the exposures are sequential.