Materials for aligning liquid crystals

• US 5,965,691 A
• Filed: 07/01/1997
• Issued: 10/12/1999
• Est. Priority Date: 03/29/1996
• Status: Expired due to Fees

• Current Assignee: Elsicon Incorporated
• Original Assignee: Elsicon Incorporated
• Inventors: Gibbons, Wayne M., Shannon, Paul J., Sun, Shao-Tang
• Primary Examiner(s): Truong, Duc
• Application Number:
  US08/886,560
• Time in Patent Office: 833 Days
• Field of Search: 528/353, 528/125, 528/128, 528/172, 528/173, 528/185, 528/188, 528/220, 528/229, 528/350, 349/123, 359/900, 428/1, 428/473.5
• 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 73/1042 Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• CPC Class Codes: C08G 73/1085 Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
• CPC Class Codes: C09K 2323/02 Alignment layer characterised by chemical composition
• CPC Class Codes: C09K 2323/025 Polyamide
• CPC Class Codes: C09K 2323/027 Polyimide
• CPC Class Codes: G02F 1/133723 Polyimide, polyamide-imide
• CPC Class Codes: G02F 1/133742 for homeotropic alignment
• CPC Class Codes: G02F 1/133753 with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
• CPC Class Codes: G02F 1/133788 by light irradiation, e.g. linearly polarised light photo-polymerisation
• CPC Class Codes: Y10S 359/90 Methods
• CPC Class Codes: Y10T 428/31721 Of polyimide

Abstract

A process for aligning liquid crystals adjacent to a surface of an optical alignment layer comprising: exposing at least one optical alignment layer, comprising anisotropically absorbing molecules, 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 a liquid crystal medium at an angle + and - with respect to the direction of the polarization of the incident light beam and along the surface of the optical alignment layer; and applying a liquid crystal medium to said optical alignment layer; wherein said anisotropically absorbing molecules consist essentially of diaryl ketones, is described. The invention also is directed to a liquid crystal optical storage medium, a liquid crystal display element, and a liquid crystal diffractive optical element made by the process of the invention and to novel polyimide compositions that are useful as optical alignment layers in the process of the invention.

Claims

1. A composition for generating alignment of liquid crystals, consisting essentially of at least one copolyimide of at least one diaryl ketone tetacarboxylic dianhydride and at least three diamines, consisting essentially of at least three structural elements of the formula IIa ##STR39## wherein Y is a divalent radical selected from the formulas IIIa and IVa ##STR40## wherein Z and Z₁ are selected, independently, from the group consisting of --S--, --SO₂ --, --O--, --CH₂ CH₂ --, --CH₂ --, --NR--, --C(CF₃)₂ --, --C(O)-- and a covalent bond, wherein R is a C₁ -C₄ hydrocarbon chain;

X₂ is independently selected from --R₃, --OR₃, --SR₃, --N(R₄)R₃ ;

wherein R₃ is selected from C₁ -C₃ perfluorinated alkyl chain and partially fluorinated alkyl chain and R₄ is independently selected from R₃ and H;

X₃ is independently selected from X₂ and H;

X is independently selected from the group consisting of H, Cl, F, and Br; and

m is 1 or 0.

2. A composition according to claim 1 wherein X₂ is --CF₃.

3. A composition according to claim 1 wherein said at least three diamines are selected from the group consisting of 2-(trifluoromethyl)-1,4-benzenediamine, 5-(trifluoromethyl)-1,3-benzenediamine, 2,2'"'"'-bis(trifluoromethyl)benzidene, 3,3'"'"'-bis(trifluoromethyl)benzidene, and 2,2'"'"'-bis(trifluoromethoxy)benzidene.

4. A composition according to claim 1 wherein the diaryl ketone tetracarboxylic dianhydride consists essentially of 3,3'"'"',4,4'"'"'-benzophenonetetracarboxylic dianhydride.

5. A composition for generating alignment of liquid crystals, consisting essentially of a polyimide polymer that is a copolyimide of at least one diaryl ketone tetracarboxylic dianhydride and at least two diamines, consisting essentially of at least one structural element of the formula IIa ##STR41## wherein Y is a divalent radical selected from the formulas IIIa and IVa ##STR42## and at least one structural element of formula VII ##STR43## wherein Z and Z₁ are selected, independently, from the group consisting of --S--, --SO₂ --, --O--, --CH₂ CH₂, --CH₂ --, --NR--,--C(CF₃)₂ --, --C(O)-- and a covalent bond, wherein R is a C₁ -C₄ hydrocarbon chain;

X₂ is independently selected from --R₃, --OR₃, --SR₃, --N(R₄)R₃, wherein R₃ is selected from C₁ -C₃ perfluorinated alkyl chain and partially fluorinated alkyl chain and R₄ is independently selected from R₃ and H;

X₃ is independently selected from X₂ and H;

X is independently selected from the group consisting of H, Cl, F, and Br; and

m is 1 or 0; and

the copolyimide consists of about from 99 to 1 mol % of at least one structural element of formula IIa and about from 1 to 99 mol % of at least one structural element of formula VII.

6. A composition of claim 5 wherein one diamine, from which structural element VII is derived, is 4,4'"'"'-diaminobenzophenone.

7. A composition of claim 5 wherein at least one diaryl ketone tetracarboxylic dianhydride is 3,3'"'"',4,4'"'"'-benzophenonetetracarboxylic dianhydride.

8. A composition for generating alignment of liquid crystals, consisting essentially of a polyimide polymer that is a copolyimide of at least one diaryl ketone tetracarboxylic dianhydride, at least one alicyclic tetracarboxylic dianhydride and at least one diamine, consisting essentially of at least two structural elements of the formula IIa and Va ##STR44## wherein Y is a divalent radical selected from the formulas IIIa and IVa ##STR45## wherein Z and Z₁ are independently selected from the group consisting of --S--, --SO₂, --O--, --CH₂ CH₂ --, --CH₂ --, --NR--, --C(CF₃)₂ --, --C(O)-- and a covalent bond, wherein R is a C₁ -C₄ hydrocarbon chain;

X₂ is independently selected from --R₃, --OR₃, --SR₃, --N(R₄)R₃, wherein R₃ is selected from C₁ -C₃ perfluorinated alkyl chain and partially fluorinated alkyl chain and R₄ is independently selected from R₃ and H;

X₃ is independently selected from X₂ and H;

X is independently selected from the group consisting of H, Cl, F, and Br;

m is 1 or 0;

P is a tetravalent radical derived from said alicyclic tetracarboxylic dianhydride; and

the copolyimide comprises 95 to 20 mol % of at least one structural element of formula IIa and 5 to 80 mol % of at least one structural element of formula Va.

9. A composition of claim 8 wherein the alicyclic tetracarboxylic dianhydride is selected from the group consisting of 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxycyclopentaneacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

10. A compostion of claim 8 wherein the diaryl ketone tetracarboxylic dianhydride is 3,3'"'"',4,4'"'"'-benzophenonetetracarboxylic dianhydride.

14. A composition of claim 11 wherein the polyimide polymer is a copolyimide additionally including at least one diaryl ketone tetracarboxylic dianhydride, consisting essentially of, additionally, at least one structural element of formula VII ##STR47## wherein Z is selected from the group consisting of --S--, --SO₂ --, --O--, --CH₂ CH₂ --, --CH₂ --, --NR--, --C(CF₃)₂ --, --C(O)-- and a covalent bond, wherein R is a C₁ -C₄ hydrocarbon chain;

m is 1 or 0; and

X is as defined in claim 10.

15. A composition of claim 14 wherein the diaryl ketone tetracarboxylic dianhydride is 3,3'"'"',4,4'"'"'-benzoplenonetetracarboxylic dianhydride.

16. A composition of claim 14 wherein the copolyimide consists essentially of about from 5 to 99.9 mol % of at least one structural element of formula VIII and about from 95 to 0.1 mol % of at least one structural element of formula VII.

17. A composition of claim 11 wherein the copolyimide further comprises the reaction product of 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and consists essentially of, additionally, at least one structural element of formula IX ##STR48## wherein X is as defined in claim 10.

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

19. A composition of claim 18 wherein at least one diaminobenzophenone from which structural element VIII is derived is 4,4'"'"'-diaminobenzophenone.

20. A composition of claim 17 wherein the copolyimide consists essentially of about from 0.1 to 99 mol % of at least one structural element of formula IX and about from 99.9 to 1 mol % of at least one structural element of formula VIII.

11. A composition for generating alignment of liquid crystals, consisting essentially of a polyimide polymer of at least one diaminobenzophenone and at least one alicyclic tetracarboxylic dianhydride, consisting essentially of at least one structural element of the formula VIII ##STR46## wherein P is a tetravalent radical derived from said alicyclic tetracarboxylic dianhydride;

and X is independently selected from the group consisting of H, Cl F, and Br.

12. A composition of claim 11 wherein said alicyclic tetacarboxylic dianhydride is selected from the group consisting of 5-(2,5-dioxotetrahydro)-3-methyl-3-cyclohexylene-1,2-dicarboxylic anhydride, 2,3,5-tricarboxycyclopentaneacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

13. A composition of claim 11 wherein at least one diaminobenzophenone from which structural element VIII is derived is 4,4'"'"'-diaminobenzophenone.