Composition of organic compounds, optical film and method of production thereof

Abstract

A composition includes at least one organic compound of a first type of the general formula I and at least one organic compound of a second type of the general structural formula II, wherein Core in formula I is a conjugated organic unit capable of forming a rigid rod-like macromolecule, Gk is a set of ionogenic side-groups providing solubility of the organic compound of the first type in a solvent and give rigidity to the rod-like macromolecule; and wherein Sys in formula II is an at least partially conjugated substantially planar polycyclic molecular system capable of forming board-like supramolecules via π-π-interaction, and X, Y, Z and Q are substituents. The composition is capable of forming a lyotropic liquid crystal solution, which can form a solid retardation layer of biaxial type substantially transparent to electromagnetic radiation in the visible spectral range. The type and degree of biaxiality of the said optical retardation layer is controlled by a molar ratio of the organic compounds of the first and the second type in the composition. An optical film comprising a solid retardation layer formed of the composition, a method of producing the optical film, and a vertical alignment liquid crystal display using said retardation layer are also provided.

What is claimed is: 
     
       1. A composition comprising:
 at least one organic compound of a first type or its salt, and 
 at least one organic compound of a second type, 
 wherein the organic compound of the first type has the general structural formula I 
 
       
         
           
           
               
               
           
         
         where Core is a conjugated organic unit capable of forming a polymeric rigid rod-like macromolecule,
 n is a number of the conjugated organic units in the polymeric rigid rod-like macromolecule, 
 G k  is a set of ionogenic side-groups, and 
 k is a number of the side-groups in the set G k ; 
 
         wherein the ionogenic side-groups and the number k provide solubility of the organic compound of the first type in a solvent and give rigidity to the rod-like macromolecule; the number n provides molecule anisotropy that promotes self-assembling of macromolecules in a solution of the organic compound or its salt, 
         wherein the number k is equal to 0, 1, 2, 3, 4, 5, 6, 7, or 8, and the number n is an integer in the range from 10 to 10000; 
         wherein the rod-like macromolecule has a polymeric main rigid-chain, 
         wherein at least one rigid-core polymer is a copolymer having conjugated organic unit has the general structural formula IV
   [-(Core1)-S1-(Core2)-S2-] n-t [-(Core3)-S3-[(Core4)-S4-] j ] t    (IV)
 
 
         wherein Core1, Core2, Core3 and Core4 are conjugated organic components, spacers S1, S2, S3 and S4 are selected independently from the group consisting of —CO—NH—, —NH—CO—, —O—NH—, linear and branched (C 1 -C 4 )alkylenes, linear and branched (C 1 -C 4 )alkenylenes, (C 2 -C 20 )polyethylene glycols, —O—CH 2 —, —CH 2 —O—, —CH═CH—, —CH═CH—COO—, —OOC—CH═CH—, —CO—CH 2 —, —OCO—O—, —OCO—, —C≡C—, —CO—S—, —S—, —S—CO—, —O—, —NH—, —N(CH 3 )—, n is an integer in the range from 10 to 10000, t is an integer in the range from 1 to n-1 and j is 0 or 1, and wherein the conjugated organic component Core3 differs from Core1or Core 2 Core1 or Core2, or Core4 differs from Core1 or Core2; 
         wherein the conjugated organic components Core1, Core2, Core3 and Core4 comprising comprise ionogenic groups side-groups G and are selected from the structures based on benzene ring and naphthalene and having general formula 1 to and 2: 
       
       
         
           
           
               
               
           
         
         wherein the ionogenic side-groups G are selected from the group consisting of —COOH, —S 0   3 H —SO 3 H, and —H 2 PO 3 , k is equal 0, 1 or 2, p is equal to 1, 2 or 3; and 
         wherein the organic compound of the second type has the general structural formula II 
       
       
         
           
           
               
               
           
         
         where Sys is an at least partially conjugated substantially planar cyclic or polycyclic molecular system;
 X, Y, Z, and Q are substituents; 
 substituent X is a carboxylic group —COOH, m is 0, 1, 2, 3 or 4; 
 substituent Y is a sulfonic group —SO 3 H, h is 0, 1, 2, 3 or 4; 
 substituent Z is a carboxamide —CONH 2 , p is 0, 1, 2, 3 or 4; 
 substituent Q is a sulfonamide —SO 2 NH 2 , v is 0, 1, 2, 3 or 4; 
 
         wherein the organic compound of the second type is capable of forming board-like supramolecules via π-π-interaction, and 
         wherein the composition is capable of forming a lyotropic liquid crystal solution, and said solution is capable of forming a solid retardation layer substantially transparent to electromagnetic radiation in the visible spectral range; 
         wherein Sys is selected from the structures with general formula 14 to 20: 
       
       
         
           
           
               
               
           
         
       
     
     
       2. A composition according to  claim 1 , wherein the type and degree of biaxiality of the solid retardation layer is controlled by a molar ratio of the organic compounds of the first and the second type in the composition. 
     
     
       3. A composition according to  claim 1 , wherein the rigid rod-like macromolecule has a copolymeric main rigid-chain, and wherein at least one conjugated organic unit is different from the others. 
     
     
       4. A composition according to  claim 1 , wherein the organic compound of the first type is selected from structures 3 to 13, wherein the ionogenic side-group G is a sulfonic group —SO 3 H, and k is equal to 0, 1 or 2: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       5. A composition according to  claim 1 , wherein the organic compound of the first type further comprises additional side-groups independently selected from the group consisting of linear and branched (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, and (C 2 -C 20 )alkinyl (C 2 -C 20 )alkynyl. 
     
     
       6. A composition according to  claim 5 , wherein at least one of the additional side-groups is connected with the Core via a bridging group A selected from the group consisting of —C(O)—, —C(O)O—, —C(O)—NH—, —(SO 2 )NH—, —O—, —CH 2 O—, —NH—, >N—, and any combination thereof.  
     
     
       7. A composition according to  claim 1 , wherein the salt of the organic compound of the first type is selected from the group consisting of ammonium and alkali-metal salts. 
     
     
       8. A composition according to  claim 1 , further comprising inorganic compounds which are selected from the group consisting of hydroxides and salts of alkali metals. 
     
     
       9. An optical film comprising:
 a substrate having front and rear surfaces, and 
 at least one solid optical retardation layer on the front surface of the substrate, 
 wherein the solid optical retardation layer comprises 
 at least one organic compound of a first type or its salt, and 
 at least one organic compound of a second type,
 wherein the organic compound of the first type has the general structural formula I 
 
 
       
         
           
           
               
               
           
         
         
           where Core is a conjugated organic unit capable of forming a polymeric rigid rod-like macromolecule,
 n is a number of the conjugated organic units in the polymeric rigid rod-like macromolecule, 
 G k  is a set of ionogenic side-groups, and 
 k is a number of the side-groups in the set G k ; 
 
           wherein the ionogenic side-groups and the number k provide solubility of the organic compound of the first type in a solvent and give rigidity to the rod-like macromolecule; 
         
         the number n provides molecule anisotropy that promotes self-assembling of macromolecules in a solution of the organic compound or its salt, 
         wherein the number k is equal to 0, 1, 2, 3, 4, 5, 6, 7, or 8, and the number n is an integer in the range from 10 to 10000; 
         wherein the rod-like macromolecule has a polymeric main rigid-chain, 
         wherein at least one rigid-core polymer is a copolymer having conjugated organic unit has the general structural formula IV
   [(Core1)-S1-(Core2)-S2-] n-t [-(Core3)-S3-[(Core4)-S4-] j ] t    (IV)
 
 
         wherein Core1, Core2, Core3 and Core4 are conjugated organic components, spacers S1, S2, S3 and S4 are selected independently from the group consisting of —CO—NH—, —NH—CO—, —O—NH—, linear and branched (C 1 -C 4 )alkylenes, linear and branched (C 1 -C 4 )alkenylenes, (C 2 -C 20 )polyethylene glycols, —O—CH 2 —, —CH 2 —O—, —CH═CH—, —CH═CH—COO—, —OOC—CH═CH—, —CO—CH 2 —, —OCO—O—, —OCO—, —C≡C—, —CO—S—, —S—, —S—CO—, —O—, —NH—, —N(CH 3 )—, n is an integer in the range from 10 to 10000, t is an integer in the range from 1 to n-1 and j is 0 or 1, and wherein the conjugated organic component Core3 differs from Core1or Core 2 Core1 or Core2, or Core4 differs from Core1 or Core2; 
         wherein the conjugated organic components Core1, Core2, Core3 and Core4 comprising comprise ionogenic groups side-groups G and are selected from the structures based on benzene ring and naphthalene and having general formula 1 to and 2: 
       
       
         
           
           
               
               
           
         
         
           wherein the ionogenic side-groups G are selected from the group consisting of —COOH, —SO 3 H, and —H 2 PO 3 , k is equal 0, 1 or 2, p is equal to 1, 2 or 3; and 
         
         wherein the organic compound of the second type has the general structural formula II 
       
       
         
           
           
               
               
           
         
         where Sys is an at least partially conjugated substantially planar cyclic or polycyclic molecular system;
 X, Y, Z, and Q are substituents; 
 substituent X is a carboxylic group —COOH, m is 0, 1, 2, 3 or 4; 
 substituent Y is a sulfonic group —SO 3 H, h is 0, 1, 2, 3 or 4; 
 substituent Z is a carboxamide —CONH 2 , p is 0, 1, 2, 3 or 4; 
 substituent Q is a sulfonamide —SO 2 NH 2 , v is 0, 1, 2, 3 or 4; 
 
         wherein the organic compound of the second type is capable of forming board-like supramolecules via π-π-interaction, and solid optical retardation layer substantially transparent to electromagnetic radiation in the visible spectral range; 
         wherein Sys is selected from the structures with general formula 14 to 20: 
       
       
         
           
           
               
               
           
         
       
     
     
       10. An optical film according to  claim 9 , wherein the type and degree of biaxiality of the said optical retardation layer is controlled by a molar ratio of the organic compounds of the first and the second type in the composition. 
     
     
       11. An optical film according to  claim 9 , wherein the rod-like macromolecule has a polymeric main rigid-chain, and wherein the conjugated organic units are the same. 
     
     
       12. An optical film according to  claim 9 , wherein the rigid rod-like macromolecule has a copolymeric main rigid-chain, and wherein at least one conjugated organic unit is different from the others. 
     
     
       13. An optical film according to  claim 9 , wherein the organic compound of the first type is selected from structures 3 to 13, wherein the ionogenic side-group G is sulfonic group —SO 3 H, and k is equal to 0, 1 or 2: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       14. An optical film according to  claim 9 , wherein the organic compound of the first type further comprises additional side-groups independently selected from the group consisting of linear and branched (C 1 -C 20 )alkyl, (C 2 -C 20 ) alkenyl, and (C 2 -C 20 )alkinyl (C 2 -C 20 )alkynyl. 
     
     
       15. A optical film according to  claim 14 , wherein at least one of the additional side-groups is connected with the Core via a bridging group A selected from the group consisting of —C(O)—, —C(O)O—, —C(O)—NH—, —(SO 2 )NH—, —O—, —CH 2 O—, —NH—, >N—, and any combination thereof. 
     
     
       16. An optical film according to  claim 9 , wherein the salt of the organic compound of the first type is selected from the group consisting of ammonium and alkali-metal salts. 
     
     
       17. An optical film according to  claim 9 , further comprising inorganic compounds which are selected from the group consisting of hydroxides and salts of alkali metals. 
     
     
       18. An optical film according to  claim 9 , wherein said solid retardation layer is generally a biaxial retardation layer possessing has two refractive indices (n x, and ny ) (n x  and n y ) corresponding to two mutually perpendicular directions in the plane of the substrate front surface and one refractive index (n z ) in the normal direction to the substrate front surface, and wherein the refractive indices obey the following condition: n x ≠n z ≠n y . 
     
     
       19. An optical film according to  claim 18 , wherein the refractive indices obey the following condition: n z <n y <n x . 
     
     
       20. An optical film according to  claim 18 , wherein the refractive indices obey the following condition: n x <n z <n y . 
     
     
       21. An optical film according to  claim 9 , wherein the substrate comprises a material is selected from the group consisting of a polymer and glass. 
     
     
       22. An optical film according to  claim 9 , wherein the substrate's front and rear surfaces are flat or curved or any combination thereof. 
     
     
       23. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, two polarizers, arranged one on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises at least one organic compound of a first type or its salt, and at least one organic compound of a second type, wherein the organic compound of the first type has the general structural formula I 
       
         
           
           
               
               
           
         
         where Core is a conjugated organic unit capable of forming a polymeric rigid rod-like macromolecule, n is a number of the conjugated organic units in the polymeric rigid rod-like macromolecule, G k  is a set of ionogenic side-groups, and k is a number of the side-groups in the set G k ; wherein the ionogenic side-groups and the number k provide solubility of the organic compound of the first type in a solvent and give rigidity to the rod-like macromolecule; the number n provides molecule anisotropy that promotes self-assembling of macromolecules in a solution of the organic compound or its salt, 
         wherein the number k is equal to 0, 1, 2, 3, 4, 5, 6, 7, or 8, and the number n is an integer in the range from 10 to 10000; 
         wherein the rod-like macromolecule has a polymeric main rigid-chain, 
         wherein at least one rigid-core polymer is a copolymer having conjugated organic unit has the general structural formula IV
   [-(Core1)-S1-(Core2)-S2-] n-t [-(Core3)-S3-[(Core4)-S4-] j ] t    (IV)
 
 
         wherein Core1, Core2, Core3 and Core4 are conjugated organic components, spacers S1, S2, S3 and S4 are selected independently from the group consisting of —CO—NH—, —NH—CO—, —O—NH—, linear and branched (C 1 -C 4 )alkylenes, linear and branched (C 1 -C 4 )alkenylenes, (C 2 -C 20 )polyethylene glycols, —O—CH 2 —, —CH 2 —O—, —CH═CH—, —CH═CH—COO—, —OOC—CH═CH—, —CO—CH 2 —, —OCO—O—, —OCO—, —C≡C—, —CO—S—, —S—, —S—CO—, —O—, —NH—, N(CH 3 )—, n is an integer in the range from 10 to 10000, t is an integer in the range from  1  to n-1 and j is 0 or 1, and 
         wherein the conjugated organic component Core3 differs from Core1 or Core 2 Core2, or Core4 differs from Core1 or Core2; 
         wherein the conjugated organic components Core1, Core2, Core3 and Core4 comprising comprise ionogenic groups side-groups G and are selected from the structures based on benzene ring and naphthalene and having general formula 1 to and 2: 
       
       
         
           
           
               
               
           
         
         wherein the ionogenic side-groups G are selected from the group consisting of —COOH, —SO 3 H, and —H 2 PO 3 , k is equal 0, 1 or 2, p is equal to 1, 2 or 3; and 
         wherein the organic compound of the second type has the general structural formula II 
       
       
         
           
           
               
               
           
         
         where Sys is an at least partially conjugated substantially planar cyclic or polycyclic molecular system; 
         X, Y, Z, and Q are substituents; 
         substituent X is a carboxylic group —COOH, m is 0, 1, 2, 3 or 4; 
         substituent Y is a sulfonic group —SO 3 H, h is 0, 1, 2, 3 or 4; 
         substituent Z is a carboxamide —CONH 2 , p is 0, 1, 2, 3 or 4; 
         substituent Q is a sulfonamide —SO 2 NH 2 , v is 0, 1, 2, 3 or 4; 
         wherein the organic compound of the second type is capable of forming board-like supramolecules via π-π-interaction, and wherein the composition is capable of forming a lyotropic liquid crystal solution, and said solution is capable of forming a solid biaxial retardation layer substantially transparent to electromagnetic radiation in the visible spectral range; 
         wherein Sys is selected from the structures with general formula 14 to 20: 
       
       
         
           
           
               
               
           
         
       
     
     
       24. A liquid crystal display according to  claim 23 , wherein the rod-like macromolecule has a polymeric main rigid-chain, and wherein the conjugated organic units are the same. 
     
     
       25. A liquid crystal display according to  claim 23 , wherein the rigid rod-like macromolecule has a copolymeric main rigid-chain, and wherein at least one conjugated organic unit is different from the others. 
     
     
       26. A liquid crystal display according to  claim 23 , wherein the organic compound of the first type is selected from structures 3 to 13, wherein the ionogenic side-group G a sulfonic group —SO 3 H, and k is equal to 0, 1 or 2: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       27. A liquid crystal display according to  claim 23 , wherein the organic compound of the first type further comprises additional side-groups independently selected from the group consisting of linear and branched (C 1 -C 20 )alkyl, (C 2 -C 20 ) alkenyl, and (C 2 -C 20 )alkinyl (C 2 -C 20 )alkynyl. 
     
     
       28. A liquid crystal display according to  claim 27 , wherein at least one of the additional side-groups is connected with the Core via a bridging group A selected from the group consisting of —C(O)—, —C(O)O—, —C(O)—NH—, —(SO 2 )NH—, —O—, —CH 2 O—, —NH—, >N—, and any combination thereof. 
     
     
       29. A liquid crystal display according to  claim 23 , wherein the salt of the organic compound of the first type is selected from the group consisting of ammonium and alkali-metal salts. 
     
     
       30. A liquid crystal display according to  claim 23 , further comprising inorganic compounds which are selected from the group consisting of hydroxides and salts of alkali metals. 
     
     
       31. A liquid crystal display according to  claim 23 , wherein the compensating structure comprises the single retardation layer which is characterized by two in-plane refractive indices (nf and ns) corresponding to a fast principal axis and a slow principal axis respectively, and one refractive index (nn) in the normal direction which obey the following conditions for electromagnetic radiation in the visible spectral range: ns>nf>nn. 
     
     
       32. A liquid crystal display according to  claim 23 , wherein at least one compensating structure is located between the liquid crystal cell and one of said polarizers. 
     
     
       33. A liquid crystal display according to  claim 23 , wherein at least one compensating structure is located inside the liquid crystal cell. 
     
     
       34. A liquid crystal display according to  claim 23 , comprising at least two compensating structures located on each side of the liquid crystal cell. 
     
     
       35. A liquid crystal display according to  claim 31 , further comprising an additional retardation layer which is characterized by two in-plane refractive indices (nf and ns) corresponding to a fast principal axis and a slow principal axis respectively, and one refractive index (nn) in the normal direction which obey the following conditions for electromagnetic radiation in the visible spectral range: ns=nf>nn. 
     
     
       36. A liquid crystal display according to  claim 23 , wherein at least one of the two polarizers comprises at least one retardation TAC-layer where TAC is triacetyl cellulose. 
     
     
       37. A composition comprising:
 (a) an organic compound of a first type or its salt, comprising structural formula I   
       
         
           
           
               
               
           
         
          wherein
 Core is a conjugated organic unit, and n is a number of conjugated organic units from 10 to 10000; 
 G k  is a set of ionogenic side-groups, and k is a number of side-groups in the set from 0 to 8; 
 Core has structural formula III
   -(Core1)-S1-(Core2)-S2-   (III)
 
 
 wherein
 Core1 and Core2 are conjugated organic components selected from structures of formula (1) and (2): 
 
 
       
       
         
           
           
               
               
           
         
         
           
             G are ionogenic side-groups selected from the group consisting of —COOH, —SO 3 H, and —H 2 PO 3 ; k is equal 0, 1 or 2; and p is equal to 1, 2 or 3; 
             S1 and S2 are spacers selected independently from the group consisting of —CO—NH—, —NH—CO—, —O—NH—, linear and branched (C 1 -C 4 )alkylenes, linear and branched (C 1 -C 4 )alkenylenes, (C 2 -C 20 )polyethylene glycols, —O—CH 2 —, —CH 2 —O—, —CH═CH—, —CH═CH—COO—, —OOC—CH═CH—, —CO—CH 2 —, —OCO—O—, —OCO—, —C≡C—, —CO—S—, —S—, —S—CO—, —O—, —NH—, and —N(CH 3 )— and 
           
         
         (b) an organic compound of a second type having structural formula II 
       
       
         
           
           
               
               
           
         
          wherein
 X, Y, Z, and Q are substituents, wherein X is —COOH, m is 0, 1, 2, 3 or 4; Y is —SO 3 H, h is 0, 1, 2, 3 or 4; Z is —CONH 2 , p is 0, 1, 2, 3 or 4; Q is —SO 2 NH 2 , v is 0, 1, 2, 3 or 4; and 
 Sys is selected from structures of formula 14 to 20: 
 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       38. The composition of claim 37, wherein the organic compound of the first type has a structure selected from any one of structures 3 to 13 or a salt of any one of structures 3 to 13: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       
        
       
     
     
       39. The composition of claim 37, wherein the organic compound of the first type has structure 3 or a salt of structure 3: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       40. The composition of claim 37, wherein the organic compound of the second type has structure 28: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       41. The composition of claim 37, wherein the organic compound of the first type has structure 3 
       
         
           
           
               
               
           
         
       
       and the compound of the second type has structure 28 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       42. An optical film comprising a substrate having front and rear surfaces and at least one solid optical retardation layer on the front surface of the substrate, wherein the solid optical retardation layer comprises a composition of claim 37.  
     
     
       43. An optical film comprising a substrate having front and rear surfaces and at least one solid optical retardation layer on the front surface of the substrate, wherein the solid optical retardation layer comprises a composition of claim 38.  
     
     
       44. An optical film comprising a substrate having front and rear surfaces and at least one solid optical retardation layer on the front surface of the substrate, wherein the solid optical retardation layer comprises a composition of claim 39.  
     
     
       45. An optical film comprising a substrate having front and rear surfaces and at least one solid optical retardation layer on the front surface of the substrate, wherein the solid optical retardation layer comprises a composition of claim 40.  
     
     
       46. An optical film comprising a substrate having front and rear surfaces and at least one solid optical retardation layer on the front surface of the substrate, wherein the solid optical retardation layer comprises a composition of claim 41.  
     
     
       47. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, a polarizer on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises a composition of claim 37.  
     
     
       48. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, a polarizer on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises a composition of claim 38.  
     
     
       49. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, a polarizer on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises a composition of claim 39.  
     
     
       50. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, a polarizer on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises a composition of claim 40.  
     
     
       51. A liquid crystal display comprising a vertical alignment mode liquid crystal cell, a polarizer on each side of the liquid crystal cell, and at least one compensating structure located between said polarizers, wherein the polarizers have transmission axes which are perpendicular to each other, and the compensating structure comprises at least one retardation layer, wherein the retardation layer comprises a composition of claim 41.