PHOTOALIGNING MATERIALS

Abstract

The present invention relates to a photoaligning compound of formula (I), to a process for the preparation of this compound, to a photoaligning composition, obtained by this process, to the use of said compositions as orienting layer for liquid crystals and in the construction of unstructured and structured optical elements and multi-layer systems, especially liquid crystal displays.

Claims

1. A compound of formula (I) ##STR00007## wherein, M.sup.1, M.sup.2 and M.sup.3 represent independently from each other an unsubstituted or substituted carbocyclic or heterocyclic aromatic or non-aromatic diamine group selected from a monocyclic ring of five or six atoms; two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, a tricyclic ring system of thirteen or fourteen atoms, and mono-, bi-, tricyclic rings, which are linked by a straight-chain or branched, substituted or unsubstituted C.sub.1-C.sub.20alkanediyl, which is unsubstituted or substituted by di-(C.sub.1-C.sub.20alkyl)amino, C.sub.1-C.sub.6alkyloxy, nitro, cyano and/or chlorine or fluorine; and wherein one or more C, CH, CH.sub.2 group may independently be replaced by a linking group; D.sup.1, D.sup.2 and D.sup.3 represent independently from each other an unsubstituted or substituted aliphatic, alicyclic group or carbocyclic or heterocyclic aromatic group substituted with at least two carboxylic acid groups, or activated carboxylic groups, or anhydride groups; m.sup.1, m.sup.2 or m.sup.3 represent independently from each other molar fractions of the comonomers with 0<m.sup.1<1, 0m.sup.20, 7 and 0m.sup.3<1; S.sup.1 and S.sup.2 represent independently from each other a spacer unit, E.sup.1 and E.sup.2 represent independently from each other an aromatic group, an oxygen atom, a sulphur atom, NH, N(C.sub.1-C.sub.6alkyl)-, CR.sup.4R.sup.5, wherein R.sup.4 and R.sup.5 are independently from each other hydrogen or a cyclic, straight-chain or branched, substituted or unsubstituted C.sub.1-C.sub.30alkyl, wherein one or more C, CH, CH.sub.2 group may be independently from each other replaced by a linking group, and with the proviso that at least one of R.sup.4 and R.sup.5 is not hydrogen; A represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group, Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 represent independently from each other a bridging group, Q.sup.1 and Q.sup.2 represent independently from each other a single bond, or a straight-chain or branched, substituted or unsubstituted C.sub.1-C.sub.20alkanediyl which is unsubstituted or substituted by di-(C.sub.1-C.sub.20alkyl)amino, C.sub.1-C.sub.6alkyloxy, nitro, cyano and/or chlorine or fluorine; and wherein one or more C, CH, CH.sub.2 group may independently be replaced by a linking group; R.sup.2 represents hydrogen or a straight-chain or branched C.sub.1-C.sub.20alky, which is unsubstituted or substituted by di-(C.sub.1-C.sub.20alkyl)amino, C.sub.1-C.sub.6alkyloxy, nitro, cyano and/or chlorine or fluorine; and wherein one or more C, CH, CH.sub.2 group may independently be replaced by a linking group; R.sup.1 and R.sup.3 represent independently from each other hydrogen or C.sub.cH.sub.F.sub., wherein c is an integer of 0 to 20, and and are integers of 0 to 2 c+1, respectively, wherein +=2 c+1; T.sup.1, T.sup.2, T.sup.3, T.sup.4 and T.sup.5 represent independently from each other hydrogen, halogen, hydroxyl, nitro, cyano or a carboxy group, and/or a cyclic, straight-chain or branched C.sub.1-C.sub.30alkyl, which is unsubstituted, mono- or poly-substituted with halogen, acryloyloxy, alkylacryloyloxy, alkoxy, alkylcarbonyloxy, alkyloxycarbonyl-oxy, alkyloxocarbonyloxy, vinyl, vinyloxy and/or allyloxy group; n.sup.1 is 0, 1 or 2, n.sup.3, n.sup.4, n.sup.5, n.sup.b and n.sup.7 represent independently from each other 0, 1, 2 or 3; w.sup.3 represents 0, 1, 2, 3 or 4; w.sup.1 and w.sup.2 represent independently from each other is 1, 2, 3 or 4, with the proviso that if w.sup.1 or w.sup.2 is 2, 3, or 4, each S.sup.1 and S.sup.2, E.sup.1 and E.sup.2, Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4, Q.sup.1 and Q.sup.2, R.sup.2, R.sup.1 and R.sup.3, T.sup.1, T.sup.2, T.sup.3, T.sup.4 and T.sup.5, n.sup.1, n.sup.3, n.sup.4, n.sup.5, n.sup.6 and n.sup.7 may be identical or different.

2. A compound according to claim 1, wherein A is a substituted or unsubstituted phenylene, naphthalene, biphenylene or triphenylene ring.

3. A compound according to claim 1, wherein m.sup.1, m.sup.2 or m.sup.3 represent independently from each other molar fractions of the comonomers 0<m<1, 0m.sup.20.5 and 0m.sup.3<1.

4. A compound according to claim 1, wherein R.sup.2 represents hydrogen, straight-chain or branched C.sub.1-C.sub.6alkyl; or a straight-chain or branched C.sub.1-C.sub.16fluoralkyl group.

5. A composition comprising at least one compound of formula (I) as described in claim 1.

6. A method for the preparation of a compound (I) as described in claim 1 comprising polymerising of at least one diamine M.sup.1, M.sup.2 or M.sup.3 with at least one D.sup.1, D.sup.2 and D3, which represent independently from each other an unsubstituted or substituted aliphatic, alicyclic group or carbocyclic or heterocyclic aromatic group substituted with at least two carboxylic acid groups, or activated carboxylic groups, or anhydride groups.

7. A compound (I), or a composition, as described in claim 1.

8. A polymer, copolymer or oligomer layer comprising a compound of formula (I) as described in claim 1.

9. A method comprising using a compound according to claim 1, in the manufacture of an optical or an electro-optical device.

10. An optical or electro-optical device including a compound according to claim 1.

11. A compound according to claim 2, wherein m.sup.1, m.sup.2 or m.sup.3 represent independently from each other molar fractions of the comonomers 0<m<1, 0m.sup.20.5 and 0m.sup.3<1.

12. A compound according to claim 2, wherein R.sup.2 represents hydrogen, straight-chain or branched C.sub.1-C.sub.6alkyl; or a straight-chain or branched C.sub.1-C.sub.16fluoralkyl group.

13. A composition comprising at least one compound of formula (I) as described in claim 2.

14. A compound (I), or a composition, obtainable according to the method as described in-claim 6.

15. A polymer, copolymer or oligomer layer comprising a compound of formula (I) as described in claim 2.

16. A method comprising using a composition according to claim 6, in the manufacture of an optical or an electro-optical device.

17. An optical or electro-optical device including a compound according to claim 5.

18. An optical or electro-optical device including a polymer, copolymer or oligomer layer according to claim 8.

Description

EXAMPLES

General Procedure for Polyamic Acid Formation

[0375] A polymer backbone which can be referred as polymer main chain is a polyimide or polyamic acid material. Polyamic acids (PAA) are precursor materials of polyimides (PI). This procedure follows the general procedure written in text books Polyimides: Fundamentals and Application where it involves reacting a dianhydride and a diamine in an aprotic solvent as a first stage to generate the Polyamic acid (PAA) intermediate polymer. PAA can be subsequently cyclized to the corresponding Polyimide (PI). Polyamic acids (PAA) were synthesized by solution polycondensation of diamines or mixture of diamines with dianhydrides or a mixture of dianhydrides and PAA were readily soluble in polar organic solvents (e.g. N-methylpyrrolidinone). The polymer composition is in accordance with the monomers (diamines, dianhydrides) structures with respect of their molar contribution and possible isomers. The polymer formation is characterized by an increase of the viscosity of the reaction mixture. An inherent viscosity >0.1 dL/g attests the formation of the polymer main chain.

Definitions Used in the Examples

[0376] 1H NMR: .sup.1H nuclear magnetic resonance spectroscopy [0377] DMSO-de: dimethylsulfoxid deuterated [0378] 300 MHz: 300 MegaHertz [0379] m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singulet, b: broad [0380] NMP: N-methyl-2-pyrrolidone [0381] DMF: N,N-dimethylformamide [0382] MeOH: methanol [0383] GBL: Gamma-Butyrolactone [0384] IBIB: Isobutyl Isobutyrate [0385] DEE: Diethylene Glycol Diethyl Ether [0386] wt %: weight percent [0387] PTFE: Polytetrafluoroethylene [0388] 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone refers to 1,2,3,4-cyclobutane [0389] tetracarboxylic dianhydride refers to CAS [4415-87-6], [0390] 4-(4-aminophenoxy) aniline refers to CAS [101-80-4], [0391] 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone refers to 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylicacid 1,4:2,3-dianhydride refers to CAS [6053-46-9], [0392] 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline refers to CAS [84-67-3], [0393] 2-(4-aminophenyl)-1H-benzimidazol-5-amine refers to 5-amino-2-(4-aminophenyl)benzimidazole refers to CAS [7621-86-5], [0394] 2-methylbenzene-1,3-diamine refers to CAS [823-40-5], [0395] 5-(trifluoromethyl)benzene-1,3-diamine refers to CAS [368-53-6], [0396] 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline refers to CAS [341-58-2]

Example 1: Preparation of Polyamic Acid, PX1

[0397] 4.897 g (24.970 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 5.000 g (24.970 mmol) of 4-(4-aminophenoxy) aniline in 39.59 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX1 is obtained as 20 wt % NMP-solution with an inherent viscosity [] of 0.37 dL/g.

Example 2: Preparation of Polyamic Acid PX2

[0398] 4.622 g (23.570 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 5.000 g (23.570 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline in 38.49 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX2 is obtained as 20 wt % NMP-solution with an inherent viscosity [] of 0.50 dL/g.

Example 3: Preparation of Polyamic Acid PX3

[0399] 2.750 g (12.267 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 2.500 g (11.776 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline and, 0.110 g (0.491 mmol) of 2-(4-aminophenyl)-1H-benzimidazol-5-amine in 21.44 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX3 is obtained as 20 wt % NMP-solution with an inherent viscosity [] of 0.57 dL/g.

Example 4: Preparation of Polyamic Acid PX4

[0400] 5.598 g (24.970 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 5.000 g (24.970 mmol) of 4-(4-aminophenoxy) aniline in 42.39 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX4 is obtained as 20 wt % NMP-solution with an inherent viscosity [] of 0.44 dL/g.

Example 5: Preparation of Polyamic Acid PX5

[0401] 5.284 g (23.570 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 5.000 g (23.570 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline in 41.14 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid PX5 is obtained as 20 wt % NMP-solution with an inherent viscosity [] of 0.62 dL/g.

Example 7a: Preparation of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid

[0402] 19.5 g (164.1 mmol) of thionylchloride are added by portion in 30 min to a suspension of 37.0 g (149.1 mmol) of 4-(4,4,4-trifluorobutoxy)benzoic acid in 100 mL of toluene and 0.8 mL of DMF at 70 C. After 2 hours at 75 C. the excess of thionyl chloride is distilled off under pressure. The reaction mixture is subsequently cooled down to room temperature and 18.9 g (155.1 mmol) of 4-hydroxybenzaldehyde, 0.91 g (7.5 mmol) of 4-Dimethylaminopyridine and 52.0 g (657.4 mmol) of pyridine are added. After 2 hours of agitation at room temperature, 26.53 g (254.9 mmol) of malonic acid and 7.3 g (102.6 mmol) of pyrrolidine are added and the reaction mixture is heated up to 80 C. After 4 h at 80 C., the reaction mixture is cooled down to 40 C., 150 mL of MeOH are added and the reaction mixture is cooled down to 0 C. After 1 h at 0 C., the precipitated is filtered off, washed with 100 mL of cold methanol and dry under vacuum at 40 C. to give 53.0 g (90%) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid as a white powder.

[0403] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 12.40 (b, 1H), 8.08 (d, 2H), 7.79 (d, 2H), 7.63 (d, 1H), 7.32 (d, 2H), 7.14 (d, 2H), 6.54 (d, 1H), 4.17 (t, 2H), 2.45 (m, 2H), 1.98 (m, 2H).

Example 7b: Preparation of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate

[0404] 2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 4.65 g (11.8 mmol) of (E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoic acid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-Dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0 C. The solution is stirred for 1 h at 0 C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered, and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 5.21 g (75%) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as colorless crystals.

[0405] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 8.74 (d, 1H), 8.51 (dd, 1H), 8.09 (dd, 2H), 7.93 (d, 1H), 7.80 (d, 2H), 7.65 (d, 1H), 7.34 (d, 2H), 7.14 (d, 2H), 6.55 (d, 1H), 4.47 (t, 2H), 4.17 (t, 2H), 2.45 (m, 2H), 2.00 (m, 2H).

Example 7c: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl] 4-(4,4,4-trifluorobutoxy)benzoate

[0406] 4.93 g (8.38 mmol) of ([4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate are dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) Zinc powder are added portion wise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Filtration of the residue on silica gel using toluene:ethyl acetate (1:3) as eluant and crystallization form ethylacetate:hexane mixture to yield 3.20 g (72%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate as orange powder.

[0407] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 8.10 (d, 2H), 7.83 (d, 2H), 7.70 (d, 1H), 7.34 (d, 2H), 7.15 (d, 2H), 6.64 (m, 1H+1H), 5.90 (m, 1H), 5.80 (m, 1H), 4.66 (m, 2H), 4.58 (m, 2H) 4.18 (m, 2H+2H), 2.70 (t, 2H), 2.47 (m, 2H), 2.01 (m, 2H).

Example 8a: Preparation of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid

[0408] 11.63 g (97.74 mmol) of thionylchloride are added by portion in 30 min to a suspension of 24.92 g (88.86 mmol) of 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid in 75 mL of toluene and 0.06 mL of DMF at 75 C. After 2 hours at 75 C. the excess of thionyl chloride is distilled off under pressure. The reaction mixture is subsequently cooled down to room temperature and 11.29 g (92.41 mmol) of 4-hydroxybenzaldehyde, 0.54 g (4.44 mmol) of 4-Dimethylaminopyridine and 30.5 g (385.64 mmol) of pyridine are added. After 2 hours of agitation at room temperature, 15.81 g (151.95 mmol) of malonic acid and 3.22 g (45.32 mmol) of pyrrolidine are added and the reaction mixture is heated up to 80 C. After 4 h at 80 C., the reaction mixture is cooled down to 40 C., 150 mL of MeOH are added and the reaction mixture is cooled down to 0 C. After 1 h at 0 C., the precipitated is filtered off, washed with 100 mL of cold methanol and dry under vacuum at 40 C. to give to give 31.54 g (83%) of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid as a white powder.

[0409] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 12.37 (b, 1H), 7.73 (d, 2H), 7.59 (d, 1H), 7.14 (d, 2H), 6.50 (d, 1H), 2.08 (m, 2H), 1.73 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).

Example 8b: Preparation of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate

[0410] 2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 5.03 g (11.8 mmol) of (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30 ml of dichloromethane. 2.48 g (13.0 mmol) of N-(3-Dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC hydrochloride) are added at 0 C. The solution is stirred for 1 h at 0 C. and allowed to stir at room temperature overnight. After 22 hours at room temperature the reaction mixture is partitioned between dichloromethane and water. The organic phase is washed repeatedly with water, dried over sodium sulphate, filtered, and concentrated by rotary evaporation. Chromatography of the residue on silica gel using toluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 5.49 g (75%) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate as colorless crystals.

[0411] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 8.74 (d, 1H), 8.51 (dd, 1H), 7.92 (d, 1H), 7.75 (d, 2H), 7.61 (d, 1H), 7.16 (d, 2H), 6.52 (d, 1H), 4.46 (t, 2H), 3.38 (t, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).

Example 8c: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexvl)cyclohexanecarboxylate

[0412] 5.20 g (8.38 mmol) of [4-[(E)-3-[2-(2,4-dinitrophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate are dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 ml water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) Zinc powder are added portion wise within 60 min. The mixture is allowed to react for 2 hours. The reaction mixture is then partitioned between ethyl acetate and water and filtered. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtered, and concentrated by rotary evaporation. Filtration of the residue on silica gel using toluene:ethyl acetate (1:3) as eluant and crystallization form ethylacetate:hexane mixture to yield 3.06 g (65%) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate as yellow-orange powder.

[0413] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 7.76 (d, 2H), 7.65 (d, 1H), 7.14 (m, 2H), 6.59 (m, 1H+1H), 5.89 (m, 1H), 5.80 (m, 1H), 4.64 (s, 2H), 4.57 (s, 2H), 4.17 (t, 2H), 3.38 (t, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 20H), 0.85 (t, 3H).

Example 9: Preparation of Polyamic Acid P1

[0414] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.741 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P1 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.36 dL/g.

Example 10: Preparation of Polyamic Acid P2

[0415] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.634 g (1.20 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.673 g (1.20 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.790 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P2 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.38 dL/g.

Example 11: Preparation of Polyamic Acid P3

[0416] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.302 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P3 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.47 dL/g.

Example 12: Preparation of Polyamic Acid P4

[0417] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.037 g (0.30 mmol) of 2-methylbenzene-1,3-diamine in 4.833 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P4 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.90 dL/g.

Example 13: Preparation of Polyamic Acid P5

[0418] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.539 g (1.02 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.555 g (0.99 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.120 g (0.99 mmol) of 2-methylbenzene-1,3-diamine in 4.208 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P5 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.30 dL/g.

Example 14: Preparation of Polyamic Acid P6

[0419] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.120 g (0.60 mmol) of 4-(4-aminophenoxy) aniline in 4.658 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P6 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.32 dL/g.

Example 15: Preparation of Polyamic Acid P7

[0420] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.106 g (0.60 mmol) of 5-(trifluoromethyl)benzene-1,3-diamine in 4.624 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P7 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.27 dL/g.

Example 16: Preparation of Polyamic Acid P8

[0421] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.096 g (0.30 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.972 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P8 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.33 dL/g.

Example 17: Preparation of Polyamic Acid P9

[0422] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.10 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.055 g (0.45 mmol) of 2-methylbenzene-1,3-diamine in 4.680 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P9 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.60 dL/g.

Example 18: Preparation of Polyamic Acid P10

[0423] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.60 mmol) of 2-methylbenzene-1,3-diamine in 4.549 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P10 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.38 dL/g.

Example 19: Preparation of Polyamic Acid P11

[0424] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.872 g (1.65 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.092 g (0.75 mmol) of 2-methylbenzene-1,3-diamine in 4.406 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P11 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.58 dL/g.

Example 20: Preparation of Polyamic Acid P12

[0425] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.80 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.60 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.826 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P12 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.32 dL/g.

Example 21: Preparation of Polyamic Acid P13

[0426] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.031 g (1.95 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.252 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.60 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.815 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P13 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.45 dL/g.

Example 22: Preparation of Polyamic Acid P14

[0427] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.793 g (1.50 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.288 g (0.90 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline in 4.680 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P14 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.87 dL/g.

Example 23: Preparation of Formulation 1

[0428] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P1 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 1.

Example 24: Preparation of Formulation 2

[0429] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P1 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 2.

Example 25: Preparation of Formulation 3

[0430] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P2 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 3.

Example 26: Preparation of Formulation 4

[0431] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P2 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 4.

Example 27: Preparation of Formulation 5

[0432] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P3 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 5.

Example 28: Preparation of Formulation 6

[0433] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P3 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 6.

Example 29: Preparation of Formulation 7

[0434] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 8.

Example 30: Preparation of Formulation 8

[0435] To a solution of 1.700 g of Polyamic acid PX5 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 3.

Example 31: Preparation of Formulation 9

[0436] To a solution of 1.910 g of Polyamic acid PX2 and 0.225 g of Polyamic acid P4 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 9.

Example 32: Preparation of Formulation 10

[0437] To a solution of 1.700 g of Polyamic acid PX4 and 0.200 g of Polyamic acid P4 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 10.

Example 33: Preparation of Formulation 11

[0438] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P5 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 11.

Example 34: Preparation of Formulation 12

[0439] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P6 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 12.

Example 35: Preparation of Formulation 13

[0440] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P7 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 13.

Example 36: Preparation of Formulation 14

[0441] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P7 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 14.

Example 37: Preparation of Formulation 15

[0442] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P8 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 15.

Example 38: Preparation of Formulation 16

[0443] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P8 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 16.

Example 39: Preparation of Formulation 17

[0444] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P9 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 17.

Example 40: Preparation of Formulation 18

[0445] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P9 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 18.

Example 41: Preparation of Formulation 19

[0446] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P10 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 19.

Example 42: Preparation of Formulation 20

[0447] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P10 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 20.

Example 43: Preparation of Formulation 21

[0448] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P11 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 21.

Example 44: Preparation of Formulation 22

[0449] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P11 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 22.

Example 45: Preparation of Formulation 23

[0450] To a solution of 1.700 g of Polyamic acid PX3 and 0.200 g of Polyamic acid P12 are added 0.900 g of NMP, 2.400 g of GBL, 3.840 g of DEE and 0.960 g of IBIB. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 23.

Example 46: Preparation of Formulation 24

[0451] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P12 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 24.

Example 47: Preparation of Formulation 25

[0452] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P13 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 25.

Example 48: Preparation of Formulation 26

[0453] To a solution of 1.910 g of Polyamic acid PX1 and 0.225 g of Polyamic acid P14 are added 0.700 g of NMP, 2.390 g of GBL, 3.82 g of DEE and 0.955 g of EEP. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 26.

APPLICATION EXAMPLES

[0454] Measurement of the pretilt angle as used in the examples: To measure the pretilt angle a rotating analyzer is used, as described by Michio Kitamura, Shunsuke Kobayashi and Katsumi Mori; Journal of the SID14/5, 2006; p509-p514.

Example 1

[0455] Formulation 1 is spin-coated onto two ITO coated glass substrates at a spin speed of c.a. 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of pre-baking for 90 seconds at 80 C. and post-baking for 40 minutes at 200 C. Then, the substrates are exposed to linearly polarized light at an incidence angle of 40 relative to the normal of the substrate surface (22 mJ.Math.cm.sup.2-PLUMBOL). The plane of polarization is parallel to the substrate's longest edges. The cells are assembled with the 2 substrates, the exposed polymer layers facing the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are parallel to each other. The cells are capillary filled with liquid crystal MLC-6610 (Merck KGA-<0). Finally, the filled cells are further subjected to a thermal annealing at 130 C. for 10 minutes, thereby completing the cell process. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.88 is measured.

Example 2

[0456] A cell is prepared as in Example 1, except that formulation 2 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.01 is measured.

Example 3

[0457] A cell is prepared as in Example 1, except that formulation 3 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.18 is measured.

Example 4

[0458] A cell is prepared as in Example 1, except that formulation 4 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.29 is measured.

Example 5

[0459] A cell is prepared as in Example 1, except that formulation 5 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.22 is measured.

Example 6

[0460] A cell is prepared as in Example 1, except that formulation 6 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 88.25 is measured.

Example 7

[0461] A cell is prepared as in Example 1, except that formulation 7 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.03 is measured.

Example 8

[0462] A cell is prepared as in Example 1, except that formulation 8 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.16 is measured.

Example 9

[0463] A cell is prepared as in Example 1, except that formulation 9 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.13 is measured.

Example 10

[0464] A cell is prepared as in Example 1, except that formulation 10 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.26 is measured.

Example 11

[0465] A cell is prepared as in Example 1, except that formulation 11 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23 is measured.

Example 12

[0466] A cell is prepared as in Example 1, except that formulation 12 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.32 is measured.

Example 13

[0467] A cell is prepared as in Example 1, except that formulation 13 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.05 is measured.

Example 14

[0468] A cell is prepared as in Example 1, except that formulation 14 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23 is measured.

Example 15

[0469] A cell is prepared as in Example 1, except that formulation 15 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.09 is measured.

Example 16

[0470] A cell is prepared as in Example 1, except that formulation 16 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.23 is measured.

Example 17

[0471] A cell is prepared as in Example 1, except that formulation 17 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.72 is measured.

Example 18

[0472] A cell is prepared as in Example 1, except that formulation 18 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.91 is measured.

Example 19

[0473] A cell is prepared as in Example 1, except that formulation 19 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.69 is measured.

Example 20

[0474] A cell is prepared as in Example 1, except that formulation 20 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.94 is measured.

Example 21

[0475] A cell is prepared as in Example 1, except that formulation 21 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.62 is measured.

Example 22

[0476] A cell is prepared as in Example 1, except that formulation 22 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.90 is measured.

Example 23

[0477] A cell is prepared as in Example 1, except that formulation 23 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.74 is measured.

Example 24

[0478] A cell is prepared as in Example 1, except that formulation 24 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 87.02 is measured.

Example 25

[0479] A cell is prepared as in Example 1, except that formulation 25 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.55 is measured.

Example 26

[0480] A cell is prepared as in Example 1, except that formulation 26 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A pretilt angle of 86.37 is measured.

Example 27

[0481] Voltage holding ratio (VHR) of the cells is measured at 60 C. using LCM-1 instrument from Toyo, Japan. The VHR was measured using a short and a long frame period (T). In the short one, the voltage decay V (at T=16.67 ms) of a voltage surge of 64 s with V.sub.0(V at t=0)=1V is then measured over a period of T=16.67 ms. The voltage holding ratio is then determined, at room temperature, given by integration of the measurement curve between V.sub.0 and V weighted by the area in the case of 100% VHR. The table below shows VHR measured for all tested cells. The results show VHR >99% for all tested cells.

TABLE-US-00001 Cell Alignment quality VHR Example 8 Good 99.6% Example 9 Good 99.7% Example 10 Good 99.5% Example 11 Good 99.5% Example 16 Good 99.7% Example 21 Good 99.7% Example 22 Good 99.7% Example 24 Good 99.5%

Example 28: Determination of AC Memory (ACM)

[0482] An AC-voltage of 60 Hz frequency and 7.5 V amplitude is applied to cells prepared examples 1 to 25. After 48 hours of stress, the cells are short-circuited, and the change of the pre-tilt angle is measured after 60 min of relaxation. The difference in pretilt measurement between before and after the stress-relaxation cycle gives AC-Memory (ACM). If ACM is excellent below 0.015, very good between 0.016 and 0.030, good between 0.031 and 0.045, medium between 0.046 and 0.060 and bad for value higher than 0.061.

TABLE-US-00002 Cell ACM [] Cell ACM [] Example 1 excellent Example 2 excellent Example 3 excellent Example 4 excellent Example 5 excellent Example 6 excellent Example 7 very good Example 8 excellent Example 9 very good Example 10 excellent Example 11 very good Example 12 very good Example 13 very good Example 14 very good Example 15 very good Example 16 very good Example 17 very good Example 18 very good Example 19 very good Example 20 very good Example 21 good Example 22 very good Example 23 very good Example 24 very good Example 25 good Example 26 medium

Examples Part 2

Example 49: Preparation of Polyamic Acid P15

[0483] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.268 g (2.40 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.336 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-4 pentylcyclohexyl)cyclohexanecarboxylate, in 5.311 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P15 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.47 dL/g.

Example 50: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate

[0484] [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate is prepared following the three steps described in example 8a, 8b and 8c but starting from 4-pentylcyclohexanecarboxylic acid instead 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid

[0485] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 7.77 (d, 2H), 7.65 (d, 1H), 7.15 (d, 2H), 6.60 (m, 1H+1H), 5.89 (d, 1H), 5.79 (dd, 1H), 4.64 (s, 2H), 4.58 (s, 2H), 4.17 (t, 2H), 3.38 (t, 2H), 2.68 (t, 2H), 2.50 (m, 1H), 2.06 (m, 2H), 1.65 (m, 2H), 1.6-0.8 (m, 13H), 0.86 (t, 3H).

Example 51: Preparation of Polyamic Acid P16

[0486] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.268 g (2.40 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.287 g (0.60 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 5.196 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P16 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.63 dL/g.

Example 52: Preparation of Polyamic Acid P17

[0487] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.189 g (2.25 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.359 g (0.75 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 5.180 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P17 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.34 dL/g.

Example 53: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl] 4-(4-pentylcyclohexvl)cyclohexanecarboxylate

[0488] [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate is prepared following the 3 steps described in example 8a, 8b and 8c but starting from 4-hydroxy-3-methoxy-benzaldehyde instead 4-hydroxybenzaldehyde

[0489] .sup.1H NMR (300 MHz) in DMSO-D.sub.6: 7.63 (d, 1H), 7.50 (d, 1H), 7.27 (m, 1H), 7.08 (m, 1H), 6.66 (m, 1H), 6.62 (m, 1H), 5.90 (m, 1H), 5.78 (m, 1H), 4.62 (m, 4H), 4.18 (t, 2H), 3.80 (s, 3H), 2.68 (m, 2H), 2.5 (m, 2H), 2.1 (m, 2H), 1.7 (m, 6H), 1.5-0.7 (m, 16H), 0.85 (t, 3H).

Example 54: Preparation of Polyamic Acid P18

[0490] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.268 g (2.4 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.354 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.156 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P18 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.84 dL/g.

Example 55: Preparation of Polyamic Acid P19

[0491] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.951 g (1.8 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.354 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.073 g (0.6 mmol) of 2-methylbenzene-1,3-diamine in 4.587 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P19 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.42 dL/g.

Example 56: Preparation of Polyamic Acid P20

[0492] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1110.0 g (2.1 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.355 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]-2-methoxy-phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.037 g (0.3 mmol) of 2-methylbenzene-1,3-diamine in 4.876 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P20 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.61 dL/g.

Example 57: Preparation of Polyamic Acid P21

[0493] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 0.673 g (1.2 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.576 g (1.8 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.482 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P21 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.53 dL/g.

Example 58: Preparation of Polyamic Acid P22

[0494] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.178 g (2.1 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.288 g (0.9 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.989 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P22 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.53 dL/g.

Example 59: Preparation of Polyamic Acid P23

[0495] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.841 g (1.5 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.480 g (1.5 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.454 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P23 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.52 dL/g.

Example 60: Preparation of Polyamic Acid P24

[0496] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.350 g (1.65 mmol) of 4-(4-amino-2-methyl-phenyl)-3-methyl-aniline, in 3.955 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P24 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.55 dL/g.

Example 61: Preparation of Polyamic Acid P25

[0497] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 0.757 g (1.35 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.330 g (1.65 mmol) of 4-(4-aminophenoxy)aniline, in 3.908 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P25 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.65 dL/g.

Example 62 Preparation of polyamic acid P26

[0498] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.346 g (2.4 mmol) [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, and 0.192 g (0.6 mmol) of 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline, in 4.961 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P26 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.72 dL/g.

Example 63: Preparation of Polyamic Acid P27

[0499] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.110 g (2.1 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, 0.287 g (0.6 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, and 0.037 g (0.3 mmol) of 2-methylbenzene-1,3-diamine in 4.208 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P27 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.61 dL/g.

Example 64: Preparation of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate

[0500] [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate is prepared following the three steps described in example 8a, 8b and 8c but starting from 4-(4-ethylcyclohexyl)cyclohexanecarboxylic acid instead 4-(4-pentylcyclohexyl)cyclohexanecarboxylic acid

[0501] .sup.1H NMR (300 MHz) in THF-D.sup.8: 7.62 (m, 1+2H), 7.11 (d, 2H), 6.64 (d, 1H), 6.49 (d, 1H), 5.88 (m, 1H+1H), 4.27 (s broad, 4H), 4.21 (t, 2H), 2.73 (t, 2H), 2.46 (m, 2H), 2.14 (m, 2H), 1.79 (m, 4H), 1.50 (m, 2H), 1.4-0.9 (m, 12H), 0.88 (t, 3H).

Example 65: Preparation of Polyamic Acid P28

[0502] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.233 g (0.45 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-ethylcyclohexyl)cyclohexanecarboxylate, in 5.257 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P28 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.30 dL/g.

Example 66: Preparation of [4-(4-pentylcyclohexyl)cyclohexyl] 4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate

[0503] [4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate is prepared following the 2 steps described in examples 8b and 8c but starting from E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexoxy]carbonylphenyl]prop-2-enoic acid instead (E)-3-[4-[4-(4-pentylcyclohexyl)cyclohexanecarbonyl]oxyphenyl]prop-2-enoic acid

[0504] .sup.1H NMR (300 MHz) in THF-D.sup.8: 8.01 (d, 2H), 7.71 (m, 2H+1H), 6.64 (m, 1H+1H), 5.88 (m, 1H+1H), 4.85 (m, 1H), 4.26 (t, 2H), 4.20 (s broad, 4H), 2.74 (t, 2H), 2.12 (m, 2H), 1.7 (m, 6H), 1.9-0.8 (m, 22H), 0.85 (t, 3H).

Example 67: Preparation of Polyamic Acid P29

[0505] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.348 g (2.55 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, and 0.252 g (0.45 mmol) of [4-(4-pentylcyclohexyl)cyclohexyl]4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]benzoate, in 5.301 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P29 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.31 dL/g.

Example 68: Preparation of Polyamic Acid P30

[0506] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.682 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.495 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P30 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.29 dL/g.

Example 69: Preparation of Polyamic Acid P31

[0507] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.682 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4-pentylcyclohexyl)cyclohexanecarboxylate, in 5.296 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P31 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.30 dL/g.

Example 70: Preparation of Polyamic Acid P32

[0508] 0.672 g (3.00 mmol) of 4,10-dioxatricyclo[6.3.1.0.sup.2,7]dodecane-3,5,9,11-tetrone is added to a solution of 1.436 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-pentylcyclohexanecarboxylate, in 4.919 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P32 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.29 dL/g.

Example 71: Preparation of Polyamic Acid P33

[0509] 0.588 g (3.00 mmol) of 4,9-dioxatricyclo[5.3.0.0.sup.2,6]decane-3,5,8,10-tetrone is added to a solution of 1.586 g (3.00 mmol) of [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, in 5.073 g of NMP. Stirring is then carried out at 0 C. for 2 hours. The mixture is subsequently allowed to react for 72 hours at room temperature. Polyamic acid P33 is obtained as 30 wt % NMP-solution with an inherent viscosity [] of 0.54 dL/g.

Example 72: Preparation of Formulation 27

[0510] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P15 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 27.

Example 73: Preparation of Formulation 28

[0511] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P16 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 28.

Example 74: Preparation of Formulation 29

[0512] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P17 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 29.

Example 75: Preparation of Formulation 30

[0513] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P18 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 30.

Example 76: Preparation of Formulation 31

[0514] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P19 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 31.

Example 77: Preparation of Formulation 32

[0515] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P20 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 32.

Example 78: Preparation of Formulation 33

[0516] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P21 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 33.

Example 79: Preparation of Formulation 34

[0517] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P22 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 34.

Example 80: Preparation of Formulation 35

[0518] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P23 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 35.

Example 81: Preparation of Formulation 36

[0519] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P24 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 36.

Example 82: Preparation of Formulation 37

[0520] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P25 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 37.

Example 83: Preparation of Formulation 38

[0521] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P26 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 38.

Example 84: Preparation of Formulation 39

[0522] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P27 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 39.

Example 85: Preparation of Formulation 40

[0523] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P28 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 40.

Example 86: Preparation of Formulation 41

[0524] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P29 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 41.

Example 87: Preparation of Formulation 42

[0525] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P30 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 42.

Example 88: Preparation of Formulation 43

[0526] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P31 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 43.

Example 89: Preparation of Formulation 44

[0527] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P32 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 44.

Example 90: Preparation of Formulation 45

[0528] To a solution of 2.125 g of Polyamic acid PX1 and 0.250 g of Polyamic acid P33 are added 2.875 g of NMP and 4.751 g of BC. The mixture is stirred for 30 minutes and filtrated on 0.2 m PTFE-filter to give Formulation 45.

Application Examples Part 2

Example 29

[0529] Formulation 27 is spin-coated onto two ITO coated glass substrates at a spin speed of c.a. 2000 rpm for 30 seconds. After spin-coating, the substrates are subjected to a baking procedure consisting of pre-baking for 90 seconds at 80 C. and post-baking for 40 minutes at 200 C. Then, the substrates are exposed to linearly polarized light at an incidence angle of 40 relative to the normal of the substrate surface (22 mJ.Math.cm.sup.2-LPUVB). The plane of polarization is parallel to the substrate's longest edges. The cells are assembled with the 2 substrates, the exposed polymer layers facing the inside of the cell. The substrates are adjusted relative to each other such that the induced alignment directions are parallel to each other. The cells are capillary filled with liquid crystal MLC-6610 (Merck KGA-<0). Finally, the filled cells are further subjected to a thermal annealing at 130 C. for 10 minutes, thereby completing the cell process. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.27 is measured using the rotating analyser method from Shintech.

Example 30

[0530] A cell is prepared as in Example 29, except that formulation 28 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.04 is measured using the rotating analyser method from Shintech.

Example 31

[0531] A cell is prepared as in Example 29, except that formulation 29 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.17 is measured using the rotating analyser method from Shintech.

Example 32

[0532] A cell is prepared as in Example 29, except that formulation 30 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.14 is measured using the rotating analyser method from Shintech.

Example 33

[0533] A cell is prepared as in Example 29, except that formulation 31 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.21 is measured using the rotating analyser method from Shintech.

Example 34

[0534] A cell is prepared as in Example 29, except that formulation 32 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.16 is measured using the rotating analyser method from Shintech.

Example 35

[0535] A cell is prepared as in Example 29, except that formulation 33 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.97 is measured using the rotating analyser method from Shintech.

Example 36

[0536] A cell is prepared as in Example 29, except that formulation 34 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.17 is measured using the rotating analyser method from Shintech.

Example 37

[0537] A cell is prepared as in Example 29, except that formulation 35 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.01 is measured using the rotating analyser method from Shintech.

Example 38

[0538] A cell is prepared as in Example 29, except that formulation 36 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.23 is measured using the rotating analyser method from Shintech.

Example 39

[0539] A cell is prepared as in Example 29, except that formulation 37 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.38 is measured using the rotating analyser method from Shintech.

Example 40

[0540] A cell is prepared as in Example 29, except that formulation 38 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.04 is measured using the rotating analyser method from Shintech.

Example 41

[0541] A cell is prepared as in Example 29, except that formulation 39 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 86.67 is measured using the rotating analyser method from Shintech.

Example 42

[0542] A cell is prepared as in Example 29, except that formulation 40 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.64 is measured using the rotating analyser method from Shintech.

Example 43

[0543] A cell is prepared as in Example 29, except that formulation 41 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.18 is measured using the rotating analyser method from Shintech.

Comparative Example 44

[0544] A cell is prepared as in Example 29, except that formulation 42 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.27 is measured using the rotating analyser method from Shintech.

Comparative Example 45

[0545] A cell is prepared as in Example 29, except that formulation 43 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 87.89 is measured using the rotating analyser method from Shintech.

Comparative Example 46

[0546] A cell is prepared as in Example 29, except that formulation 44 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 88.29 is measured using the rotating analyser method from Shintech.

Comparative Example 47

[0547] A cell is prepared as in Example 29, except that formulation 45 is coated. The liquid crystal in the cell showed well defined and homogeneous vertical orientation before and after thermal annealing of the cell. A tilt angle of 86.66 is measured using the rotating analyser method from Shintech.

Example 48

[0548] Voltage holding ratio (VHR) of the cells is measured at 60 C. using LCM-1 instrument from Toyo, Japan. The VHR was measured using a short and a long frame period (T). In the short one, the voltage decay V (at T=16.67 ms) of a voltage surge of 64 s with V.sub.0(V at t=0)=1V is then measured over a period of T=16.67 ms. The voltage holding ratio is then determined, at room temperature, given by integration of the measurement curve between V.sub.0 and V weighted by the area in the case of 100% VHR. The table below shows VHR measured for all tested cells. The results show VHR >99% for all tested cells except the comparative examples 44, 45 and 46 which led to poor electrical property.

TABLE-US-00003 Cell Alignment quality VHR Example 29 Good 99.7% Example 30 Good 99.7% Example 31 Good 99.8% Example 32 Good 99.7% Example 33 Good 99.8% Example 34 Good 99.7% Example 35 Good 99.7% Example 36 Good 99.6% Example 37 Good 99.7% Example 40 Good 99.6% Example 41 Good 99.7% Example 42 Good 99.7% Example 43 Good 99.6% Comparative example 44 Good 96.0% Comparative example 45 Good 85.1% Comparative example 46 Good 89.6% Comparative example 47 Good 99.4%

Example 49: determination of AC memory (ACM)

[0549] An AC-voltage of 60 Hz frequency and 7.5 V amplitude is applied to cells prepared examples 1 to 25. After 48 hours of stress, the cells are short-circuited, and the change of the pre-tilt angle is measured after 60 min of relaxation. The difference in pretilt measurement between before and after the stress-relaxation cycle gives AC-Memory (ACM). If ACM is excellent below 0.015, very good between 0.016 and 0.030, good between 0.031 and 0.045, medium between 0.046 and 0.060 and bad for value higher than 0.061.

TABLE-US-00004 Cell Tilt angle ACM [] Example 29 88.27 excellent Example 30 88.04 excellent Example 31 88.17 very good Example 32 88.14 very good Example 33 88.21 very good Example 34 88.16 very good Example 35 87.97 good Example 36 87.17 excellent Example 37 87.01 good Example 38 87.23 good Example 39 87.38 very good Example 40 87.04 good Example 41 86.67 good Example 42 88.64 excellent Example 43 88.18 excellent Comparative example 47 86.66 bad