Liquid crystal mixture and liquid crystal display

Abstract

The invention relates to a liquid crystal mixture characterised in that it comprises one or more photoreactive mesogens of formula I ##STR00001##
wherein the parameters and groups occurring are defined as indicated in claim 1, to a process for the fabrication of liquid crystal displays using these liquid crystal mixtures and to a liquid crystal display obtainable by this process. The invention further relates to new compounds of formula I.

Claims

1. A liquid crystalline mixture comprising a photoalignment component A) comprising one or more photoreactive compounds of formula I, and a liquid-crystalline component B), comprising one or more mesogenic liquid-crystalline compounds, wherein formula I is as follows: ##STR00433## wherein A.sup.11 denotes an aryl or heteroaryl group, which may be substituted by one or more radicals L, A.sup.12, A.sup.13 are each, independently of one another, defined like A.sup.11 or denote a cycloalkyl group having 3 to 10 C atoms, in which 1 to 4 non-adjacent CH.sub.2 groups may be replaced by O and in which one or more H atoms may be replaced by a group L, L on each occurrence, identically or differently, denotes OH, F, Cl, Br, I, CN, NO.sub.2, SF.sub.5, NCO, NCS, OCN, SCN, C(O)N(R.sup.z).sub.2, C(O)R.sup.z, N(R.sup.z).sub.2, optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, Z.sup.11 on each occurrence, identically or differently, denotes CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, C(O)O, OC(O), CHCHCOO, OCOCHCH, or a single bond, R.sup.11 and R.sup.12 identically or differently, denote a group P-Sp-, or halogen, CN, optionally fluorinated alkyl or alkenyl with up to 15 C atoms in which one or more non adjacent CH.sub.2-groups may be replaced by O, S, CO, C(O)O, OC(O), OC(O)O, with the proviso that at least one of R.sup.11 and R.sup.12 denotes a group P-Sp-, R.sup.z each, independently of one another, denote H or alkyl having 1-12 C atoms, P a polymerisable group, Sp a spacer group or a single bond, a denotes 0 to 1.

2. The liquid crystalline mixture according to claim 1, wherein component A) comprises one or more compounds of formula I of formulae I-1 to I-8 ##STR00434## wherein R.sup.11 and R.sup.12 and L are defined as indicated in claim 1, and r, on each occurrence, identically or differently, is 0, 1 or 2.

3. The liquid crystalline mixture according to claim 1, wherein the total concentration of compounds of formula I in the mixture is from 0.01 to 10% by weight.

4. The liquid crystalline mixture according to claim 1, additionally comprising a polymerisable component C) comprising one or more compounds of formula P
P.sup.a-(Sp.sup.a).sub.s1-A.sup.2-(Z.sup.1-
A.sup.1).sub.n2-(Sp.sup.b).sub.s2-P.sup.bP wherein P.sup.a, P.sup.b each, independently of one another, denote a polymerisable group, Sp.sup.a, Sp.sup.b on each occurrence, identically or differently, denote a spacer group, s1, s2 each, independently of one another, are 0 or 1, A.sup.1, A.sup.2 each, independently of one another, denote: a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 4,4-bicyclohexylene, wherein, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by O and/or S and wherein, in addition, one or more H atoms may be replaced by F, b) 1,4-phenylene or 1,3-phenylene, wherein, in addition, one or two CH groups may be replaced by N and wherein, in addition, one or more H atoms may be replaced by L, c) tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl or selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by L, d) saturated, partially unsaturated or fully unsaturated, optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, selected from: ##STR00435## where, in addition, one or more H atoms in these radicals may be replaced by L, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, n2 is 0, 1, 2 or 3, Z.sup.1 in each case, independently of one another, denotes COO, OCO, CH.sub.2O, OCH.sub.2, CF.sub.2O, OCF.sub.2, or (CH.sub.2).sub.n, where n is 2, 3 or 4, O, CO, C(R.sup.0R.sup.00), CH.sub.2CF.sub.2, CF.sub.2CF.sub.2 or a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having up to 12 C atoms, R.sup.0, R.sup.00 each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, wherein, in addition, one or more H atoms may be replaced by F, M denotes O, S, CH.sub.2, CHY.sup.1 or CY.sup.1Y.sup.2, and Y.sup.1 and Y.sup.2 each, independently of one another, have one of the meanings indicated above for R.sup.0 or denote Cl or CN.

5. The liquid crystalline mixture according to claim 1, wherein the concentration of polymerisable compounds of formula P is 0.01 to 10% by weight.

6. The liquid crystalline mixture according to claim 1, additionally comprising one or more compounds of formula P of the sub-formulae P10-1-1 or P10-1-2 ##STR00436## wherein n4 is an integer from 1 to 10.

7. The liquid crystalline mixture according to claim 1, wherein the LC host mixture has negative dielectric anisotropy.

8. The liquid crystalline mixture according to claim 1, wherein the LC host mixture comprises one or more compounds of the following formulae: ##STR00437## wherein a is 1 or 2, b is 0 or 1, ##STR00438## R.sup.1 and R.sup.2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, Z.sup.x denotes CHCH, CH.sub.2O, OCH.sub.2, CF.sub.2O, OCF.sub.2, O, CH.sub.2, CH.sub.2CH.sub.2 or a single bond, L.sup.1-4 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2.

9. The liquid crystalline mixture according to claim 1, wherein the LC host mixture has positive dielectric anisotropy.

10. The liquid crystalline mixture according to claim 1, wherein the LC host mixture comprises one or more compounds of formulae II or III, ##STR00439## wherein R.sup.20 each, identically or differently, denote a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by CC, CF.sub.2O, CHCH, ##STR00440## O, COO or OCO in such a way that O atoms are not linked directly to one another, X.sup.20 each, identically or differently, denote F, Cl, CN, SF.sub.5, SCN, NCS, a halogenated alkyl radical, a halogenated alkenyl radical, a halogenated alkoxy radical or a halogenated alkenyloxy radical, each having up to 6 C atoms, and Y.sup.20-24 each, identically or differently, denote H or F, ##STR00441## each, identically or differently, denote ##STR00442##

11. The liquid crystalline mixture according to claim 1, further comprising one or more compounds of formulae XI or XII ##STR00443## wherein R.sup.20 each, identically or differently, denote a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH.sub.2 groups in these radicals may each be replaced, independently of one another, by CC, CF.sub.2O, CHCH, ##STR00444## O, COO or OCO in such a way that O atoms are not linked directly to one another, X.sup.20 each, identically or differently, denote F, Cl, CN, SF.sub.5, SCN, NCS, a halogenated alkyl radical, a halogenated alkenyl radical, a halogenated alkoxy radical or a halogenated alkenyloxy radical, each having up to 6 C atoms, and Y.sup.20-23 each, identically or differently, denote H or F, and ##STR00445## each, independently of one another, denote ##STR00446##

12. The liquid crystalline mixture according to claim 1, wherein the LC host mixture comprises one or more compounds of the following formula: ##STR00447## wherein the individual radicals have the following meanings: ##STR00448## R.sup.3 and R.sup.4 each, independently of one another, denote alkyl having 1 to 12 C atoms, wherein, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, Z.sup.y denotes CH.sub.2CH.sub.2, CHCH, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF or a single bond.

13. The liquid crystalline mixture according to claim 1, wherein the LC host mixture comprises one or more compounds of the following formulae: ##STR00449##

14. A process for the fabrication of a liquid crystal display, comprising at least: providing a first substrate which includes a pixel electrode and a common electrode for generating an electric field substantially parallel to a surface of the first substrate in a pixel region; providing a second substrate, the second substrate being disposed opposite to the first substrate; interposing a liquid crystal mixture according to claim 1 as a liquid crystal layer between the first and second substrates; irradiating the liquid crystal mixture with linearly polarised light causing photoalignment of the liquid crystal layer; curing polymerisable compounds of the liquid crystal layer by irradiation with ultraviolet light or visible light having a wavelength of 450 nm or below.

15. The process according to claim 14, wherein the linearly polarised light is ultraviolet light or visible light having a wavelength of 450 nm or below.

16. A display produced by a process according to claim 14.

17. The display according to claim 16, wherein the display is an IPS or FFS display.

18. The display according to claim 16, in which both the first and the second substrate contain a rubbed or unrubbed polyimide layer.

19. The display according to claim 16, in which (1) none or (2) only one of the first and second substrates contains a polyimide layer.

20. A compound of formula I ##STR00450## wherein A.sup.11 denotes an aryl or heteroaryl group, which may be substituted by one or more radicals L, A.sup.12, A.sup.13 are each, independently of one another, defined like A.sup.11 or denote a cycloalkyl group having 3 to 10 C atoms, in which 1 to 4 non-adjacent CH.sub.2 groups may be replaced by O and in which one or more H atoms may be replaced by a group L, L on each occurrence, identically or differently, denotes OH, F, Cl, Br, I, CN, NO.sub.2, SF.sub.5, NCO, NCS, OCN, SCN, C(O)N(R.sup.z).sub.2, C(O)R.sup.z, N(R.sup.z).sub.2, optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, Z.sup.11 on each occurrence, identically or differently, denotes CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, C(O)O, OC(O), CHCHCOO, or a single bond, R.sup.11 denotes a group P-Sp- in which Sp is a spacer group or a single bond, or R.sup.11 denotes halogen, CN, optionally fluorinated alkyl or alkenyl with up to 15 C atoms in which one or more non adjacent CH.sub.2-groups may be replaced by O, S, CO, C(O)O, OC(O), OC(O)O, R.sup.12 denotes P-Sp, in which Sp is a single bond, R.sup.z each, independently of one another, denote H or alkyl having 1-12 C atoms, P a polymerisable group, a denotes 0 or 1, wherein one or both of the groups Sp denote a single bond.

Description

EXAMPLES

Synthesis Examples

Synthesis Example 1

3-methyl-4-{[(2E)-3-[4-({6-[(3-oxoprop-1-en-2-yl)oxy]hexyl}oxy)phenyl]prop-2-enoyl]oxy}phenyl 4-{[6-(prop-2-enoyloxy)hexyl]oxy}benzoate 14

1.1 Synthesis of 1-[4-(benzyloxy)-3-methylphenyl]ethan-1-one 1

(1) ##STR00374##

(2) 12.7 g (85.0 mmol) of 1-(4-hydroxy-3-methyl-phenyl)-ethanone, 12.7 mL (107 mmol) benzyl bromide and 7.62 g (55.0 mmol) potassium carbonate are dissolved/suspended in methyl(ethyl)ketone and stirred for 18 h under reflux. The reaction mixture is cooled down to room temperature (RT) and the precipitating solid is filtered and washed with methyl tertiary-butyl ether (MTB-E). The product is further crystallized out of heptane at 50 C. and is directly used in the next synthesis step.

1.2 Synthesis of 4-(benzyloxy)-3-methylphenyl acetate 2

(3) ##STR00375##

(4) 39.1 mL (0.165 mmol) m-chloroperbenzoic acid are suspended in 102 mL methylene chloride and a solution of 19.3 g (80.0 mmol) of ketone 1 in 72 mL methylene chloride is added dropwise to the reaction mixture. The yellow reaction mixture is then stepwise heated up to reflux and stirred for 16 h. The reaction mixture is cooled to room temperature (RT) and poured onto ice water. The phases are separated and the organic layer is filtered off from precipitated 3-chlorobenzoic acid, washed with sodium hydrogen carbonate, tested for peroxide remnants (with ammonia iron(II) sulphate solution), dried over sodium sulphate, filtered and evaporated under vacuum. The crude product is filtered through 900 g silica gel with toluene and ethyl acetate (95:5) to give the product as a yellow oil.

1.3 Synthesis of 4-(benzyloxy)-3-methylphenol 3

(5) ##STR00376##

(6) 23.4 g (91.0 mmol) acetate 2 are solved in 181.0 mL ethanol and 5.84 mL (197.0 mmol) sodium hydroxide solution (32%) are added dropwise to the solution (the reaction solution turned to red color). The reaction mixture is stirred for 2 h at ambient temperature and then poured onto ice water and trated with HCl solution till a pH value of 1 is achieved. The reaction mixture is extracted with methyl tertiary-butyl ether (MTB-E), the organic layer dried over sodium sulphate, filtered and evaporated under vacuum. The black oil is filtered over silica gel with methylene chloride and the obtained solid is then crystallized out of heptane at 25 C. to give slightly brown colored crystals.

(7) .sup.1H NMR (500 MHz, DMSO-d6)

(8) =2.13 ppm (s, 3H, CH.sub.3), 4.99 (s, 2H, CH.sub.2O), 6.51 (dd, J=2.86, 8.62 Hz, 1H), 6.58 (d, J=2.49 Hz, 1H), 6.81 (d, J=8.70 Hz, 1H), 7.32 (d, J=7.23 Hz, 1H), 7.39 (t, J=7.71 Hz, 2H), 7.44 (d, J=8.70 Hz, 2H).

1.4 Synthesis of methyl 4-[(6-hydroxyhexyl)oxy]benzoate 4

(9) ##STR00377##

(10) 40.0 g (263 mmol) methyl 4-hydroxybenzoate and 43.6 g (315 mmol) are dissolved in 150 mL methyl(ethyl)ketone and 49.9 g (276 mmol) 6-bromohexan-1-ol are added and the reaction mixture is heated up to reflux and stirred for 16 h. The reaction mixture is then cooled to room temperature (RT) and the precipitating residue is filtered off, is washed with acetone and dried under vacuum. The crude product is crystallized at 5 C. out of toluene and the product can be used in the next step without further purification.

1.5 Synthesis of methyl 4-[(6-{[tris(propan-2-yl)silyl]oxy}hexyl)oxy]benzoate 5

(11) ##STR00378##

(12) 18.8 g (74.51 mmol) ester 4 and 0.45 g (3.73 mmol) 4-dimethylaminopyridine are solved in 90 mL N,N-dimethylformamide (DMF). 15.8 g (81.96 mmol) chloro-triisopropyl-silane (dissolved in 30 mL DMF) are added dropwise to the reaction mixture at room temperature (RT) and stirred for 16 h. The reaction mixture is diluted with methyl tertiary-butyl ether (MTB-E) and poured in ice water. The layers are separated and the organic layer is dried over sodium sulphate, filtered and evaporated under vacuum to give the product as an oil which is further purified by column chromatography with silica gel and 1-chlorobutane. The product is a slightly yellow oil.

1.6 Synthesis of 4-[(6-{[tris(propan-2-yl)silyl]oxy}hexyl)oxy]benzoic acid 6

(13) ##STR00379##

(14) 27.0 g (66.0 mmol) of ester 5 are dissolved in a mixture of 160 mL methanol and 80 mL tetrahydrofuran and 90 mL NaOH (2N). The reaction mixture is stirred for 2 h at 40 C. The reaction mixture is cooled to room temperature (RT), poured cautiously onto ice water, neutralized with HCl (2N) and extracted with ethyl acetate. The organic layer is washed with brine, dried over sodium sulphate, filtered and evaporated under vacuum to give the product as a white solid which is purified by crystallization out of ethyl acetate at 3 C. to give white crystalline solid.

(15) .sup.1H NMR (500 MHz, DMSO-d6)

(16) =1.02 ppm (m.sub.c, 21 H, Si(C.sub.3H.sub.7).sub.3), 1.34-1.47 (m, 4H, CH.sub.2), 1.51 (quint, J=6.57 Hz, 2H, CH.sub.2), 1.73 (quint, J=6.01 Hz, 2H, CH.sub.2), 3.69 (t, J=6.33 Hz, 2H, CH.sub.2), 4.02 (t, J=6.45 Hz, 2H, CH.sub.2), 6.98 (d, J=8.91 Hz, 2H), 7.87 (J=8.89 Hz, 2H).

1.7 Synthesis of 4-(benzyloxy)-3-methylphenyl 4-[(6-{[tris(propan-2-yl)silyl]oxy}hexyl)oxy]benzoate 7

(17) ##STR00380##

(18) 28.0 g (70.7 mmol) of acid 6, 15.5 g (72.18 mmol) phenol 3 and 1.72 g (14.15 mmol) 4-dimethylaminopyridine are solved in 280 mL methylene chloride. The reaction mixture is treated successively with 16.2 g (84.89 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide hydrochloride and stirred for 16 h at room temperature (RT). The reaction mixture is diluted with water and extracted with methylene chloride. The combined organic layers are washed with brine, dried over sodium sulphate, filtered and evaporated under vacuum to yield a yellow solid. The crude product is purified via column chromatography with silica gel and heptane/ethyl acetate (8:2) to give a colorless solid.

1.8 Synthesis of 4-hydroxy-3-methylphenyl 4-[(6-{[tris(propan-2-yl)silyl]oxy}hexyl)oxy]benzoate 8

(19) ##STR00381##

(20) 39.0 g (65.8 mmol) of compound 7 are dissolved in 390 mL tetrahydrofuran and 15.0 g (140.9 mmol) PdC (5% basic) are added and the reaction mixture is treated with hydrogen atmosphere under normal pressure and room temperature for 45 min. The catalyst was filtered off and the reaction mixture was evaporated under vacuum. The crude product (oil which crystallizes) is purified via column chromatography with 1-chlorobutane and ethyl acetate (8:2). The resulting product is crystallized with acetonitrile.

(21) .sup.1H NMR (500 MHz, CDCl.sub.3)

(22) =1.06 (m.sub.c, 21 H, Si(C.sub.3H.sub.7).sub.3), 1.40-1.53 (m, 2H, CH.sub.2), 1.56 (quint, J=7.73 Hz, 2H, CH.sub.2), 1.83 (7.82 Hz, 2H, CH.sub.2), 2.25 (s, 3H, CH.sub.3), 3.70 (t, J=6.46 Hz, 2H, CH.sub.2), 4.04 (t, J=6.53 Hz, 2H, CH.sub.2), 4.78 (s, 1H, OH), 6.76 (d, J=8.58 Hz, 1H), 6.88 (dd, J=2.76, 8.56 Hz, 1H), 6.95 (m.sub.c, 3 H), 8.12 (d, J=8.91 Hz).

1.9 Synthesis of methyl (2E)-3-{4-[(6-hydroxyhexyl)oxy]phenyl}-prop-2-enoate 9

(23) ##STR00382##

(24) 25.9 g (145 mmol) methyl (2E)-3-(4-hydroxyphenyl)prop-2-enoate, 24.2 g (175 mmol) potassium carbonate are solved in 451 mL N,N-dimethylformamide (DMF) and heated to 90 C. 28.7 g (159 mmol) 6-bromohexan-1-ol is added and the mixture is stirred at 90 C. for 16 h. The reaction mixture is cooled to room temperature (RT), diluted with water and methyl tertiary-butyl ether (MTB-E) and the layers are separated. The organic layer is washed with water and brine and is filtered and evaporated under vacuum. The resulting crude product is crystallized from toluene to give white crystalline solid.

1.10 Synthesis of methyl (2E)-3-{4-[(6-{[tris(propan-2-yl)silyl]oxy}-hexyl)oxy]phenyl}prop-2-enoate 10

(25) ##STR00383##

(26) 26.5 g (93.5 mmol) ester 9 are dissolved in N,N-dimethylformamide (DMF) and 0.57 g (4.67 mmol) 4-dimethylaminopyridine is added. 19.8 g (102.8 mmol) chloro-triisopropyl-silane (dissolved in 36 mL DMF) are added dropwise and the reaction mixture is stirred at room temperature for 16 h. The reaction mixture is diluted with methyl tertiary-butyl ether (MTB-E) and poured onto ice water. The organic layer is separated, dried over sodium sulphate, filtered and evaporated under vacuum. The crude product is purified via column chromatography (silica gel, heptane/MTB-E 9:1) to yield a colorless oil.

1.11 Synthesis of methyl (2E)-3-{4-[(6-{[tris(propan-2-yl)silyl]oxy}-hexyl)oxy]phenyl}prop-2-enoate 11

(27) ##STR00384##

(28) 33.7 g (77.0 mmol) is dissolved in 187 mL methanol and 94 mL tetrahydrofuran. 97.4 mL (195 mmol) NaOH (2N) is added and the reaction mixture is stirred at 38 C. for 4 h. The mixture is cooled to room temperature (RT) and poured in ice water. 2N HCl is added to get a pH value of 5-6 followed by an extraction with ethyl acetate. The combined organic layers are washed with brine, dried over sodium sulphate, filtered and evaporated under vacuum. The crude product is crystallized with acetonitrile to give a white crystalline solid.

(29) .sup.1H NMR (500 MHz, DMSO-d6)

(30) =1.02 ppm (s, 21H, Si(C.sub.3H.sub.7).sub.3), 1.41 (m.sub.c, 4 H, CH.sub.2), 1.52 (quint, J=6.77 Hz, 2H, CH.sub.2), 1.72 (quint, J=7.39 Hz, 2H, CH.sub.2), 3.66 (t, J=6.36 Hz, 2H, CH.sub.2), 4.00 (t, J=6.46 Hz, 2H, CH.sub.2), 6.37 (d, J=15.96 Hz, 1H, trans HCCH), 6.94 (d, J=8.78 Hz, 1H), 7.54 (d, J=15.94 Hz, 1H, trans HCCH), 7.62 (d, J=8.78 Hz, 1H).

1.12 Synthesis of 3-methyl-4-{[(2E)-3-{4-[(6-{[tris(propan-2-yl)silyl]-oxy}hexyl)oxy]phenyl}prop-2-enoyl]oxy}phenyl 4-[(6-{[tris(propan-2-yl)silyl]oxy}hexyl)oxy]benzoate 12

(31) ##STR00385##

(32) 15.7 g (31.4 mmol) phenole 8, 13.9 g (32.9 mmol) acid 11, 0.76 g (6.29 mmol) 4-dimethylaminopyridine are dissolved in 100 mL methylene chloride and 7.22 g (37.71 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide hydrochloride is added portionwise to the reaction mixture. The yellow reaction mixture is stirred for 16 h at room temperature (RT), diluted with water an extracted with methylene chloride. The organic layer is dried over sodium sulphate, filtered and evaporated under vacuum. The crude product is crystallized from ethyl acetate to give white crystalline solid.

1.13 Synthesis of 4-{[(2E)-3-{4-[(6-hydroxyhexyl)oxy]phenyl}prop-2-enoyl]oxy}-3-methylphenyl 4-[(6-hydroxyhexyl)oxy]benzoate 13

(33) ##STR00386##

(34) 21.5 g (23.8 mmol) cinnamate 12 are dissolved in 151 mL methylene chloride and cooled to 3 C. 19.1 mL (118.9 mmol) triethylamin tris hydrofluoride are added dropwise. The reaction mixture is then stirred for 16 h at room temperature and poured in water. The layers are separated and the organic layer is washed with brine, dried over sodium sulphate and evaporated under vacuum to give a white solid. The crude product is crystallized out of acetonitrile and the product is obtained as a white crystalline solid.

1.14 Synthesis of 3-methyl-4-{[(2E)-3-[4-({6-[(3-oxoprop-1-en-2-yl)oxy]hexyl}oxy)phenyl]prop-2-enoyl]oxy}phenyl 4-{[6-(prop-2-enoyloxy)hexyl]oxy}benzoate 14

(35) ##STR00387##

(36) 7.50 g (12.6 mmol) of cinnamate 13 is dissolved in 243 mL methylene chloride. 2.74 g (38.0 mmol) acrylic acid, 0.93 g (7.61 mmol) 4-dimethylaminopyridine are added to the solution and the mixture is cooled to 3 C. 6.7 mL (38.0 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide (dissolved in 5 mL methylene chloride) are added dropwise to the reaction mixture so that the temperature stays below 100 C. The mixture is stirred for further 30 min with ice cooling and is stirred for 16 h at room temperature. During this time the reaction mixture turned to a clear solution. The reaction solution is evaporated under vacuum and purified via column chromatography with 1-chlorobutane and ethyl acetate (9:1). The obtained product is then crystallized from acetonitrile to give a white crystalline solid.

(37) Phase sequence: K 59 N 147.6 I

(38) .sup.1H NMR (500 MHz, CDCl.sub.3)

(39) =1.38-1.63 ppm (m, 8H, CH.sub.2), 1.75 (m.sub.c, 4 H, CH.sub.2), 1.86 (m.sub.c, 4 H, CH.sub.2), 2.26 (s, 3H, CH.sub.3), 4.04 (t, J=6.4 Hz, 2H, CH.sub.2), 4.07 (t, J=6.4 Hz, 2H, CH.sub.2), 4.20 (t, J=6.62 Hz, 2H, CH.sub.2), 4.21 (t, J=6.62 Hz, 2H, CH.sub.2), 5.84 (d, J=10.44 Hz, 2H, O(CO)CHCH.sub.(cis)H), 6.15 (dd, J=10.44, 17.35 Hz, 2H, O(CO)CHCH.sub.2), 6.43 (d, J=17.34 Hz, 2H, O(CO)CHCH.sub.(trans)H), 6.54 (d, J=15.92 Hz, 1H, trans HCCH), 6.95 (d, J=8.69, 2H), 6.99 (d, J=8.86, 2H), 7.09 (dd, J=2.71, 8.59 Hz, 1H), 7.14 (d.sub.(overlapped), J=3.0 Hz, 1H), 7.15 (d.sub.(overlapped), J=8.82 Hz, 1H), 7.57 (d, J=8.68 Hz, 2H), 7.87 (d, J=15.89 Hz, 1H, trans HCCH), 8.16 (d, J=8.82 Hz, 2H).

Synthesis Example 2

Synthesis of [3-ethyl-4-[(E)-3-(4-prop-2-enoyloxyphenyl)prop-2-enoyl]oxy-phenyl] (E)-3-(4-prop-2-enoyloxyphenyl)prop-2-enoate (19)

2.1 Synthesis of methyl (E)-3-(4-tetrahydropyran-2-yloxyphenyl)prop-2-enoate (15)

(40) ##STR00388##

(41) 10.00 g (56.12 mmol) methyl (2E)-3-(4-hydroxyphenyl)prop-2-enoate are suspended in 100 ml methylene chloride. After adding 2.12 g (8.44 mmol) toluene-4-sufonatepyridinium 10.15 ml (112 mmol) 3,4-dihydro-2H-pyrane dissolved in 70 ml methyle chloride are added dropwise. The mixture is stirred overnight. After adding water the organic layer is separated, washed with bicarbonate sol. and brine, dried over sodium sulfate and evaporated. The residue is purified via column chromatography with n-heptane/ethyl acetate to give a white solid.

2.2 Synthesis of (E)-3-(4-tetrahydropyran-2-yloxyphenyl)prop-2-enoic acid (16)

(42) ##STR00389##

(43) 14.5 g (55.28 mmol) of cinnamate 15 are dissolved in 200 ml methanol at 40 C. 70 ml of 2 mol/l sodium hydroxide sol. are added. After 2 h refluxing the mixture is acidified (pH 4.5) with hydrochloric acid an extracted with ethyl acetate. The organic layer is dried over sodiumsulfate and the solvent is evaporated. 16 is obtained as a yellowish solid.

2.3 Synthesis of [3-ethyl-4-[(E)-3-(4-tetrahydropyran-2-yloxyphenyl)prop-2-enoyl]oxy-phenyl] (E)-3-(4-tetrahydropyran-2-yloxyphenyl)prop-2-enoate (17)

(44) ##STR00390##

(45) 10.07 g (52.55 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbo-diimide hydro chloride are added to a solution of 11.86 g (47.77 mmol) of the cinnamatic acid 16, 1.17 g (9.55 mmol) dithylamino pyridine (DMAP) and 3.3 g (23.88 mmo) 2-ethyl benzene-1,4-diol are dissolved in 150 ml methylene chloride. The solution was stirred at room temperature over night. Water is added to the mixture which is extracted with methylene chloride afterwards. The organic layer is dried over sodium sulfate and evaporated. The residue is purified via column chromatography with 1-chlorobutane and ethyl acetate to obtain a white solid.

2.4 Synthesis of [3-ethyl-4-[(E)-3-(4-hydroxyphenyl)prop-2-enoyl]oxy-phenyl] (E)-3-(4-hydroxyphenyl)prop-2-enoate (18)

(46) ##STR00391##

(47) 30.0 ml hydrochloric acid (2 mol/l, 60 mmol) are added to a solution of 11.60 g (19.38 mmol) 18 in 400 ml THF at a temperature below 10 C. The mixture is stirred at room temperature for 4, neutralized with sodium bicarbonate sol. and extracted with ethylene acetate. The organic layer is washed with brine, dried over sodium sulfate, filtrated and evaporated obtain a white solid.

2.5 Synthesis of methyl [3-ethyl-4-[(E)-3-(4-prop-2-enoyloxyphenyl)prop-2-enoyl]oxy-phenyl] (E)-3-(4-prop-2-enoyloxyphenyl)prop-2-enoate (19)

(48) ##STR00392##

(49) 2.00 g (4.65 mmol) of cinnamate 18 is suspended in 60 mL methylene chloride. 0.77 g (10.69 mmol) acrylic acid, 56.8 mg (0.46 mmol) 4-dimethylaminopyridine are added to the suspension and the mixture is cooled to 3 C. 1.89 mL (10.69 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbo-diimide (dissolved in 5 mL methylene chloride) are added dropwise to the reaction mixture so that the temperature stays below 10 C. The mixture is stirred for further 30 min with ice cooling and is stirred for 16 h at room temperature. During this time the reaction mixture turned to a clear solution. The reaction solution is evaporated under vacuum and purified via column chromatography with 1-chlorobutane and ethyl acetate. The obtained product is then crystallized from acetonitrile to give a white crystalline solid, m.p. 175 C. (decomp.).

(50) .sup.1H NMR (500 MHz, DMSO)

(51) =1.16 ppm (t, J=7.61 Hz, 3H, CH.sub.3), 2.55 (q, J=7.61 Hz, 2H, CH.sub.2), 6.21 (dd, J=1.1 Hz, J=10.44 Hz, 2H, O(CO)CHCH.sub.(cis)H), 6.46 (dd, J=10.38, 17.35 Hz, 2H, O(CO)CHCH.sub.2), 6.60 (d, J=17.35 Hz, 2H, O(CO)CHCH.sub.(trans)H), 6.92 (d, J=16.23 Hz, 1H, trans HCCH), 6.97 (d, J=16.17 Hz, 1H, trans HCCH), 7.16 (dd, J=2.89, J=8.67, 1H), 7.25 (m, 2H), 7.33 (dd, J=1.16, 8.56 Hz, 4H), 7.95 (m.sub.c, 6H).

Synthesis Example 3

Synthesis of

(52) ##STR00393##

3.1 Synthesis of methyl 4-triisopropylsilyloxybenzoate (20)

(53) ##STR00394##

(54) 5.61 g (37.25 mmol) methyl 4-hydroxybenzoate and 0.22 g (1.86 mmol) 4-dimethylaminopyridine are solved in 45 mL N,N-dimethylformamide (DMF). 7.9 g (41.00 mmol) chloro-triisopropyl-silane (dissolved in 30 mL DMF) are added dropwise to the reaction mixture at room temperature (RT) and stirred for 16 h. The reaction mixture is diluted with methyl tertiary-butyl ether (MTB-E) and poured in ice water. The layers are separated and the organic layer is dried over sodium sulphate, filtered and evaporated under vacuum to give the product as an oil which is further purified by column chromatography with silica gel and chloro butane as a solvent.

3.2 Synthesis of 4-triisopropylsilyloxybenzoic acid 21

(55) ##STR00395##

(56) 9.26 g (30.0 mmol) of ester 20 are dissolved in a mixture of 130 mL methanol and 65 mL tetrahydrofuran and 75 mL NaOH (2N). The reaction mixture is stirred for 2 h at 40 C. The reaction mixture is cooled to room temperature (RT), poured cautiously onto ice water, neutralized with HCl (2N) and extracted with ethyl acetate. The organic layer is washed with brine, dried over sodium sulphate, filtered and evaporated under vacuum to give the product as a white solid which is purified by crystallization out of ethyl acetate at 3 C. to give white crystalline solid.

3.3 Synthesis of (4-benzyloxy-3-methyl-phenyl) 4-triisopropylsilyloxybenzoate 22

(57) ##STR00396##

(58) 7.3 g (25 mmol) of acid 21, 5.2 g (26 mmol) phenol 3 and 0.62 g (5.1 mmol) 4-dimethylaminopyridine are solved in 100 mL methylene chloride. The reaction mixture is treated successively with 5.8 g (29.5 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide hydrochloride and stirred for 16 h at room temperature (RT). The reaction mixture is diluted with water and extracted with methylene chloride. The combined organic layers are washed with brine, dried over sodium sulphate, filtered and evaporated under vacuum to yield a yellow solid. The crude product is purified via column chromatography with silica gel and heptane/ethyl acetate (8:2)

3.4 Synthesis of (4-hydroxy-3-methyl-phenyl) 4-triisopropylsilyloxybenzoate 23

(59) ##STR00397##

(60) 9.85 g (20 mmol) of compound 22 are dissolved in 120 mL tetrahydrofuran and 4.56 g (42.8 mmol) PdC (5% basic) are added and the reaction mixture is treated with hydrogen atmosphere under normal pressure and room temperature for 45 min. The catalyst was filtered off and the reaction mixture was evaporated under vacuum. The crude product (oil which crystallizes) is purified via column chromatography with 1-chlorbutane and ethyl acetate (8:2). The resulting product is crystallized with acetonitrile.

3.5 Synthesis of [3-methyl-4-[(E)-3-[4-(6-triisopropylsilyloxyhexoxy)-phenyl]prop-2-enoyl]oxy-phenyl] 4-triisopropylsilyloxybenzoate 24

(61) ##STR00398##

(62) 6.0 g (15.0 mmol) phenole 23, 6.7 g (16 mmol) acid 11, 0.37 g (3.04 mmol) 4-dimethylaminopyridine are dissolved in 50 mL methylene chloride and 3.5 g (18.2 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide hydrochloride is added portionwise to the reaction mixture. The yellow reaction mixture is stirred for 16 h at room temperature (RT), diluted with water an extracted with methylene chloride. The organic layer is dried over sodium sulphate, filtered and evaporated under vacuum. The crude product is crystallized from ethyl acetate to give white crystalline solid.

3.6 Synthesis of [4-[(E)-3-[4-(6-hydroxyhexoxy)phenyl]prop-2-enoyl]oxy-3-methyl-phenyl] 4-hydroxybenzoate 25

(63) ##STR00399##

(64) 16.1 g (20.0 mmol) cinnamate 24 are dissolved in 125 mL methylene chloride and cooled to 3 C. 15.9 mL (157 mmol) triethylamin tris hydrofluoride are added dropwise. The reaction mixture is then stirred for 16 h at room temperature and poured in water. The layers are separated and the organic layer is washed with brine, dried over sodium sulphate and evaporated under vacuum to give a white solid. The crude product is crystallized out of acetonitrile and the product is obtained as a white crystalline solid.

3.7 Synthesis of [3-methyl-4-[(E)-3-[4-[6-(2-methylprop-2-enoyloxy)hexoxy]phenyl]prop-2-enoyl]oxy-phenyl] 4-(2-methylprop-2-enoyloxy)benzoate 26

(65) ##STR00400##

(66) 8.34 g (17.0 mmol) of cinnamate 25 is dissolved in 330 mL methylene chloride. 4.41 g (51.3 mmol) methacrylic acid, 1.43 g (10.16 mmol) 4-dimethylaminopyridine are added to the solution and the mixture is cooled to 3 C. 8.9 mL (51.0 mmol) N-(3-dimethylaminoproyl)-N-ethylcarbodiimide (dissolved in 77 mL methylene chloride) are added dropwise to the reaction mixture so that the temperature stays below 10 C. The mixture is stirred for further 30 min with ice cooling and is stirred for 16 h at room temperature. During this time the reaction mixture turned to a clear solution. The reaction solution is evaporated under vacuum and purified via column chromatography with 1-chlorobutane and ethyl acetate (9:1). The obtained product is then crystallized from acetonitrile to give a white crystalline solid.

(67) In analogy to Synthesis examples 1 to 3, the following compounds are obtained:

(68) TABLE-US-00007 Nr Structure 1 01 2 02 3 03 4 04 5 05 6 06 7 07 8 08 9 09 10 0 11 12 13 14 15 16 17 18 19 20 0 21 22 23 24 25 26 27 28 29 30 0 31 32
Fabrication of Display Cells

(69) The display cells are made with raw untreated alkali free glass using 5 m spacer beads in Norland 65 adhesive. The cells are assembled by hand and then cured using a high pressure mercury lamp with 50 mW/cm.sup.2 and 3000 mJ/cm.sup.2.

(70) Cell Filling and Curing

(71) The LC mixtures are capillary filled using capillary action at room temp., annealed for 1 h at 100 C. and then irradiated at the same temperature with linearly polarised UV light (50 mW/cm.sup.2) for 60 s. The cells are then cooled to room temperature.

(72) Nematic Host Mixtures

(73) The nematic LC host mixture N-1 to N-16 are prepared as indicated in the following tables.

(74) TABLE-US-00008 Mixture N-1: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 37.00 T(N, I) = 73.5 C. 2 CCY-3-O1 5.00 n.sub.e (20 C., 589.3 nm) = 1.583 3 CCY-3-O2 9.50 n (20 C., 589.3 nm) = 0.1005 4 CCY-4-O2 5.00 .sub.| | (20 C., 1 kHz) = 3.70 5 CPY-2-O2 10.00 (20 C., 1 kHz) = 3.65 6 CPY-3-O2 10.00 k.sub.1 (20 C.) = 12.7 7 CY-3-O2 11.50 k.sub.3 (20 C.) = 14.7 8 PY-3-O2 12.00 .sub.1 (20 C.) = 93 100.0

(75) TABLE-US-00009 Mixture N-2: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 36.00 T(N, I) = 78.0 C. 2 CC-3-V1 5.00 n.sub.e (20 C., 589.3 nm) = 1.5907 3 CCP-V-1 8.00 n (20 C., 589.3 nm) = 0.1095 4 PGP-2-2V 3.00 .sub.| | (20 C., 1 kHz) = 16.6 5 CCQU-3-F 9.50 (20 C., 1 kHz) = 9.6 6 PUQU-3-F 8.50 k.sub.1 (20 C.) = 12.1 7 APUQU-2-F 5.00 k.sub.3 (20 C.) = 13.4 8 APUQU-3-F 8.00 .sub.1 (20 C.) = 78 9 PGUQU-3-F 4.00 10 PGUQU-4-F 8.00 11 PGUQU-5-F 5.00 100.0

(76) TABLE-US-00010 Mixture N-3: Composition Compound No. Abbreviation c/% Physical properties 1 APUQU-2-F 6.00 T (N, I) = 73.5 C. 2 APUQU-3-F 6.00 n.sub.e (20 C., 589.3 nm) = 1.5902 3 CC-3-V 44.5 n (20 C., 589.3 nm) = 0.1086 4 CC-3-V1 4.00 .sub.| | (20 C., 1 kHz) = 12.9 5 CCP-3-OT 7.00 (20 C., 1 kHz) = 9.6 6 CCP-V-1 5.00 k.sub.1 (20 C.) = 12.4 7 CPGU-3-OT 3.00 k.sub.3 (20 C.) = 13.8 8 PGP-2-2V 5.50 .sub.1 (20 C.) = 67 9 PGUQU-3-F 3.00 10 PGUQU-4-F 7.00 11 PGUQU-5-F 3.00 12 PUQU-3-F 6.00 100.0

(77) TABLE-US-00011 Mixture N-4: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 44.00 T (N, I) [ C.] = 80.5 2 CC-3-V1 12.00 n.sub.e (20 C., 589.3 nm) = 1.5865 3 CCP-V-1 11.00 n (20 C., 589.3 nm) = 0.0991 4 CCP-V2-1 9.00 .sub.| | (20 C., 1 kHz) = 5.3 5 PGP-2-3 6.00 (20 C., 1 kHz) = 2.7 6 PGUQU-3-F 6.00 k.sub.1 (20 C.) = 14.6 7 APUQU-3-F 4.50 k.sub.3 (20 C.) = 15.9 8 PP-1-2V1 7.00 .sub.1 (20 C.) [mPa s] = 53 9 PPGU-3-F 0.50 100.0

(78) TABLE-US-00012 Mixture N-5: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 37.00 T (N, I) = 94.5 2 CC-3-V1 9.50 n.sub.e (20 C., 589.3 nm) = 1.5894 3 CCP-V-1 11.50 n (20 C., 589.3 nm) = 0.1049 4 CCP-V2-1 3.00 .sub.| | (20 C., 1 kHz) = 7.8 5 PGP-2-2V 10.50 (20 C., 1 kHz) = 4.9 6 APUQU-3-F 5.00 k.sub.1 (20 C.) = 15.6 7 APUQU-2-F 5.00 k.sub.3 (20 C.) = 17.1 8 PGUQU-4-F 3.50 .sub.1 (20 C.) [mPa s] = 67 9 PGUQU-3-F 2.00 10 CCP-3-OT 9.00 11 CCP-5-OT 2.00 12 CCQU-3-F 2.00 100.0

(79) TABLE-US-00013 Mixture N-6: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 34.00 T (N, I) [ C.] = 100 2 CC-3-V1 2.50 n.sub.e (20 C., 589.3 nm) = 1.5782 3 CCP-V-1 10.00 n (20 C., 589.3 nm) = 0.1003 4 PUQU-3-F 7.00 .sub.| | (20 C., 1 kHz) = 12.3 5 PGUQU-n-F 4.00 (20 C., 1 kHz) = 9.1 6 CPGU-3-OT 6.00 k.sub.1 (20 C.) = 14.2 7 CCGU-3-F 4.00 k.sub.3 (20 C.) = 17.3 8 APUQU-3-F 8.00 .sub.1 (20 C.) [mPa s] = 99 9 CCU-3-F 4.50 10 CCP-3-OT 4.00 11 CCP-5-OT 3.00 12 CCQU-3-F 10.00 13 CPPC-3-3 3.00 100.0

(80) TABLE-US-00014 Mixture N-7: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 40.50 T (N, I) [ C.] = 80 2 CC-3-V1 6.00 n.sub.e (20 C., 589.3 nm) = 1.5996 3 CCP-V-1 9.50 n (20 C., 589.3 nm) = 0.1127 4 CPU-3-F 7.00 .sub.| | (20 C., 1 kHz) = 10.1 5 CPGU-3-OT 5.00 (20 C., 1 kHz) = 6.9 6 APUQU-2-F 5.00 k.sub.1 (20 C.) = 13.2 7 APUQU-3-F 7.50 k.sub.3 (20 C.) = 13.3 8 PGP-2-3 6.00 .sub.1 (20 C.) [mPa s] = 63 9 PGP-2-4 6.00 10 PPGU-3-F 0.50 11 PUQU-3-F 7.00 100.0

(81) TABLE-US-00015 Mixture N-8: Composition Compound No. Abbreviation c/% Physical properties 1 CGPC-3-3 3.00 T (N, I) [ C.] = 90.4 2 CGPC-5-3 3.00 n.sub.e (20 C., 589.3 nm) = 1.5760 3 CC-3-V 42.50 n (20 C., 589.3 nm) = 0.0913 4 CC-3-V1 8.00 .sub.| | (20 C., 1 kHz) = 7.0 5 CCP-3-1 5.00 (20 C., 1 kHz) = 4.3 6 CCP-3-3 5.00 k.sub.1 (20 C.) = 14.3 7 CCP-V-1 12.00 k.sub.3 (20 C.) = 18.1 8 CCP-V2-1 3.50 .sub.1 (20 C.) [mPa s] = 77 9 DGUQU-4-F 2.00 10 PGUQU-3-F 1.50 11 PGUQU-4-F 1.00 12 PGUQU-5-F 3.00 13 PPGU-3-F 0.50 14 PUQU-3-F 10.00 100.00

(82) TABLE-US-00016 Mixture N-9: Composition Compound No. Abbreviation c/% Physical properties 1 APUQU-2-F 6.00 T (N, I) [ C.] = 79.5 2 APUQU-3-F 6.00 n.sub.e (20 C., 589.3 nm) = 1.5937 3 CC-3-V 44.50 n (20 C., 589.3 nm) = 0.1095 4 CCP-V-1 12.50 .sub.| | (20 C., 1 kHz) = 15.1 5 CPGU-3-OT 5.00 (20 C., 1 kHz) = 11.6 6 DPGU-4-F 2.00 k.sub.1 (20 C.) = 11.9 7 PGP-2-2V 1.50 k.sub.3 (20 C.) = 13.5 8 PGUQU-3-F 4.50 .sub.1 (20 C.) [mPa s] = 72 9 PGUQU-4-F 8.00 10 PUQU-3-F 10.00 100.00

(83) TABLE-US-00017 Mixture N-10: Composition Compound No. Abbreviation c/% Physical properties 1 APUQU-2-F 6.00 T (N, I) [ C.] = 94.6 2 APUQU-3-F 6.00 n.sub.e (20 C., 589.3 nm) = 1.5767 3 PGUQU-3-F 3.00 n (20 C., 589.3 nm) = 0.0919 4 CCGU-3-F 4.00 .sub.| | (20 C., 1 kHz) = 7.0 5 CC-3-V 42.00 (20 C., 1 kHz) = 4.3 6 CC-3-V1 8.00 k.sub.1 (20 C.) = 15.0 7 PP-1-2V1 3.00 k.sub.3 (20 C.) = 18.8 8 CCP-V-1 15.50 .sub.1 (20 C.) [mPa s] = 75 9 CCP-V2-1 15.50 10 PPGU-3-F 0.50 100.00

(84) TABLE-US-00018 Mixture N-11: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 36.00 T (N, I) [ C.] = 78 2 CC-3-V1 5.00 n.sub.e (20 C., 589.3 nm) = 1.5907 3 CCP-V-1 8.00 n (20 C., 589.3 nm) = 0.1095 4 PGP-2-2V 3.00 .sub.| | (20 C., 1 kHz) = 16.6 5 CCQU-3-F 9.50 (20 C., 1 kHz) = 12.9 6 PUQU-3-F 8.50 k.sub.1 (20 C.) = 12.1 7 APUQU-2-F 5.00 k.sub.3 (20 C.) = 13.4 8 APUQU-3-F 8.00 .sub.1 (20 C.) [mPa s] = 78 PGUQU-3-F 4.00 PGUQU-4-F 8.00 PGUQU-5-F 5.00 100.00

(85) TABLE-US-00019 Mixture N-12: Composition Compound No. Abbreviation c/% Physical properties 1 APUQU-2-F 6.00 T (N, I) [ C.] = 94 2 APUQU-3-F 8.00 n.sub.e (20 C., 589.3 nm) = 1.5776 3 CDUQU-3-F 10.00 n (20 C., 589.3 nm) = 0.1038 4 DGUQU-4-F 4.00 .sub.| | (20 C., 1 kHz) = 21.1 5 DPGU-4-F 5.00 (20 C., 1 kHz) = 17.3 6 PGUQU-3-F 3.00 k.sub.1 (20 C.) = 15.9 7 PGUQU-4-F 7.00 k.sub.3 (20 C.) = 16.1 8 CCQU-3-F 9.00 .sub.1 (20 C.) [mPa s] = 111 9 CC-3-2V1 10.00 10 CC-3-V 24.50 11 CC-3-V1 9.50 12 CCP-3-OT 4.00 100.00

(86) TABLE-US-00020 Mixture N-13: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 30.00 T (N, I) [ C.] = 87 2 CC-3-V1 10.00 n.sub.e (20 C., 589.3 nm) = 1.5829 3 CC-3-4 2.50 n (20 C., 589.3 nm) = 0.1019 4 CCP-V-1 1.50 .sub.| | (20 C., 1 kHz) = 3.5 5 PGIY-2-O4 4.00 (20 C., 1 kHz) = 3.7 6 CCY-3-O2 10.00 k.sub.1 (20 C.) = 15.2 7 CCY-5-O2 2.00 k.sub.3 (20 C.) = 18.0 8 CLY-3-O2 8.00 .sub.1 (20 C.) [mPa s] = 112 9 CPY-2-O2 6.00 10 CPY-3-O2 10.00 11 CY-3-O2 12.00 12 B-2O-O5 4.00 100.00

(87) TABLE-US-00021 Mixture N-14: Composition Compound No. Abbreviation c/% Physical properties 1 CPP-3-2 4.50 T (N, I) [ C.] = 86 2 CC-3-V 23.50 n.sub.e (20 C., 589.3 nm) = 1.5962 3 CC-3-O1 4.00 n (20 C., 589.3 nm) = 0.1118 4 CCY-3-O2 4.00 .sub.| | (20 C., 1 kHz) = 3.7 5 CCY-3-O3 7.00 (20 C., 1 kHz) = 4.3 6 CCY-4-O2 8.00 k.sub.1 (20 C.) = 15.0 7 CLY-3-O2 8.00 k.sub.3 (20 C.) = 16.7 8 CPY-2-O2 7.00 .sub.1 (20 C.) [mPa s] = 143 9 CPY-3-O2 11.00 10 CY-3-O2 11.00 11 PY-3-O2 12.00 100.00

(88) TABLE-US-00022 Mixture N-15: Composition Compound No. Abbreviation c/% Physical properties 1 CC-3-V 37.00 T (N, I) [ C.] = 75.2 2 PY-3-O2 11.50 n.sub.e (20 C., 589.3 nm) = 1.5837 3 CCY-3-O2 5.00 n (20 C., 589.3 nm) = 0.1016 4 CY-3-O2 11.50 .sub.| | (20 C., 1 kHz) = 3.7 5 CCY-3-O1 5.00 (20 C., 1 kHz) = 3.7 6 CCY-4-O2 4.00 k.sub.1 (20 C.) = 13.2 7 CLY-3-O2 7.00 k.sub.3 (20 C.) = 15.2 8 CPY-2-O2 9.00 .sub.1 (20 C.) [mPa s] = 99 9 CPY-3-O2 10.00 100.00

(89) TABLE-US-00023 Mixture N-16: Composition Compound No. Abbreviation c/% Physical properties 1 CCY-3-O1 6.00 T (N, I) [ C.] = 75.5 2 CC-3-V 31.50 n.sub.e (20 C., 589.3 nm) = 1.5823 3 CPY-2-O2 10.00 n (20 C., 589.3 nm) = 0.1011 4 CPY-3-O2 10.00 .sub.| | (20 C., 1 kHz) = 3.8 5 PYP-2-3 4.00 (20 C., 1 kHz) = 4.1 6 CCY-3-O2 6.00 k.sub.1 (20 C.) = 13.3 7 CCY-4-O2 2.00 k.sub.3 (20 C.) = 15.1 8 CLY-3-O2 5.00 .sub.1 (20 C.) [mPa s] = 113 9 CY-3-O2 15.00 10 CY-5-O2 5.00 11 CY-3-O4 5.50 100.00

Mixture Examples

(90) Nematic LC mixtures M-1 to M-16 according to the invention are prepared from the nematic host mixtures N-1 to N-16 listed above and photoalignment additives of formula I, according to the compositions given in the following table.

(91) TABLE-US-00024 c [%] of Mixture Host Host Photoalignment additive example Mixture Mixture Compound c [%] M-1 N-1 99.00 Synthesis Example 1 1.00 M-2 N-2 99.00 Synthesis Example 1 1.00 M-3 N-3 99.00 Synthesis Example 1 1.00 M-4 N-4 99.00 Synthesis Example 1 1.00 M-5 N-5 99.00 Synthesis Example 1 1.00 M-6 N-6 99.00 Synthesis Example 1 1.00 M-7 N-7 99.00 Synthesis Example 1 1.00 M-8 N-8 99.00 Synthesis Example 1 1.00 M-9 N-9 99.00 Synthesis Example 1 1.00 M-10 N-10 99.00 Synthesis Example 1 1.00 M-11 N-11 99.00 Synthesis Example 1 1.00 M-12 N-12 99.00 Synthesis Example 1 1.00 M-13 N-13 99.00 Synthesis Example 1 1.00 M-14 N-14 99.00 Synthesis Example 1 1.00 M-15 N-15 99.00 Synthesis Example 1 1.00 M-16 M-16 99.00 Synthesis Example 1 1.00

Alignment Experiments

(92) Test displays are fabricated using raw untreated glass or ITO glass, are then filled with a nematic mixture according to mixture examples M-1 and M-2, respectively, and then cured, as described above.

(93) Next, the alignment quality is studied between crossed polarisers on a light box. A good dark state is observed when the cells are placed between crossed polarisers. A good transmissive state is observed when the cells are rotated by 45.

(94) This shows, that excellent uniform planar alignment is achieved with mixtures from examples M1 and M-2.

(95) In a comparative experiment, a test display is filled with a nematic host mixture N-1 without a photoalignment additive of formula I and is cured in the same way as described for Mixture Examples M-1 and M-2 according to the invention. In the comparative experiment, under all polarizer configurations an inhomogeneous transmissive state is observed.