LIQUID CRYSTAL COMPOUNDS

Abstract

The invention relates to novel polymerizable liquid crystals of formula (I), to LCP mixtures comprising these compounds and to their uses for optical and electro-optical devices:

##STR00001##

with the proviso the at least one of the polymerisable groups G.sup.1 or G.sup.2 is a naphthalenediyl group.

Claims

1. A compound of formula (I) ##STR00005## wherein G.sup.1 and G.sup.2 independently represent a polymerisable mesogenic residue; Ar represents an aromatic group selected from the group consisting of phenyl or naphthalenediyl; w is 1 or 2; X represents a group selected from the group consisting of —CH2-, —O—, —CO—, —COO—, —OOC—, —CONR′—, —OCOO— and —OCONR′; Sp represents a group of the formula —(CH2)p- in which p is an integer of 1 to 18 and in which one or two non-adjacent —CH.sub.2— groups are optionally replaced by —CH═CH—; or in which one or two —CH.sub.2— groups are optionally replaced by one or two groups selected from the group consisting of —O—, —CO—, —COO—, —OOC—, —CONR′—, —OCOO—, —OCONR′ with the proviso that firstly the spacer group does not contain two adjacent heteroatoms and secondly when X is —CH.sub.2—, p can also have a value of 0; and M represents an achiral group of formula (II) ##STR00006## in which A and B independently represent an optionally substituted six membered isocyclic or heterocyclic group or naphthalenediyl; C is selected from the group consisting of an optionally substituted five and six membered isocyclic or heterocyclic group or naphthalenediyl; n.sup.1 and n.sup.2 are 0 or 1 with the proviso that firstly 1≤n.sup.1+n.sup.2≤2 and secondly, when C is naphthalenediyl 0≤n.sup.1+n.sup.2≤2; Z.sup.1 is selected from the group consisting of —O—, —COO—, —OOC—, —CO—, —CONR′—, —NR′CO—, OCOO—, —OCONR′—, —NR′COO— and a single bond; in which R′ is selected from the group consisting of hydrogen, a lower achiral alkyl group and a lower achiral alkenyl group; Z.sup.2 and Z.sup.3 are independently selected from the group consisting of single bond, —COO—, —OOC—, —CH.sub.2—CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CH═CH—, —C≡C—, —(CH.sub.2).sub.4— and —(CH.sub.2).sub.3O—; and R.sup.1 is selected from the group consisting of —CN, —COR, —COOR, —OCOR, —CONR′R, —NR′COR, OCOOR, —OCONR′R, —NR′COOR, —F, —Cl, —CF.sub.3, —OCF.sub.3, —OR and —R in which R is selected from the group consisting of hydrogen, an achiral C.sub.1-18 alkyl group and an achiral C.sub.4-18 alkenyl group with the double bond at 3-position or higher; and R′ is as defined above.

2. A compound according to claim 1, in which X is selected from —CH.sub.2—, —O—, —COO—, —OOC— and —OCOO—.

3. A compound according to claim 1, in which the integer p of the group Sp has a value of from 1 to 12.

4. A compound according to claim 1, in which the group Z.sup.1 is selected from the group consisting of —O—, —COO—, —OOC—, —OCOO— and a single bond.

5. A compound according to claim 1, in which the groups Z.sup.2 and Z.sup.3 are selected from the group consisting of —COO—, —OOC—, —CH.sub.2CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CH═CH—, —C≡C— and a single bond.

6. A compound according to claim 1, in which the group R.sup.1 is selected from the group consisting of —CN, —COOR, —OCOR, F, Cl, CF.sub.3, OCF.sub.3, OR, R, in which R represents a C.sub.1-12 achiral alkyl, or C.sub.4-12 achiral alkenyl group, with the double bond at position 3 or higher, or hydrogen.

7. A compound according to claim 1, in which the polymerisable mesogenic residues G.sup.1 and G.sup.2 are each independently represented by the group of formula III ##STR00007## wherein D is selected from the group consisting of 1,4-naphthalenediyl, 2,6-naphthalenediyl and 1,5-naphthalenediyl E is selected from the group consisting of optionally substituted 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,4-cyclohexane, trans-1,3-dioxane-2,5-diyl, 1,4-naphthalenediyl, 2,6-naphthalenediyl and 1,5-naphthalenediyl; m is 1 or 0, Z.sup.4 and Z.sup.5 are independently selected from the group consisting of a single bond, —COO—, —OOC—, and —OCOO—, —CH.sub.2—CH.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CH═CH—, —C≡C—, —(CH.sub.2).sub.4— and —(CH.sub.2).sub.3O—; Z.sup.6 represent a group of formula —(CH.sub.2).sub.qX— in which q is an integer having a value of 1 to 18 and X is as defined in claim 1, and in which one or two non-adjacent —CH.sub.2— groups may be optionally replaced by —CH═CH— or in which one or two —CH.sub.2— groups may be replaced by one or two additional linking groups X with the proviso that firstly the group Z.sup.6 does not contain two adjacent heteroatoms and secondly when X is —CH.sub.2, q can also have a value of 0 R.sup.2 represents a polymerisable group selected from the group consisting of CH.sub.2═C(Ph)-, CH.sub.2═CW—COO—, CH.sub.2═CH—COO-Ph-, CH.sub.2═CW—CO—NH—, CH.sub.2═CH—O—, CH.sub.2═CH—OOC—, Ph-CH═CH—, CH.sub.2═CH-Ph-, CH.sub.2═CH-Ph-O—, R.sup.3-Ph-CH═CH—COO—, R.sup.3—OOC—CH═CH-Ph-O— and 2-W-epoxyethyl in which W represents H, Cl, Ph or a lower alkyl, R.sup.3 represents a lower alkyl with the proviso that when R.sup.3 is attached to a phenylene group (-Ph-) it may also represent hydrogen or a lower alkoxy.

8. A compound according to claim 7, in which the group R.sup.2 is selected from the group consisting of CH.sub.2═CW—COO— and CH.sub.2═CH—O—.

9. A LCP mixture comprising the compound of formula (I) according to claim 1.

10. A LCP network comprising a compound according to claim 1 in cross-linked or polymerised form.

11. A method of using a compound according to claim 1, comprising manufacturing an optical or an electro-optical device with the compound according to claim 1.

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

13. A compound according to claim 2, in which the integer p of the group Sp has a value of from 1 to 12.

Description

EXAMPLES

Definitions Used in the Examples

[0086] .sup.1H NMR: .sup.1H nuclear magnetic resonance spectroscopy

[0087] DMSO-d.sub.6: dimethylsulfoxide deuterated

[0088] 300 MHz: 300 MegaHertz

[0089] m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singulet

[0090] DMF: dimethylformamide

[0091] HCl solution (25%): volume percent

[0092] CH.sub.2Cl.sub.2: dichloromethane

[0093] THF: tetrahydrofuran

[0094] In the following examples, the thermotropic phases are abbreviated as follow:

[0095] T.sub.(Cr-N): transition temperature from crystal phase to nematic phase

[0096] T.sub.(N-I): transition temperature from nematic phase to isotrope phase

Example 1: Preparation of 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile Compound 1

[0097] A mixture of 39.1 g (0.2 mol) of 4-(4-cyanophenyl)phenol, 34.5 g (0.26 mol) of potassium carbonate, 4.35 g (0.026 mol) of potassium iodide and 35.5 g (0.26 mol) of 6-chlorohexanol in DMF is heated at 80° C. for 18 h. The solution is then cooled down and poured into 1.2 L of water. The obtained precipitate is filtered off and washed two times with 2 L of water. The solid is then recrystallized from acetonitrile to give 50.4 g of 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile as a white crystalline powder.

Example 2: Preparation of 4-[4-(8-hydroxyoctoxy)phenyl]benzonitrile Compound 2

[0098] The compound 2 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol is replaced by 8-chlorooctanol.

Example 3: Preparation of 4-[4-(10-hydroxydecoxy)phenyl]benzonitrile Compound 3

[0099] The compound 3 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol is replaced by 10-chlorodecanol.

Example 4: Preparation of 4-[4-(11-hydroxyundecoxy)phenyl]benzonitrile Compound 4

[0100] The compound 4 is prepared according to the process described in example 1 for compound 1 with the proviso that 6-chlorohexanol is replaced by 11-chloroundecanol.

Example 5: Preparation of 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate Compound 5

[0101] 52.1 g (0.51 mol) of triethylamine is added dropwise to a solution of 50.4 g (0.17 mol) of 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile dissolved in 450 mL of THF. The mixture is cooled down to 0° C. and 23.5 g (0.204 mol) of methanesulfonyl chloride is slowly added. After 3 hours of stirring, the mixture is filtered off under silica and dried by removing the solvent under reduced pressure to give 70.7 g of a yellow oil of 6-[4-(4-cyanophenyl)phenoxy]hexyl methanesulfonate. 27.2 g (0.175 mol) of 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine is added to a solution of 28.1 g (0.179 mol) of 2,5 dihydroxybenzoic acid in 190 mL of DMF. 7.65 g of sodium iodide, 70.7 g (0.170 mol) 6-[4-(4-cyanophenyl)phenoxy]hexyl methanesulfonate in 190 mL of DMF is introduced onto the mixture. After 4 hours, the resulting mixture was poured onto 2 L of cold water. The precipitate is filtered off and washed 2 times with water. The pale yellow solid is recrystallized in CH.sub.3CN to give 57.7 g of 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate as a white powder.

Example 6: Preparation of 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate Compound 6

[0102] The compound 6 is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by 4-[4-(8-hydroxyoctoxy)phenyl]benzonitrile compound 2.

Example 7: Preparation of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate Compound 7

[0103] The compound 7 is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by compound 3.

Example 8: Preparation of 11-[4-(4-cyanophenyl)phenoxy]undecyl 2,5-dihydroxybenzoate Compound 8

[0104] The compound 8 is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by compound 4.

Example 9: Preparation of 6-(6-hydroxyhexoxy)naphthalene-2-carboxylic acid Compound 9

[0105] A mixture of 76.3 g (0.377 mol) of methyl 6-hydroxynaphthalene-2-carboxylate, 68.5 g (0.49 mol) of potassium carbonate, 8.2 g (0.049 mol) of potassium iodide and 67 g (0.49 mol) of 6-chlorohexanol in 250 mL of DMF is heated to 80° C. for 18 h. The solution is then cooled down and poured into 2.6 L of cold water. The precipitate is filtered off and washed two times with water. The product is then recrystallized from acetonitrile to give 94.2 g of a white powder. A mixture of this solid in 680 mL of DMF, 37.95 g of hydroxide sodium, 340 mL of methanol and 75 mL of water is stirred at 60° C. for 4 hours. 122.2 g of hydrochloric acid in 782 mL of water is added dropwise. The suspension is filtered off to give 85.8 g of white solid of 6-(6-hydroxyhexoxy)naphthalene-2-carboxylic acid

Example 10: Preparation of 6-(8-hydroxyoctoxy)naphthalene-2-carboxylic acid Compound 10

[0106] The compound 10 is prepared according to the process described in example 9 for compound 9 with the proviso that 6-chlorohexanol is replaced by 8-chlorooctanol.

Example 11: Preparation of 6-(8-hydroxydecoxy)naphthalene-2-carboxylic acid Compound 11

[0107] The compound 11 is prepared according to the process described in example 9 for compound 9 with the proviso that 6-chlorohexanol is replaced by 10-chlorodecanol

Example 12: Preparation of 6-(11-hydroxyundecoxy)naphthalene-2-carboxylic acid Compound 12

[0108] The compound 12 is prepared according to the process described in example 9 for compound 9 with the proviso that 6-chlorohexanol is replaced by 11-chloroundecanol

Example 13: Preparation of [3-[6-[4-(4-cyanophenyl)phenoxy]hexoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 13

[0109] 45.3 g (0.357 mol) of chloropropionic acid chloride in 50 mL of N-Methyl-2-pyrrolidon is added dropwise to 85.8 g (0.297 mol) of 6-(6-hydroxyhexoxy)naphthalene-2-carboxylic acid in 220 ml of N-Methyl-2-pyrrolidon. The mixture is stirred at room temperature for 2 h. Then the solution is poured onto 810 mL of water and the solid is filtered off, dried under vacuum to give 105.25 g.

[0110] 6.1 g (0.0161 mol) of the previous product, 3 g (0.0070 mol) of 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate, 0.2 g of 4-(Dimethylamino)-pyridin and 3.65 g of dicyclohexylcarbodiimide (0.0175 mol) are mixed in 120 mL CH.sub.2Cl.sub.2 and stirred at room temperature overnight. The solution is filtered through hyflo silica and the solution is dried under vacuum to give a white solid. The solid is dissolved in 50 mL CH.sub.2Cl.sub.2 with 3.2 g of triethylamine. The mixture is stirred overnight at 40° C., filtered off and dried under vacuum. The white solid is recrystallized in acetonitrile to give 5.95 g of a white solid [3-[6-[4-(4-cyanophenyl)phenoxy]hexoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate compound 13

[0111] Liquid crystal phase Transition: Compound 13 was observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increased, the crystalline phase changed into nematic phase at 105° C. (T.sub.(Cr-N)) and the isotropic phase appeared to be above 150° C. (T.sub.(N-I)).

[0112] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.80 (s, 2H), 8.11 (m, 4H), 7.95 (m, 3H), 7.86 (d, 4H), 7.80 (d, 1H), 7.76 (d, 2H), 7.58 (d, 1H), 7.43 (d, 2H), 7.28 (d, 2H), 6.94 (d, 2H), 6.32 (m, 2H), 6.13 (m, 2H), 5.93 (m, 2H), 4.10 (m, 10H), 3.73 (t, 2H), 2-0.8 (m, 24H).

Example 14: (acry6-8) Preparation of [3-[8-[4-(4-cyanophenyl)phenoxy]octoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 14

[0113] The compound 14 is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate.

[0114] Liquid crystal phase transition: T.sub.(Cr-N):96° C., T.sub.(N-I)>150° C.

[0115] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.80 (s, 2H), 8.09 (m, 4H), 7.94 (m, 3H), 7.83 (d, 4H), 7.80 (d, 1H), 7.66 (d, 2H), 7.58 (d, 1H), 7.45 (d, 2H), 7.28 (d, 2H), 7.02 (d, 2H), 6.30 (m, 2H), 6.16 (m, 2H), 5.92 (m, 2H), 4.14 (m, 10H), 3.90 (t, 2H), 1.9-0.7 (m, 28H).

Example 15: (acry6-10) Preparation of [3-[10-[4-(4-cyanophenyl)phenoxy]decoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 15

[0116] The compound 15 is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-[4-(4-cyanophenyl)decoxy]octyl 2,5-dihydroxybenzoate.

[0117] Liquid crystal phase transition: T.sub.(Cr-N):107° C., T.sub.(N-I)>150° C.

[0118] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.68 (d, 2H), 7.98 (m, 4H), 7.84 (m, 3H), 7.73 (d, 4H), 7.67 (dd, 1H), 7.58 (d, 2H), 7.47 (d, 1H), 7.36 (d, 2H), 7.17 (d, 2H), 6.92 (d, 2H), 6.24 (m, 2H), 6.10 (m, 2H), 5.81 (m, 2H), 3.98 (m, 10H), 3.85 (t, 2H), 1.9-0.7 (m, 32H).

Example 16: Preparation of [3-[11-[4-(4-cyanophenyl)phenoxy]undecoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 16

[0119] The compound 16 is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 11-[4-(4-cyanophenyl)undecoxy]octyl 2,5-dihydroxybenzoate.

[0120] Liquid crystal phase transition: T.sub.(Cr-N): 90° C., T.sub.(N-I):141° C.

Example 17: Preparation of [3-[6-[4-(4-cyanophenyl)phenoxy]hexoxycarbonyl]-4-[6-(11-prop-2-enoyloxyundecoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 17

[0121] The compound 17 is prepared according to the process described in example 13 for compound 13 with the proviso that 6-(6-hydroxyhexoxy)naphthalene-2-carboxylic acid is replaced by 6-(11-hydroxyundecoxy)naphthalene-2-carboxylic acid

[0122] Liquid crystal phase transition: T.sub.(Cr-N):120° C., T.sub.(N-I)>150° C.

Example 18: Preparation of [3-[8-[4-(4-cyanophenyl)phenoxy]octoxycarbonyl]-4-[6-(11-prop-2-enoyloxyundecoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 18

[0123] The compound 18 is prepared according to the process described in example 17 for compound 17 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate

[0124] Liquid crystal phase transition: T.sub.(Cr-N):109° C., T.sub.(N-I)>150° C.

Example 19: Preparation of [3-[10-[4-(4-cyanophenyl)phenoxy]decoxycarbonyl]-4-[6-(11-prop-2-enoyloxyundecoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 19

[0125] The compound 19 is prepared according to the process described in example 17 for compound 17 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-dihydroxybenzoate.

[0126] Liquid crystal phase transition: T.sub.(Cr-N):98° C., T.sub.(N-I)>150° C.

[0127] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.82 (d, 2H), 8.15 (m, 4H), 7.95 (m, 6H), 7.85 (d, 4H), 7.71 (m, 3H), 7.60 (d, 1H), 7.48 (s, 2H), 7.30 (d, 2H), 7.15 (d, 2H), 6.35 (m, 2H), 6.20 (m, 2H), 5.94 (m, 2H), 4.10 (m, 10H), 3.95 (t, 2H), 1.9-0.7 (m, 54H).

Example 20: Preparation of [3-[10-[4-(4-cyanophenyl)phenoxy]decoxycarbonyl]-4-[6-(10-prop-2-enoyloxydecoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 20

[0128] The compound 20 is prepared according to the process described in example 19 for compound 19 with the proviso that 6-(11-hydroxyundecoxy)naphthalene-2-carboxylic acid is replaced by 6-(10-hydroxydecoxy)naphthalene-2-carboxylic acid

[0129] Liquid crystal phase transition: T.sub.(Cr-N):80° C., T.sub.(N-I)>150° C.

Example 21: Preparation of [3-[6-[4-(4-cyanophenyl)phenoxy]hexoxycarbonyl]-4-[6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carbonyl]oxy-phenyl]6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carboxylate Compound 21

[0130] 5 g (0.0140 mol) of 6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carboxylic acid (prepared according to the process described in the U.S. Pat. No. 7,670,505 B2) and 35 mg of BHT are mixed in 50 mL of CH.sub.2Cl.sub.2. 3.5 ml of DMF and 1.9 g (0.0145 mol) of oxalyl chloride are added to this solution. The reaction mixture is subsequently stirred at room temperature for 1 hour and then the excess of oxalyl chloride is removed under reduced pressure. The product is dissolved in CH.sub.2Cl.sub.2 and added dropwise to a solution of 2.7 g (0.0062 mol) of 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate compound 5, 3.85 g of N,N-dimethylcyclohexylamine and 5 mg of 2,6-di-tert-butyl-4-methylphenol in 50 mL of CH.sub.2Cl.sub.2. The resulting mixture is stirred at room temperature for 4 h. Afterward, 3 g of hydrochloric acid 25% and 100 mL of water are added and the phases separated. The organic phase is washed two times with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue is recrystallized on CH.sub.3CN to give 2.45 g of a white solid compound 21.

[0131] Liquid crystal phase transition: T.sub.(Cr-N): 99° C., T.sub.(N-I)>150° C.

[0132] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.95 (s, 2H), 8.32 (m, 2H), 8.16 (m, 4H), 7.96 (d, 3H), 7.80 (m, 5H), 7.57 (m, 5H), 6.96 (d, 2H), 6.34 (m, 2H), 6.20 (m, 2H), 5.96 (m, 2H), 4.26 (m, 4H), 4.09 (m, 6H), 3.77 (t, 2H), 1.75 (m, 8H), 1.6-1.2 (m, 4H), 1.15 (m, 4H).

Example 22: Preparation of [3-[8-[4-(4-cyanophenyl)phenoxy]octoxycarbonyl]-4-[6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carbonyl]oxy-phenyl]6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carboxylate Compound 22

[0133] The compounds 22 is prepared according to the process described in example 21 for compound 21 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 8-[4-(4-cyanophenyl)phenoxy]octyl 2,5-dihydroxybenzoate.

[0134] Liquid crystal phase transition: T.sub.(Cr-N):103° C., T.sub.(N-I)>150° C.

Example 22A: Preparation of 10-(4-phenylphenoxy)decan-1-ol Compound 22A

[0135] The compound 22A is prepared according to the process described in example 3 for compound 3 with the proviso that 4-(4-cyanophenyl)phenol is replaced by 4-phenylphenol.

Example 22B: Preparation of 10-[4-(p-tolyl)phenoxy]decan-1-ol compound 22B

[0136] The compound 22B is prepared according to the process described in example 3 for compound 3 with the proviso that 4-(4-cyanophenyl)phenol is replaced by 4-(p-tolyl)phenol.

Example 22C: Preparation of 6-(10-hydroxydecoxy)naphthalene-2-carbonitrile Compound 22C

[0137] The compound 22C is prepared according to the process described in example 3 for compound 3 with the proviso that 4-(4-cyanophenyl)phenol is replaced by 6-hydroxynaphthalene-2-carbonitrile.

Example 22D: Preparation of 6-(3-hydroxypropoxy)naphthalene-2-carboxylic acid Compound 22D

[0138] The compound 22D is prepared according to the process described in example 9 for compound 9 with the proviso that 6-chlorohexanol is replaced by 3-bromopropanol.

Example 22E: Preparation of 10-(4-phenylphenoxy)decyl 2,5-dihydroxybenzoate Compound 22E

[0139] The compound 22E is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by 10-(4-phenylphenoxy)decan-1-ol compound.

Example 22F: Preparation of 10-[4-(p-tolyl)phenoxy]decyl 2,5-dihydroxybenzoate Compound

[0140] The compound 22F is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by 10-[4-(p-tolyl)phenoxy]decan-1-ol compound.

Example 22G: Preparation of 10-[(6-cyano-2-naphthyl)oxy]decyl 2,5-dihydroxybenzoate Compound 22G

[0141] The compound 22G is prepared according to the process described in example 5 for compound 5 with the proviso that 4-[4-(6-hydroxyhexoxy)phenyl]benzonitrile is replaced by 6-(10-hydroxydecoxy)naphthalene-2-carbonitrile compound 22G.

Example 22H: Preparation of [3-[10-(4-phenylphenoxy)decoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate compound 22H

[0142] The compound 22H is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-(4-phenylphenoxy)decyl 2,5-dihydroxybenzoate.

[0143] Liquid crystal phase transition: T.sub.(Cr-N): 90° C., T.sub.(N-I):127° C.

[0144] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.78 (d, 2H), 8.12 (m, 4H), 7.96 (m, 3H), 7.75 (dd, 1H), 7.57 (m, 5H), 7.42 (dd, 4H), 7.28 (m, 3H), 6.97 (d, 2H), 6.32 (m, 2H), 6.18 (m, 2H), 5.89 (m, 2H), 4.10 (m, 10H), 3.93 (t, 2H), 1.9-0.7 (m, 32H).

Example 22I: Preparation of [4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-3-[10-[4-(p-tolyl)phenoxy]decoxycarbonyl]phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 22I

[0145] The compound 22I is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-[4-(p-tolyl)phenoxy]decyl 2,5-dihydroxybenzoate.

[0146] Liquid crystal phase transition: T.sub.(Cr-N): 93° C., T.sub.(N-I): 152° C.

[0147] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.80 (d, 2H), 8.12 (m, 4H), 7.94 (m, 3H), 7.76 (dd, 1H), 7.52 (m, 7H), 7.24 (dd, 4H), 6.96 (d, 2H), 6.30 (m, 2H), 6.17 (m, 2H), 5.95 (m, 2H), 4.13 (m, 10H), 3.93 (t, 2H), 2.32 (s, 3H), 1.9-0.7 (m, 32H).

Example 22J: Preparation of [3-[10-[(6-cyano-2-naphthyl)oxy]decoxycarbonyl]-4-[6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(6-prop-2-enoyloxyhexoxy)naphthalene-2-carboxylate Compound 22J

[0148] The compound 22J is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-[(6-cyano-2-naphthyl)oxy]decyl 2,5-dihydroxybenzoate.

[0149] Liquid crystal phase transition: T.sub.(Cr-N): 71° C., T.sub.(N-I): 137° C.

[0150] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.80 (d, 2H), 8.45 (d, 1H), 8.11 (m, 4H), 7.96 (m, 5H), 7.75 (m, 2H), 7.58 (d, 1H), 7.45 (dd, 3H), 7.29 (d, 3H), 6.30 (m, 2H), 6.19 (m, 2H), 5.94 (m, 2H), 4.10 (m, 12H), 3.85 (t, 2H), 1.9-0.6 (m, 32H).

Example 22K: Preparation of [3-[10-[4-(4-cyanophenyl)phenoxy]decoxycarbonyl]-4-[6-(3-prop-2-enoyloxypropoxy)naphthalene-2-carbonyl]oxy-phenyl]6-(3-prop-2-enoyloxypropoxy)naphthalene-2-carboxylate compound 22K

[0151] The compound 22K is prepared according to the process described in example 13 for compound 13 with the proviso that 6-[4-(4-cyanophenyl)phenoxy]hexyl 2,5-dihydroxybenzoate is replaced by 10-[(6-cyano-2-naphthyl)oxy]decyl 2,5-dihydroxybenzoate and 6-(6-hydroxyhexoxy)naphthalene-2-carboxylic acid is replaced by 6-(3-hydroxypropoxy)naphthalene-2-carboxylic acid.

[0152] Liquid crystal phase transition: T.sub.(Cr-N): 110.4° C., T.sub.(N-I)>160° C.

[0153] .sup.1H NMR (300 MHz) in DMSO-d.sub.6: 8.79 (d, 2H), 8.10 (m, 4H), 7.94 (m, 3H), 7.81 (d, 5H), 7.66 (d, 2H), 7.57 (d, 1H), 7.48 (d, 2H), 7.29 (d, 2H), 7.02 (d, 2H), 6.35 (m, 2H), 6.16 (m, 2H), 5.95 (m, 2H), 4.33 (m, 6H), 4.25 (t, 2H), 4.07 (t, 2H), 3.95 (t, 2H), 2.17 (m, 4H), 1.64 (t, 2H), 1.5-0.5 (m, 14H).

Example 23A: Preparation of an Orientation Layer Using Photoalignment Materials

[0154] A glass substrate is spin-coated with a Photoalignment Composition (2% solid content of a photoaligning material in cyclopentanone as described in patent publication WO2012/085048). The film is dried at 80° C. for 30 s and the resulting film thickness is about 100 nm. Then, the film is exposed to aligning light, which is collimated and linearly polarized UV (LPUV) light (280-320 nm) with 250 mJ/cm.sup.2. The plane of polarization is 0° with regard to a reference edge on the substrate.

Example 23

[0155] A 15.0 w % solution is prepared by mixing the 14.79 w % compound 16, 0.03 w % of 2,6-di-tert-butyl-4-methylphenol, 0.18 w % of Irgacure 369 in cyclohexanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 23A to form a liquid crystal film. This film is dried at 90° C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0156] The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 24

[0157] A film is prepared as in Example 23, with the single difference that the compound 16 is replaced by the compound 21. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 25

[0158] A film is prepared as in Example 23, with the single difference that the compound 16 is replaced by compound 22. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a well oriented nematic mesophase at room temperature.

Example 26

[0159] A film is prepared as in Example 23, with the single difference that Compound 16 is replaced by compound 15. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 26B

[0160] A film is prepared as in Example 23, with the single difference that Compound 16 is replaced by compound 22H. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 26C

[0161] A film is prepared as in Example 23, with the single difference that Compound 16 is replaced by compound 22I. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 26D

[0162] A film is prepared as in Example 23, with the single difference that Compound 16 is replaced by compound 22J. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 26E

[0163] A film is prepared as in Example 23, with the single difference that Compound 16 is replaced by compound 22K. This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Comparative Example 1

[0164] A film is prepared as in Example 23, with the single difference that compound 16 is replaced by 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-(6-prop-2-enoyloxyhexoxy)benzoyl]oxy]benzoate described in the patent application WO2011/003846 A1. This film was dried at 90° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Comparative Example 2

[0165] A film is prepared as in Example 23, with the single difference that compound 16 is replaced by [4-[6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carbonyl]oxyphenyl]6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carboxylate from U.S. Pat. No. 7,670,505 B2 described U.S. Pat. No. 7,670,505 B2 (Paliocolor® LC1057). This film was dried at 100° C. for 5 min onto a temperature controlled hot plate. The resulting film exhibited a very well oriented nematic mesophase at room temperature.

Example 27

[0166] The retardation at 550 nm of the sample described in example 23, example 25, example 26, in comparative example 1 and in comparative example 2 are measured with an Ellipsometer. The thicknesses of the samples are measured by a contact stylus profilometer. The birefringence (Δn) was obtained from the determined retardation and thickness values according to the formula (Δn=Retardation/Thickness). The values are listed in Table 1.

TABLE-US-00001 TABLE 1 Thickness Retardation Example (μm) at 550 nm Δn 23  1.05 236 0.23 25  1.04 233 0.22 26  1.06 256 0.24 26B 1.07 221 0.21 26C 1.12 250 0.22 26D 1.16 271 0.23 26E 1.14 322 0.28 Comparative 1.03 206 0.20 example 2 Comparative 1.03 205 0.20 example 1

[0167] The films of Example 23, 25, 26, 26B, 26C, 26D and 26E have higher birefringence than the films of the comparative example 1 and 2. These new LCPs could be used for preparing phase retarder optical films as Quarter-Waveplate (QWP) and Half-Waveplate (HWP). A retarder transmits light and modifies its polarization state and is widely used in various display application or in security elements. The particularly high birefringence of these new LCPs leads to a significant thickness reduction of the retarder's films. As an example, Table 2 shows the required thickness to get a Half-Waveplate (λ/2) retarder (HWP) at 550 nm with the compounds 15, 16, 22, 22H, 22I, 22J, 22K used in respectively example 26, 23, 25, 26B, 26C, 26D and 26E.

TABLE-US-00002 TABLE 2 Required Thickness for HWP at 550 nm Example (μm) 23   1.20 25   1.25 26   1.15 26B  1.31 26C  1.23 26D 1.2 26E  0.98 Comparative  1.38 example 2 Comparative  1.38 example 1

Example 28: Formation of Polarizing Film Comparative Example 3

[0168] A composition is obtained by mixing the following components:

[0169] 29.26 part of compound of 10-[4-(4-cyanophenyl)phenoxy]decyl 2,5-bis[[4-(6-prop-2-enoyloxyhexoxy)benzoyl]oxy]benzoate described in the patent application WO2011/003846 A1 is mixed with 1.24 part of a black mixture of Dichroic Dyes® X13 manufactured by BASF, 0.95 part of Irgacure OXE03 manufactured by BASF and 0.016 part of 2,6-Di-tert-butyl-4-methylphenol. This mixture is dissolved in 68.5 part of cyclohexanone.

[0170] The solution is coated by K-bar coating with bar N°3 on a 100 nm photoalignment layer coated on a Glass (D263) substrate which has been subjected exposed to Linear polarized light of 250 mJ. Subsequently the substrate is heated in an oven at 90° C. for 5 min and cooled down to room temperature. The coated LCP layer is then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

Example 29: Formation of Polarizing Film with Comparative Example 4

[0171] A composition is obtained by mixing the following components:

[0172] 29.33 part of [4-[6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carbonyl]oxyphenyl]6-(4-prop-2-enoyloxybutoxycarbonyloxy)naphthalene-2-carboxylate from U.S. Pat. No. 7,670,505 B2 described U.S. Pat. No. 7,670,505 B2 (Paliocolor® LC1057) is mixed with 1.18 part of a black mixture of Dichroic Dyes® X13 manufactured by BASF, 0.95 part of Irgacure OXE03 manufactured by BASF and 0.016 part of 2,6-Di-tert-butyl-4-methylphenol. This mixture is dissolved in 68.5 part of cyclohexanone.

[0173] The solution is coated by K-bar coating with bar N°3 on a 100 nm photoalignment layer coated on a Glass (D263) substrate which has been subjected exposed to Linear polarized light of 250 mJ. Subsequently the substrate is heated in an oven at 90° C. for 5 min and cooled down to room temperature. The coated LCP layer is then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

Example 30: Formation of Polarizing Film with Compound from Example 15

[0174] A composition is obtained by mixing the following components:

[0175] 29.45 part of compound of example 15 is mixed with 1.06 part of a black mixture of Dichroic Dyes® X13 manufactured by BASF, 0.95 part of Irgacure OXE03 manufactured by BASF and 0.016 part of 2,6-Di-tert-butyl-4-methylphenol. This mixture is dissolved in 68.5 part of cyclohexanone.

[0176] The solution is coated by K-bar coating with bar N°3 on a 100 nm photoalignment layer coated on a Glass (D263) substrate which has been subjected exposed to Linear polarized light of 250 mJ. Subsequently the substrate is heated in an oven at 90° C. for 5 min and cooled down to room temperature. The coated LCP layer is then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

Example 31: Formation of Polarizing Film with Compound from Example 15

[0177] A composition was obtained by mixing the following components:

[0178] 16.42 part of compound of example 15 is mixed with 1.00 part of a black mixture of Dichroic Dyes® X13 manufactured by BASF, 0.95 part of Irgacure OXE03 manufactured by BASF and 0.016 part of 2,6-Di-tert-butyl-4-methylphenol. This mixture is dissolved in 82 part of cyclohexanone.

[0179] The solution is coated by K-bar coating with bar N°3 on a 100 nm photoalignment layer coated on a Glass (D263) substrate which has been subjected exposed to Linear polarized light of 250 mJ. Subsequently the substrate is heated in an oven at 90° C. for 5 min and cooled down to room temperature. The coated LCP layer is then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

Example 32: Formation of Polarizing film with compound from example 22K

[0180] A composition is obtained by mixing the following components:

[0181] 16.42 part of compound of example 22K is mixed with 1.00 part of a black mixture of Dichroic Dyes® X13 manufactured by BASF, 0.54 part of Irgacure OXE03 manufactured by BASF and 0.009 part of 2,6-Di-tert-butyl-4-methylphenol. This mixture is dissolved in 82 part of cyclohexanone.

[0182] The solution is coated by K-bar coating with bar N°3 on a 100 nm photoalignment layer coated on a Glass (D263) substrate which has been subjected exposed to Linear polarized light of 250 mJ. Subsequently the substrate is heated in an oven at 100° C. for 5 min and cooled down to room temperature. The coated LCP layer is then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

Example 33: Polarising Film Characteristics

[0183] The dichroic ratio (DR) in absorbance allow to define the polarization performance of a polarizing film. The DR is a material property and therefore it is independent on the thickness of the polarizer. The DR in absorbance can be determined through polarized spectroscopy and is defined as

DR=Log(1/Tperp)/(Log(1/Tparal))

[0184] Tperp is the transmittance of the light entering perpendicular to the transmissive axis of the polarisation film. Tparal is the transmittance of the light entering parallel to the transmissive axis of the polarisation film. The transmittances Tperp and Tparal of example 28 to 32 are measured using an AxoScan polarimeter and they are used to determine the dichroic ratio (DR) at the wavelength 450 nm, 550 nm, 650 nm.

[0185] The thickness of the polarising film of example 28 to 32 is determined by Alpha-Step Stylus profiler.

[0186] The results of the thickness and the DR of the polarising film of example 28 to 32 are summarized in the Table 3.

TABLE-US-00003 TABLE 3 Thickness Dichroic ratio Example Compound (μm) 450 nm 550 nm 650 nm 28 Comparative 5.0 7.2 9.0 10.2  example 3 29 Comparative 5.4 7.0 8.6 9.1 example 4 30 Compound 5.2 8.2 10.9  12.6  15 31 Compound 3.3 8.9 11.7  13.0  15 32 Compound 3.6 10.3  13.6  14.8  22K

[0187] It can be said that as the dichroic ratio is higher, the polarizing film is more efficient. A polarizing film with a high dichroic ratio can be obtained by using the composition of the present invention. Indeed, the polarising films made from the compound 15 and from the compound 22k of the present invention present Dichroic Ratio above 13 where as the DR of the polarising film of comparative example 3 and of comparative example 4 have a maximum DR of 10.2.