Polymerizable compounds and the use thereof in liquid-crystal displays

Abstract

The present invention relates to polymerizable compounds, to processes and intermediates for the preparation thereof, to liquid-crystal media comprising them, and to the use of the polymerizable compounds and liquid crystalline media for optical, electro-optical and electronic purposes, in particular in liquid crystalline displays, especially in liquid crystalline displays of the polymer sustained alignment type.

Claims

1. A compound of formula I
P-Sp-Ar-R  I wherein Ar is ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## which is substituted by at least one group L.sup.a and optionally substituted by one or more groups L, L.sup.a is an alkoxy group with 1 to 12 C atoms that is straight-chain or branched, with the proviso that L.sup.a is not fluorinated, L is on each occurrence identically or differently F, Cl, —CN, P-Sp-, or straight chain alkyl having 1 to 25 C atoms, or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH.sub.2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl, or L has the meaning of L.sup.a, P is a polymerizable group consisting of acrylate or methacrylate, Sp is a spacer group that is a single bond, R is P-Sp-, H or has one of the meanings given for L, wherein, if Ar is one of Ar1 to Ar3, all groups P that are present in the compound have the same meaning.

2. The compound according to claim 1, of the following subformulae ##STR00380## ##STR00381## wherein P, L′, L.sup.a and Sp are as defined in claim 1.

3. A liquid crystalline medium comprising one or more polymerizable compounds formula I as defined in claim 1.

4. The liquid crystalline medium of claim 3, comprising a polymerizable component A) comprising one or more polymerizable compounds of formula I, and a liquid-crystalline liquid crystalline component B) comprising one or more mesogenic or liquid-crystalline compounds.

5. The liquid crystalline medium of claim 3, comprising one or more compounds of the formulae CY and/or PY: ##STR00382## in which the individual radicals have the following meanings: a denotes 1 or 2, b denotes 0 or 1, ##STR00383## denotes ##STR00384## 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—, —CH═CH—, —CO—, —O—CO— or CO—O— in such a way that 0 atoms are not linked directly to one another, Z.sup.x denotes —CH═CH—, —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.

6. The liquid crystalline medium according to claim 3 comprising one or more compounds of the following formulae: ##STR00385## in which the individual radicals, on each occurrence identically or differently, each, independently of one another, have the following meaning: ##STR00386## is ##STR00387## is ##STR00388## is ##STR00389## R.sup.A1 is alkenyl having 2 to 9 C atoms or, if at least one of the rings X, Y and Z denotes cyclohexenyl, also one of the meanings of R.sup.A2, R.sup.A2 is alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that 0 atoms are not linked directly to one another, Z.sup.x is —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —CO—O—, —O—CO—, —C.sub.2F.sub.4—, —CF═CF—, —CH═CH—CH.sub.2O—, or a single bond, L.sup.1-4 each, independently of one another, are H, F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F or CHF.sub.2H, x is 1 or 2, z is 0 or 1.

7. The liquid crystalline medium according to claim 3, comprising one or more compounds of the following formula: ##STR00390## in which the individual radicals have the following meanings: ##STR00391## denotes ##STR00392## ##STR00393## denotes ##STR00394## R.sup.3 and R.sup.4 each, independently of one another, denote alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH.sub.2 groups may be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O— in such a way that 0 atoms are not linked directly to one another, Z.sup.y denotes —CH.sub.2CH.sub.2—, —CH═CH—, —CF.sub.2O—, —OCF.sub.2—, —CH.sub.2O—, —OCH.sub.2—, —COO—, —OCO—, —C.sub.2F.sub.4—, —CF═CF— or a single bond.

8. The liquid crystalline medium according to claim 3, wherein the polymerizable compounds of formula I are polymerized.

9. A process of preparing an liquid crystalline medium of claim 3, comprising mixing one or more mesogenic or liquid-crystalline compounds with one or more compounds of formula I and optionally with further liquid-crystalline compounds and/or additives.

10. A liquid crystalline display comprising a liquid crystalline medium as defined in claim 3.

11. The liquid crystalline display of claim 10, which is a PSA display.

12. The liquid crystalline display of claim 11, which is a PS-VA, PS-OCB, PS-IPS, PS-FFS, PS—UB-FFS, PS-posi-VA or PS-TN display.

13. The liquid crystalline display of claim 10 comprising two substrates, at least one which is transparent to light, an electrode provided on each substrate or two electrodes provided on only one of the substrates, and located between the substrates a layer of an liquid crystalline medium, wherein the polymerizable compounds are polymerized between the substrates of the display.

14. A process for the production of a liquid crystalline display according to claim 13, comprising providing the liquid crystalline medium comprising one or more polymerizable compounds, as defined in claim 7, between the substrates of the display, and polymerizing the polymerizable compounds.

15. A compound of the following formulae ##STR00395## which is substituted by at least one group L.sup.a, wherein L is on each occurrence identically or differently F, Cl, —CN, P-Sp—, or straight chain alkyl having 1 to 25 C atoms, or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH.sub.2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl, or L has the meaning of L.sup.a, L.sup.a is an alkoxy group with 1 to 12 C atoms that in straight-chain or branched and is optionally fluorinated, Sp is a spacer group or a single bond, P is a polymerizable group consisting of acrylate or methacrylate, r1, r3, r7 are independently of each other 0, 1, 2 or 3, r2 is 0, 1, 2, 3 or 4, and r4, r5, r6 are independently of each other 0, 1 or 2, with r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1, R denotes H.

16. A process for preparing a compound of formula I P-Sp-Ar-R I wherein Ar is ##STR00396## which is substituted by at least one group L.sup.a and optionally substituted by one or more groups L, L.sup.a is an alkoxy group with 1 to 12 C atoms that is straight-chain or branched, with the proviso that L.sup.a is not fluorinated, L is on each occurrence identically or differently F, Cl, —CN, P-Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH.sub.2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl, or L has the meaning of L.sup.a, P is a polymerizable group consisting of acrylate or methacrylate, Sp is a spacer group that is a single bond, R is P-Sp-, H or has one of the meanings given for L, wherein, if Ar is one of Ar1 to Ar3, all groups P that are present in the compound have the same meaning, by esterification of a compound of the formula ##STR00397## wherein L is on each occurrence identically of differently F, Cl, —Cn, P-Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH.sub.2- groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O— and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl, or L has the meaning of L.sup.a, Sp is a spacer group or a single bond, r1, r3, r7 are independently of each other 0, 1, 2 or 3, r2 is 0, 1, 2, 3 or 4, r4, r5, r6 are independently of each other 0, 1 or 2, with r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1, R denotes H or Pg-Sp, and Pg denotes OH, using corresponding acids, acid derivatives, or halogenated compounds containing a group P, in the presence of a dehydrating reagent.

Description

EXAMPLE 1

(1) Polymerizable monomeric compound 1 is prepared as follows.

(2) ##STR00367##
1a:

(3) To a solution of 4-bromo-3-methoxylphenol (10.00 g, 49.2 mmol) and 4-benzyloxyphenylboronic acid (13.00 g, 54.2 mmol) in 170 ml 1,4-dioxane was added sodium carbonate (10.44 g, 98.5 mmol) and 40 ml distilled water. After thoroughly degassing with argon, [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (1.08 g, 1.50 mmol) is added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature, the reaction mixture is carefully neutralized with 2 M HCl. The aqueous phase is separated and extracted with ethyl acetate. The organic phase is combined, dried over anhydrous sodium sulfate, and filtrated through silica gel. After removing solvent in vacuo, the obtained crude product is recrystallized from heptane/toluene solvent mixture to provide the product as off-white crystal (8.6 g).

(4) 1b:

(5) A solution of 1a (6.54 g, 21.0 mmol) in tetrahydrofuran (70 ml) is treated with palladium (5%) on activated charcoal (2.0 g) and submitted to hydrogenation for 17 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The residue is recrystallized from toluene/heptane solvent mixture to 1b as off-white solid (4.3 g).

(6) 1:

(7) Methacrylic acid (3.56 g, 41.5 mmol) and 4-(dimethylamino)pyridine (0.17 g, 1.4 mmol) is added to a suspension of 1b (3.0 g, 13.9 mmol) in 40 ml dichloromethane. The reaction mixture is treated dropwise at 0° C. with a solution of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (6.44 g, 41.5 mmol) in dichloromethane (20 ml) and stirred for 20 h at room temperature.

(8) After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with dichcloromethane/ethyl acetate 20:1 as eluent. The obtained product is recrystallized from acetonitril to afford white crystals of 1 (2.1 g, mp. 105° C.).

EXAMPLE 2

(9) Polymerizable monomeric compound 2 is prepared from the commercially available 3-fluoro-4-benzyloxylphenyl boronic acid in analogy to Example 1 as follows.

(10) ##STR00368##
2a:

(11) To a solution of 4-bromo-3-methoxylphenol (15.00 g, 70.2 mmol) in 135 ml ethyl methylketone is added potassium carbonate (11.60 g. 84.0 mmol) in several portions. The reaction mixture is heated to reflux, to which benzylbromide (10.0 ml, 84.0 mmol) is added dropwise, and stirred overnight while refluxing. After cooling to room temperature, the reaction mixture is filtrated. The solid residue is washed thoroughly with aceton. After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with heptane/ethyl acetate 9:1 as eluent to provide 2a as yellowish oil (23.6 g).

(12) 2b:

(13) To a solution of 2a (23.50 g, 80.1 mmol) and 4-hydoxylphenyl boronic acid (12.2 g, 88.2 mmol) in 275 ml 1,4-dioxane was added 65 ml dist. water and sodium carbonate (17.00 g, 160.3 mmol). The resulted suspension is degassed carefully with argon. [1,1′-bis(diphenylphosphino)ferrocene]-(II) (1.76 g, 2.4 mmol) is then added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature, the reaction mixture is neutralized carefully with 2 M HCl acid. The aqueous phase is extracted with methyl t-butyl ether. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent, the solid residue is purified by column chromatography with THF/toluene 9:1 as eluent and further recrystallized from hepane/toluene 1:1 to provide 2b as off-white solid (11.7 g).

(14) 2c:

(15) To a solution of 2b (11.7 g, 37.4 mmol) and ethylenecarbonate (3.46 g. 39.2 mmol) in DMF (120 ml) is added dry potassium carbonate (0.52 g, 3.7 mmol). The reaction mixture is refluxed overnight. After cooling to room temperature, the reaction mixture is added into 100 ml water and neutralized carefully with 2 M HCl. The aqueous phase is extracted with ethylacetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent, the solid residue is recrystallized with heptane/ethyl acetate 1:1 to provide 2c as yellowish solid (13.6 g).

(16) 2d:

(17) A suspension of 2c (13.4 g, 37.4 mmol) in tetrahydrofuran (150 ml) is treated with palladium (5%) on activated charcoal (4.3 g) and submitted to hydrogenation for 30 hs. The catalyst is then filtered off. After removing solvent, 2d is obtained as solid (8.5 g).

(18) 2:

(19) Methacrylic acid (7.8 g, 91.4 mmol) and 4-(dimethylamino)pyridine (0.40 g, 3.3 mmol) is added to a suspension of 2d (8.50 g, 32.7 mmol) in dichloromethane (90 ml). The reaction mixture is treated dropwise at 0° C. with a solution of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (15.2 g, 98.9 mmol) in dichloromethane (60 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo, and the oily residue is purified by column chromatography on silica gel with dichloromethane as eluent. The obtained product is recrystallized from ethanol to afford white crystals of 2 (3.7 g, mp. 74° C.).

EXAMPLE 3

(20) Polymerizable monomeric compound 3 is prepared as follows.

(21) ##STR00369##
3a:

(22) To a solution of 1-bromo-3-iodobenzene (100.0 g, 346.0 mmol) and 4-benzyloxylphenyl boronic acid (77.41 g, 340.0 mmol) in 1000 ml toluene was added 500 ml dist. water and 250 ml ethanol. Sodium carbonate (101.0 g, 604.4 mmol) is added. The resulted suspension is degassed carefully with argon. Tetrakis(triphenylphosphine)palladium(0) (14.4 g, 12.4 mmol) is then added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature, the reaction mixture is neutralized carefully with 2 M HCl acid. The aqueous phase is extracted with ethylacetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, the solid residue is purified by column chromatography with heptane/ethyl acetate 4:1 as eluent. The crude product is further recrystallized from toluene to provide 3a as yellowish solid (80.6 g).

(23) 3b:

(24) To a solution of 4-bromo-2-methoxylohenol (25.00 g, 120.6 mmol) and bis(pinacolato)diboron (27.6 g, 108.6 mmol) in 350 ml 1,4-dioxane was added sodium acetate (35.5 g, 362.0 mmol). After thoroughly degassing with argon, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (2.67 g, 3.62 mmol) is added. The reaction mixture is heated to reflux and stirred for 4 hours. After cooling to room temperature, 200 ml dist. water is added. The aqueous phase is separated and extracted with ethyl acetate. The organic phase is combined and dried over anhydrous sodium sulfate, and filtrated through silica gel. After removing solvent in vacuo, the crude product is recrystallized from toluene/ethyl acetate 9:1 to provide 3b as yellowish solid (12.1 g)

(25) 3c:

(26) To a solution of 3a (10.0 g, 28.4 mmol) and 3b (8.25 g, 31.2 mmol) in 100 ml 1,4-dioxane was added 25 ml dist. water. Sodium carbonate (6.04 g, 56.8 mmol) is added. The resulted suspension is degassed carefully with argon, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.63 g, 0.85 mmol) is then added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature, the reaction mixture is neutralized carefully with 2 M HCl acid. The aqueous phase is extracted with ethylacetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, the solid residue is purified by column chromatography with heptane/ethyl acetate mixture as eluent. The crude product is further recrystallized from ethanol to provide 3c as grayisch solid (6.03 g).

(27) 3d:

(28) To a solution of 3c (6.03 g, 14.9 mmol) in 60 ml dichloromethane are added 4-(dimethylamino)pyridine (0.18 g, 1.50 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimidhydrochlorid (DAPECl) (4.00 g, 20.8 mmol). The reaction mixture is stirred at room temperature overnight. 200 ml water is added. The aqueous phase is extracted with dichloromethane. The organic phase is combined and dried over anhydrous sodium sulfate. After removing solvent in vacuo, the solid residue is purified by column chromatography with dichloromethane as eluent to provide 3d as off-white solid (4.5 g).

(29) 3e:

(30) A solution of 3d (4.5 g, 8.43 mmol) in tetrahydrofuran (45 ml) is treated with palladium (5%) on activated charcoal (3.0 g) and submitted to hydrogenation for 20 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The residue is recrystallized from toluene/heptane solvent mixture to provide 3e as yellowish oil (3.04 g).

(31) 3:

(32) Methacrylic acid (2.21 ml, 26.0 mmol) and 4-(dimethylamino)pyridine (0.11 g, 0.86 mmol) is added to a suspension of 3e (3.04 g, 8.6 mmol) in dichloromethane (40 ml). The reaction mixture is treated dropwise at 0° C. with a solution of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (4.6 g, 26.0 mmol) in dichloromethane (30 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo, and the oily residue is purified by column chromatography on silica gel with heptane/ethyl acetate mixture as eluent. The obtained product is recrystallized from heptane/ethanol 1:1 to afford white crystals of 3 (1.6 g, mp. 88° C.).

EXAMPLE 4

(33) Polymerizable monomeric compound 4 is prepared as follows.

(34) ##STR00370##
4a:

(35) To a solution of 5-bromoresorcinol (26.00 g, 135.4 mmol) and ethylenecarbonate (29.00 g. 329.3 mmol) in 400 ml DMF is added dry potassium carbonate (3.75 g, 27.1 mmol). The reaction mixture is refluxed overnight. After cooling to room temperature, the reaction mixture is added into 1000 ml water and neutralized carefully with 2 M HCl. The aqueous phase is extracted with ethyl acetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, the solid residue is recrystallized with heptane/ethyl acetate 4:1 to provide 4a as white solid (24.3 g).

(36) 4b:

(37) To a solution of 4a (5.60 g, 20.1 mol) and 4-benzyloxyl-3-methoxylphenyl boronic acid (5.7 g, 22.0 mmol) in 120 ml 1,4-dioxane was added 23.1 g (100.2 mmol) potassium phosphate. The resulted suspension is degassed carefully with argon. Tris(dibenzylidene acetone)dipalladium(0) (0.37 g, 0.4 mmol) and 2-dicyclohexylphosphine-2′,6′-dimethoxylbiphenyl (SPhos) (0.68 g, 1.6 mmol) is then added. The reaction mixture is heated to reflux and stirred overnight. After cooling to room temperature 200 ml dist. water and 150 ml ethylacetate is added, and the mixture is neutralized carefully with 6 M HCl acid under cooling to pH4. The aqueous phase is extracted with ethylacetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, the solid residue is purified by column chromatography with ethylacetate as eluent, and the obtained crude product is recrystallized from heptane/toluene 1:1 to provide 4b as white solid (3.7 g).

(38) 4c:

(39) A solution of 4b (3.6 g, 7.48 mmol) in 36 ml tetrahydrofuran is treated with palladium (5%) on activated charcoal (0.5 g) and submitted to hydrogenation for 19 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The oily residue is purified by column chromatography on silica gel with ethyl acetate as eluent to provide 4c as light yellow oil (2.5 g).

(40) 4:

(41) Methacrylic acid (2.68 g, 31.2 mmol) and 4-(dimethylamino)pyridine (0.1 g, 0.82 mmol) is added to a suspension of 4c (2.5 g, 7.8 mmol) in 50 ml dichloromethane. The reaction mixture is treated dropwise at 0° C. with a solution of N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide (4.97 g, 32.0 mmol) in 20 ml dichloromethane and stirred for 20 h at room temperature. After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with heptane/ethyl acetate 7:3 as eluent to afford 4 as colorless oil (2.0 g).

EXAMPLES 5-14

(42) The following polymerizable monomeric compounds are prepared in analogy to the methods described in Examples 1-4.

(43) ##STR00371## ##STR00372##

MIXTURE EXAMPLE 1

(44) The nematic LC host mixture N1 is formulated as follows.

(45) TABLE-US-00005 CCH-501 9.00% cl.p. 70.0° C. CCH-35 14.00% Δn 0.0825 PCH-53 8.00% Δε −3.5 CY-3-O4 14.00% ε.sub.|| 3.5 CY-5-O4 13.00% K.sub.3/K.sub.1 1.00 CCY-2-1 9.00% γ.sub.1 141 mPa s CCY-3-1 9.00% V.sub.0 2.10 V CCY-3-O2 8.00% CCY-5-O2 8.00% CPY-2-O2 8.00%

MIXTURE EXAMPLE 2

(46) The nematic LC host mixture N2 is formulated as follows.

(47) TABLE-US-00006 CY-3-O2 18.00% cl.p. +74.5° C. CPY-2-O2 10.00% Δn 0.1021 CPY-3-O2 10.00% Δε −3.1 CCY-3-O2 9.00% ε.sub.|| 3.5 CCY-4-O2 4.00% K.sub.3/K.sub.1 1.16 PYP-2-3 9.00% γ.sub.1 86 mPa s CC-3-V 40.00% V.sub.0 2.29 V

MIXTURE EXAMPLE 3

(48) The nematic LC host mixture N3 is formulated as follows.

(49) TABLE-US-00007 CC-3-V1 9.00% cl.p. 75.4° C. CCH-23 14.00% Δn 0.1055 CCH-34 6.00% Δε −2.8 CCH-35 6.00% ε.sub.|| 3.30 CCP-3-1 7.00% K.sub.3/K.sub.1 1.07 CCY-3-O1 5.00% γ.sub.1 102 mPa s CCY-3-O2 10.00% V.sub.0 2.67 CPY-3-O2 12.00% CY-3-O2 9.50% PP-1-2V1 8.50% PY-3-O2 12.00% PY-4-O2 1.00%

MIXTURE EXAMPLE 4

(50) The nematic LC host mixture N4 is formulated as follows.

(51) TABLE-US-00008 CC-3-V 35.50% cl.p. +75.1° C. CC-3-V1 10.00% Δn 0.1096 CCP-3-1 1.50% Δε −3.1 CLY-3-O2 10.00% ε.sub.|| 3.51 CLY-3-O3 3.00% K.sub.3/K.sub.1 1.115 CPY-2-O2 9.00% γ.sub.1 84 mPa s CPY-3-O2 10.50% V.sub.0 2.37 PY-3-O2 16.50% PYP-2-3 1.00% B-2O-O5 3.00%

POLYMERIZABLE MIXTURE EXAMPLE A

(52) Polymerizable mixtures are prepared by adding one of polymerizable compounds 1 to 14 of Examples 1 to 14, respectively, to nematic LC host mixtures N1 and N2 at a concentration of 0.3% by weight.

(53) For comparison purposes further polymerizable mixtures are prepared by adding polymerizable compound CO of prior art, which has two different polymerizable groups, or one of polymerizable compounds C1-C14 of prior art, which do not contain an alkoxy substituent, respectively, to nematic LC host mixtures N1 and N2 at a concentration of 0.3% by weight.

(54) ##STR00373## ##STR00374##

(55) The composition of the polymerizable mixtures is shown in Table 1.

(56) TABLE-US-00009 TABLE 1 Polymerizable mixture composition Mix. No. P11 P12 P13 P14 P15 P16 P17 P18 P112 P113 P114 LC Host N1 N1 N1 N1 N1 N1 N1 N1 N1 N1 N1 RM 1 2 3 4 5 6 7 8 12 13 14 Mix. No. C10 C11 C12 C13 C14 C15 C16 C17 C18 C112 C114 LC Host N1 N1 N1 N1 N1 N1 N1 N1 N1 N1 N1 RM C0 C1 C2 C3 C4 C5 C6 C7 C8 C12 C14 Mix. No. P21 P22 P23 P24 P25 P26 P27 P28 P212 P213 P214 LC Host N2 N2 N2 N2 N2 N2 N2 N2 N2 N2 N2 RM 1 2 3 4 5 6 7 8 12 13 14 Mix. No. C20 C21 C22 C23 C24 C25 C26 C27 C28 C212 C214 LC Host N2 N2 N2 N2 N2 N2 N2 N2 N2 N2 N2 RM C0 C1 C2 C3 C4 C5 C6 C7 C8 C12 C14

POLYMERIZABLE MIXTURE EXAMPLE B

(57) Polymerizable mixtures are prepared by adding polymerizable compound C1 of prior art or polymerizable compound 1 of Example 1, respectively, to nematic LC host mixtures N3 and N4 at a concentration of 0.3% by weight.

(58) The composition of the polymerizable mixtures is shown in Table 2.

(59) TABLE-US-00010 TABLE 2 Polymerizable mixture composition Mix. No. C31 C41 P31 P41 LC Host N3 N4 N3 N4 RM C1 C1 1 1

USE EXAMPLE A

(60) Polymerizable mixtures C10-C114 and C20-C214, which contain RM C0 of prior art with two different polymerizable groups or one of RMs C.sub.1-C.sub.14 of prior art without an alkoxy substituent, are compared with polymerizable mixtures P11-P114 and P21-C214, which contain one of RMs 1-14 according to the invention with an alkoxy substituent and two identical polymerizable groups.

(61) Residual RM

(62) The polymerization speed is measured by determining the residual content of residual, unpolymerized RM (in % by weight) in the mixture after UV exposure at a given intensity and lamp spectrum.

(63) For this purpose the polymerizable mixtures are inserted into electrooptic test cells. The test cells comprise two soda-lime glass substrates with an ITO electrode layer of approx. 200 nm thickness and a VA-polyimide alignment layer (JALS-2096-R1) of approx. 30 nm thickness. The LC layer thickness is approx. 25 μm.

(64) The test cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 (metal halide lamp with a 320 nm cut-off filter) for the time indicated, causing polymerization of the RM.

(65) The mixture is then rinsed out of the test cell using MEK (methyl ethyl ketone) and the residual amount of unreacted RM is measured by HPLC. The results are shown in Table 3.

(66) TABLE-US-00011 TABLE 3 Residual monomer content Residual RM (%) after Residual RM (%) after Exposure Time (min) Exposure Time (min) Mixture 0 2 4 6 Mixture 0 2 6 C10 0.300 0.247 0.160 0.081 C20 0.300 0.204 0.059 P11 0.300 0.192 0.107 0.044 P21 0.300 0.136 0.034 C11 0.300 0.264 0.203 0.173 C21 0.300 0.185 0.067 P12 0.300 0.201 0.149 0.121 P22 0.300 0.168 0.057 C12 0.300 0.275 0.209 0.153 C22 0.300 0.210 0.069 P13 0.300 0.238 0.165 0.103 P23 0.300 0.197 0.091 C13 0.300 0.283 0.231 0.190 C23 0.300 0.223 0.123 P14 0.300 0.121 0.103 0.077 P24 0.300 0.105 0.030 C14 0.300 0.265 0.160 0.091 C24 0.300 0.176 0.055 P15 0.300 0.266 0.200 0.155 P25 0.300 0.196 0.100 C15 0.300 0.286 0.264 0.230 C25 0.300 0.229 0.134 P16 0.300 0.245 0.195 0.148 P26 0.300 0.188 0.079 C16 0.300 0.276 0.241 0.225 C26 0.300 0.214 0.108 P17 0.300 0.256 0.177 0.138 P27 0.300 0.198 0.080 C17 0.300 0.296 0.222 0.197 C27 0.300 0.215 0.110 P18 0.300 0.107 0.051 0.029 P28 0.300 0.095 0.022 C18 0.300 0.227 0.141 0.091 C28 0.300 0.189 0.066 P112 0.300 0.275 0.194 0.143 P212 0.300 0.192 0.095 P113 0.300 0.246 0.173 0.114 P213 0.300 0.202 0.088 C112 0.300 0.277 0.221 0.212 C212 0.300 0.212 0.128 P114 0.300 0.243 0.185 0.121 P214 0.300 0.204 0.079 C114 0.300 0.291 0.237 0.197 C214 0.300 0.224 0.124

(67) It can be seen that the polymerizable mixtures P11-P114 and P21-P214 containing alkoxy-substituted RMs 1-14 according to the present invention show a significantly faster polymerization and lower amount of residual RM, compared to corresponding polymerizable mixtures C10-C114 and C20-C214 containing RMs C0-C14 of prior art.

(68) Tilt Angle Generation

(69) For measuring the tilt angle generation the polymerizable mixtures are inserted into electrooptic test cells. The test cells comprise two soda-lime glass substrates with an ITO electrode layer of approx. 200 nm thickness and a VA-polyimide alignment layer (JALS-2096-R1) of approx. 30 nm thickness which is rubbed antiparallel. The LC-layer thickness d is approx. 6 μm.

(70) The test cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 (metal halide lamp with a 320 nm cut-off filter) for the time indicated, with application of a voltage of 24 V.sub.RMS (alternating current), causing polymerization of the RM.

(71) The tilt angle is determined before and after UV irradiation by a crystal rotation experiment (Autronic-Melchers TBA-105). The results are shown in Table 4.

(72) TABLE-US-00012 TABLE 4 Tilt angles Tilt Angle (°) after Tilt Angle (°) after Exposure Time (min) Exposure Time (min) Mixture 0 2 6 Mixture 0 2 6 C10 89.5 83.6 74.3 P112 89.9 80.2 74.7 P11 88.6 80.2 73.0 P113 89.7 79.4 72 C11 89.6 84.9 77.5 C112 88.7 84.3 77.8 P12 89.1 80.4 67.3 P114 89.8 83.8 72.4 C12 88.0 84.0 73.8 C114 89.5 85.7 75.6 P13 89.7 82.9 71.1 C13 88.6 77.7 70.4 P14 89.1 83.4 75.0 C14 88.9 82.7 71.1 P15 88.7 83.3 74.6 C15 89.0 84.5 78.7 P16 88.7 83.5 77.3 C16 88.0 86.2 77.4 P17 89.6 81.6 74.7 C17 88.1 82.9 73.5 P18 89.7 77.5 74.0 C18 88.7 77.4 66.2 Tilt Angle (°) after Tilt Angle (°) after Exposure Time (min) Exposure Time (min) Mixture 0 2 6 Mixture 0 2 6 C20 89.5 85.0 76.4 P212 89.6 81.7 78.4 P21 88.6 77.5 74.7 P213 89.9 81.1 78.7 C21 88.8 77.2 70.3 C212 88.7 80.4 77.2 P22 88.3 78.0 73.9 P214 89.7 79.2 74.8 C22 88.9 77.8 77.3 C214 89.4 81.5 76.9 P23 89.5 81.2 76.5 C23 88.6 79.8 75.6 P24 88.8 76.8 70.9 C24 88.7 71.8 P25 88.4 81.3 77.4 C25 88.9 81.1 77.9 P26 88.5 81.0 76.6 C26 88.8 81.5 73.9 P27 88.8 77.7 72.9 C27 88.2 77.6 73.3 P28 89.3 81.7 80.9 C28 88.5 78.2 74.5

(73) It can be seen that polymerizable mixtures P11-P114 and P21-P214 containing alkoxy-substituted RMs 1-14 according to the present invention show a tilt angle generation that is in most cases comparable to, and in some even stronger and faster than, that of corresponding polymerizable mixtures C10-C114 and C20-C214 containing RMs C0-C14 of prior art.

(74) Voltage Holding Ratio (VHR)

(75) For measuring the VHR the polymerizable mixtures are inserted into electrooptic test cells. The test cells comprise two AF glass substrates with an ITO electrode layer of approx. 20 nm thickness and a VA-polyimide alignment layer (PI-4) of approx. 100 nm thickness. The LC layer thickness is approx. 4 am.

(76) The VHR is measured at 100° C. with application of a voltage of 1 V/60 Hz. For the sun-test the test cells are irradiated at 20° C. for 2 h with light having an intensity of 750 W/m.sup.2 using a CPs/CPS+ type lamp. For the UV test the test cells are irradiated for 10 min with UV light having an intensity of 100 mW/cm.sup.2 (metal halide lamp with a 320 nm cut-off filter).

(77) The results are shown in Table 5.

(78) TABLE-US-00013 TABLE 5 VHR values VHR (%) Mix- VHR (%) Mix- UV ture no illumination Suntest ture no illumination Suntest Test C10 99.2 97.7 C20 98.8 45.2 33.1 P11 98.7 98.3 P21 97.5 73.0 76.8 C11 98.2 97.6 C21 98.3 85.6 74.8 P12 98.6 97.5 P22 81.2 84.1 70.1 C12 99.3 99.2 C22 98.7 91.7 86.8 P13 99.2 98.8 P23 98.7 93.7 90.8 C13 98.2 98.2 C23 98.4 89.6 88.6 P14 97.4 98.1 P24 96.4 91.9 93.4 C14 99.2 99.3 C24 98.8 97.4 96.5 P15 98.0 98.2 P25 98.5 91.1 87.7 C15 99.1 98.7 C25 98.4 90.5 88.9 P16 98.8 98.2 P26 97.2 72.7 81.7 C16 98.9 98.1 C26 97.9 84.9 78.3 P17 98.5 98.1 P27 97.6 89.8 90.4 C17 98.6 98.8 C27 97.2 94.3 94.1 P18 99.1 98.5 P28 98.7 68.9 61.0 C18 98.8 98.0 C28 98.3 89.8 83.5 P112 99.1 98.6 P212 98.8 92.0 89.5 P113 99.1 98.4 P213 98.7 91.5 88.7 C112 99.1 98.8 C212 99.0 93.1 92.4 P114 98.5 98.2 P214 97.8 89.1 81.9 C114 98.9 98.6 C214 98.4 91.4 86.9

(79) It can be seen that polymerizable mixtures P11-P114 and P21-P214 containing alkoxy-substituted RMs 1-14 according to the present invention invention show a VHR after suntest or UV test that is in most cases comparable to, and in some even higher than, that of corresponding polymerizable mixtures C10-C114 and C20-C214 containing RMs C0-C14 of prior art.

USE EXAMPLE B

(80) Polymerizable mixtures C31 and D41, which contain RM C1 of to prior art without an alkoxy substituent, are compared with polymerizable mixtures P31 and P41, which contain the RM 1 according to the present invention having an alkoxy substituent.

(81) Residual RM

(82) The polymerization speed is measured by determining the residual content of residual, unpolymerized RM (in % by weight) in the mixture after UV exposure at a given intensity and lamp spectrum as described in Use Example A, but using a UV intensity of 3.5 mW/cm.sup.2/UV C-type lamp).

(83) The results are shown in Table 6.

(84) TABLE-US-00014 TABLE 6 Residual monomer content Residual RM (%) after Exposure Time (min) Mixture 0 10 C31 0.300 0.114 P31 0.300 0.046 C41 0.300 0.038 P41 0.300 0.012

(85) It can be seen that polymerizable mixtures P31 and P41 containing alkoxy-substituted RM1 according to the present invention show a significantly faster polymerization and lower amount of residual RM, compared to polymerizable mixtures C31 and C41 containing RM C1 of prior art.

(86) In conclusion, the use examples demonstrate that the polymerizable compounds and polymerizable mixtures according to the present invention show in particular a quick polymerization with low amount of residual RM, while maintaining sufficient pretilt angle generation and sufficient VHR values after suntest or UV exposure for display applications.

(87) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

(88) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.