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 (LC) media comprising them, and to the use of the polymerizable compounds and LC media for optical, electro-optical and electronic purposes, in particular in LC displays, especially in LC displays of the PSA (polymer sustained alignment) type.

Claims

1. A polymerizable compound according to the following formula
P.sup.1-(A.sup.1-Z.sup.1).sub.m-A.sup.2-(COO).sub.y-Sp.sup.2-P.sup.2I wherein Sp.sup.2 is a spacer group which is optionally substituted by P.sup.1Sp-, Sp is alkylene with 1 to 12 C atoms, P.sup.1 and P.sup.2 independently of each other are each a polymerizable group, A.sup.1 , A.sup.2 independently of each other, and on each occurrence identically or differently, are each an aryl, heteroaryl alicyclic or heterocyclic group having 4 to 25 C atoms, optionally containing fused rings, and which is unsubstituted or mono- or polysubstituted by L, Z.sup.1 is, on each occurrence identically or differently, O, S, CO, COO, OCOOCOO, OCH.sub.2, CH.sub.2O, SCH.sub.2, CH.sub.2S, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, (CH.sub.2).sub.n, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n, CHCH, CFCF, CHCF, CFCH,CC, CHCHCOO, OCOCHCH, CH.sub.2CH.sub.2COO,OCOCH.sub.2CH.sub.2, CR.sup.00R.sup.000, or a single bond, L is P.sup.1-, P.sup.1-Sp.sup.1-(OCO).sub.xF, Cl, Br, I,CN,NO.sub.2,NCO,NCS, OCN, SCN, C(O )N(R.sup.x).sub.2, C(O)Y.sup.1, C(O)R.sup.x, N(R.sup.x).sub.2, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight -chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, or OCOO in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms are each optionally replaced by F, Cl, CN, P.sup.1, P.sup.1-Sp.sup.1- or P.sup.1-Sp.sup.1(OCO).sub.x, Sp.sup.1 is a spacer group which is optionally substituted by P.sup.1-Sp'- or is a single bond, R.sup.00and R.sup.000are each, independently of one another, H or alkyl having 1 to 12 C atoms, Y.sup.1 is halogen, R.sup.x is P.sup.1, P.sup.1-Sp.sup.1-, P.sup.1-(Sp.sup.1OCO).sub.x, H, halogen, straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH.sub.2-groups are each optionally replaced by O, S,CO, COO,CO, or OCOOin 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, Cl, P.sup.1-, P.sup.1-Sp.sup.1- or P.sup.1-(Sp.sup.1OCO).sub.x, optionally substituted aryl, aryloxy, heteroaryl or heteroaryloxy having 5 to 20 ring atoms, m is 1, 2, 3 or 4, n is 1, 2, 3 or 4, x is 0 or 1, and y is 1; with at least one of the following provisos: (a) at least one of A.sup.1and A.sup.2 is substituted by a group L denoting P.sup.1-Sp.sup.1(OCO).sub.x, (b) Sp.sup.2 is substituted by P.sup.1-Sp.sup.1-, (c) m is 2, 3, or 4, and/or (d) P.sup.l and P.sup.2 are selected from acrylate and methacrylate.

2. A polymerizable compound according to claim 1 , wherein A.sup.1 and A.sup.2 are each, independently of one another, 1,4-phenylene, 1,3-phenylene, or 1,2-phenylene, which in each case is unsubstituted or mono- or polysubstituted by L.

3. A polymerizable compound according to claim 1, wherein Sp.sup.1 is selected from (CH.sub.2).sub.p1, (CH.sub.2).sub.p2O(CH.sub.2 p3, (CH.sub.2).sub.p1O, O(CH.sub.2).sub.p1,and ##STR00353## and Sp.sup.2 is selected from (CH.sub.2).sub.p1,,(CH.sub.2).sub.p2O(CH.sub.2).sub.p3, and ##STR00354## in which p 1 is an integer from 1 to 6, and p2 and p3 are independently of each other 1, 2 or 3 provided that, in a group Sp.sup.1(OCO).sub.x, if x is 1 then Sp.sup.1is not (CH.sub.2).sub.p1Oor O(CH.sub.2).sub.p1.

4. A polymerizable compound according to claim 1, wherein P.sup.l and P.sup.2 are independently of each other selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.

5. A polymerizable compound according to claim 1, wherein said compound is selected from the following sub-formulae: ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## wherein r is 0, 1, 2, 3 or 4.

6. A liquid crystalline (LC) medium comprising a polymerizable component A) comprising one or more polymerizable compounds according to claim 1, and a liquid crystalline component B) comprising one or more compounds selected from mesogenic or liquid crystalline compounds.

7. The liquid crystalline medium according to claim 6, wherein component B comprises one or more compounds of formulae CY and/or PY: ##STR00360## in which the individual radicals have the following meanings: a denotes 1 or 2, b denotes 0 or 1, ##STR00361## denotes ##STR00362## 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 are each optionally replaced by O, CHCH, CO, OCOor COOin 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.2or a single bond, and L.sup.1-4 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, or CHF.sub.2.

8. The liquid crystalline medium according to claim 6, wherein component B comprises one or more compounds of the following formula: ##STR00363## in which the individual radicals have the following meanings: ##STR00364## denotes ##STR00365## ##STR00366## denotes ##STR00367## 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 are each optionally replaced by O, CHCH, CO, OCOor COOin such a way that 0 atoms are not linked directly to one another, and 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, CFCFor a single bond.

9. The liquid crystalline medium according to claim 6, wherein component B comprises one or more compounds comprising an alkenyl group, which is stable to a polymerization reaction under the conditions used for the polymerization of the polymerizable compounds.

10. The liquid crystalline medium according to claim 6, wherein the polymerizable compounds are polymerized.

11. A method of generating an electro-optical effect comprising applying a voltage to a liquid crystalline medium containing a polymerizable compound according to claim 1, in a liquid crystalline display.

12. A method of generating an electro-optical effect comprising applying a voltage to a liquid crystalline medium according to claim 6, in a liquid crystalline display.

13. A liquid crystalline display comprising one or more polymerizable compounds according to claim 1.

14. A liquid crystalline display comprising a liquid crystalline medium according to claim 6.

15. The liquid crystalline display according to claim 13, which is a PSA type display.

16. The liquid crystalline display according to claim 15, which is a PSA-VA, PSA-OCB, PSA-IPS, PS-FFS, PSA-posi-VA or PSA-TN display.

17. The liquid crystalline display according to claim 13, wherein said display contains a liquid crystalline cell having two substrates and two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two elec-trodes, and a layer, located between the substrates, of said liquid crystalline medium comprising a polymerized component and a lowmolecularweight component, where the polymerized component is obtainable by polymerization of one or more polymerizable compounds between the substrates of the liquid crystalline cell in the liquid crystalline medium.

18. A process for the production of a liquid crystalline display according to claim 13, comprising the steps of filling the liquid crystalline medium into a liquid crystalline cell having two substrates and two electrodes, and polymerizing the polymerizable compounds.

19. A process of preparing an LC medium according to claim 6, comprising the steps of mixing one or more unpolymerizable liquidcrystalline compounds, or a liquid-crystalline component B) as defined in claim 6, with one or more of said polymerizable compounds, and optionally with further liquidcrystalline compounds and/or additives.

20. A polymerizable compound according to claim 3, wherein P.sup.l and P.sup.2 are independently of each other selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.

21. The method according to claim 11, wherein said liquid crystalline display is a display of the polymer sustained alignment type.

22. The method according to claim 12, wherein said liquid crystalline display is a display of the polymer sustained alignment type.

23. A polymerizable compound according to claim 1, wherein spacer groups Sp.sup.1 and Sp.sup.2 are of the formula Sp-X, wherein Sp is linked to the polymerizable group, Sp is straight-chain or branched alkylene having 1 to 20 C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I, CN or P.sup.1-Sp-, and in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by O, S , -NH- ,) N(R.sup.0) , Si(R.sup.00R.sup.000), CO, COO, OCO, OCOO, SCO, COS,)N(R.sup.00)COO, OCON(R.sup.00),N(R.sup.00),CON(R.sup.00, CHCHor CCin such a way that O and/or S atoms are not linked directly to one another, Xis O, S, CO, COOCO, OCOO,)CON(R.sup.00,)N(R.sup.00)CO, N(R.sup.00)CON(R.sup.00), OCH.sub.2, CH.sub.2O, SCH.sub.2, CH.sub.2S, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2, CHN , NCH NN, CHCR.sup.0, CY.sup.2CY.sup.3, CC, CHCHCOO, OCOCHCHor a single bond, wherein X denotes a single bond if it is adjacent to an ester group (OCO or COO), R.sup.0, R.sup.00and R.sup.000each, independently of one another, are H or alkyl having 1 to 12 C atoms, and Y.sup.2 and Y.sup.3 each, independently of one another, are H, F, Cl or CN.

Description

DEFINITIONS OF TERMS

(1) As used herein, the terms tilt and tilt angle mean a tilted alignment of the LC molecules of an LC medium relative to the surfaces of the cell in an LC display (here preferably a PSA display). The tilt angle here denotes the average angle (<90) between the longitudinal molecular axes of the LC molecules (LC director) and the surface of the plane-parallel outer plates which form the LC cell. A low value for the tilt angle (i.e. a large deviation from the 90 angle) corresponds to a large tilt here. A suitable method for measurement of the tilt angle is given in the examples. Unless indicated otherwise, tilt angle values disclosed above and below relate to this measurement method.

(2) The term mesogenic group as used herein is known to the person skilled in the art and described in the literature, and means a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystal (LC) phase in low-molecular-weight or polymeric substances. Compounds containing mesogenic groups (mesogenic compounds) do not necessarily have to have an LC phase themselves. It is also possible for mesogenic compounds to exhibit LC phase behavior only after mixing with other compounds and/or after polymerization. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units. An overview of the terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.

(3) The term spacer group, hereinafter also referred to as Sp, is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. As used herein, the terms spacer group or spacer mean a flexible group, for example an alkylene group, which connects the mesogenic group and the polymerizable group(s) in a polymerizable mesogenic compound.

(4) As used herein, the terms reactive mesogen and RM mean a compound containing one mesogenic group and one or more functional groups which are suitable for polymerization, the latter also being referred to as polymerizable group or P.

(5) The term polymerizable compound as used hereinafter, unless stated otherwise, means a polymerizable monomeric compound.

(6) As used herein, the terms low-molecular-weight compound and unpolymerizable compound mean compounds, usually monomeric, which contain no functional group that is suitable for polymerization under the usual conditions known to the person skilled in the art, in particular under the conditions used for the polymerization of the polymerizable compounds or RMs as described above and below.

(7) As used herein, the terms active layer and switchable layer mean a layer in an electrooptical display, for example an LC display, that comprises one or more molecules having structural and optical anisotropy, like for example LC molecules, which change their orientation upon an external stimulus like an electric or magnetic field, resulting in a change of the transmission of the layer for polarized or unpolarized light.

DETAILED DESCRIPTION OF THE INVENTION

(8) Unless stated otherwise, the compounds of formula I are preferably selected from achiral compounds.

(9) Above and below organic group denotes a carbon or hydrocarbon group.

(10) Carbon group denotes a mono- or polyvalent organic group containing at least one carbon atom, where this either contains no further atoms (such as, for example, CC) or optionally contains one or more further atoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge (for example carbonyl, etc.). The term hydrocarbon group denotes a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as, for example, N, O, S, P, Si, Se, As, Te or Ge.

(11) Halogen denotes F, Cl, Br or I.

(12) CO, C(O) and C(O) denote a carbonyl group, i.e.

(13) ##STR00002##

(14) Conjugated radical or conjugated group denotes a radical or group which contains principally sp.sup.2-hybridized (or possibly also sp-hybridized) carbon atoms, which may also be replaced by corresponding heteroatoms. In the simplest case, this means the alternating presence of double and single bonds. Principally in this connection means that naturally (non-randomly) occurring defects which result in conjugation interruptions do not devalue the term conjugated. Furthermore, the term conjugated is likewise used in this application text if, for example, arylamine units or certain heterocycles (i.e. conjugation via N, O, P or S atoms) are located in the radical or group.

(15) A carbon or hydrocarbon group can be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. A carbon or hydrocarbon radical having more than 3 C atoms can be straight-chain, branched and/or cyclic and may also contain spiro links or condensed rings.

(16) The terms alkyl, aryl, heteroaryl, etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.

(17) The term aryl denotes an aromatic carbon group or a group derived therefrom. The term heteroaryl denotes aryl as defined above, containing one or more heteroatoms.

(18) Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18, C atoms, optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, aryl carbonyloxy and aryloxycarbonyloxy having 6 to 40, preferably 6 to 25, C atoms.

(19) Further preferred carbon and hydrocarbon groups are C.sub.1-C.sub.40 alkyl, C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl, C.sub.3-C.sub.40 allyl, C.sub.4-C.sub.40 alkyldienyl, C.sub.4-C.sub.40 polyenyl, C.sub.6-C.sub.40 aryl, C.sub.6-C.sub.40 alkylaryl, C.sub.6-C.sub.40 arylalkyl, C.sub.6-C.sub.40 alkylaryloxy, C.sub.6-C.sub.40 arylalkyloxy, C.sub.2-C.sub.40 heteroaryl, C.sub.4-C.sub.40 cycloalkyl, C.sub.4-C.sub.40 cycloalkenyl, etc. Particular preference is given to C.sub.1-C.sub.22 alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.2-C.sub.22 alkynyl, C.sub.3-C.sub.22 allyl, C.sub.4-C.sub.22 alkyldienyl, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.20 arylalkyl and C.sub.2-C.sub.20 heteroaryl.

(20) Further preferred carbon and hydrocarbon groups are straight-chain, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN and in which one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.x)C(R.sup.x), CC, N(R.sup.x), O, S, CO, COO, OCO, OCOO in such a way that O and/or S atoms are not linked directly to one another.

(21) R.sup.x preferably denotes H, halogen, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which, in addition, one or more non-adjacent C atoms may each be replaced by O, S, CO, COO, OCO, OCOO and in which one or more H atoms may each be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms.

(22) Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.

(23) Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoron-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc.

(24) Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, etc.

(25) Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, etc.

(26) Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.

(27) Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e. they can contain one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently bonded (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.

(28) Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6- or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may each be replaced by N, S or O in such a way that O atoms and/or S atoms are not linked directly to one another.

(29) Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1:3,1]terphenyl-2-yl, naphthyl, anthracene, binaphthyl, phenanthrene, 9,10-dihydro-phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.

(30) Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups, such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups.

(31) The aryl and heteroaryl groups mentioned above and below may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

(32) The (non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings, i.e. those containing exclusively single bonds, and also partially unsaturated rings, i.e. those which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.

(33) The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6-, 7- or 8-membered carbocyclic groups, in which, in addition, one or more C atoms may each be replaced by Si and/or one or more CH groups may each be replaced by N and/or one or more non-adjacent CH.sub.2 groups may each be replaced by O or S.

(34) Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]-pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl.

(35) Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy, electron-withdrawing groups, such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) in the polymer, in particular bulky groups, such as, for example, t-butyl or optionally substituted aryl groups.

(36) Preferred substituents, also referred to as L above and below, are, for example, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.x).sub.2, C(O)Y.sup.1, C(O)R.sup.x, N(R.sup.x).sub.2, in which R.sup.x has the meaning indicated above, and Y.sup.1 denotes halogen, optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20, C atoms, and straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or Cl.

(37) Substituted silyl or aryl preferably means substituted by halogen, CN, R.sup.0, OR.sup.0, COR.sup.0, COOR.sup.0, OCOR.sup.0 or OCOOR.sup.0, in which R.sup.0 denotes H or alkyl having 1 to 12 C atoms.

(38) Particularly preferred substituents L are, for example, F, Cl, CN, NO.sub.2, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, OC.sub.2H.sub.5, COCH.sub.3, COC.sub.2H.sub.5, COOCH.sub.3, COOC.sub.2H.sub.5, CF.sub.3, OCF.sub.3, OCHF.sub.2, OC.sub.2F.sub.5, furthermore phenyl.

(39) In the compounds wherein r is different from 0, the group

(40) ##STR00003##
is preferably

(41) ##STR00004##
in which L has one of the meanings indicated above.

(42) The polymerizable group (P, P.sup.1, P.sup.2)) is a group which is suitable for a polymerization reaction, such as, for example, free-radical or ionic chain polymerization, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain. Particular preference is given to groups for chain polymerization, in particular those containing a CC double bond or CC triple bond, and groups which are suitable for polymerization with ring opening, such as, for example, oxetane or epoxide groups.

(43) Preferred polymerizable groups are selected from the group consisting of CH.sub.2CW.sup.1COO, CH.sub.2CW.sup.1CO,

(44) ##STR00005##
CH.sub.2CW.sup.2(O).sub.k3, CW.sup.1CHCO(O).sub.k3, CW.sup.1CHCONH, CH.sub.2CW.sup.1CONH, CH.sub.3CHCHO, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CHCH.sub.2).sub.2CHOCO, (CH.sub.2CH).sub.2CHO, (CH.sub.2CHCH.sub.2).sub.2N, (CH.sub.2CHCH.sub.2).sub.2NCO, HOCW.sup.2W.sup.3, HSCW.sup.2W.sup.3, HW.sup.2N, HOCW.sup.2W.sup.3NH, CH.sub.2CW.sup.1CONH, CH.sub.2CH(COO).sub.k1Phe-(O).sub.k2, CH.sub.2CH(CO).sub.k1Phe-(O).sub.k2, Phe-CHCH, HOOC, OCN and W.sup.4W.sup.5W.sup.6Si, in which W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH.sub.3, W.sup.2 and W.sup.3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W.sup.4, W.sup.5 and W.sup.6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W.sup.7 and W.sup.8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more non-polymerizable radicals L as defined above, k.sub.1, k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1, k.sub.3 preferably denotes 1, and k.sub.4 denotes an integer from 1 to 10.

(45) Particularly preferred polymerizable groups are selected from the group consisting of CH.sub.2CW.sup.1COO, CH.sub.2CW.sup.1CO,

(46) ##STR00006##
CH.sub.2CW.sup.2O, CH.sub.2CW.sup.2, CW.sup.1CHCO(O).sub.k3, CW.sup.1CHCONH, CH.sub.2CW.sup.1CONH, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CHCH.sub.2).sub.2CHOCO, (CH.sub.2CH).sub.2CHO, (CH.sub.2CHCH.sub.2).sub.2N, (CH.sub.2CHCH.sub.2).sub.2NCO, CH.sub.2CW.sup.1CONH, CH.sub.2CH(COO).sub.k1Phe-(O).sub.k2, CH.sub.2CH(CO).sub.k1Phe-(O).sub.k2, Phe-CHCH and W.sup.4W.sup.5W.sup.6Si, in which W.sup.1 denotes H, F, Cl, CN, CF.sub.3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH.sub.3, W.sup.2 and W.sup.3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W.sup.4, W.sup.5 and W.sup.6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W.sup.7 and W.sup.8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, k.sub.1, k.sub.2 and k.sub.3 each, independently of one another, denote 0 or 1, k.sub.3 preferably denotes 1, and k.sub.4 denotes an integer from 1 to 10.

(47) Very particularly preferred polymerizable groups are selected from the group consisting of CH.sub.2CW.sup.1COO, in particular CH.sub.2CHCOO, CH.sub.2C(CH.sub.3)COO and CH.sub.2CFCOO, furthermore CH.sub.2CHO, (CH.sub.2CH).sub.2CHOCO, (CH.sub.2CH).sub.2CHO,

(48) ##STR00007##

(49) Further very particularly preferred polymerizable groups are selected from the group consisting of vinyl, vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide groups, and particularly preferably denote an acrylate, methacrylate or oxetane group.

(50) The spacer groups Sp, Sp.sup.1 and Sp.sup.2 are preferably selected of the formula Sp-X, wherein Sp is linked to the polymerizable group (so that e.g. the radical P-Sp-, P.sup.1-Sp.sup.1- or P.sup.2-Sp.sup.2- is of the formula P-Sp-X or P.sup.1/2-Sp-X-, respectively), wherein Sp and X have the following meanings: Sp denotes straight-chain or branched alkylene having 1 to 20, preferably 1 to 15, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I, CN or P.sup.1-Sp-, and in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by O, S, NH, N(R.sup.0), Si(R.sup.00R.sup.000), CO, COO, OCO, OCOO, SCO, COS, N(R.sup.00)COO, OCON(R.sup.00), N(R.sup.00)CON(R.sup.00), CHCH or CC in such a way that O and/or S atoms are not linked directly to one another, X denotes O, S, CO, COO, OCO, OCOO, CON(R.sup.00), N(R.sup.00)CO, N(R.sup.00)CON(R.sup.00), OCH.sub.2, CH.sub.2O, SCH.sub.2, CH.sub.2S, CF.sub.2O, OCF.sub.2, CF.sub.2S, SCF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CF.sub.2CF.sub.2, CHN, NCH, NN, CHCR.sup.0, CY.sup.2CY.sup.3, CC, CHCHCOO, OCOCHCH or a single bond, wherein X denotes a single bond if it is adjacent to an ester group (OCO or COO) in formula I, R.sup.0, R.sup.00 and R.sup.000 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, Y.sup.2 and Y.sup.3 each, independently of one another, denote H, F, Cl or CN, and P.sup.1 and Sp.sup.1 are as defined in formula I. X is preferably O, S, CO, COO, OCO, OCOO, CONR.sup.0, NR.sup.0CO, NR.sup.0CONR.sup.0 or a single bond, very preferably O or a single bond.

(51) Preferred spacer groups Sp, Sp.sup.1, Sp.sup.2 and Sp-X include, without limitation, (CH.sub.2).sub.p1, (CH.sub.2).sub.p2O(CH.sub.2).sub.p3, (CH.sub.2).sub.p2S(CH.sub.2).sub.p3, (CH.sub.2).sub.p2NH(CH.sub.2).sub.p3, (CH.sub.2).sub.p1O, O(CH.sub.2).sub.p1, or

(52) ##STR00008##
wherein p1 is an integer from 1 to 12, preferably from 1 to 6, and p2 and p3 are, independently of each other, an integer from 1 to 6, preferably 1, 2 or 3, provided that, in a group Sp.sup.1-(OCO).sub.x if x is 1 then Sp.sup.1 is not (CH.sub.2).sub.p1O or O(CH.sub.2).sub.p1, and in a group (COO).sub.y-Sp.sup.2-P.sup.2 if y is 1 then Sp.sup.2 is not (CH.sub.2).sub.p1O or O(CH.sub.2).sub.p1.

(53) A preferred embodiment of the present invention relates to compounds of formula I wherein the spacer groups Sp, Sp.sup.1, and Sp.sup.2 denote Sp-X in which Sp is selected from straight-chain alkylene as defined above.

(54) Another preferred embodiment of the present invention relates to compounds of formula I containing at least one group P-Sp-, P.sup.1-Sp-, P.sup.2-Sp.sup.2- or P.sup.3-Sp.sup.3-, wherein Sp, Sp.sup.1, or Sp.sup.2, respectively, denote Sp-X in which Sp.sup.1 is branched alkylene that is substituted by a group P as defined above (branched polymerizable groups).

(55) Further preferred are compounds of formula I in which A.sup.1, A.sup.2 each, independently of one another, denote 1,4-phenylene, 1,3-phenylene-, 1,2-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where one or more CH groups in these groups are optionally replaced by N, cyclohexane-1,4-diyl, in which, in addition, one or more non-adjacent CH.sub.2 groups are each optionally replaced by O or S, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl, octahydro-4,7-methanoindane-2,5-diyl, anthracene-2,7-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl or 9,10-dihydro-phenanthrene-2,7-diyl, where all these groups are unsubstituted or mono- or polysubstituted by L.

(56) Further preferred compounds of formula I are those in which x and y denote 1, x is 0 and y is 1, m is 1 or 2, at least one of A.sup.1 and A.sup.2 is substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, m is 1 or 2 and one or both groups A.sup.1 are substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, m is 1 or 2 and A.sup.2 is substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, m is 1 and A.sup.2 is substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, m is 2 and A.sup.2 is substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, m is 2 and the central group A.sup.1 is substituted by a group L denoting P.sup.1-Sp.sup.1-(OCO).sub.x, the sum of all x and y in formula I is 1 (the compounds contain only one group selected from the formulae P.sup.1-Sp.sup.1-OCO and COO-Sp.sup.2-P.sup.2), P.sup.1 and P.sup.2 are selected from the group consisting of acrylate, methacrylate and oxetane, Sp.sup.1 and Sp.sup.2 are selected from (CH.sub.2).sub.p1, (CH.sub.2).sub.p2O(CH.sub.2).sub.p3, (CH.sub.2).sub.p1O, O(CH.sub.2).sub.p1, or

(57) ##STR00009## in which p1 is an integer from 1 to 6, preferably 1, 2 or 3, and p2 and p3 are independently of each other 1, 2 or 3, at least one group Sp.sup.1 or Sp.sup.2 denotes Sp-X in which Sp is substituted by a group P.sup.1-Sp- as defined above, wherein preferably Sp preferably denotes alkylene having 1, 2 or 3 C atoms, and P.sup.1 preferably denotes acrylate, methacrylate or oxetane, A.sup.1 and A.sup.2 are selected from the group consisting of 1,4-phenylene, 1,3-phenylene-, 1,2-phenylene, naphthalene-2,6-diyl, phenanthrene-2,7-diyl and 9,10-dihydro-phenanthrene-2,7-diyl, where, in addition, one or two CH groups in these rings are optionally replaced by N, and where these rings are optionally mono- or polysubstituted by L, as described above and below, A.sup.1 and A.sup.2 are selected from the group consisting of 1,4-phenylene, 1,3-phenylene-, 1,2-phenylene, and naphthalene-2,6-diyl, A.sup.1 and A.sup.2 are selected from the group consisting of 1,4-phenylene, 1,3-phenylene- and 1,2-phenylene, Z.sup.1 in each occurrence is independently selected from the group consisting of O, COO, OCO, OCH.sub.2, CH.sub.2O, CF.sub.2O, OCF.sub.2, CH.sub.2CH.sub.2, CHCH, CFCF, CHCF, CFCH, CC, and a single bond, Z.sup.1 is a single bond, at least one of A.sup.1 and A.sup.2 is substituted by a group L that is an unpolymerizable group, preferably selected from F, Cl, CN and straight-chain or branched alkyl having 1 to 25, particularly preferably 1 to 10, C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.00)C(R.sup.000), CC, N(R.sup.00), O, S, CO, COO, OCO, OCOO in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may each be replaced by F, Cl, Br, I or CN.

(58) Preferred compounds of formula I are selected from the following subformulae:

(59) ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014##
wherein P.sup.1, P.sup.2, Sp.sup.1, Sp.sup.2 and L are as defined in formula I, p2 and p3 are, independently of each other, an integer from 1 to 6, preferably 1, 2 or 3, and r is 0, 1, 2, 3 or 4.

(60) Very preferred compounds of formula I are selected from the following subformulae:

(61) ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
wherein Me denotes a methyl group, that MeOCO denotes CH.sub.3COO and MeO.sub.2C denotes CH.sub.3OCO.

(62) Further preferred are compounds of subformulae I1-1 to I33-1 as listed above, wherein the methacrylate groups are replaced by acrylate groups.

(63) The invention furthermore relates to novel compounds of formula I and its subformulae I1 to I33 and I1-1 to I33-1 as listed above.

(64) The invention furthermore relates to novel compounds of formula II, which are suitable, and preferably used as, intermediates for the preparation of compounds of the formula I and its subformulae,
Pg.sup.1-Sp.sup.1-(OCO).sub.x-(A.sup.1-Z.sup.1).sub.m-A.sup.2-(COO).sub.y-Sp.sup.2-Pg.sup.2II
in which Sp.sup.1, Sp.sup.2, A.sup.1, A.sup.2, Z.sup.1 and m have the meaning indicated in formula I or above and below, and Pg.sup.1 and Pg.sup.2 denote independently of each other OH or a protected hydroxyl group or a masked hydroxyl group.

(65) Suitable protected hydroxyl groups Pg.sup.1,2 are known to the person skilled in the art. Preferred protecting groups for hydroxyl groups are alkyl, alkoxyalkyl, acyl, alkylsilyl, arylsilyl and arylmethyl groups, especially 2-tetrahydropyranyl, methoxymethyl, methoxyethoxymethyl, acetyl, triisopropylsilyl, tert-butyldimethylsilyl or benzyl.

(66) The term masked hydroxyl group is understood to mean any functional group that can be chemically converted into a hydroxyl group. Suitable masked hydroxyl groups Pg.sup.1,2 are known to the person skilled in the art. Preferred masked hydroxyl groups are alkene, ether, aldehyde, ketone, ester, Br, Cl, I or epoxides.

(67) Especially preferred compounds of formula II are selected from the above formulae I1 to I33 wherein P.sup.1 and P.sup.2 are replaced by Pg.sup.1 and Pg.sup.2, respectively.

(68) The compounds and intermediates of formulae I and II and sub-formulae thereof can be prepared analogously to processes known to the person skilled in the art and described in standard works of organic chemistry, such as, for example, in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart.

(69) Particularly suitable and preferred processes for the preparation of compounds and intermediates of formulae I and II are depicted by way of example in the following schemes and preferably comprise one or more of the steps described below.

(70) For example, compounds of formula I can be synthesized by esterification or etherification of the intermediates of formula II, wherein Pg.sup.1,2 denote OH, using corresponding acids, acid derivatives, or halogenated compounds containing a polymerizable group P.sup.1.

(71) As exemplarily shown in Scheme 1, acrylic or methacrylic esters (wherein Sp.sup.1,2, A.sup.1-2, Z.sup.1, m, x and y have the meanings given above, and Acr denotes an acrylate or methacrylate group) can be prepared by esterification of the corresponding alcohols with acid derivatives like, for example, (meth)acryloyl chloride or (meth)acrylic anhydride in the presence of a base like pyridine or triethyl amine, and 4-(N,N-dimethylamino)pyridine (DMAP). Alternatively the esters can be prepared by esterification of the alcohols with (meth)acrylic acid in the presence of a dehydrating reagent, for example according to Steglich with dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (EDC) or N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride and DMAP.

(72) ##STR00027##

(73) The intermediates of formula II can be synthesized according to or in analogy to known methods that are described in the literature. The synthesis of the compound of formula I, like compound (1), and its intermediate of formula II, like compound (1.3), is exemplarily shown in Scheme 2.

(74) ##STR00028##

(75) 4-Benzyloxy-biphenyl-3,5-dicarboxylic acid (1.1) is prepared from commercially available [4-(benzyloxy)phenyl]boronic acid and 5-bromoisophthalic acid by aryl-aryl coupling. Esterification with (2-bromoethoxymethyl)-benzene gives compound (1.2). Removal of the benzyl protecting group gives compound (1.3). Esterification with methacrylic acid gives compound (1).

(76) Other compounds of formula I can be prepared in analogy to the method described above.

(77) For the production of PSA displays, the polymerizable compounds are polymerized or crosslinked (if one compound contains two or more polymerizable groups) by in-situ polymerization in the LC medium between the substrates of the LC display with application of a voltage. The polymerization can be carried out in one step. It is also possible firstly to carry out the polymerization with application of a voltage in a first step in order to produce a pretilt angle, and subsequently, in a second polymerization step without an applied voltage, to polymerize or crosslink the compounds which have not reacted in the first step (end curing).

(78) Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, in particular UV photopolymerization. One or more initiators can optionally also be added here. Suitable conditions for the polymerization and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, the commercially available photoinitiators Irgacure651, Irgacure184, Irgacure907, Irgacure369 or Darocure1173 (Ciba AG). If an initiator is employed, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

(79) The polymerizable compounds according to the invention are also suitable for polymerization without an initiator, which is accompanied by considerable advantages, such, for example, lower material costs and in particular less contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof. The polymerization can thus also be carried out without the addition of an initiator. In a preferred embodiment, the LC medium thus comprises no polymerization initiator.

(80) The polymerizable component A) or the LC medium may also comprise one or more stabilizers in order to prevent undesired spontaneous polymerization of the RMs, for example during storage or transport. Suitable types and amounts of stabilizers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilizers from the Irganox series (Ciba AG), such as, for example, Irganox 1076. If stabilizers are employed, their proportion, based on the total amount of RMs or the polymerizable component A), is preferably 10-500,000 ppm, particularly preferably 50-50,000 ppm.

(81) Preferably the LC medium according to the present invention does essentially consist of one or more polymerizable compounds of formula I and an LC host mixture as described above and below. However, the LC medium or LC host mixture may additionally comprise one or more further components or additives, preferably selected from the list including but not limited to comonomers, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricating agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments and nanoparticles.

(82) The LC media according to the invention for use in PSA displays preferably comprise from >0 to <5% by weight, particularly preferably from >0 to <1% by weight, very particularly preferably from 0.01 to 0.5% by weight, of polymerizable compounds, in particular polymerizable compounds of the formulae indicated above.

(83) Particular preference is given to LC media comprising one, two or three polymerizable compounds according to the invention.

(84) Preference is furthermore given to LC media in which the polymerizable component (component A) comprises exclusively polymerizable compounds according to the invention.

(85) Preference is furthermore given to LC media in which component B) is an LC compound or an LC mixture which has a nematic liquid-crystal phase.

(86) Preference is furthermore given to achiral polymerizable compounds according to the invention and LC media in which the compounds of component A) and/or B) are selected exclusively from the group consisting of achiral compounds.

(87) Preference is furthermore given to LC media in which the polymerizable component or component A) comprises one or more polymerizable compounds according to the invention containing one polymerizable group (monoreactive) and one or more polymerizable compounds according to the invention containing two or more, preferably two, polymerizable groups (di- or multireactive).

(88) Preference is furthermore given to PSA displays and LC media in which the polymerizable component or component A) comprises exclusively polymerizable compounds according to the invention containing two polymerizable groups (direactive).

(89) The proportion of the polymerizable component or component A) in the LC media according to the invention is preferably from >0 to <5%, particularly preferably from >0 to <1%, very particularly preferably from 0.01 to 0.5%.

(90) The proportion of the liquid-crystalline component or component B) in the LC media according to the invention is preferably from 95 to <100%, particularly preferably from 99 to <100%.

(91) The polymerizable compounds according to the invention can be polymerized individually, but it is also possible to polymerize mixtures which comprise two or more polymerizable compounds according to the invention, or mixtures comprising one or more polymerizable compounds according to the invention and one or more further polymerizable compounds (co-monomers), which are preferably mesogenic or liquid-crystalline. In the case of polymerization of such mixtures, copolymers are formed. The invention furthermore relates to the polymerizable mixtures mentioned above and below. The polymerizable compounds and comonomers are mesogenic or non-mesogenic, preferably mesogenic or liquid-crystalline.

(92) Suitable and preferred mesogenic comonomers, particularly for use in PSA displays, are selected, for example, from the following formulae:

(93) ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033##
in which the individual radicals have the following meanings: P.sup.1, P.sup.2 and P.sup.3 each, independently of one another, denote a polymerizable group having one of the meanings indicated above and below for P.sup.1, particularly preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyl, vinyloxy or epoxide group, Sp.sup.1, Sp.sup.2 and Sp.sup.a each, independently of one another, denote a single bond or a spacer group having one of the meanings indicated above and below for Sp.sup.1, and particularly preferably denote (CH.sub.2).sub.p1, (CH.sub.2).sub.p1O, (CH.sub.2).sub.p1COO or (CH.sub.2).sub.p1OCOO, in which p1 is an integer from 1 to 12, and where the linking to the adjacent ring in the last-mentioned groups takes place via the O atom, where, in addition, one or more of the radicals P.sup.1-Sp.sup.1-, P.sup.1-Sp.sup.2- and P.sup.3-Sp.sup.3- may denote R.sup.aa, with the proviso that at least one of the radicals P.sup.1-Sp.sup.1-, P.sup.2-Sp.sup.2 and P.sup.3-Sp.sup.3- present is different from R.sup.aa, R.sup.aa denotes H, F, Cl, CN or straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced, independently of one another, by C(R.sup.0)C(R.sup.00), CC, N(R.sup.0), O, S, CO, COO, OCO, OCOO in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may each be replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, particularly preferably straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms (where the alkenyl and alkynyl radicals have at least two C atoms and the branched radicals have at least three C atoms), R.sup.0, R.sup.00 each, independently of one another and identically or differently on each occurrence, denote H or alkyl having 1 to 12 C atoms, X.sup.1, X.sup.2 and X.sup.3 each, independently of one another, denote COO, OCO or a single bond, Z.sup.1 denotes O, CO, C(R.sup.yR.sup.z) or CF.sub.2CF.sub.2, R.sup.y and R.sup.z each, independently of one another, denote H, F, CH.sub.3 or CF.sub.3, Z.sup.2 and Z.sup.3 each, independently of one another, denote 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, L on each occurrence, identically or differently, denotes F, Cl, CN or straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F, L and L each, independently of one another, denote H, F or Cl, r denotes 0, 1, 2, 3 or 4, s denotes 0, 1, 2 or 3, t denotes 0, 1 or 2, x denotes 0 or 1.

(94) Especially preferred are compounds of formulae M1 to M28.

(95) In the compounds of formulae M1 to M42

(96) ##STR00034##
is preferably

(97) ##STR00035##
wherein L on each occurrence, identically or differently, has one of the meanings given above or below, and is preferably F, Cl, CN, NO.sub.2, CH.sub.3, C.sub.2H.sub.5, C(CH.sub.3).sub.3, CH(CH.sub.3).sub.2, CH.sub.2CH(CH.sub.3)C.sub.2H.sub.5, OCH.sub.3, OC.sub.2H.sub.5, COCH.sub.3, COC.sub.2H.sub.5, COOCH.sub.3, COOC.sub.2H.sub.5, CF.sub.3, OCF.sub.3, OCHF.sub.2, OC.sub.2F.sub.5 or P-Sp-, very preferably F, Cl, CN, CH.sub.3, C.sub.2H.sub.5, OCH.sub.3, COCH.sub.3, OCF.sub.3 or P-Sp-, more preferably F, Cl, CH.sub.3, OCH.sub.3, COCH.sub.3 or OCF.sub.3, especially F or CH.sub.3.

(98) Besides the polymerizable compounds described above, the LC media for use in the LC displays according to the invention comprise an LC mixture (host mixture) comprising one or more, preferably two or more, low-molecular-weight (i.e. monomeric or unpolymerized) compounds. The latter are stable or unreactive to a polymerization reaction under the conditions used for polymerization of the polymerizable compounds. In principle, any LC mixture which is suitable for use in conventional VA and OCB displays is suitable as host mixture. Suitable LC mixtures are known to the person skilled in the art and are described in the literature, for example mixtures in VA displays in EP 1 378 557 A1 and mixtures for OCB displays in EP 1 306 418 A1 and DE 102 24 046 A1.

(99) The polymerizable compounds of formula I are especially suitable for use in an LC host mixture that comprises one or more compounds comprising an alkenyl group, (alkenyl compound), where this alkenyl group is stable to a polymerization reaction under the conditions used for the polymerization of the polymerizable compounds of formula I or of the other polymerizable compounds contained in the LC medium. Compared to reactive mesogens known from prior art the polymerizable compounds of formula I in such an LC host mixture shows improved properties, like solubility, reactivity or capability of generating a tilt angle.

(100) The LC host mixture is preferably a nematic LC mixture.

(101) The alkenyl groups in the alkenyl compounds are preferably selected from straight-chain, branched or cyclic alkenyl, in particular having 2 to 25 C atoms, particularly preferably having 2 to 12 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may each be replaced by O, S, CO, COO, OCO, or OCOO in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may each be replaced by F or Cl.

(102) Preferred alkenyl groups are straight-chain alkenyl having 2 to 7 C atoms and cyclohexenyl, in particular ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, 1,4-cyclohexen-1-yl and 1,4-cyclohexen-3-yl.

(103) The concentration of compounds containing an alkenyl group in the LC host mixture (i.e. without any polymerizable compounds) is preferably from 5% to 100%, very preferably from 20% to 60%.

(104) Especially preferred are LC mixtures containing 1 to 5, preferably 1, 2 or 3 compounds having an alkenyl group.

(105) The compounds containing an alkenyl group are preferably selected from the following formulae:

(106) ##STR00036##
in which the individual radicals, on each occurrence identically or differently, each, independently of one another, have the following meaning:

(107) ##STR00037## R.sup.11 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.12, R.sup.12 alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH.sub.2 groups may each 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.xCH.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, CHCHCH.sub.2O, or a single bond, preferably a single bond, L.sup.1-4 each, independently of one another, H, F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F or CHF.sub.2H, preferably H, F or Cl, x 1 or 2, z 0 or 1. R.sup.12 is preferably straight-chain alkyl or alkoxy having 1 to 8 C atoms or straight-chain alkenyl having 2 to 7 C atoms.

(108) The LC medium preferably comprises no compounds containing a terminal vinyloxy group (OCHCH.sub.2), in particular no compounds of formulae AN and AY in which R.sup.11 or R.sup.12 denotes or contains a terminal vinyloxy group (OCHCH.sub.2).

(109) Preferably, L.sup.1 and L.sup.2 denote F, or one of L.sup.1 and L.sup.2 denotes F and the other denotes Cl, and L.sup.3 and L.sup.4 denote F, or one of L.sup.3 and L.sup.4 denotes F and the other denotes Cl.

(110) The compounds of the formula AN are preferably selected from the following sub-formulae:

(111) ##STR00038##
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(112) The compounds of the formula AY are preferably selected from the following sub-formulae:

(113) ##STR00039## ##STR00040## ##STR00041## ##STR00042##
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(114) Very particularly preferred compounds of the formula AN are selected from the following sub-formulae:

(115) ##STR00043##
in which m denotes 1, 2, 3, 4, 5 or 6, i denotes 0, 1, 2 or 3, and R.sup.b1 denotes H, CH.sub.3 or C.sub.2H.sub.5,

(116) Especially preferred are the following compounds:

(117) ##STR00044##

(118) Most preferred is the compound of formula AN1a1.

(119) Very particularly preferred compounds of the formula AY are selected from the following sub-formulae:

(120) ##STR00045##
in which m and n each, independently of one another, denote 1, 2, 3, 4, 5 or 6, and alkenyl denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2.

(121) In a first preferred embodiment the LC medium contains an LC host mixture based on compounds with negative dielectric anisotropy. Such LC media are especially suitable for use in PSA-VA displays. Particularly preferred embodiments of such an LC medium are those of sections a)-y) below: a) LC medium which comprises one or more compounds of the formulae CY and/or PY:

(122) ##STR00046## wherein a denotes 1 or 2, b denotes 0 or 1,

(123) ##STR00047## denotes

(124) ##STR00048## 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 each be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms, Z.sup.x and Z.sup.y each, independently of one another, denote 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, CHCHCH.sub.2O or a single bond, preferably 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. Preferably, both L.sup.1 and L.sup.2 denote F or one of L.sup.1 and L.sup.2 denotes F and the other denotes Cl, or both L.sup.3 and L.sup.4 denote F or one of L.sup.3 and L.sup.4 denotes F and the other denotes Cl. The compounds of the formula CY are preferably selected from the group consisting of the following sub-formulae:

(125) ##STR00049## ##STR00050## ##STR00051## ##STR00052## in which a denotes 1 or 2, alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. The compounds of the formula PY are preferably selected from the group consisting of the following sub-formulae:

(126) ##STR00053## ##STR00054## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. b) LC medium which additionally comprises one or more compounds of the following formula:

(127) ##STR00055## in which the individual radicals have the following meanings:

(128) ##STR00056## denotes

(129) ##STR00057## denotes

(130) ##STR00058## 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 each 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, CHCHCH.sub.2O or a single bond, preferably a single bond. The compounds of the formula ZK are preferably selected from the group consisting of the following sub-formulae:

(131) ##STR00059## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. c) LC medium which additionally comprises one or more compounds of the following formula:

(132) ##STR00060## in which the individual radicals on each occurrence, identically or differently, have the following meanings: R.sup.5 and R.sup.6 each, independently of one another, have one of the meanings indicated above for R.sup.1,

(133) ##STR00061## denotes

(134) ##STR00062## denotes

(135) ##STR00063## and e denotes 1 or 2. The compounds of the formula DK are preferably selected from the group consisting of the following sub-formulae:

(136) ##STR00064## ##STR00065## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. d) LC medium which additionally comprises one or more compounds of the following formula:

(137) ##STR00066## in which the individual radicals have the following meanings:

(138) ##STR00067## denotes

(139) ##STR00068## f denotes 0 or 1, 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 each 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 and Z.sup.y each, independently of one another, denote 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, CHCHCH.sub.2O or a single bond, preferably a single bond, L.sup.1 and L.sup.2 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2. Preferably, both radicals L.sup.1 and L.sup.2 denote F or one of the radicals L.sup.1 and L.sup.2 denotes F and the other denotes Cl. The compounds of the formula LY are preferably selected from the group consisting of the following sub-formulae:

(140) ##STR00069## ##STR00070## in which R.sup.1 has the meaning indicated above, alkyl denotes a straight-chain alkyl radical having 1-6 C atoms, (O) denotes an oxygen atom or a single bond, and v denotes an integer from 1 to 6. R.sup.1 preferably denotes straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, in particular CH.sub.3, C.sub.2H.sub.5, n-C.sub.3H.sub.7, n-C.sub.4H.sub.9, n-C.sub.5H.sub.11, CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. e) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(141) ##STR00071## in which alkyl denotes C.sub.1-6-alkyl, L.sup.x denotes H or F, and X denotes F, Cl, OCF.sub.3, OCHF.sub.2 or OCHCF.sub.2. Particular preference is given to compounds of the formula G1 in which X denotes F. f) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(142) ##STR00072## ##STR00073## in which R.sup.5 has one of the meanings indicated above for R.sup.1, alkyl denotes C.sub.1-6-alkyl, d denotes 0 or 1, and z and m each, independently of one another, denote an integer from 1 to 6. R.sup.5 in these compounds is particularly preferably C.sub.1-6-alkyl or -alkoxy or C.sub.2-6-alkenyl, d is preferably 1. The LC medium according to the invention preferably comprises one or more compounds of the above-mentioned formulae in amounts of 5% by weight. g) LC medium which additionally comprises one or more biphenyl compounds selected from the group consisting of the following formulae:

(143) ##STR00074## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. The proportion of the biphenyls of the formulae B1 to B3 in the LC mixture is preferably at least 3% by weight, in particular 5% by weight. The compounds of the formula B2 are particularly preferred. The compounds of the formulae B1 to B3 are preferably selected from the group consisting of the following sub-formulae:

(144) ##STR00075## in which alkyl* denotes an alkyl radical having 1-6 C atoms. The medium according to the invention particularly preferably comprises one or more compounds of the formulae B1a and/or B2c. h) LC medium which additionally comprises one or more terphenyl compounds of the following formula:

(145) ##STR00076## in which R.sup.5 and R.sup.6 each, independently of one another, have one of the meanings indicated above for R.sup.1, and

(146) ##STR00077## each, independently of one another, denote

(147) ##STR00078## in which L.sup.5 denotes F or Cl, preferably F, and L.sup.6 denotes F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F or CHF.sub.2, preferably F. The compounds of the formula T are preferably selected from the group consisting of the following sub-formulae:

(148) ##STR00079## ##STR00080## ##STR00081## in which R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms, R* denotes a straight-chain alkenyl radical having 2-7 C atoms, (O) denotes an oxygen atom or a single bond, and m denotes an integer from 1 to 6. R* preferably denotes CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy. The LC medium according to the invention preferably comprises the terphenyls of the formula T and the preferred sub-formulae thereof in an amount of 0.5-30% by weight, in particular 1-20% by weight. Particular preference is given to compounds of the formulae T1, T2, T3 and T21. In these compounds, R preferably denotes alkyl, furthermore alkoxy, each having 1-5 C atoms. The terphenyls are preferably employed in mixtures according to the invention if the n value of the mixture is to be 0.1. Preferred mixtures comprise 2-20% by weight of one or more terphenyl compounds of the formula T, preferably selected from the group of compounds T1 to T22. i) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(149) ##STR00082## in which R.sup.1 and R.sup.2 have the meanings indicated above and preferably each, independently of one another, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms. Preferred media comprise one or more compounds selected from the formulae O1, O3 and O4. k) LC medium which additionally comprises one or more compounds of the following formula:

(150) ##STR00083##
in which denotes

(151) ##STR00084## R.sup.9 denotes H, CH.sub.3, C.sub.2H.sub.5 or n-C.sub.3H.sub.7, (F) denotes an optional fluorine substituent, q denotes 1, 2 or 3, and R.sup.7 has one of the meanings indicated for R.sup.1, preferably in amounts of >3% by weight, in particular 5% by weight and very particularly preferably 5-30% by weight. Particularly preferred compounds of the formula FI are selected from the group consisting of the following sub-formulae:

(152) ##STR00085## in which R.sup.7 preferably denotes straight-chain alkyl, and R.sup.9 denotes CH.sub.3, C.sub.2H.sub.5 or n-C.sub.3H.sub.7. Particular preference is given to the compounds of the formulae FI1, FI2 and FI3. l) LC medium which additionally comprises one or more compounds selected from the group consisting of the following formulae:

(153) ##STR00086## in which R.sup.8 has the meaning indicated for R.sup.1, and alkyl denotes a straight-chain alkyl radical having 1-6 C atoms. m) LC medium which additionally comprises one or more compounds which contain a tetrahydronaphthyl or naphthyl unit, such as, for example, the compounds selected from the group consisting of the following formulae:

(154) ##STR00087## ##STR00088## in which R.sup.10 and R.sup.11 each, independently of one another, have one of the meanings indicated for R.sup.1, preferably denote straight-chain alkyl or alkoxy having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, and Z.sup.1 and Z.sup.2 each, independently of one another, denote C.sub.2H.sub.4, CHCH, (CH.sub.2).sub.4, (CH.sub.2).sub.3O, O(CH.sub.2).sub.3, CHCHCH.sub.2CH.sub.2, CH.sub.2CH.sub.2CHCH, CH.sub.2O, OCH.sub.2, COO, OCO, C.sub.2F.sub.4, CFCF, CFCH, CHCF, CH.sub.2 or a single bond. n) LC medium which additionally comprises one or more difluorodibenzochromans and/or chromans of the following formulae:

(155) ##STR00089## in which R.sup.11 and R.sup.12 each, independently of one another, have the meanings indicated above, ring M is trans-1,4-cyclohexylene or 1,4-phenylene, Z.sup.mC.sub.2H.sub.4, CH.sub.2O, OCH.sub.2, COO or OCO, c is 0 or 1, preferably in amounts of 3 to 20% by weight, in particular in amounts of 3 to 15% by weight. Particularly preferred compounds of the formulae BC, CR and RC are selected from the group consisting of the following sub-formulae:

(156) ##STR00090## ##STR00091## in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, (O) denotes an oxygen atom or a single bond, c is 1 or 2, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. Very particular preference is given to mixtures comprising one, two or three compounds of the formula BC-2. o) LC medium which additionally comprises one or more fluorinated phenanthrenes and/or dibenzofurans of the following formulae:

(157) ##STR00092## in which R.sup.11 and R.sup.12 each, independently of one another, have the meanings indicated above, b denotes 0 or 1, L denotes F, and r denotes 1, 2 or 3. Particularly preferred compounds of the formulae PH and BF are selected from the group consisting of the following sub-formulae:

(158) ##STR00093## in which R and R each, independently of one another, denote a straight-chain alkyl or alkoxy radical having 1-7 C atoms. p) LC medium which additionally comprises one or more monocyclic compounds of the following formula

(159) ##STR00094## wherein 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 each be replaced by O, CHCH, CO, OCO or COO in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms, L.sup.1 and L.sup.2 each, independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CH.sub.3, CH.sub.2F, CHF.sub.2. Preferably, both L.sup.1 and L.sup.2 denote F or one of L.sup.1 and L.sup.2 denotes F and the other denotes Cl,

(160) The compounds of the formula Y are preferably selected from the group consisting of the following sub-formulae:

(161) ##STR00095## in which, Alkyl and Alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, Alkoxy denotes a straight-chain alkoxy radical having 1-6 C atoms, Alkenyl and Alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms, and O denotes an oxygen atom or a single bond. Alkenyl and Alkenyl* preferably denote CH.sub.2CH, CH.sub.2CHCH.sub.2CH.sub.2, CH.sub.3CHCH, CH.sub.3CH.sub.2CHCH, CH.sub.3(CH.sub.2).sub.2CHCH, CH.sub.3(CH.sub.2).sub.3CHCH or CH.sub.3CHCH(CH.sub.2).sub.2. Particularly preferred compounds of the formula Y are selected from the group consisting of the following sub-formulae:

(162) ##STR00096## wherein Alkoxy preferably denotes straight-chain alkoxy with 3, 4, or 5 C atoms. q) LC medium which, apart from the polymerizable compounds according to the invention, in particular of the formula I or sub-formulae thereof and the comonomers, comprises no compounds which contain a terminal vinyloxy group (OCHCH.sub.2). r) LC medium which comprises 1 to 5, preferably 1, 2 or 3, polymerizable compounds, preferably selected from polymerizable compounds according to the invention, in particular of the formula I or sub-formulae thereof. s) LC medium in which the proportion of polymerizable compounds, in particular of the formula I or sub-formulae thereof, in the mixture as a whole is 0.05 to 5%, preferably 0.1 to 1%. t) LC medium which comprises 1 to 8, preferably 1 to 5, compounds of the formulae CY1, CY2, PY1 and/or PY2. The proportion of these compounds in the mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably in each case 2 to 20%. u) LC medium which comprises 1 to 8, preferably 1 to 5, compounds of the formulae CY9, CY10, PY9 and/or PY10. The proportion of these compounds in the mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably in each case 2 to 20%. v) LC medium which comprises 1 to 10, preferably 1 to 8, compounds of the formula ZK, in particular compounds of the formulae ZK1, ZK2 and/or ZK6. The proportion of these compounds in the mixture as a whole is preferably 3 to 25%, particularly preferably 5 to 45%. The content of these individual compounds is preferably in each case 2 to 20%. w) LC medium in which the proportion of compounds of the formulae CY, PY and ZK in the mixture as a whole is greater than 70%, preferably greater than 80%. x) LC medium in which the LC host mixture contains one or more compounds containing an alkenyl group, preferably selected from the group consisting of formula CY, PY and LY, wherein one or both of R.sup.1 and R.sup.2 denote straight-chain alkenyl having 2-6 C atoms, formula ZK and DK, wherein one or both of R.sup.3 and R.sup.4 or one or both of R.sup.5 and R.sup.6 denote straight-chain alkenyl having 2-6 C atoms, and formula B2 and B3, very preferably selected from formulae CY15, CY16, CY34, CY32, PY15, PY16, ZK3, ZK4, DK3, DK6, B2 and B3, most preferably selected from formulae ZK3, ZK4, B2 and B3. The concentration of these compounds in the LC host mixture is preferably from 2 to 70%, very preferably from 3 to 55%. y) LC medium which contains one or more, preferably 1 to 5, compounds selected of formula PY1PY8, very preferably of formula PY2. The proportion of these compounds in the mixture as a whole is preferably 1 to 30%, particularly preferably 2 to 20%. The content of these individual compounds is preferably in each case 1 to 20%. z) LC medium which contains one or more, preferably 1, 2 or 3, compounds of formula T2. The content of these compounds in the mixture as a whole is preferably 1 to 20%.

(163) In a second preferred embodiment the LC medium contains an LC host mixture based on compounds with positive dielectric anisotropy. Such LC media are especially suitable for use in PSA-OCB-, PSA-TN-, PSAPosi-VA-, PSA-IPS- or PSA-FFS-displays.

(164) Particularly preferred is an LC medium of this second preferred embodiment, which contains one or more compounds selected from the group consisting of compounds of formula AA and BB

(165) ##STR00097##
and optionally contains, in addition to the compounds of formula AA and/or BB, one or more compounds of formula CC

(166) ##STR00098##
in which the individual radicals have the following meanings:

(167) ##STR00099##
each, independently of one another, and on each occurrence, identically or differently

(168) ##STR00100##
each, independently of one another, and on each occurrence, identically or differently

(169) ##STR00101## R.sup.21, R.sup.31, R.sup.41, R.sup.42 each, independently of one another, alkyl, alkoxy, oxaalkyl or fluoroalkyl having 1 to 9 C atoms or alkenyl having 2 to 9 C atoms, X.sup.0 F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms, Z.sup.31 CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O or a single bond, preferably CH.sub.2CH.sub.2, COO, trans-CHCH or a single bond, particularly preferably COO, trans-CHCH or a single bond, Z.sup.41, Z.sup.42 CH.sub.2CH.sub.2, COO, trans-CHCH, trans-CFCF, CH.sub.2O, CF.sub.2O, CC or a single bond, preferably a single bond, L.sup.21, L.sup.22, L.sup.31, L.sup.32 H or F, g 0, 1, 2 or 3, e.g., 1, 2, or 3 h 0, 1, 2 or 3. X.sup.0 is preferably F, Cl, CF.sub.3, CHF.sub.2, OCF.sub.3, OCHF.sub.2, OCFHCF.sub.3, OCFHCHF.sub.2, OCFHCHF.sub.2, OCF.sub.2CH.sub.3, OCF.sub.2CHF.sub.2, OCF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CHF.sub.2, OCFHCF.sub.2CF.sub.3, OCFHCF.sub.2CHF.sub.2, OCF.sub.2CF.sub.2CF.sub.3, OCF.sub.2CF.sub.2CClF.sub.2, OCClFCF.sub.2CF.sub.3 or CHCF.sub.2, very preferably F or OCF.sub.3

(170) The compounds of formula AA are preferably selected from the group consisting of the following formulae:

(171) ##STR00102##
in which A.sup.21, R.sup.21, X.sup.0, L.sup.21 and L.sup.22 have the meanings given in formula AA, L.sup.23 and L.sup.24 each, independently of one another, are H or F, and X.sup.0 is preferably F. Particularly preferred are compounds of formulae AA1 and AA2.

(172) Particularly preferred compounds of formula AA1 are selected from the group consisting of the following subformulae:

(173) ##STR00103##
in which R.sup.0 has one of the meanings given for R.sup.21 in formula AA1, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA1, L.sup.23, L.sup.24, L.sup.25 and L.sup.26 are each, independently of one another, H or F, and X.sup.0 is preferably F.

(174) Very particularly preferred compounds of formula AA1 are selected from the group consisting of the following subformulae:

(175) ##STR00104##
In which R.sup.0 has the meaning given for R.sup.21 in formula AA1.

(176) Very preferred compounds of formula AA2 are selected from the group consisting of the following subformulae:

(177) ##STR00105##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA2, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA2, L.sup.23, L.sup.24, L.sup.25, L.sup.26, L.sup.27 and L.sup.28 each, independently of one another, are H or F, and X.sup.0 is preferably F.

(178) Very particularly preferred compounds of formula AA2 are selected from the group consisting of the following subformulae:

(179) ##STR00106##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA2.

(180) Particularly preferred compounds of formula AA3 are selected from the group consisting of the following subformulae:

(181) ##STR00107##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA3, X.sup.0, L.sup.21 and L.sup.22 have the meaning given in formula AA3, and X.sup.0 is preferably F.

(182) Particularly preferred compounds of formula AA4 are selected from the group consisting of the following subformulae:

(183) ##STR00108##
in which R.sup.0 has the meaning given for R.sup.21 in formula AA3.

(184) The compounds of formula BB are preferably selected from the group consisting of the following formulae:

(185) ##STR00109##
in which A.sup.31, A.sup.32, R.sup.31, g, X.sup.0, L.sup.31 and L.sup.32 have the meanings given in formula BB, and X.sup.0 is preferably F. Particularly preferred are compounds of formulae BB1 and BB2.

(186) Particularly preferred compounds of formula BB1 are selected from the group consisting of the following subformulae:

(187) ##STR00110##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1, X.sup.0, L.sup.31 and L.sup.32 have the meaning given in formula BB1, L.sup.33 and L.sup.34 each, independently of one another, are H or F, and X.sup.0 is preferably F.

(188) Very particularly preferred compounds of formula BB1a are selected from the group consisting of the following subformulae:

(189) ##STR00111##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1.

(190) Very particularly preferred compounds of formula BB1b are selected from the group consisting of the following subformulae:

(191) ##STR00112##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB1.

(192) Particularly preferred compounds of formula BB2 are selected from the group consisting of the following subformulae:

(193) ##STR00113## ##STR00114##
in which R.sup.3 has one of the meanings given for R.sup.21 in formula BB2, X.sup.3 has one of the meanings given for X.sup.0 in formula BB2, X.sup.0, L.sup.31 and L.sup.32 have the meaning given in formula BB2, L.sup.33, L.sup.34, L.sup.35 and L.sup.36 are each, independently of one another, H or F, and X.sup.3 is preferably F.

(194) Very particularly preferred compounds of formula BB2 are selected from the group consisting of the following subformulae:

(195) ##STR00115##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(196) Very particularly preferred compounds of formula BB2b are selected from the group consisting of the following subformulae

(197) ##STR00116##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(198) Very particularly preferred compounds of formula BB2c are selected from the group consisting of the following subformulae:

(199) ##STR00117##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(200) Very particularly preferred compounds of formula BB2d and BB2e are selected from the group consisting of the following subformulae:

(201) ##STR00118##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(202) Very particularly preferred compounds of formula BB2f are selected from the group consisting of the following subformulae:

(203) ##STR00119##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(204) Very particularly preferred compounds of formula BB2g are selected from the group consisting of the following subformulae:

(205) ##STR00120##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2.

(206) Very particularly preferred compounds of formula BB2h are selected from the group consisting of the following subformulae:

(207) ##STR00121##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2, and X.sup.3 has one of the meanings given for X.sup.0 in formula BB2.

(208) Very particularly preferred compounds of formula BB21 are selected from the group consisting of the following subformulae:

(209) ##STR00122##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2, and X.sup.3 has one of the meanings given for X.sup.0 in formula BB2.

(210) Very particularly preferred compounds of formula BB2k are selected from the group consisting of the following subformulae:

(211) ##STR00123##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB2, and X.sup.3 has one of the meanings given for X.sup.0 in formula BB2.

(212) Alternatively to, or in addition to, the compounds of formula BB1 and/or BB2 the LC media may also comprise one or more compounds of formula BB3 as defined above.

(213) Particularly preferred compounds of formula BB3 are selected from the group consisting of the following subformulae:

(214) ##STR00124##
in which R.sup.3 has the meaning given for R.sup.31 in formula BB3.

(215) Preferably the LC media according to this second preferred embodiment comprise, in addition to the compounds of formula AA and/or BB, one or more dielectrically neutral compounds having a dielectric anisotropy in the range from 1.5 to +3, preferably selected from the group of compounds of formula CC as defined above.

(216) Particularly preferred compounds of formula CC are selected from the group consisting of the following subformulae:

(217) ##STR00125## ##STR00126##
in which R.sup.41 and R.sup.42 have the meanings given in formula CC, and preferably denote each, independently of one another, alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1 to 7 C atoms, or alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 7 C atoms, and L.sup.4 is H or F.

(218) Preferably the LC media according to this second preferred embodiment comprise, in addition or alternatively to the dielectrically neutral compounds of formula CC, one or more dielectrically neutral compounds having a dielectric anisotropy in the range from 1.5 to +3, selected from the group of compounds of formula DD.

(219) ##STR00127##

(220) In which A.sup.41, A.sup.42, Z.sup.41, Z.sup.42, R.sup.41, R.sup.42 and h have the meanings given in formula CC.

(221) Particularly preferred compounds of formula DD are selected from the group consisting of the following subformulae:

(222) ##STR00128##
in which R.sup.41 and R.sup.42 have the meanings given in formula DD and R.sup.41 preferably denotes alkyl, and in formula DD1 R.sup.42 preferably denotes alkenyl, particularly preferably (CH.sub.2).sub.2CHCHCH.sub.3, and in formula DD2 R.sup.42 preferably denotes alkyl, (CH.sub.2).sub.2CHCH.sub.2 or (CH.sub.2).sub.2CHCHCH.sub.3.

(223) The compounds of formula AA and BB are preferably used in the LC medium according to the invention in a concentration from 2% to 60%, more preferably from 3% to 35%, and very particularly preferably from 4% to 30% in the mixture as a whole.

(224) The compounds of formula CC and DD are preferably used in the LC medium according to the invention in a concentration from 2% to 70%, more preferably from 5% to 65%, even more preferably from 10% to 60%, and very particularly preferably from 10%, preferably 15%, to 55% in the mixture as a whole.

(225) The combination of compounds of the preferred embodiments mentioned above with the polymerized compounds described above causes low threshold voltages, low rotational viscosities and very good low-temperature stabilities in the LC media according to the invention at the same time as constantly high clearing points and high HR values, and allows the rapid establishment of a particularly low pretilt angle in PSA displays. In particular, the LC media exhibit significantly shortened response times, in particular also the grey-shade response times, in PSA displays compared with the media from the prior art.

(226) The liquid-crystal mixture preferably has a nematic phase range of at least 80 K, particularly preferably at least 100 K, and a rotational viscosity of not greater than 250 mPa.Math.s, preferably not greater than 200 mPa.Math.s, at 20 C.

(227) In the VA-type displays according to the invention, the molecules in the layer of the LC medium in the switched-off state are aligned perpendicular to the electrode surfaces (homeotropically) or have a tilted homeotropic alignment. On application of an electrical voltage to the electrodes, a realignment of the LC molecules takes place with the longitudinal molecular axes parallel to the electrode surfaces.

(228) LC media according to the invention based on compounds with negative dielectric anisotropy according to the first preferred embodiment, in particular for use in displays of the PSA-VA type, have a negative dielectric anisotropy , preferably from 0.5 to 10, in particular from 2.5 to 7.5, at 20 C. and 1 kHz.

(229) The birefringence n in LC media according to the invention for use in displays of the PSA-VA type is preferably below 0.16, particularly preferably from 0.06 to 0.14, very particularly preferably from 0.07 to 0.12.

(230) In the OCB-type displays according to the invention, the molecules in the layer of the LC medium have a bend alignment. On application of an electrical voltage, a realignment of the LC molecules takes place with the longitudinal molecular axes perpendicular to the electrode surfaces.

(231) LC media according to the invention for use in displays of the PSA-OCB type are preferably those based on compounds with positive dielectric anisotropy according to the second preferred embodiment, and preferably have a positive dielectric anisotropy from +4 to +17 at 20 C. and 1 kHz.

(232) The birefringence n in LC media according to the invention for use in displays of the PSA-OCB type is preferably from 0.14 to 0.22, particularly preferably from 0.16 to 0.22.

(233) LC media according to the invention, based on compounds with positive dielectric anisotropy according to the second preferred embodiment, for use in displays of the PSA-TN-, PSA-posi-VA-, PSA-IPS- or PSA-FFS-type, preferably have a positive dielectric anisotropy from +2 to +30, particularly preferably from +3 to +20, at 20 C. and 1 kHz.

(234) The birefringence n in LC media according to the invention for use in displays of the PSA-TN-, PSA-posi-VA-, PSA-IPS- or PSA-FFS-type is preferably from 0.07 to 0.15, particularly preferably from 0.08 to 0.13.

(235) The LC media according to the invention may also comprise further additives which are known to the person skilled in the art and are described in the literature, such as, for example, polymerization initiators, inhibitors, stabilizers, surface-active substances or chiral dopants. These may be polymerizable or non-polymerizable. Polymerizable additives are accordingly ascribed to the polymerizable component or component A). Non-polymerizable additives are accordingly ascribed to the non-polymerizable component or component B).

(236) In a preferred embodiment the LC media contain one or more chiral dopants, preferably in a concentration from 0.01 to 1%, very preferably from 0.05 to 0.5%. The chiral dopants are preferably selected from the group consisting of compounds from Table B below, very preferably from the group consisting of R- or S-1011, R- or S-2011, R- or S-3011, R- or S-4011, and R- or S-5011.

(237) In another preferred embodiment the LC media contain a racemate of one or more chiral dopants, which are preferably selected from the chiral dopants mentioned in the previous paragraph.

(238) Furthermore, it is possible to add to the LC media, for example, 0 to 15% by weight of pleochroic dyes, furthermore nanoparticles, conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylborate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)), for improving the conductivity, or substances for modifying the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

(239) The individual components of the preferred embodiments a)-z) of the LC media according to the invention are either known or methods for the preparation thereof can readily be derived from the prior art by the person skilled in the relevant art, since they are based on standard methods described in the literature. Corresponding compounds of the formula CY are described, for example, in EP-A-0 364 538. Corresponding compounds of the formula ZK are described, for example, in DE-A-26 36 684 and DE-A-33 21 373.

(240) The LC media which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above, and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing. The invention furthermore relates to the process for the preparation of the LC media according to the invention.

(241) It goes without saying to the person skilled in the art that the LC media according to the invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.

(242) The structure of the LC displays according to the invention corresponds to the usual geometry for PSA displays, as described in the prior art cited at the outset. Geometries without protrusions are preferred, in particular those in which, in addition, the electrode on the color filter side is unstructured and only the electrode on the TFT side has slots. Particularly suitable and preferred electrode structures for PSA-VA displays are described, for example, in US 2006/0066793 A1.

(243) The following examples explain the present invention without restricting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible.

(244) The following abbreviations are used:

(245) (m, m, z: in each case, independently of one another, 1, 2, 3, 4, 5 or 6)

(246) TABLE-US-00001 TABLE A CCH-nm 0 CCH-nOm CC-n-V CC-n-V1 CC-n-mV PP-n-m PP-n-Om PP-n-Vm PCH-nm PCH-nOm CY-n-Om 0 CY-n-m CY-V-Om CY-nV-(O)m CVC-n-m CVY-V-m CEY-V-m PY-n-(O)m CCP-V-m CCP-Vn-m CCY-n-m 0 CCY-n-Om CCY-V-m CCY-Vn-m CCY-V-Om CCY-n-OmV CCY-n-zOm CCOC-n-m CPY-n-(O)m CPY-V-Om CEY-n-Om 0 CEY-n-m COY-n-Om COY-n-m CCEY-n-Om CCEY-n-m CCOY-n-Om CCOY-n-m CQY-n-(O)m CQIY-n-(O)m CCQY-n-(O)m 0 CCQIY-n-(O)m CPQY-n-(O)m CPQIY-n-Om CLY-n-(O)m CYLI-n-m LYLI-n-m LY-n-(O)m PGIGI-n-F PGP-n-m PYP-n-(O)m 0 PYP-n-mV YPY-n-m YPY-n-mV BCH-nm BCH-nmF CPYP-n-(O)m CPGP-n-m CCZPC-n-m CGCC-n-m CPYC-n-m 0 CYYC-n-m CCYY-n-m CPYG-n-(O)m CBC-nm CBC-nmF CNap-n-Om CCNap-n-Om CENap-n-Om CTNap-n-Om CETNap-n-Om 00 CK-n-F 01 DFDBC-n(O)-(O)m 02 C-DFDBF-n-(O)m

(247) In a preferred embodiment of the present invention, the LC media according to the invention comprise one or more compounds selected from the group consisting of compounds from Table A.

(248) TABLE-US-00002 TABLE B Table B shows possible chiral dopants which can be added to the LC media according to the invention. 03 C 15 04 CB 15 05 CM 21 06 R/S-811 07 CM 44 08 CM 45 09 CM 47 0 CN R/S-2011 R/S-3011 R/S-4011 R/S-5011 R/S-1011

(249) The LC media preferably comprise 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, of dopants. The LC media preferably comprise one or more dopants selected from the group consisting of compounds from Table B.

(250) TABLE-US-00003 TABLE C Table C shows possible stabilizers which can be added to the LC media according to the invention. 0 0 0 0 (n here denotes an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8, terminal methyl groups are not shown).

(251) The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1% by weight, of stabilizers. The LC media preferably comprise one or more stabilizers selected from the group consisting of compounds from Table C.

(252) TABLE-US-00004 TABLE D Table D shows illustrative compounds which can be used in the LC media in accordance with the present invention, preferably as reactive mesogenic compounds. RM-1 RM-2 RM-3 RM-4 RM-5 RM-6 RM-7 RM-8 RM-9 0 RM-10 RM-11 RM-12 RM-13 RM-14 RM-15 RM-16 RM-17 RM-18 RM-19 0 RM-20 RM-21 RM-22 RM-23 RM-24 RM-25 RM-26 RM-27 RM-28 RM-29 0 RM-30 RM-31 RM-32 RM-33 RM-34 RM-35 RM-36 RM-37 RM-38 RM-39 0 RM-40 RM-41 RM-42 RM-43 RM-44 RM-45 RM-46 RM-47 RM-48 RM-49 00 RM-50 01 RM-51 02 RM-52 03 RM-53 04 RM-54 05 RM-55 06 RM-56 07 RM-57 08 RM-58 09 RM-59 0 RM-60 RM-61 RM-62 RM-63 RM-64 RM-65 RM-66 RM-67 RM-68 RM-69 0 RM-70 RM-71 RM-72 RM-73 RM-74 RM-75 RM-76 RM-77 RM-78 RM-79 0 RM-80 RM-81 RM-82 RM-83 RM-84

(253) In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table D.

(254) In addition, the following abbreviations and symbols are used: V.sub.0 threshold voltage, capacitive [V] at 20 C., n.sub.e extraordinary refractive index at 20 C. and 589 nm, n.sub.o ordinary refractive index at 20 C. and 589 nm, n optical anisotropy at 20 C. and 589 nm, dielectric permittivity perpendicular to the director at 20 C. and 1 kHz, dielectric permittivity parallel to the director at 20 C. and 1 kHz, dielectric anisotropy at 20 C. and 1 kHz, cl.p., T(N,I) clearing point [ C.], .sub.1 rotational viscosity at 20 C. [mPa.Math.s], K.sub.1 elastic constant, splay deformation at 20 C. [pN], K.sub.2 elastic constant, twist deformation at 20 C. [pN], K.sub.3 elastic constant, bend deformation at 20 C. [pN].

(255) Unless explicitly noted otherwise, all concentrations in the present application are quoted in percent by weight and relate to the corresponding mixture as a whole, comprising all solid or liquid-crystalline components, without solvents.

(256) Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, for the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are quoted in degrees Celsius ( C.). M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures.

(257) All physical properties are and have been determined in accordance with Merck Liquid Crystals, Physical Properties of Liquid Crystals, Status November 1997, Merck KGaA, Germany, and apply for a temperature of 20 C., and n is determined at 589 nm and at 1 kHz, unless explicitly indicated otherwise in each case.

(258) The term threshold voltage for the present invention relates to the capacitive threshold (V.sub.0), also known as the Freedericks threshold, unless explicitly indicated otherwise. In the examples, the optical threshold may also, as generally usual, be quoted for 10% relative contrast (V.sub.10).

(259) Unless stated otherwise, the process of polymerizing the polymerizable compounds in the PSA displays as described above and below is carried out at a temperature where the LC medium exhibits a liquid crystal phase, preferably a nematic phase, and most preferably is carried out at room temperature.

(260) Unless stated otherwise, methods of preparing test cells and measuring their electrooptical and other properties are carried out by the methods as described hereinafter or in analogy thereto.

(261) The display used for measurement of the capacitive threshold voltage consists of two plane-parallel glass outer plates at a separation of 25 m, each of which has on the inside an electrode layer and an unrubbed polyimide alignment layer on top, which effect a homeotropic edge alignment of the liquid-crystal molecules.

(262) The display or test cell used for measurement of the tilt angles consists of two plane-parallel glass outer plates at a separation of 4 m, each of which has on the inside an electrode layer and a polyimide alignment layer on top, where the two polyimide layers are rubbed antiparallel to one another and effect a homeotropic edge alignment of the liquid-crystal molecules.

(263) The polymerizable compounds are polymerized in the display or test cell by irradiation with UVA light of defined intensity for a prespecified time, with a voltage simultaneously being applied to the display (usually 10 V to 30 V alternating current, 1 kHz). In the examples, unless indicated otherwise, a metal halide lamp and an intensity of 100 mW/cm.sup.2 is used for polymerization. The intensity is measured using a standard UVA meter (Hoenle UV-meter high end with UVA sensor).

(264) The tilt angle is determined by crystal rotation experiment (Autronic-Melchers TBA-105). A low value (i.e. a large deviation from the 90 angle) corresponds to a large tilt here.

(265) The VHR value is measured as follows: 0.3% of a polymerizable monomeric compound is added to the LC host mixture, and the resultant mixture is introduced into VA-VHR test cells (not rubbed, VA-polyimide alignment layer, LC-layer thickness d6 m). The HR value is determined after 5 min at 100 C. before and after UV exposure at 1 V, 60 Hz, 64 s pulse (measuring instrument: Autronic-Melchers VHRM-105).

EXAMPLE 1

(266) Polymerizable monomeric compound 1 of formula I2-1 is prepared as follows.

(267) ##STR00335## ##STR00336##

1.1 4-Benzyloxy-biphenyl-3,5-dicarboxylic acid

(268) 4-benzyloxy-biphenyl-3,5-dicarboxylic acid is prepared from commercially available [4-(benzyloxy)phenyl]-boronic acid and 5-bromo-isophthalic acid.

(269) To a solution of sodium carbonate (31.26 g, 295.0 mol) in dist. water (135 ml) is added 1,4-dioxane (210 ml), 5-bromo-isophthalic acid (14.46 g, 59.0 mmol) and [4-(benzyloxy)phenyl]-boronic acid (14.82 g, 65.0 mol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.83 g, 1.2 mmol), triphenylphosphine (0.31 g, 1.2 mmol) and triethylamine (0.12 g, 1.2 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature 400 ml dist. water is added, and the reaction mixture is neutralized with conc. HCl acid under cooling to pH1. The precipitated crude product is filtrated, washed with dist. water, and further purified by recrystallization from acetonitrile to provide gray crystals of 4-benzyloxy-biphenyl-3,5-dicarboxylic acid (17.4 g).

1.2 4-Benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(2-benzyloxy-ethyl)ester

(270) To a solution of 4-benzyloxy-biphenyl-3,5-dicarboxylic acid (8.00 g, 105.64 mmol) in DMF (50 ml) is added potassium carbonate (7.62 g, 55.12 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (10.87 g. 50.52 mmol) is added. The reaction mixture is stirred at 70 C. overnight. After cooling to room temperature, the reaction mixture is added into 100 ml water and extracted with 60 ml methyl-t-butyl ether (MTBE). The organic phase is washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with heptane/ethylacetate 7:3 to provide 4-benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(2-benzyloxy-ethyl)ester as white oil (8.0 g).

1.3 4-Hydroxy-biphenyl-3,5-dicarboxylic acid bis-(2-hydroxy-ethyl)ester

(271) A solution of 4-benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(2-benzyloxyethyl)ester (8.0 g, 13.0 mmol) in tetrahydrofuran (80 ml) is treated with palladium (5%) on activated charcoal (2.0 g) and submitted to hydrogenation for 15 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The residue is recrystallized from toluene/ethylacetate solvent mixture to afford 4-hydroxy-biphenyl-3,5-dicarboxylic acid bis-(2-hydroxy-ethyl)ester as white solid (4.2 g).

1.4 4-(2-Methyl-acryloyloxy)-biphenyl-3,5-dicarboxylic acid bis-[2-(2-methyl-acryloyloxy)-ethyl]ester

(272) Methacrylic acid (5.95 g, 69.1 mmol) and 4-(dimethylamino)pyridine (0.15 g, 1.2 mmol) is added to a suspension of 4-hydroxy-biphenyl-3,5-dicarboxylic acid bis-(2-hydroxy-ethyl)ester (4.2 g, 12.1 mmol) in dichloromethane (110 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (10.7 g, 69.1 mmol) in dichloromethane (50 ml) 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 8:2. The obtained product is recrystallized from ethanol/acetonitrile solvent mixture affords white crystals of 4-(2-Methyl-acryloyloxy)-biphenyl-3,5-dicarboxylic acid bis-[2-(2-methylacryloyloxy)-ethyl]ester (2.6 g, m.p. 47 C.).

(273) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.45 (m, 1 H, ArH), 8.42 (m, 2 H, ArH), 7.80 (d, J=8.5 Hz, 2 H, ArH), 7.35 (d, J=8.5 Hz, 2 H, ArH), 6.32 (m, 1 H, H.sub.olefin), 6.04 (m, 2 H, H.sub.olefin), 5.93 (m, 1 H, H.sub.olefin), 5.68 (m, 2 H, H.sub.olefin), 4.62-4.60 (m, 2 H, OCH.sub.2), 4.51-4.49 (m, 2 H, OCH.sub.2), 2.03 (br. s, 3 H, CH.sub.3), 1.87 (m, 6H, 2CH.sub.3).

EXAMPLE 2

(274) Polymerizable monomeric compound 2 of formula I2-4 is prepared as follows.

(275) ##STR00337##

2.1 4-Benzyloxy-biphenyl-3,5-dicarboxylic acid

(276) 4-benzyloxy-biphenyl-3,5-dicarboxylic acid is prepared as described in Example 1.

2.2 4-Benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(3-benzyloxy-propyl)ester

(277) To a solution of 4-benzyloxy-biphenyl-3,5-dicarboxylic acid (8.00 g, 22.96 mmol) in DMF (50 ml) is added potassium carbonate (7.62 g, 55.12 mmol). To the resulted suspension (2-bromo-propoxymethyl)-benzene (11.58 g. 50.52 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hs. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the solid residue is recrystallization from isopropanol. 4-benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(3-benzyloxy-propyl)ester is obtained as white crystals (8.1 g).

2.3 4-Hydroxy-biphenyl-3,5-dicarboxylic acid bis-(3-hydroxy-propyl)ester

(278) A solution of 4-benzyloxy-biphenyl-3,5-dicarboxylic acid bis-(3-benzyloxypropyl)ester (8.1 g, 12.6 mmol) in tetrahydrofuran (80 ml) is treated with palladium (5%) on activated charcoal (2.0 g) and submitted to hydrogenation for 15 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The residue is recrystallized from toluene/ethylacetate solvent mixture to give white crystals of 4-hydroxy-biphenyl-3,5-dicarboxylic acid bis-(3-hydroxy-propyl)ester (4.5 g).

2.4 4-(2-Methyl-acryloyloxy)-biphenyl-3,5-dicarboxylic acid bis-[3-(2-methyl-acryloyloxy)-propyl]ester

(279) Methacrylic acid (5.77 g, 67.0 mmol) and 4-(dimethylamino)pyridine (0.14 g, 1.2 mmol) is added to a suspension of 4-hydroxy-biphenyl-3,5-dicarboxylic acid bis-(3-hydroxy-propyl)ester (4.40 g, 11.8 mmol) in dichloromethane (100 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (10.4 g, 67.0 mmol) in dichloromethane (60 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is recrystallization from ethanol/acetonitrile solvent mixture to afford white crystals of 4-(2-methylacryloyloxy)-biphenyl-3,5-dicarboxylic acid bis-[3-(2-methyl-acryloyloxy)propyl]ester (2.5 g, m.p. 42 C.).

(280) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.46 (m, 1 H, ArH), 8.41 (m, 2 H, ArH), 7.80 (d, J=8.5 Hz, 2 H, ArH), 7.35 (d, J=8.5 Hz, 2 H, ArH), 6.32 (m, 1 H, H.sub.olefin), 6.02 (m, 2 H, H.sub.olefin), 5.93 (m, 1 H, H.sub.olefin), 5.61 (m, 2 H, H.sub.olefin), 4.47-4.44 (m, 2 H, OCH.sub.2), 4.30-4.28 (m, 2 H, OCH.sub.2), 2.16-2.14 (m, 2 H, OCH.sub.2CH.sub.2CH.sub.2O), 2.04 (br. s, 3 H, CH.sub.3), 1.84 (m, 6H, 2CH.sub.3).

EXAMPLE 3

(281) Polymerizable monomeric compound 3 of formula I3-4 is prepared as follows.

(282) ##STR00338##

3.1 4-Benzyloxy-biphenyl-3,4-dicarboxylic acid

(283) 4-benzyloxy-biphenyl-3,4-dicarboxylic acid is prepared from commercially available [4-(benzyloxy)phenyl]-boronic acid and 5-bromo-phthalic acid.

(284) To a solution of sodium carbonate (31.27 g, 295.1 mmol) in dist. water (135 ml) is added 1,4-dioxane (210 ml), 5-bromo-phthalic acid (14.46 g, 59.0 mmol) and [4-(benzyloxy)phenyl]-boronic acid (14.82 g, 65.0 mmol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.83 g, 1.2 mmol), triphenylphosphine (0.31 g, 1.2 mmol) and triethylamine (0.12 g, 1.2 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature, 400 ml dist. water is added and the reaction mixture is neutralized with conc. HCl acid to pH1 under cooling. The precipitated crude product is filtrated, washed with dist. water, and further purified by recrystallization from acetonitrile to provide gray crystals of 4-benzyloxy-biphenyl-3,4-dicarboxylic acid (15.8 g.

3.2 4-Benzyloxy-biphenyl-3,4-dicarboxylic acid bis-(3-benzyloxy-propyl)ester

(285) To a solution of 4-benzyloxy-biphenyl-3,4-dicarboxylic acid (8.00 g, 22.96 mmol) in DMF (50 ml) is added potassium carbonate (7.62 g, 55.12 mmol). To the resulted suspension (2-bromo-propoxymethyl)-benzene (11.58 g. 50.52 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hs. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with elute heptane/ethylacetate 7:3. 4-benzyloxy-biphenyl-3,4-dicarboxylic acid bis-(3-benzyloxy-propyl)ester is obtained as colorless solid (6.0 g).

3.2 4-Hydroxy-biphenyl-3,4-dicarboxylic acid bis-(3-hydroxy-propyl)ester

(286) A solution of 4-benzyloxy-biphenyl-3,4-dicarboxylic acid bis-(3-benzyloxypropyl)ester (6.0 g, 9.3 mmol) in tetrahydrofuran (60 ml) is treated with palladium (5%) on activated charcoal (0.6 g) and submitted to hydrogenation for 20 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. After further drying in high vacuo 4-hydroxy-biphenyl-3,4-dicarboxylic acid bis-(3-hydroxy-propyl)ester is obtained as oil and used without further purification (3.4 g).

3.3 4-(2-Methyl-acryloyloxy)-biphenyl-3,4-dicarboxylic acid bis-[3-(2-methyl-acryloyloxy)-propyl]ester

(287) Methacrylic acid (4.46 g, 51.8 mmol) and 4-(dimethylamino)pyridine (0.11 g, 0.9 mmol) is added to a suspension of 4-hydroxy-biphenyl-3,4-dicarboxylic acid bis-(3-hydroxy-propyl)ester (3.40 g, 9.1 mmol) in dichloromethane (100 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (8.04 g, 51.8 mmol) in dichloromethane (60 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is purified by silica gel chromatography with elute heptane/ethylacetate 7:3. 4-(2-Methyl-acryloyloxy)-biphenyl-3,4-dicarboxylic acid bis-[3-(2-methyl-acryloyloxy)-propyl]ester is obtained as colorless oil (1.7 g).

(288) .sup.1H-NMR (CDCl.sub.3, 500 MHz): (ppm)=7.86 (d, .sup.4J.sub.H,H=1.5 Hz, 1 H, ArH), 7.82 (d, .sup.3J.sub.H,H=8.0 Hz, 1 H, ArH), 7.72 (dd, .sup.3J.sub.H,H=8.0 Hz, .sup.4J.sub.H,H=1.5 Hz 1 H, ArH), 7.62 (d, J=8.5 Hz, 2 H, ArH), 7.24 (d, J=8.5 Hz, 2 H, ArH), 6.37 (m, 1H, H.sub.olefin), 6.10 (m, 2 H, H.sub.olefin), 5.78 (m, 1 H, H.sub.olefin), 5.56-5.53 (m, 2 H, H.sub.olefin), 4.46-4.42 (m, 2 H, OCH.sub.2), 4.31-4.27 (m, 2 H, OCH.sub.2), 2.16-2.13 (m, 2 H, OCH.sub.2CH.sub.2CH.sub.2O), 2.08 (br. s, 3 H, CH.sub.3), 1.94 (br. s, 3H, CH.sub.3), 1.92 (br. s, 3H, CH.sub.3).

EXAMPLE 4

(289) Polymerizable monomeric compound 4 of formula I4-1 is prepared as follows.

(290) ##STR00339##

4.1 4-Benzyloxy-4-hydroxy-biphenyl-3-carboxylic acid

(291) 4-Benzyloxy-4-hydroxy-biphenyl-3-carboxylic acid is prepared from commercially available [4-(benzyloxy)phenyl]-boronic acid and 5-bromo-2-hydroxyl benzoic acid.

(292) To a solution of sodium carbonate (36.63 g, 345.6 mmol) in dist. water (160 ml) is added 1,4-dioxane (245 ml), 5-bromo-2-hydroxyl benzoic acid (15.00 g, 69.1 mmol) and [4-(benzyloxy)phenyl]-boronic acid (15.76 g, 69.1 mmol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.97 g, 1.4 mmol), triphenylphosphine (0.36 g, 1.4 mmol) and triethylamine (0.14 g, 1.4 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature, 200 ml dist. water is added and the reaction mixture is neutralized with conc. HCl acid to pH1 under cooling. The precipitated crude product is filtrated, washed with dist. water. After drying in vacuo, the obtained gray crystals of 4-benzyloxy-4-hydroxyl biphenyl-3-carboxylic acid (22 g) were used without further purification.

4.2 4-Benzyloxy-4-hydroxy-biphenyl-3-carboxylic acid 2-benzyloxy-ethyl ester

(293) To a solution of 4-benzyloxy-4-hydroxyl-biphenyl-3-carboxylic acid (18.00 g, 39.3 mmol) in DMF (50 ml) is added potassium bicarbonate (4.72 g, 47.2 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (12.69 g. 59.0 mmol) is added. The reaction mixture is stirred at 40 C. for overnight. After cooling to room temperature, the reaction mixture is poured into 200 ml ice-water mixture and extracted with 120 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the oily residue is purified by silica gel chromatography with elute heptane/ethylacetate 8:2 and recrystallized from acetonitrile to afford 4-benzyloxy-4-hydroxyl biphenyl-3-carboxylic acid 2-benzyloxy-ethyl ester as white crystals (4.2 g).

4.3 4,4-Dihydroxy-biphenyl-3-carboxylic acid 2-hydroxy-ethyl ester

(294) A solution of 4-benzyloxy-4-hydroxyl biphenyl-3-carboxylic acid 2-benzyloxyethyl ester (4.2 g, 9.2 mmol) in tetrahydrofuran (40 ml) is treated with palladium (5%) on activated charcoal (1.0 g) and submitted to hydrogenation for 21 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The solid residue is recrystallized from acetonitrile to provide white crystals of 4,4-dihydroxy-biphenyl-3-carboxylic acid 2-hydroxyethyl ester (1.8 g).

4.4 4,4-Bis-(2-methyl-acryloyloxy)-biphenyl-3-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester

(295) Methacrylic acid (3.22 g, 37.4 mmol) and 4-(dimethylamino)pyridine (0.08 g, 0.66 mmol) is added to a suspension of 4,4-dihydroxy-biphenyl-3-carboxylic acid 2-hydroxy-ethyl ester (1.80 g, 6.6 mmol) in dichloromethane (80 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (5.81 g, 37.4 mmol) in dichloromethane (30 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is recrystallized from ethanol to afford white crystals of 4,4-bis-(2-methyl-acryloyloxy)-biphenyl-3-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (2.2 g, m.p. 84 C.).

(296) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.17 (m, 1 H, ArH), 8.01 (m, 1 H, ArH), 7.76 (d, J=8.5 Hz, 2 H, ArH), 7.40 (m, 1 H, ArH), 7.32 (d, J=8.5 Hz, 2 H, ArH), 6.32 (m, 2 H, H.sub.olefin), 6.28 (m, 1 H, H.sub.olefin), 6.03 (m, 1 H, H.sub.olefin), 5.93 (m, 2 H, H.sub.olefin), 5.90 (m, 1 H, H.sub.olefin), 5.68 (m, 1 H, H.sub.olefin), 4.50-4.48 (m, 2 H, OCH.sub.2), 4.39-4.37 (m, 2 H, OCH.sub.2), 2.03 (br. s, 3 H, CH.sub.3), 2.01 (br. s, 3 H, CH.sub.3), 1.86 (br. s, 6H, CH.sub.3).

EXAMPLE 5

(297) Polymerizable monomeric compound 5 of formula I9-1 is prepared as follows.

(298) ##STR00340##

5.1 3,4-Bis-benzyloxy-phenyl-boronic acid

(299) 3,4-Bis-benzyloxy-phenyl-boronic acid is prepared from commercially available 1,2-bis-benzyloxy-4-bromo-benzene.

(300) 1,2-bis-benzyloxy-4-bromo-benzene (20.00 g, 54.2 mmol) is dissolved in dry THF (250 ml) under nitrogen atmosphere. The solution is cooled down in a dry ice bath to 70 C. 37 ml 15% solution of n-butyllithium in n-hexane is added dropwise with the temperature controlled below 60 C. The reaction mixture is continued stirring at this temperature for 1 h. The solution of trimethylborate (6.19 g, 59.6 mmol) in 6 ml dry THF is added dropwise. The reaction mixture is allowed slowly warming up to 0 C. under stirring, and then hydrolyzed carefully by dropwise addition of water. The reaction mixture is acidified with conc. HCl acid to pH1 under cooling. The organic phase is separated. The aqueous is extracted with MTBE. The combined organic phase is dried over sodium sulfate. After removing solvent in vacuo, the crude product is recrystallized from heptane to provide pinkish crystals of 3,4-bis-benzyloxy-phenyl-boronic acid (13.8 g).

5.2 3,4-Bis-benzyloxy-biphenyl-4-carboxylic acid

(301) To a solution of sodium carbonate (21.88 g, 206.5 mmol) in dist. water (95 ml) is added 1,4-dioxane (150 ml), 4-bromobenzoic acid (8.38 g, 41.3 mmol) and 3,4-bis-benzyloxy-phenyl-boronic acid (13.80 g, 41.3 mmol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.58 g, 0.8 mmol), triphenylphosphine (0.22 g, 0.8 mmol) and triethylamine (0.08 g, 0.8 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature, 200 ml dist. water is added and the reaction mixture is neutralized with conc. HCl acid to pH1 under cooling. The precipitated crude product is filtrated, washed with dist. water. After drying in vacuo, the obtained gray crystals of 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid (14.6 g) were used without further purification.

5.3 3,4-Bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester

(302) To a solution of 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid (8.00 g, 19.5 mmol) in DMF (30 ml) is added potassium carbonate (3.23 g, 23.4 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (4.61 g. 21.4 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hs. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the crude product is purified by recrystallization from isopropanol/acetonitrile to afford 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester as off-white crystals (7.2 g).

5.4 3,4-Dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester

(303) A solution of 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester (7.2 g, 12.0 mmol) in tetrahydrofuran (70 ml) is treated with palladium (5%) on activated charcoal (2.0 g) and submitted to hydrogenation for 18 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The solid residue is recrystallized from acetonitrile to provide gray crystals of 3,4-dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester (2.7 g).

5.5 3,4-Bis-(2-methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester

(304) Methacrylic acid (4.83 g, 56.1 mmol) and 4-(dimethylamino)pyridine (0.12 g, 0.98 mmol) is added to a suspension of 3,4-dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester (2.7 g, 9.8 mmol) in dichloromethane (100 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (8.71 g, 56.1 mmol) in dichloromethane (40 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is recrystallized from ethanol/acetonitrile to afford white crystals of 3,4-bis-(2-methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (1.7 g, m.p. 63 C.).

(305) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.04 (d, J=8.5 Hz, 2 H, ArH), 7.89 (d, J=8.5 Hz, 2 H, ArH), 7.79 (m, 1 H, ArH), 7.75 (m, 1 H, ArH), 7.50 (m, 1H, ArH), 6.22 (m, 2 H, H.sub.olefin), 6.05 (m, 1 H, H.sub.olefin), 5.91 (m, 2 H, H.sub.olefin), 5.69 (m, 1 H, H.sub.olefin), 4.57-4.55 (m, 2 H, OCH.sub.2), 4.49-4.47 (m, 2 H, OCH.sub.2), 1.96 (br. s, 6 H, 2CH.sub.3), 1.88 (br. s, 3H, CH.sub.3).

EXAMPLE 6

(306) Polymerizable monomeric compound 6 of formula I9-2 is prepared as follows.

(307) ##STR00341##

(308) 3,4-Bis-benzyloxy-phenyl-boronic acid and 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid are prepared as described in Example 5.

6.1 3,4-Bis-benzyloxy-biphenyl-4-carboxylic acid 3-benzyloxy-propyl ester

(309) To a solution of 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid (8.00 g, 19.5 mmol) in DMF (30 ml) is added potassium carbonate (3.23 g, 23.4 mmol). To the resulted suspension (3-bromo-propoxymethyl)-benzene (4.91 g. 21.4 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hs. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the crude product is purified by recrystallization from isopropanol/acetonitrile to afford 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid 3-benzyloxy-propyl ester as white crystals (7.5 g).

6.2 3,4-Dihydroxy-biphenyl-4-carboxylic acid 3-hydroxy-propyl ester

(310) A solution of 3,4-bis-benzyloxy-biphenyl-4-carboxylic acid 3-benzyloxypropyl ester (7.5 g, 13.4 mmol) in tetrahydrofuran (80 ml) is treated with palladium (5%) on activated charcoal (2.0 g) and submitted to hydrogenation for 19 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The solid residue is recrystallized from acetonitrile to provide white crystals of 3,4-dihydroxy-biphenyl-4-carboxylic acid 3-hydroxypropyl ester (3.3 g).

6.3 3,4-Bis-(2-methyl-acryloyloxy)-biphenyl-4-carboxylic acid 3-(2-methyl-acryloyloxy)-propyl ester

(311) Methacrylic acid (5.45 g, 63.3 mmol) and 4-(dimethylamino)pyridine (0.14 g, 1.11 mmol) is added to a suspension of 3,4-dihydroxy-biphenyl-4-carboxylic acid 3-hydroxy-propyl ester (3.2 g, 11.1 mmol) in dichloromethane (100 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (9.82 g, 63.2 mmol) in dichloromethane (40 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and the oily residue is purified by silica gel chromatography with dichloromethane to provide 3,4-bis-(2-methylacryloyloxy)-biphenyl-4-carboxylic acid 3-(2-methyl-acryloyloxy)-propyl ester colorless oil (2.3 g).

(312) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.05 (d, J=8.5 Hz, 2 H, ArH), 7.87 (d, J=8.5 Hz, 2 H, ArH), 7.78 (m, 1 H, ArH), 7.74 (m, 1 H, ArH), 7.50 (m, 1 H, ArH), 6.22 (m, 2 H, H.sub.olefin), 6.04 (m, 1 H, H.sub.olefin), 5.92 (m, 2 H, H.sub.olefin), 5.66 (m, 1 H, H.sub.olefin), 4.41-4.39 (m, 2 H, OCH.sub.2), 4.30-4.27 (m, 2 H, OCH.sub.2), 2.12 (m, 2 H, OCH.sub.2CH.sub.2CH.sub.2O), 1.97 (br. s, 6 H, 2CH.sub.3), 1.87 (br. s, 3H, CH.sub.3).

EXAMPLE 7

(313) Polymerizable monomeric compound 7 of formula I8-1 is prepared as follows.

(314) ##STR00342##

7.1 3,5-Bis-benzyloxy-phenyl-boronic acid

(315) 3,5-Bis-benzyloxy-phenyl-boronic acid is prepared from commercially available 1,3-bis-benzyloxy-5-bromo-benzene.

(316) 1,3-bis-benzyloxy-5-bromo-benzene (20.00 g, 54.16 mmol) is dissolved in dry THF (250 ml) under nitrogen atmosphere. The solution is cooled down in a dry ice bath to 70 C. 37 ml 15% solution of n-butyllithium in n-hexane is added dropwise with the temperature controlled below 60 C. The reaction mixture is continued stirring at this temperature for 1 h. The solution of trimethylborate (6.19 g, 59.6 mmol) in 6 ml dry THF is added dropwise. The reaction mixture is allowed slowly warming up to 0 C. under stirring, and then hydrolyzed carefully by dropwise addition of water. The reaction mixture is acidified with conc. HCl acid to pH1 under cooling. The organic phase is separated. The aqueous is extracted with MTBE. The combined organic phase is dried over sodium sulfate. After removing solvent in vacuo, the crude product is recrystallized from heptane to provide pinkish crystals of 3,5-bis-benzyloxy-phenyl-boronic acid (13.8 g).

7.2 3,5-Bis-benzyloxy-biphenyl-4-carboxylic acid

(317) To a solution of sodium carbonate (21.88 g, 206.5 mmol) in dist. water (95 ml) is added 1,4-dioxane (150 ml), 4-bromobenzoic acid (8.38 g, 41.3 mmol) and 3,5-bis-benzyloxy-phenyl-boronic acid (13.80 g, 41.3 mmol) followed by bis(triphenylphosphine)palladium(II) dichloride (0.58 g, 0.8 mmol), triphenylphosphine (0.22 g, 0.8 mmol) and triethylamine (0.08 g, 0.8 mmol) under nitrogen atmosphere. The reaction mixture is heated at reflux for 2 hs. After cooling to room temperature, 200 ml dist. water is added and the reaction mixture is neutralized with conc. HCl acid to pH1 under cooling. The precipitated crude product is filtrated, washed with dist. water. After drying in vacuo, the crude product is recrystallized in acetonitrile to provide gray crystals of 3,5-bis-benzyloxy-biphenyl-4-carboxylic acid (6.0 g).

7.3 3,5-Bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester

(318) To a solution of 3,5-bis-benzyloxy-biphenyl-4-carboxylic acid (6.00 g, 14.6 mmol) in DMF (30 ml) is added potassium carbonate (2.42 g, 17.5 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (3.46 g. 16.1 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hs. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, 3,5-bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester is obtained (8.0 g) and used for the next step without further purification.

7.4 3,5-Dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester

(319) A solution of 3,5-bis-benzyloxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester (8.0 g, 14.6 mmol) in tetrahydrofuran (100 ml) is treated with palladium (5%) on activated charcoal (1.0 g) and submitted to hydrogenation for 20 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The solid residue is recrystallized from acetonitrile to provide white crystals of 3,5-dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester (2.3 g).

7.5 3,5-Bis-(2-methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester

(320) Methacrylic acid (4.12 g, 47.8 mmol) and 4-(dimethylamino)pyridine (0.10 g, 0.84 mmol) is added to a suspension of 3,5-dihydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester (2.30 g, 8.4 mmol) in dichloromethane (100 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (7.42 g, 47.8 mmol) in dichloromethane (40 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is recrystallized from ethanol to afford white crystals of 3,5-bis-(2-methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (2.5 g, m.p. 66 C.).

(321) .sup.1H-NMR (CDCl.sub.3, 500 MHz): (ppm)=8.10 (d, J=8.5 Hz, 2 H, ArH), 7.65 (d, J=8.5 Hz, 2 H, ArH), 7.29 (m, 2 H, ArH), 7.05 (t, J=2.0 Hz, 1 H, ArH), 6.37 (m, 2 H, H.sub.olefin), 6.15 (m, 1 H, H.sub.olefin), 5.79 (m, 2 H, H.sub.olefin), 5.60 (m, 1 H, H.sub.olefin), 4.60-4.58 (m, 2 H, OCH.sub.2), 4.52-4.50 (m, 2 H, OCH.sub.2), 2.07 (br. s, 6 H, 2CH.sub.3), 1.96 (m, 3H, CH.sub.3).

EXAMPLE 8

(322) Polymerizable monomeric compound 8 of formula I1-1 is prepared as follows.

(323) ##STR00343##

8.1 4-Hydroxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester

(324) 4-Hydroxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester is prepared from commercially available 4-hydroxy-biphenyl-4-carboxylic acid.

(325) To a solution of 4-hydroxy-biphenyl-4-carboxylic acid (4.28 g, 20 mmol) in DMF (30 ml) is added potassium bicarbonate (2.40 g, 24.0 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (6.45 g. 30.0 mmol) is added. The reaction mixture is stirred at 40 C. overnight. After cooling to room temperature, the reaction mixture is poured into 100 ml ice-water mixture and extracted with 60 ml MTBE. The organic phase is washed with sat. aq. NaCl solution and dried over sodium sulfate. After removing solvent in vacuo, the crude product is purified by recrystallization from heptane to afford 4-hydroxybiphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester as white crystals (3.0 g).

8.2 4-Hydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester

(326) A solution of 4-hydroxy-biphenyl-4-carboxylic acid 2-benzyloxy-ethyl ester (3.0 g, 8.0 mmol) in tetrahydrofuran (30 ml) is treated with palladium (5%) on activated charcoal (1.0 g) and submitted to hydrogenation for 15 hs. The catalyst is then filtered off, and the solvent of the remaining solution is removed in vacuo. 4-Hydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester is obtained as white crystals and used for the next step without further purification (2.1 g).

8.3 4-(2-Methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methylacryloyloxy)-ethyl ester

(327) Methacrylic acid (2.05 g, 23.0 mmol) and 4-(dimethylamino)pyridine (0.1 g, 0.8 mmol) is added to a suspension of 4-hydroxy-biphenyl-4-carboxylic acid 2-hydroxy-ethyl ester (2.10 g, 7.9 mmol) in dichloromethane (90 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (3.70 g, 23.8 mmol) in dichloromethane (30 ml) and stirred for 20 hs at room temperature. The reaction mixture is concentrated in vacuo and filtrated through silica gel. After removing solvent, the crude product is recrystallized from ethanol to afford white crystals of 4-(2-Methyl-acryloyloxy)-biphenyl-4-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (1.7 g, m.p. 79 C.).

(328) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.04 (d, J=8.5 Hz, 2 H, ArH), 7.86 (d, J=8.5 Hz, 2 H, ArH), 7.81 (d, J=8.5 Hz, 2 H, ArH), 7.32 (d, J=8.5 Hz, 2 H, ArH), 6.31 (br. s, 1 H, H.sub.olefin), 6.05 (m, 1 H, H.sub.olefin), 5.92 (m, 1 H, H.sub.olefin), 5.69 (m, 1 H, H.sub.olefin), 4.58-4.56 (m, 2 H, OCH.sub.2), 4.49-4.47 (m, 2 H, OCH.sub.2), 2.03 (br. s, 3 H, CH.sub.3), 1.88 (br. s, 3 H, CH.sub.3).

EXAMPLE 9

(329) Applying the same synthetic strategy as in Example 4, polymerizable monomeric compound 9 is prepared analogically as follows, starting from commercially available [4-(benzyloxy)phenyl]-boronic acid and 3-bromo-5-hydroxyl benzoic acid.

(330) ##STR00344##

(331) For the last step the prepared 5,4-dihydroxy-biphenyl-3-carboxylic acid 2-hydroxy-ethyl ester (5.30 g, 19.3 mmol) is dissolved in 50 ml dichloromethane. To this solution is added methacrylic acid (6.56 ml, 77.3 mmol) and 4-(dimethylamino)pyridine (0.24 g, 1.93 mmol) at room temperature. The reaction mixture is then cooled down to 0 C. and treated with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (13.56 ml, 77.3 mmol) in dichloromethane (10 ml). After allowed to warm up to room temperature, the reaction mixture is stirred further for 20 hs. After removing solvent, the crude product is purified by column chromatography on silica gel with dichloromethane/ethylacetate 9:1 as eluent. Further recrystallization from ethanol afford white crystals of 5,4-bis-(2-methyl-acryloyloxy)-biphenyl-3-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (4.8 g, m.p. 62 C.).

(332) .sup.1H-NMR (CDCl.sub.3, 500 MHz): (ppm)=8.15 (tr, J=2.0 Hz, 1 H, ArH), 7.77 (dd, J=2.0 Hz, 1 H, ArH), 7.63 (d, J=8.5 Hz, 2 H, ArH), 7.55 (tr, J=2.0 Hz, 1 H, ArH), 7.23 (d, J=8.5 Hz, 2 H, ArH), 6.40 (m, 2 H, H.sub.olefin), 6.15 (m, 1 H, H.sub.olefin), 5.81 (m, 2 H, H.sub.olefin), 5.59 (m, 1 H, H.sub.olefin), 4.60 (m, 2 H, OCH.sub.2), 4.50 (m, 2 H, OCH.sub.2), 2.09 (m, 3 H, CH.sub.3), 2.08 (m, 3 H, CH.sub.3), 1.95 (m, 3 H, CH.sub.3).

EXAMPLE 10

(333) Applying the same synthetic strategy as in Example 1, polymerizable monomeric compound 10 is prepared analogically as follows, starting from commercially available [4-(benzyloxy)phenyl]-boronic acid and 3,5-dibromobenzoic acid.

(334) ##STR00345##

(335) For the last step the prepared 4,4-dihydroxy-[1,1;3,1]terphenyl-5-carboxylic acid 2-hydroxy-ethyl ester (7.00 g, 20.0 mmol) is dissolved in 80 ml dichloromethane. To this solution is added methacrylic acid (6.27 ml, 73.9 mmol) and 4-(dimethylamino)pyridine (0.25 g, 2.00 mmol) at room temperature. The reaction mixture is then cooled down to 0 C. and treated with a solution of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (12.97 ml, 73.9 mmol) in dichloromethane (20 ml). After allowed to warm up to room temperature, the reaction mixture is stirred further for 20 hs. After removing solvent, the crude product is purified by column chromatography on silica gel with heptane/ethylacetate as eluent to afford white crystals of 4,4-bis-(2-methyl-acryloyloxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-(2-methylacryloyloxy)-ethyl ester (7.0 g, m.p. 125 C.).

(336) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.24 (tr, J=2.0 Hz, 1 H, ArH), 8.17 (d, J=2.0 Hz, 2 H, ArH), 7.89 (d, J=8.0 Hz, 4 H, ArH), 7.33 (d, J=8.0 Hz, 4 H, ArH), 6.32 (m, 2 H, H.sub.olefin), 6.06 (m, 1 H, H.sub.olefin), 5.93 (m, 2 H, H.sub.olefin), 5.69 (m, 1 H, H.sub.olefin), 4.60 (m, 2 H, OCH.sub.2 ), 4.52 (m, 2 H, OCH.sub.2), 2.03 (m, 6 H, CH.sub.3), 1.87 (m, 3 H, CH.sub.3).

EXAMPLE 11

(337) Polymerizable monomeric compound 11 is prepared as follows.

(338) ##STR00346## ##STR00347##

11.1 3-Bromo-5-iodo-benzoic acid 2-benzyloxy-ethyl ester

(339) 3-Bromo-5-iodo-benzoic acid 2-benzyloxy-ethyl ester is prepared from commercially available 3-bromo-5-iodo-benzoic acid and 2-bromoethoxymethyl-benzene.

(340) To a solution of 3-bromo-5-iodo-benzoic acid (25.00 g, 76.5 mmol) in DMF (70 ml) is added potassium carbonate (12.68 g, 91.8 mmol). To the resulted suspension (2-bromo-ethoxymethyl)-benzene (13.30 ml, 84.12 mmol) is added. The reaction mixture is stirred at 70 C. for 3 hours. After cooling to room temperature, the reaction mixture is added into 1000 ml water and extracted with 3300 ml methyl-t-butyl ether (MTBE). The organic phase is washed with sat. aq. NaCl solution, dried over sodium sulfate. After removing solvent in vacuo, 3-bromo-5-iodo-benzoic acid 2-benzyloxy-ethyl ester is obtained as brown oil (38.0 g).

11.2 4-Benzyloxy-5-bromo-biphenyl-3-carboxylic acid 2-benzyloxy-ethyl ester (11a)

(341) To a solution of sodium metaborate tetrahydrate (18.49 g, 132.7 mmol) in dist. water (70 ml) is added the solution of 3-bromo-5-iodo-benzoic acid 2-benzyloxy-ethyl ester (34.00 g, 73.7 mmol) and [4-(benzyloxy)phenyl]-boronic acid (16.82 g, 73.7 mmol) in 250 ml THF. After thoroughly degassing with argon, bis(triphenylphosphine)-palladium(II) chloride (2.95 g, 4.1 mmol) is added, followed by the addition of hydrazinium hydroxide (0.05 ml, 1 mmol). The reaction mixture is heated to reflux and stirred for 3 hours. After cooling to room temperature, the reaction mixture is carefully neutralized with HCl acid. The aqueous phase is separated and extracted with ethyl acetate. The organic phase is combined and dried over anhydrous sodium sulfate. After removing organic solvent, the oily residue is purified by column chromatography on silica gel with heptane/ethyl acetate as eluent. Further recrystallization from acetonitrile provide white crystals of 4-benzyloxy-5-bromo-biphenyl-3-carboxylic acid 2-benzyloxy-ethyl ester 11a (14.3 g).

11.3 1-(2-Benzyloxy-ethoxy)-4-bromo-benzene

(342) 1-(2-Benzyloxy-ethoxy)-4-bromo-benzene is prepared from commercially available 2-bromo-ethoxymethyl-benzene and 4-bromo-phenol.

(343) To a solution of 4-bromo-phenol (28.00 g, 157.0 mmol) in 300 ml methyl ethyl ketone is added potassium carbonate (26.03 g, 188.0 mmol). To the resulted suspension 2-bromo-ethoxymethyl-benzene (40.0 g, 186.0 mmol) is added. The reaction mixture is heated to 80 C. and stirred overnight. After cooling to room temperature, the reaction mixture is added into 500 ml water and extracted with 3200 ml methyl-t-butyl ether (MTBE). The organic phase is washed with sat. aq. NaCl solution, dried over anhydrous sodium sulfate. After removing solvent in vacuo, the oily residue is purified by column chromatography on silica gel with 1-chlorobutane as eluent to afford 1-(2-benzyloxy-ethoxy)-4-bromobenzene as colorless oil (48.0 g).

11.4 4-(2-Benzyloxy-ethoxy)-phenyl-boric acid (11b)

(344) To a solution of 1-(2-benzyloxy-ethoxy)-4-bromo-benzene (46.00 g, 150.0 mmol) and triisopropylborate (41.22 ml, 180.0 mmol) in 500 ml dry THF is added n-butyllithium solution (15% solution in n-hexane, 103.5 ml, 164.7 mmol) dropwise at 70 C. The reaction mixture is stirred at this temperature for 1 hour. After allowed slowly warming up to 0 C., the reaction mixture is added into 500 ml ice-water mixture and carefully neutralized to pH1 with concentrated HCl acid. The aqueous phase is separated and extracted with 2300 ml MTBE. The organic phase is combined and dried over anhydrous sodium sulfate. After removing solvent in vacuo, the solid residue is recrystallized with heptane/ethylacetate to afford 4-(2-benzyloxy-ethoxy)-phenyl-boric acid (11b) as white crystals (18.1 g).

11.5 4-Benzyloxy-4-(2-benzyloxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-benzyloxy-ethyl ester

(345) To a solution of 4-(2-benzyloxy-ethoxy)-phenyl-boric acid (17.40 g, 64.0 mmol) and 4-benzyloxy-5-bromo-biphenyl-3-carboxylic acid 2-benzyloxyethyl ester (33.09 g, 64.0 mmol) in 1000 ml dry 1,4-dioxane is added potassium phosphate (73.6 g, 320.0 mmol). After thoroughly degassing with argon, tris(dibenzylidene-acetone)dipalladium(0) (1.17 g, 1.3 mmol) and 2-dicyclohexylphosphino-2,6-dimethoxy-biphenyl (SPhos, 2.16 g, 5.1 mmol) is added to the resulted suspension. The reaction mixture is heated to reflux and stirred 3 hours. After cooling to room temperature, the reaction mixture is added into 1000 ml ice-water and carefully neutralized with conc. HCl acid. The aqueous phase is separated and extracted with 3300 ml ethylacetate. The organic phase is combined and washed with sat. aq. NaCl solution, dried over anhydrous sodium sulfate. After removing solvent in vacuo, the oily residue is purified by column chromatography on silica gel with heptane/ethylacetate as eluent to afford 4-benzyloxy-4-(2-benzyloxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-benzyloxy-ethyl ester as white crystal (19.2 g).

11.6 4-Hydroxy-4-(2-hydroxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-hydroxy-ethyl ester

(346) A solution of 4-benzyloxy-4-(2-benzyloxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-benzyloxy-ethyl ester (19.2 g, 28.9 mmol) in tetrahydrofuran (200 ml) is treated with palladium (5%) on activated charcoal (8.5 g) and submitted to hydrogenation for 20 hs. The catalyst is then filtered off, and the remaining solution is concentrated in vacuo. The solid residue is recrystallized from acetonitrile to afford 4-hydroxy-4-(2-hydroxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-hydroxy-ethyl ester as white crystals (10.0 g).

11.7 4-(2-Methyl-acryloyloxy)-4-[2-(2-methyl-acryloyloxy)-ethoxy]-[1,1;3,1]terphenyl-5-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester

(347) Methacrylic acid (12.44 g, 144.5 mmol) and 4-(dimethylamino)pyridine (0.31 g, 2.5 mmol) is added to a suspension of 4-hydroxy-4-(2-hydroxyethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-hydroxy-ethyl ester (10.0 g, 25.3 mmol) in dichloromethane (240 ml). The reaction mixture is treated dropwise at 0 C. with a solution of N-(3-dimethylaminopropyl)-N ethylcarbodiimide (22.4 g, 144.5 mmol) in dichloromethane (50 ml) 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. The obtained product is recrystallized from heptane/MTBE solvent mixture to afford white crystals of 4-(2-methyl-acryloyloxy)-4-[2-(2-methyl-acryloyloxy)-ethoxy]-[1,1;3,1]terphenyl-5-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (10.3 g, m.p. 73 C.).

(348) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.16 (tr, J=2.0 Hz, 1 H, ArH), 8.11 (m, 2 H, ArH), 7.86 (d, J=7.0 Hz, 2 H, ArH), 7.76 (d, J=7.0 Hz, 2 H, ArH), 7.33 (d, J=7.0 Hz, 2 H, ArH), 7.11 (d, J=7.0 Hz, 2 H, ArH), 6.32 (m, 1 H, H.sub.olefin), 6.06 (m, 2 H, H.sub.olefin), 5.93 (m, 1 H, H.sub.olefin), 5.70 (m, 2 H, H.sub.olefin), 4.60 (m, 2 H, OCH.sub.2), 4.53 (m, 2 H, OCH.sub.2), 4.47 (m, 2 H, OCH.sub.2), 4.33 (m, 2 H, OCH.sub.2), 2.04 (br. s, 3 H, CH.sub.3), 1.90 (br. s, 3H, CH.sub.3), 1.88 (br. s, 3H, CH.sub.3).

EXAMPLE 12

(349) Applying the same synthetic strategy as in Example 11, polymerizable monomeric compound 12 is prepared analogically as follows, starting from commercially available 3-bromo-5-iodo-benzoic acid and 4-bromo-2-fluorophenol.

(350) ##STR00348## ##STR00349##

(351) For the last step the prepared 3-fluoro-4-hydroxy-4-(2-hydroxy-ethoxy)-[1,1;3,1]terphenyl-5-carboxylic acid 2-hydroxy-ethyl ester (2.30 g, 5.7 mmol) is dissolved in 50 ml dichloromethane. To this solution is added methacrylic acid (2.74 ml, 31.8 mmol) and 4-(dimethylamino)pyridine (0.068 g, 0.56 mmol) at room temperature. The reaction mixture is then cooled down to 0 C. and treated with a solution of N-(3-dimethylaminopropyl)-N ethylcarbodiimide (4.94 ml, 31.8 mmol) in dichloromethane (10 ml). After allowed to warm up to room temperature, the reaction mixture is stirred further for 20 hs. After removing solvent, the crude product is purified by column chromatography on silica gel with heptane/ethylacetate as eluent. Further recrystallization from heptane/MTBE solvent mixture afford white solid of 3-fluoro-4-(2-methyl-acryloyloxy)-4-[2-(2-methyl-acryloyloxy)-etho xy]-[1,1;3,1]terphenyl-5-carboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester (1.8 g, m.p. 72 C.).

(352) .sup.1H-NMR (DMSO-d.sub.6, 500 MHz): (ppm)=8.20 (tr, J=2.0 Hz, 1 H, ArH), 8.13 (dd, J=2.0 Hz, 2 H, ArH), 7.88 (d, J=7.0 Hz, 2 H, ArH), 7.78 (dd, J=12.5 Hz, 1 H, ArH), 7.61 (d, J=8.5 Hz, 1 H, ArH), 7.34 (m, 3 H, ArH), 6.33 (m, 1 H, H.sub.olefin), 6.05 (m, 2 H, H.sub.olefin), 5.94 (m, 1 H, H.sub.olefin), 5.70 (m, 2 H, H.sub.olefin), 4.60 (m, 2 H, OCH.sub.2), 4.53 (m, 2 H, OCH.sub.2), 4.49 (m, 2 H, OCH.sub.2), 4.43 (m, 2 H, OCH.sub.2), 2.04 (m, 3 H, CH.sub.3), 1.89 (m, 3 H, CH.sub.3), 1.88 (m, 3 H, CH.sub.3).

MIXTURE EXAMPLE 1

(353) The nematic LC host mixture A is formulated as follows.

(354) TABLE-US-00005 CCH-501 9.00% cl.p. 70.0 C. CCH-35 14.00% n 0.0825 PCH-53 8.00% 3.5 PCH-304FF 14.00% .sub.|| 3.5 PCH-504FF 13.00% K.sub.3/K.sub.1 1.00 CCP-302FF 8.00% .sub.1 141 mPa s CCP-502FF 8.00% V.sub.0 2.10 V CCP-21FF 9.00% CCP-31FF 9.00% CPY-2-O2 8.00%

(355) Polymerizable mixtures are prepared by adding monomer 1, 2, 5, 8, 9, 11 or 12 of Example 1, 2, 5, 8, 9, 11 and 12, respectively, to LC host mixture A at a concentration of 0.3% by weight.

MIXTURE EXAMPLE 2

(356) The nematic LC host mixture B is formulated as follows.

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

(358) Polymerizable mixtures are prepared by adding monomer 1 or 8 of Example 1 and 8, respectively, to LC host mixture B at a concentration of 0.3% by weight.

MIXTURE EXAMPLE 3

(359) The nematic LC host mixture C is formulated as follows.

(360) TABLE-US-00007 CY-3-O2 15.00% cl.p. 74.5 C. CY-5-O2 6.50% n 0.1082 CCY-3-O2 11.00% 3.0 CPY-2-O2 5.50% .sub.|| 3.6 CPY-3-O2 10.50% K.sub.3/K.sub.1 1.21 CC-3-V 28.50% .sub.1 97 mPa s CC-3-V1 10.00% V.sub.0 2.42 V PYP-2-3 12.50% PPGU-3-F 0.50%

(361) Polymerizable mixtures are prepared by adding monomer 1, 2, 5, 8, 9, 11 or 12 of Example 1, 2, 5, 8, 9, 11 or 12, respectively, to LC host mixture C at a concentration of 0.3% by weight.

MIXTURE EXAMPLE 4

(362) The nematic LC host mixture D is formulated as follows.

(363) TABLE-US-00008 CC-3-V 20.00% cl.p. 74.5 C. CC-3-V1 10.00% n 0.1084 CCH-34 8.00% 3.2 CCH-35 4.00% CCY-3-O1 5.50% K.sub.3/K.sub.1 1.04 CCY-3-O2 12.00% .sub.1 94 mPa s CPY-2-O2 2.00% V.sub.0 2.33 V CPY-3-O2 12.00% PY-3-O2 15.00% PY-4-O2 8.50% PYP-2-3 3.00%

(364) Polymerizable mixtures are prepared by adding Monomer 2, 5, 9, 11 or 12 of Example 2, 5, 9, 11 or 12, respectively, to LC host mixture D at a concentration of 0.3% by weight.

MIXTURE EXAMPLE 5

(365) The nematic LC host mixture E is formulated as follows.

(366) TABLE-US-00009 CC-3-V 20.00% cl.p. 74.6 C. CC-3-V1 10.00% n 0.1042 CCH-35 9.00% 3.1 CCP-3-1 7.00% CCY-3-O2 13.00% K.sub.3/K.sub.1 1.13 CPY-3-O2 13.00% .sub.1 94 mPa s CY-3-O2 8.00% V.sub.0 2.48 V PY-3-O2 15.00% PY-4-O2 5.00%

(367) Polymerizable mixtures are prepared by adding Monomer 2, 5, 9, 11 or 12 of Example 2, 5, 9, 11 or 12, respectively, to LC host mixture E at a concentration of 0.3% by weight.

COMPARISON EXAMPLES

(368) For comparison purposes, further polymerizable mixture were prepared from the nematic LC host mixtures A, B and C and trireactive polymerizable monomer C1 which is similar to monomer 1 but wherein the ester groups between spacer and aromatic ring are replaced by ether groups, trireactive polymerizable monomer C8 which is similar to monomer 8 but wherein the ester groups between spacer and aromatic ring are reversed, direactive monomer C-D1 having an alkyl spacer without an ester group, direactive monomer C-D2 having no spacer group.

(369) Further comparison mixtures were prepared from the nematic LC host mixtures D and E and direactive monomer C-D2.

(370) In all polymerizable mixtures the concentration of the respective monomer in the nematic LC host mixture was 0.3% by weight.

(371) The structures of monomers 1, 2, 5, 8, 9, 11 and 12 according to the present invention and of monomers C1, C8, C-D1 and C-D2 of the comparison examples are shown below.

(372) ##STR00350## ##STR00351## ##STR00352##

USE EXAMPLES

(373) The polymerizable mixtures according to the invention and the polymerizable comparison mixtures are each inserted into a VA e/o test cell. The test cells comprise a VA-polyimide alignment layer (JALS-2096-R1) which is rubbed antiparallel (for the test cells with host mixture D and E the polyimide AL64101 was used). The LC-layer thickness d is approx. 4 m.

(374) Each test cell is irradiated with UV light having an intensity of 100 mW/cm.sup.2 for the time indicated with application of a voltage of 24 V.sub.rms (alternating current), causing polymerization of the polymerizable monomeric compound.

(375) The VHR values of the polymerizable mixtures before and after UV exposure are measured as described above. The VHR values of the mixtures are shown in Table 1.

(376) TABLE-US-00010 TABLE 1 VHR values Host B + C-D2 Host B + 8 Host B + 1 VHR/% 0 min UV 99.0 99.0 98.6 10 min UV 86.4 90.8 94.8 2 h Suntest 89.8 93.5 95.6 * Suntest means a second irradiation step with lower UV intensity but longer exposure time than the first step.

(377) As can be seen from Table 1, the VHR values of the polymerizable mixture comprising monomer 1 or 8 according to the invention after UV exposure are significantly higher than the VHR values of polymerizable mixture comprising monomer C-D2.

(378) In order to determine the polymerization rate, the residual content of unpolymerized RM (in % by weight) in the test cells is measured by HPLC after various exposure times. For this purpose each mixture is polymerized in the test cell under the stated conditions. The mixture is then rinsed out of the test cell using MEK (methyl ethyl ketone) and measured.

(379) The residual concentrations of the respective monomer in the mixture after different exposure times are shown in Table 2.

(380) TABLE-US-00011 TABLE 2 Residual monomer content Host A + Host A + Host A + Host B + Host B + Host B + Host A + Host A + Host B + Host B + Time/ C-D1 C8 8 C-D1 C8 8 C1 1 C1 1 min Residual RM/% 0 0.300 0.300 0.300 0.300 0.300 0.300 0.300 0.300 0.300 0.300 2 0.278 0.286 0.243 0.244 0.229 0.212 0.265 0.197 0.176 0.092 4 0.256 0.264 0.192 0.160 0.091 0.101 6 0.235 0.230 0.138 0.145 0.134 0.100 0.091 0.052 0.055 0.026 Host C + Host C + Time/ C1 1 min Residual RM/% 0 0.300 0.300 0.5 0.269 0.236 1 0.189 0.155 3 0.100 0.064

(381) As can be seen from Table 2, significantly more rapid and complete polymerization is achieved in PSA displays containing a polymerizable mixture with monomer 1 or 8 according to the invention, compared to PSA displays containing a polymerizable mixture with monomer C-D1, C1 or C8.

(382) The tilt angle is determined before and after UV irradiation by a crystal rotation experiment (Autronic-Melchers TBA-105).

(383) The tilt angles are shown in Table 3.

(384) TABLE-US-00012 TABLE 3 Tilt angles Host A + C-D1 Host A + C8 Host A + 8 UV-Time/sec Pretilt Angle/ 0 89.1 89.0 88.8 30 89.0 89.0 88.6 60 88.7 87.3 88.1 120 87.4 84.5 83.5 240 84.2 80.0 75.9 360 81.3 78.7 73.8 Host B + C-D1 Host B + C8 Host B + 8 UV-Time/sec Pretilt Angle/ 0 89.1 88.9 88.8 30 60 120 85.3 81.8 80.2 240 360 79.5 77.9 76.1 Host A + C1 Host A + 1 UV-Time/sec Pretilt Angle/ 0 88.9 88.4 30 88.5 85.4 60 86.8 82.0 120 82.7 77.3 240 74.2 72.3

(385) As can be seen from Table 3, a small tilt angle after polymerization is achieved quickly in PSA displays containing a polymerizable mixture with monomer 1 or 8 according to the invention, which is smaller than in a PSA display containing a polymerizable mixture with monomer C-D1, C1 or C8.

(386) The above measurements of the VHR, the residual monomer content and the pretilt angle were also carried out for polymerizable mixtures comprising monomer 2, 5, 9, 11 or 12 in one of the LC host mixtures A, B, D and E, respectively, in comparison with polymerizable mixtures comprising monomer C-D2 in one of the LC host mixtures A, B, D and E, respectively. The results are shown below.

(387) TABLE-US-00013 TABLE 4 VHR values Host A + Host A + Host A + Host A + Host A + Host A + C-D2 5 2 12 11 9 VHR/% 0 min UV 98.2 97.7 98.9 98.2 98.4 98.2 2 h Suntest 97.6 98.6 98.2 98.5 98.9 98.3 Host B + Host B + Host B + Host B + Host B + Host B + C-D2 5 2 12 11 9 VHR/% 0 min UV 98.5 98.5 98.2 98.6 96.9 96.8 2 h Suntest 85.6 93.2 91.0 94.0 94.4 95.3 10 min UV 83.5 91.2 90.6 90.0 93.8 93.2 Host D + Host D + Host D + Host E + Host E + C-D2 5 11 C-D2 5 VHR/% 0 min UV 98.3 98.3 97.9 98.3 97.0 2 min UV 94.8 96.4 97.5 94.8 96.8 15 min UV 93.6 94.0 96.2 93.6 95.1 2 min UV + 95.5 96.6 97.7 95.5 96.8 2 h suntest

(388) In the host mixture A without an alkenyl compound, the monomers 2, 5, 9, 11 and 12 according to the present invention lead to higher VHR values after suntest, compared to the monomer C-D2. In addition, the monomers of the present invention do either show only a very small decrease or even an increase of the VHR after 2 h suntest compared to the initial VHR value.

(389) In the host mixtures B, D and E containing an alkenyl compound (CC-3-V) the monomers 2, 5, 9, 11 and 12 according to the present invention show also higher VHR values after suntest compared to the monomer C-D2.

(390) TABLE-US-00014 TABLE 5 Residual monomer content Host A + Host A + Host A + Host A + Host A + Host A + Time/ C-D2 5 2 12 11 9 min Residual RM/% 0 0.3 0.3 0.3 0.3 0.3 0.3 2 0.264 0.256 0.193 0.062 0.174 0.250 4 0.203 0.182 0.102 0.023 0.059 0.126 6 0.173 0.128 0.044 0.008 0.022 0.065 Host B + Host B + Host B + Host B + Host B + Host B + Time/ C-D2 5 2 12 11 9 min Residual RM/% 0 0.3 0.3 0.3 0.3 0.3 0.3 2 0.185 0.182 0.134 0.048 0.072 0.152 6 0.067 0.074 0.041 0.006 0.01 0.048 Host D + Host D + Host D + Time/ C-D2 5 11 min Residual RM/% 0 0.3 0.3 0.3 0.5 0.256 0.232 0.207 1 0.199 0.163 0.111 2 0.142 0.092 0.030 5 0.05 0.025 0.001 Host E + Host E + Time/ C-D2 5 min Residual RM/% 0 0.3 0.3 0.5 0.256 0.255 1 0.199 0.167 2 0.142 0.115

(391) In all host mixtures A, B, D and E the monomers 2, 5, 9, 11 and 12 according to the present invention show faster polymerization with a lower residual RM content, compared to the monomer C-D2 of prior art.

(392) TABLE-US-00015 TABLE 6 Pretilt angles Host A + Host A + Host A + Host A + Host A + Host A + UV-Time/ C-D2 5 2 12 11 9 sec Pretilt Angle/ 0 89.6 88.4 88.4 88.7 89.0 89.5 30 89.0 87.2 86.1 83.4 86.2 88.0 60 88.2 86.6 83.1 75.2 78.7 83.9 120 84.9 81.9 77.1 69.6 71.9 77.0 Host B + Host B + Host B + Host B + Host B + Host B + UV-Time/ C-D2 5 2 12 11 9 sec Pretilt Angle/ 0 88.8 88.9 88.7 88.7 88.7 89.2 120 77.2 77.4 78.5 69.3 72.0 77.5 Host D + Host D + Host D + Host E + Host E + Host E + UV-Time/ C-D2 5 11 C-D2 5 11 sec Pretilt Angle/ 0 89.1 89.1 89.6 89.9 89.7 90.0 60 86.4 85.5 72.5 89.6 89.8 86.3 120 78.0 75.0 67.6 89.6 86.7 67.2 180 76.1 72.2 65.4 85.1 79.8 63.2 300 73.5 70.2 65.2 79.6 70.6 56.9

(393) The tilt angle measurements confirm the results of the residual monomer content measurements. Thus, in all host mixtures A, B, D and E the monomers 2, 5, 9, 11 and 12 according to the present invention show faster generation of a higher tilt, angle compared to the monomer C-D2 of prior art.

(394) For measuring the solubility, monomers 1, 5, 8 and 9 of Example 1, 5, 8, 9 and 11, respectively, and monomer C-D2 of prior art are each dissolved at various concentrations from 0.3 to 3.0% by weight in the commercially available nematic LC mixture MJ011412 (Merck Japan Ltd.). The samples are stored for 1000 h at room temperature and checked if they remain a homogeneous solution. Afterwards the samples are centrifuged and filtrated, and the residual monomer concentration in the supernatant liquid is determined.

(395) Maximum residual monomer concentration after 1000 h at RT: Monomer C-D2: 0.46% Monomer 8: 1.66% Monomer 1: 1.00% Monomer 5: 1.00% Monomer 9: 1.00% Monomer 11: 0.60%

(396) It can be seen that the monomers according to the invention exhibit significantly better solubility than monomer C-D2 of prior art.

(397) It can be seen that even monomer 11 shows a residual concentration of 0.6%, which is 100% higher than the RM concentration of 0.3% as typically used in PSA displays, whereas monomer C-D2 has residual concentration 0.46% which is only 50% higher than the typically used RM concentration of 0.3%.

(398) Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

(399) 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.

(400) 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.

(401) The entire disclosures of all applications, patents and publications, cited herein and of corresponding European patent application no. 13003221.2, filed Jun. 25, 2013, are incorporated by reference herein.