Liquid crystalline media having homeotropic alignment

Abstract

The present invention relates to liquid-crystalline media (LC media) having negative or positive dielectric anisotropy, comprising a low-molecular-weight component and a polymerizable component. The polymerizable component comprises self-aligning, polymerizable mesogens (polymerizable self-alignment additives) which effect homeotropic (vertical) alignment of the LC media at a surface or the cell walls of a liquid-crystal display (LC display). The invention therefore also encompasses LC displays having homeotropic alignment of the LC medium without alignment layers. The invention discloses novel structures for polymerizable self-alignment additives which have a certain position of the functional groups.

Claims

1. A LC medium comprising: i) a low-molecular-weight, non polymerizable liquid-crystalline component and ii) one or more polymerizable compounds of the formula I, or a polymerized component obtainable by polymerization of the polymerisable compound of formula I,
P-Sp-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.n-A.sup.1-R.sup.a(I) in which A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be mono- or polysubstituted by a group L, L in each case, independently of one another, denotes H, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.0).sub.2, C(O)R.sup.0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, Z.sup.2 in each case, independently of one another, denotes O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, Z.sup.3 in each case, independently of one another, denotes a single bond, O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, n1 denotes 1, 2, 3 or 4, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, k denotes 0 or 1, R.sup.0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R.sup.00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, R.sup.a denotes an anchor group of the formula ##STR00455## p denotes 1 or 2, q denotes 2 or 3, B denotes a substituted or unsubstituted ring system or condensed ring system, Y, independently of one another, denotes O, S, C(O), C(O)O, OC(O), NR.sup.11 or a single bond, o denotes 0 or 1, X.sup.1, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH.sub.2, NHR.sup.11, NR.sup.11.sub.2, OR.sup.11, C(O)OH, CHO, where at least one group X.sup.1 denotes a radical selected from OH, NH.sub.2, NHR.sup.11, C(O)OH and CHO, R.sup.11 denotes alkyl having 1 to 12 C atoms, Sp.sup.a, Sp.sup.c, Sp.sup.d each, independently of one another, denote a spacer group or a single bond, and Sp.sup.b denotes a tri- or tetravalent group.

2. A Medium according to claim 1, wherein, for formula I, A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where, in addition, one or more CH groups in these groups may be replaced by N, cyclohexane-1,4-diyl, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by O and/or S, 3,3-bicyclobutylidene, 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 or octahydro-4,7-methanoindane-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl (in particular gonane-3,17-diyl), where all these groups may be unsubstituted or mono- or polysubstituted by a group L.

3. A Medium according to claim 1, wherein the compound of the formula I is a compound of the formula I1, ##STR00456## in which R.sup.a, A.sup.1, A.sup.2, A.sup.3, Z.sup.2, Z.sup.3, L, Sp, P, k, m and n independently are as defined in claim 1, and r1, r2, r3 independently denote 0, 1, 2 or 3.

4. A LC medium according to claim 1, wherein the compound of the formula I contains in total at least one group L on the groups A.sup.1, A.sup.2 and A.sup.3, as are present.

5. A LC medium according to claim 1, wherein the one or more compounds of the formula I are selected from compounds of the formulae IA, IB, IC, ID, IE or IF: ##STR00457## in which R.sup.a, Z.sup.2, Z.sup.3, L, Sp, P and n independently are as defined in claim 1, and r1, r2, r3 independently denote 0, 1, 2 or 3.

6. A LC medium according to claim 1, wherein, besides one or more compounds of the formula I, the polymerizable or polymerized component comprises one or more further polymerizable or polymerized compounds, where the polymerized component is obtainable by polymerization of the polymerizable component.

7. A LC medium according to claim 1, wherein one or more compounds of the formula I, additionally comprises one or more non-polymerizable compounds of the formula I,
R.sup.1-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.a-A.sup.1-R.sup.aI in which m, k, n and the group R.sup.a are as defined for formula I according to claim 1, and A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be mono- or polysubstituted by a group L, Z.sup.2 in each case, independently of one another, denotes O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, Z.sup.3 in each case, independently of one another, denotes a single bond, O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, n1 denotes 1, 2, 3 or 4, L in each case, independently of one another, denotes H, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.0).sub.2, C(O)R.sup.0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, R.sup.0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R.sup.00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, and R.sup.1, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by 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 be replaced by F or Cl.

8. A LC medium according to claim 7, which comprises one or more polymerizable compounds selected from the following formulae: ##STR00458## in which R.sup.1, R.sup.a, Z.sup.2, Z.sup.3, L and n independently are as defined in claim 7, and r1, r2, r3 independently denote 0, 1, 2, 3 or 4.

9. A LC medium according to claim 1, which comprises one or more compounds of the formula I selected from the following formulae: ##STR00459## ##STR00460## in which L, Sp, P and R.sup.a independently are as defined in claim 1.

10. A LC medium according to claim 1, wherein the group R.sup.a in formula I or the sub-formulae contains one, two or three OH groups.

11. A LC medium according to claim 1, wherein the group R.sup.a denotes a group selected from ##STR00461## in which Sp.sup.a, Sp.sup.b, Sp.sup.c, p and X.sup.1 have the meaning as in claim 1.

12. A LC medium according to claim 1, wherein the group R.sup.a denotes a group selected from the part-formulae ##STR00462## ##STR00463##

13. A LC medium according to claim 1, wherein for the compound of the formula I, n=0.

14. A LC medium according to claim 1, wherein for the compound of the formula I, the group P is selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.

15. A LC medium according to claim 1, which in it comprises the compounds of the formula I in a concentration of less than 10% by weight.

16. A LC medium according to claim 1, which comprises one or more polymerizable compounds of the formula M or a (co)polymer comprising compounds of the formula M:
P.sup.1-Sp.sup.1-A.sup.2-(Z.sup.1-A.sup.1).sub.n-Sp.sup.2-P.sup.2M in which the individual radicals have the following meanings: P.sup.1, P.sup.2 each independently denote a polymerizable group, Sp.sup.1, Sp.sup.2 each independently denote a spacer group, A.sup.1, A.sup.2 each, independently of one another, denote a radical selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4-bicyclohexylene, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by O and/or S and in which, in addition, one or more H atoms may be replaced by a group L, or selected from ##STR00464## b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by a group L or -Sp.sup.3-P, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by a group L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, preferably selected from the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro-[3.3]heptane-2,6-diyl, ##STR00465## ##STR00466## where, in addition, one or more H atoms in these radicals may be replaced by a group L or -Sp.sup.3-P, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, P.sup.3 denotes a polymerizable group, Sp.sup.3 denotes a spacer group, n denotes 0, 1, 2 or 3, Z.sup.1 in each case, independently of one another, denotes COO, OCO, CH.sub.2O, OCH.sub.2, CF.sub.2O, OCF.sub.2, or (CH.sub.2).sub.n, where n is 2, 3 or 4, O, CO, C(R.sup.cR.sup.d), CH.sub.2CF.sub.2, CF.sub.2CF.sub.2 or a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, R.sup.0, R.sup.00 each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more H atoms may be replaced by F, M denotes O, S, CH.sub.2, CHY.sup.1 or CY.sup.1Y.sup.2, Y.sup.1 and Y.sup.2 each, independently of one another, have one of the meanings indicated above for R.sup.0 or denote Cl or CN, W.sup.1, W.sup.2 each, independently of one another, denote CH.sub.2CH.sub.2, CHCH, CH.sub.2O, OCH.sub.2, C(R.sup.cR.sup.d) or O, and R.sup.c and R.sup.d each, independently of one another, denote H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, where one or more of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 may denote a radical R.sup.aa, with the proviso that at least one of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 present does not denote 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, 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 be replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, where the groups OH, NH.sub.2, SH, NHR, C(O)OH and CHO are not present in R.sup.aa.

17. A LC medium according to claim 1, wherein the polymerizable or polymerized component comprises 0.01 to 5% by weight of one or more compounds of the formula M
P.sup.1-Sp.sup.1-A.sup.2-(Z.sup.1-A.sup.1).sub.n-Sp.sup.2-P.sup.2M in which the individual radicals have the following meanings: p.sup.1, P.sup.2 each independently denote a polymerizable group, Sp.sup.1, Sp.sup.2 each independently denote a spacer group, A.sup.1, A.sup.2 each, independently of one another, denote a radical selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene and 4,4-bicyclohexylene, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by O and/or S and in which, in addition, one or more H atoms may be replaced by a group L, or selected from ##STR00467## b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by a group L or -Sp.sup.3-P, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by a group L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, preferably selected from the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro-[3.3]heptane-2,6-diyl, ##STR00468## ##STR00469## where, in addition, one or more H atoms in these radicals may be replaced by a group L or -Sp.sup.3-P, and/or one or more double bonds may be replaced by single bonds, and/or one or more CH groups may be replaced by N, P.sup.3 denotes a polymerizable group, Sp.sup.3 denotes a spacer group, n denotes 0, 1, 2 or 3, Z.sup.1 in each case, independently of one another, denotes COO, OCO, CH.sub.2O, OCH.sub.2, CF.sub.2O, OCF.sub.2, or (CH.sub.2).sub.n, where n is 2, 3 or 4, O, CO, C(R.sup.cR.sup.d), CH.sub.2CF.sub.2, CF.sub.2CF.sub.2 or a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF.sub.5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, R.sup.0, R.sup.00 each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more H atoms may be replaced by F, M denotes O, S, CH.sub.2, CHY.sup.1 or CY.sup.1Y.sup.2, Y.sup.1 and Y.sup.2 each, independently of one another, ha one of the meanings indicated above for R.sup.0 or denote Cl or CN, W.sup.1, W.sup.2 each, independently of one another, denote CH.sub.2CH.sub.2, CHCH, CH.sub.2O, OCH.sub.2, C(R.sup.cR.sup.d) or O, and R.sup.c and R.sup.d each, independently of one another, denote H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, where one or more of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 may denote a radical R.sup.aa, with the proviso that at least one of the groups P.sup.1-Sp.sup.1-, -Sp.sup.2-P.sup.2 and -Sp.sup.3-P.sup.3 present does not denote 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, 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 be replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, where the groups OH, NH.sub.2, SH, NHR, C(O)OH and CHO are not present in R.sup.aa, and/or 0.01 to 10% by weight of one or more non-polymerizable compounds of the formula I
R.sup.1-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.n-A.sup.1-R.sup.aI in which m, k, n and the group R.sup.a are as defined for formula I according to claim 1, and A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be mono- or polysubstituted by a group L, Z.sup.2 in each case, independently of one another, denotes O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, Z.sup.3 in each case, independently of one another, denotes a single bond, O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, n1 denotes 1, 2, 3 or 4, L in each case, independently of one another, denotes H, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.0).sub.2, C(O)R.sup.0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, R.sup.0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R.sup.00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, and R.sup.1, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH.sub.2 groups may be replaced by 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 be replaced by F or Cl.

18. A LC medium according to claim 1, wherein the polymerizable or polymerized component comprises one or more compounds selected from the compounds of the following formulae: ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## 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, Sp.sup.1, Sp.sup.2 and Sp.sup.3 each, independently of one another, denote a single bond or a spacer group, where, in addition, one or more of the radicals P.sup.1-Sp.sup.1-, P.sup.2-Sp.sup.2- and P.sup.3-Sp.sup.3- may denote a radical 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 does not denote 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 be replaced by F, Cl, CN or P.sup.1-Sp.sup.1-, where OH, NH.sub.2, SH, NHR, C(O)OH and CHO are not present in the group R.sup.aa, R.sup.0, R.sup.00 each, independently of one another and on each occurrence identically or differently, denote H or alkyl having 1 to 12 C atoms, R.sup.y and R.sup.z each, independently of one another, denote H, F, CH.sub.3 or CF.sub.3, X.sup.1, X.sup.2 and X.sup.3 each, independently of one another, denote COO, O-CO- or a single bond, Z.sup.1 denotes O, CO, C(R.sup.yR.sup.z) or CF.sub.2CF.sub.2, 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, SCN, SF.sub.5 or straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, 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, and x denotes 0 or 1.

19. A LC display comprising an LC cell having two substrates and at least two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two electrodes, and having a layer of an LC medium according to claim 1 located between the substrates, where the compound of the formula I is suitable for effecting homeotropic alignment of the LC medium with respect to the substrate surfaces.

20. A LC display according to claim 19, wherein the substrates have no alignment layers for homeotropic alignment.

21. A LC display according to claim 19, wherein the substrates have alignment layers on one or both sides.

22. A LC display according to claim 19, which is a VA display containing an LC medium having negative dielectric anisotropy and electrodes arranged on opposite substrates.

23. A LC display according to claim 19, which is a VA-IPS display containing an LC medium having positive dielectric anisotropy and interdigital electrodes arranged on at least one substrate.

24. A Process for the preparation of an LC medium, wherein one or more compounds of the formula I according to claim 1 are mixed with a low-molecular-weight liquid-crystalline component, and one or more polymerizable compounds and/or any desired additives are optionally added.

25. A compound of the formula I
P-Sp-[A.sup.3-Z.sup.3].sub.m-[A.sup.2].sub.k-[Z.sup.2].sub.n-A.sup.1-R.sup.a(I) in which A.sup.1, A.sup.2, A.sup.3 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be mono- or polysubstituted by a group L, L in each case, independently of one another, denotes H, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(R.sup.0).sub.2, C(O)R.sup.0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, Z.sup.2 in each case, independently of one another, denotes O, S, CO, COO, OCO, OCOO, 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.n1, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, Z.sup.3 in each case, independently of one another, denotes a single bond, O, S, CO, COO, OCO, OCOO, 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.n1CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, (CF.sub.2).sub.n1, CHCH, CFCF, CC, CHCHCOO, OCOCHCH, (CR.sup.0R.sup.00).sub.n1, n1 denotes 1, 2, 3 or 4, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, k denotes 0 or 1, R.sup.0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R.sup.00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, R.sup.a denotes an anchor group of the formula ##STR00475## p denotes 1 or 2, q denotes 2 or 3, B denotes a substituted or unsubstituted ring system or condensed ring system, Y, independently of one another, denotes O, S, C(O), C(O)O, OC(O), NR.sup.11 or a single bond, o denotes 0 or 1, X.sup.1, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH.sub.2, NHR.sup.11, NR.sup.11.sub.2, OR.sup.11, C(O)OH, CHO, where at least one group X.sup.1 denotes a radical selected from OH, NH.sub.2, NHR.sup.11, C(O)OH and CHO, R.sup.11 denotes alkyl having 1 to 12 C atoms, Sp.sup.a, Sp.sup.c, Sp.sup.d each, independently of one another, denote a spacer group or a single bond, and Sp.sup.b denotes a tri- or tetravalent group.

26. A compound according to claim 25, wherein m=1 or 2, and k=1.

27. A compound according to claim 25, wherein A.sup.1 and A.sup.2 independently denote 1,4-phenylene or cyclohexane-1,4-diyl, each of which may independently be mono- or polysubstituted by a group L.

28. A method for effecting homeotropic alignment with respect to a surface delimiting the LC medium, which comprises including compound of formula I according to claim 25 as an additive in said LC medium where the compounds of formula I are optionally polymerized after the homeotropic alignment has been effected.

29. A Process for the production of an LC display comprising an LC cell having two substrates and at least two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two electrodes, comprising the process steps of: filling of the cell with an LC medium according to claim 1, where homeotropic alignment of the LC medium with respect to the substrate surfaces is established, and polymerization of the polymerizable component(s), optionally with application of a voltage to the cell or under the action of an electric field, in one or more process steps.

Description

(1) Further combinations of the embodiments and variants of the invention in accordance with the description also arise from the claims.

EXAMPLES

(2) The compounds employed, if not commercially available, are synthesised by standard laboratory procedures. The LC media originate from Merck KGaA, Germany.

A) Synthesis Examples

Example 1

2-Fluoro-4-(3-hydroxypropyl)-[1,1;4,1]terphenyl-4-yl 2-methylacrylate

(3) ##STR00342##

(4) 6.50 g (20.1 mmol) of 2-fluoro-4-(3-hydroxypropyl)-[1,1;4,1]terphenyl-4-ol (CAS No. 1299463-47-0) are suspended in 100 ml of dichloromethane (DCM) and 10 ml of THF, 1.75 ml (20.6 mmol) of methacrylic acid and 245 mg (2.0 mmol) of DMAP are added, and a solution of 3.44 g (22.2 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) in 50 ml of dichloromethane is added dropwise with ice-cooling. After 1 h, the cooling is removed, and the batch is stirred at room temperature (RT) overnight. The solvent is removed in vacuo, the residue is chromatographed on silica gel with heptane/ethyl acetate (10%-70%), and the product obtained (R.sub.f=0.3, heptane/ethyl acetate (1:1)) is recrystallised from acetonitrile, giving 2-fluoro-4-(3-hydroxypropyl)-[1,1;4,1]terphenyl-4-yl 2-methylacrylate as colourless crystals.

(5) Phases: C 139 C. I

(6) .sup.1H-NMR (500 MHz, DMSO-d.sub.6)

(7) =1.74 ppm (q, 6.71 Hz, 2H, CH.sub.2), 2.01 (s, 3H, CH.sub.3), 2.65 (t, 7.67 Hz, 2H, CH.sub.2), 3.43 (t, 6.17 Hz, 2H, CH.sub.2O), 4.47 (t, 5.06 Hz, 1H, OH), 5.90 (s, 1H), 6.30 (s, 1H), 7.29 (m.sub.e, 4H), 7.69-7.54 (m, 7H).

Example 2

4-(4-Hydroxy-3-hydroxymethylbutyl)biphenyl-4-yl 2-methylacrylate

(8) ##STR00343##

(9) 1) 5-[2-(4-Benzyloxybiphenyl-4-yl)ethyl]-2,2-di-tert-butyl-1,3,2-dioxasilinane

(10) ##STR00344##

(11) 60 ml of THF, 5.00 g (22 mmol) of 4-benzyloxybenzeneboronic acid, 8.00 g (22 mmol) of 5-[2-(4-bromophenyl)ethyl]-2,2-di-tert-butyl-1,3,2-dioxasilinane and 0.28 g of bis(triphenylphosphine)palladium(II) chloride and 0.02 ml of hydrazinium hydroxide are added to 4.14 g (30 mmol) of sodium metaborate tetrahydrate in 12 ml of water, and the batch is heated under reflux overnight. 100 ml of methyl tert-butyl ether (MTB ether) and 100 ml of water are subsequently added, and the mixture is acidified using 2 M hydrochloric acid. The aq. phase is separated off and extracted three times with MTB ether. The combined org. phases are washed with sat. sodium chloride solution and dried over sodium sulfate. The solvent is removed in vacuo, the residue is filtered through silica gel with heptane/ethyl acetate (7:3 to 1:1), and the crude product is recrystallised from acetonitrile, giving 5-[2-(4-benzyloxy-biphenyl-4-yl)ethyl]-2,2-di-tert-butyl-1,3,2-dioxasilinane as a colourless solid.

2) 4-[2-(2,2-Di-tert-butyl-1,3,2-dioxasilinan-5-yl)ethyl]biphenyl-4-ol

(12) ##STR00345##

(13) 5-[2-(4-Benzyloxybiphenyl-4-yl)ethyl]-2,2-di-tert-butyl-1,3,2-dioxasilinane is hydrogenated to completeness in THF on palladium/activated carbon catalyst. The catalyst is filtered off, the filtrate is evaporated, and the residue is recrystallised from heptane, giving 4-[2-(2,2-di-tert-butyl-1,3,2-dioxasilinan-5-yl)-ethyl]biphenyl-4-ol as colourless, wadding-like needles.

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

(15) =1.02 ppm (s, 9H, tBu) 1.06 (s, 9H, tBu), 1.42 (m.sub.e, 2H, CH.sub.2), 2.19 (m.sub.e, 1H, >CH), 2.68 (m.sub.e, 2H, ArCH.sub.2), 3.83 (t, J=11.1 Hz, 2H, CH.sub.2O), 4.17 (dd, J=4.3 Hz, J=11.1 Hz, 2H, CH.sub.2O), 4.93 (s, 1H, OH), 6.95 (AB-d, J=8.6 Hz, 2H, ArH), 7.26 (AB-d, J=8.2 Hz, 2H, ArH), 7.52 (AB-d, J=8.5 Hz, 2H, ArH).

3) 4-[2-(2,2-Di-tert-butyl-1,3,2-dioxasilinan-5-yl)ethyl]biphenyl-4-yl 2-methylacrylate

(16) ##STR00346##

(17) 4-[2-(2,2-Di-tert-butyl-1,3,2-dioxasilinan-5-yl)ethyl]biphenyl-4-ol is reacted with methacrylic acid analogously to Example 1, giving 4-[2-(2,2-di-tert-butyl-1,3,2-dioxasilinan-5-yl)ethyl]biphenyl-4-yl2-methylacrylate as colourless crystals.

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

(19) =1.03 ppm (s, 9H, tBu) 1.06 (s, 9H, tBu), 1.43 (m.sub.e, 2H, CH.sub.2), 2.12 (m.sub.e, 3H, CH.sub.3), 2.19 (m.sub.e, 1H, >CH), 2.69 (m.sub.e, 2H, ArCH.sub.2), 3.85 (t, J=11.2 Hz, 2H, CH.sub.2O), 4.18 (dd, J=4.2 Hz, J=11.2 Hz, 2H, CH.sub.2O), 5.83 (m.sub.e, 1H, CHH), 6.43 (m.sub.e, 1H, CHH), 7.25 (AB-d, J=8.7 Hz, 2H, ArH), 7.29 (AB-d, J=8.3 Hz, 2H, ArH), 7.57 (AB-d, J=8.3 Hz, 2H, ArH), 7.67 (AB-d, J=8.7 Hz, 2H, ArH).

4) 4-(4-Hydroxy-3-hydroxymethylbutyl)biphenyl-4-yl 2-methylacrylate

(20) ##STR00347##

(21) 300 mg (0.624 mmol) of 4-[2-(2,2-di-tert-butyl-1,3,2-dioxasilinan-5-yl)ethyl]-biphenyl-4-yl 2-methylacrylate are dissolved in 10 ml of dichloromethane, and 1.2 g (7.4 mmol) of triethylamine trishydrogenfluoride are added with ice-cooling. The cooling is removed, and the batch is left to stir at RT overnight. The solution is subsequently filtered through 100 g of silica gel, subsequently eluted with dichloromethane/methanol (9:1), and the filtrate is evaporated. The residue is digested with heptane and filtered off, giving 4-(4-hydroxy-3-hydroxymethylbutyl)biphenyl-4-yl 2-methylacrylate as a colourless solid.

(22) .sup.1H-NMR (500 MHz, DMSO-d.sub.6)

(23) =1.62-1.46 (m, 3H), 2.02 (s, 3H, CH.sub.3), 2.65 (m.sub.e, 2H), 3.43 (m.sub.e, 4H), 4.33 (t, 5.23 Hz, 2H, OH), 5.91 (m.sub.e, 1H), 6.30 (s, 1H), 7.24 (d, 8.67 Hz, 2H), 7.30 (d, 8.21 Hz, 2H), 7.58 (d, 8.21 Hz, 2H), 7.69 (d, 8.68 Hz, 2H).

Example 3

Synthesis of 4-{2-[2-ethyl-2-fluoro-4-(3-hydroxypropyl)biphenyl-4-yl]ethyl}-phenyl 2-methylacrylate

(24) ##STR00348##

(25) 1) Synthesis of 4-bromo-2-ethylbiphenyl-4-ol A

(26) ##STR00349##

(27) 100.0 g (380 mmol) of 1-benzyloxy-4-bromobenzene and 55.99 g (570 mmol) of ethynyltrimethylsilane are dissolved in 1.07 I of diisopropylamine, and the mixture is degassed using a stream of argon for 60 min. 2.56 g (11.40 mmol) of palladium(II) acetate, 6.62 g (22.8 mmol) of tri-tert-butylphosphonium tetra-fluoroborate and 724 mg (3.80 mmol) of copper(I) iodide are then added, and the mixture is stirred at 60 C. for 18 h. When the reaction is complete, the reaction mixture is carefully added to a mixture of ice and methyl tert-butyl ether (MTB ether) and adjusted to pH=7-8. The organic phase is separated off, and the water phase is washed twice with MTB ether. The combined organic phases are then washed 1 with water and 1 with saturated NaCl solution, dried over sodium sulfate, filtered and evaporated in vacuo. The crude product obtained is filtered through 3 l of silica gel with heptane, giving 88.8 g of the product as a brown oil.

(28) MS (El): 280.1 [M.sup.+]

(29) .sup.1H NMR (500 MHz, CDCl.sub.3) =0.24 (s, 9H, Si(CH.sub.3).sub.3), 5.04 (s, 2H, benzylic CH.sub.2), 6.88 (d, 8.9 Hz, arom.-H), 7.29-7.41 (m, 7H, arom.-H).

2) Synthesis of 1-benzyloxy-4-ethynylbenzene B

(30) ##STR00350##

(31) 17.7 g (317 mmol) of KOH are carefully dissolved in 577 ml of methanol under a nitrogen atmosphere with stirring. The alkyne A is then added, and the reaction mixture is stirred at room temperature (RT) for 18 h. Water is carefully added to the reaction mixture, the latter is neutralised using dilute HCl, the water phase is extracted twice with MTB ether, and the combined organic phases are washed with water, dried over sodium sulfate, filtered and evaporated, giving 70 g of the crude product as a brown liquid, which is chromatographed on silica gel with heptane/chlorobutane (3:1), giving 54 g of the product having a purity of 99.9% (GC).

3) Synthesis of 4-(4-benzyloxyphenylethynyl)-1-bromo-2-fluorobenzene C

(32) ##STR00351##

(33) 50.0 g (240.1 mmol) of alkyne B and 73.7 g (240 mmol) of 1-bromo-2-fluoro-4-iodobenzene are dissolved in a mixture of 166 ml of triethylamine and 389 ml of tetrahydrofuran (THF) with stirring, and the mixture is degassed. 3.37 g (5.0 mmol) of bis(triphenylphosphine)palladium(II) chloride and 0.91 g (4.82 mmol) of copper(I) iodide are subsequently added. After addition of the catalyst, the reaction mixture warms to 60 C., and the reaction is complete after about 10 min. The cooled reaction mixture is then introduced into a mixture of ice-water and ethyl acetate (EA) and carefully acidified using dilute hydrochloric acid. The organic phase is separated off, and the water phase is extracted twice with EA. The combined organic phases are washed with water and saturated NaCl solution, dried over sodium sulfate, filtered and evaporated. The crude product obtained is dissolved in warm toluene and filtered through 4 l of silica gel. The product obtained is subsequently crystallised from a mixture of 3 l of heptane and 300 ml of toluene at 5 C., giving 80 g of the product as golden-coloured crystals.

Synthesis of 4-(4-benzyloxyphenylethynyl)-2-fluorophenylboronic acid D

(34) ##STR00352##

(35) 86.4 g (227 mmol) of bromide C are dissolved in 1380 ml of THF and cooled to 78 C. The starting material precipitates out again at this temperature, but redissolves after addition of 155.8 ml (249 mmol) of n-butyllithium. After the addition, the mixture is stirred at 78 C. for a further 60 min, 28.3 ml (249 mmol) of trimethyl borate are subsequently carefully added, and the mixture is stirred at 78 C. for 20 min. The reaction mixture is then allowed to warm slowly to 0 C., acidified using 2 N hydrochloric acid with cooling, subsequently stirred briefly, and the phases are separated. The water phase is extracted by stirring with MTB ether, and the combined organic phases are washed with saturated NaCl solution and dried over sodium sulfate, filtered and evaporated. The crude product obtained (dark-brown crystals) is washed by stirring with hot toluene (1:20) and cooled to RT overnight, filtered off with suction and dried in a vacuum drying cabinet, giving 54 g of the product as beige crystals.

4) Synthesis of 4-(4-benzyloxyphenylethynyl)-4-bromo-2-ethyl-2-fluorobiphenyl E

(36) ##STR00353##

(37) 25.0 g (72.0 mmol) of boronic acid D, 22.4 g (72.0 mmol) of 4-bromo-2-ethyl-1-iodobenzene and 18.3 g (173 mmol) of sodium carbonate are suspended in a mixture of 337 ml of ethanol, 230 ml of toluene and 68 ml of water and degassed under argon. 1.67 g (1.44 mmol) of tetrakis(triphenylphosphine)-palladium(0) are subsequently added, and the mixture is heated to 80 C. The beige suspension is subsequently refluxed for 3 h and, when the conversion is complete (thin-layer check), cooled to RT. A sufficient amount of water and ethyl acetate (EA) are then added to the reaction mixture, and the organic phase is separated off. The water phase is extracted twice with EA, and the combined organic phases are washed with saturated NaCl solution. The organic phase remains a suspension and is warmed to complete dissolution, sodium sulfate is added at the temperature for drying, and the mixture is filtered while warm and allowed to cool (5 C.) for crystallisation. The crystalline product is filtered off with suction and rinsed with cold toluene, giving the product (22.2 g) as white crystals.

(38) MS (El): 486.1 [M.sup.+]

(39) .sup.1H NMR (500 MHz, CDCl.sub.3) =1.07 ppm (t, 7.5 Hz, 3H, CH.sub.3), 2.48 (q, 7.4, 14.8 Hz, CH.sub.2CH.sub.3), 5.08 (s, 2H, benzylic CH.sub.2), 6.96 (d, 8.7 Hz, 2H, arom.-H), 7.04 (d, 8.2 Hz, 1H, arom.-H), 7.16 (t, 7.8 Hz, 1 h, arom.-H), 7.27 (d, 10 Hz, 1H, arom.-H), 7.32-7.52 (m, 10H, arom.-H).

5) Synthesis of {3-[4-(4-benzyloxyphenylethynyl)-2-ethyl-2-fluorobiphenyl-4-yl]prop-2-ynyloxy}-tert-butyldimethylsilane F

(40) ##STR00354##

(41) 19.2 g (40.0 mmol) of bromide E and 24.06 ml (118.7 mmol) of tert-butyl-dimethylprop-2-ynyloxysilane are dissolved in 403 ml of diisopropylamine and degassed while argon is passed in (30 min). 444 mg (1.98 mmol) of palladium(II) acetate, 573.8 mg (1.978 mmol) of tri-tert-butylphosphonium tetra-fluoroborate and 301.3 mg (1.582 mmol) of copper(I) iodide are then added to the reaction mixture, and the mixture is stirred under reflux for 3 h. The reaction mixture is allowed to cool to RT, water is added, and the mixture is extracted with MTB ether. The phases are separated, the water phase is extracted with MTB ether, and the combined organic phases are washed with saturated NaCl solution, dried over sodium sulfate, filtered and evaporated in vacuo. The crude product is filtered through silica gel with chlorobutane/heptane (1:1) and crystallised from isopropanol (1:20), giving 17.4 g of the product.

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

(43) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.78 (s, 9H, Si(C(CH.sub.3).sub.3), 0.89 (t, 7.57 Hz, 3H, CH.sub.3), 2.30 (q, 7.53, 2H, CH.sub.2CH.sub.3), 4.38 (s, 2H, CH.sub.2OSi(CH.sub.3).sub.2C(CH.sub.3).sub.3, 4.91 (s, 2H, benzylic CH.sub.2), 6.78 (d, 8.85 Hz, 2H, arom.-H), 6.93 (d, 7.85 Hz, 1H, arom.-H), 7.25-7.04 (m, 9H, arom.-H), 7.29 (d, 8.83 Hz, 2H, arom.-H).

6) Synthesis of 4-(2-{4-[3-(tert-butyldimethylsilanyloxy)propyl]-2-ethyl-2-fluorobiphenyl-4-yl}ethyl)phenol G

(44) ##STR00355##

(45) 16.7 g (28.0 mmol) of alkyne F are dissolved in 170 ml of THF and hydrogenated at room temperature (RT) and atmospheric pressure for 58 h with 5.7 g of sponge nickel catalyst (water-wet) and 4.2 l of hydrogen. When the reaction is complete, the reaction solution is filtered, evaporated and filtered through silica gel with dichloromethane (DCM), giving 13.5 g of the product.

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

(47) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.84 (s, 9H, Si(C(CH.sub.3).sub.3), 0.99 (t, 7.58 Hz, 3H, CH.sub.3), 1.82 (m.sub.e, 2H), 2.41 (q, 7.54 Hz, 2H), 2.63 (t, 7.95 Hz, 2H), 2.96 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.45 (q, 6.4 Hz, 2H), 4.46 (t, 5.15 Hz, 1H, OH), 6.67 (d, 8.49 Hz, 2H, arom.-H), 6.84 (dd, 1.41, 10.61 Hz, 1H, arom.-H), 6.88 (dd, 1.53, 7.73 Hz, 1H, arom.-H), 6.96 (d, 8.43 Hz, 2H, arom.-H), 7.06-6.98 (m, 4H, arom.-H).

7) Synthesis of 4-(2-{4-[3-(tert-butyldimethylsilanyloxy)propyl]-2-ethyl-2-fluorobiphenyl-4-yl}ethyl)phenyl 2-methylacrylate H

(48) ##STR00356##

(49) 3.00 g (6.09 mmol) of alcohol G, 37.2 mg (0.30 mmol) of 4-(dimethylamino)-pyridine and 0.72 ml (8.52 mmol) of methacrylic acid are initially introduced in 45 ml of dichloromethane and cooled to 0 C. A solution of 1.51 ml (8.52 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide in 20 ml of dichloromethane is then added dropwise, and the mixture is allowed to warm to RT. After stirring at RT for a further 2 days and when the reaction is complete, the reaction mixture is chromatographed directly on silica gel with dichloromethane, giving 2.6 g of the product having a purity of 99% (HPLC).

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

(51) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.85 (s, 9H, Si(C(CH.sub.3).sub.3), 1.00 (t, 7.57 Hz, 3H, CH.sub.3), 1.82 (m.sub.e, 2H, CH.sub.2), 1.99 (s, 3H, CH.sub.3), 2.42 (q, 7.53, 2H), 2.64 (t, 7.93 Hz, 2H), 2.89 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.61 (t, 6.32 Hz, 2H), 5.67 (s, 1H), 6.27 (s, 1H), 6.64 (d, 11.9 Hz, 1H, arom.-H), 6.91 (dd, 1.53, 7.72 Hz, 1H, arom.-H), 6.98 (d, 8.5 Hz, 2H, arom.-H), 7.09-6.98 (m, 4H, arom.-H), 7.13 (d, 8.47 Hz, 2H, arom.-H).

8) Synthesis of 4-{2-[2-ethyl-2-fluoro-4-(3-hydroxypropyl)biphenyl-4-yl]ethyl}-phenyl 2-methylacrylate

(52) ##STR00357##

(53) 2.60 g (4.63 mmol) of silyl ether H are dissolved in 56 ml of tetrahydrofuran (THF), the solution is cooled to 0 C., and 2.66 ml (2 mol/l, 5.33 mmol) of HCl are added dropwise. The reaction solution is allowed to warm to room temperature and, after 3 hours, carefully neutralised using sodium hydrogen-carbonate solution. MTB ether is added, the mixture is extracted, and the phases are separated. The organic phase is washed with water, dried over sodium sulfate, filtered and evaporated. The crude product is chromatographed on silica gel with heptane/ethyl acetate, and the product fractions are evaporated, giving 1.3 g (67%) of the product as a crystalline solid having a purity of 99.9% (HPLC).

(54) Phases: Tg 15 C. C 88 C. I

(55) .sup.1H NMR (500 MHz, DMSO-D.sub.6)

(56) =1.00 (t, 7.57 Hz, 3H, CH.sub.3), 1.76 (m.sub.e, 2H), 2.07 (s, 3H, CH.sub.3), 2.42 (q, 7.55 Hz, 2H), 2.64 (t, 7.92 Hz, 2H), 2.96 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.46 (q, 6.4 Hz, 2H), 4.46 (t, 5.15, 1H, OH), 5.89 (s, 1H), 6.27 (s, 1H), 6.64 (d, 11.9 Hz, 1H, arom.-H), 7.04 (d, 7.71 Hz, 1H, arom.-H), 7.15-7.06 (m, 3H, arom.-H), 7.21-7.16 (m, 4H, arom.-H), 7.32 (d, 8.54 Hz, 2H, arom.-H).

Example 4

2-(4-{2-[2-Ethyl-2-fluoro-4-(3-hydroxypropyl)biphenyl-4-yl]ethyl}phenoxy)ethyl 2-methacrylate

(57) ##STR00358##

(58) 1) Synthesis of 4-{2-[2-ethyl-2-fluoro-4-(3-hydroxypropyl)biphenyl-4-yl]ethyl}-phenyl 2-methylacrylate H

(59) ##STR00359##

(60) 8.20 g (16.5 mmol) of alcohol G (cf. example above) are dissolved in 119 ml of ethyl methyl ketone, and 5.69 g (41 mmol) of potassium carbonate are added. 13.14 g (61.1 mmol) of 2-bromoethoxymethylbenzene are subsequently added in portions, and the mixture is refluxed for 48 h. The reaction mixture is subsequently allowed to cool to room temperature (RT), filtered and rinsed with acetone. The organic phases are evaporated and purified by chromatography on silica gel with toluene, giving 7.3 g of the desired product.

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

(62) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.84 (s, 9H, Si(C(CH.sub.3).sub.3), 1.00 (t, 7.56 Hz, 3H, CH.sub.3), 1.80 (m.sub.e, 2H), 2.42 (q, 7.53 Hz, 2H), 2.63 (t, 7.92 Hz, 2H), 2.84 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.61 (t, 6.3 Hz, 2H), 3.76 (t, 4.84 Hz, 2H), 4.07 (t, 5.08 Hz, 2H), 4.57 (s, 2H), 6.68 (d, 8.6 Hz, 2H, arom.-H), 6.86 (dd, 10.61, 1.42 Hz, 1H, arom.-H), 6.89 (dd, 7.72, 1.56 Hz, 1H, arom.-H), 7.11-6.97 (m, 7H, arom.-H), 7.24-7.16 (m, 1H, arom.-H, superimposed with toluene) 7.32-7.25 (m, 3H, arom.-H, superimposed with toluene).

2) Synthesis of 2-[4-(2-{4-[3-(tert-butyldimethylsilanyloxy)propyl]-2-ethyl-2-fluorobiphenyl-4-yl}ethyl)phenoxy]ethanol I

(63) ##STR00360##

(64) 6.4 g (10.0 mmol) of benzyl ester K are dissolved in 70 ml of tetrahydrofuran, and 0.39 g (3.87 mmol) of NEt.sub.3 and 12.0 g of 5% Pd/C (54% of water) are added. The mixture is subsequently stirred at 50 C. and a hydrogen pressure of 5 bar for 82 h. The reaction mixture is filtered, and the crude product is filtered through silica gel with dichloromethane and MTB ether, giving 5.5 g of the desired product.

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

(66) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.85 (s, 9H, Si(C(CH.sub.3).sub.3), 1.00 (t, 7.57 Hz, 3H, CH.sub.3), 1.82 (m.sub.e, 2H), 1.92 (t, 6.25 Hz, 1H, OH), 2.42 (q, 7.52 Hz, 2H), 2.64 (t, 7.95 Hz, 2H), 2.85 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.61 (t, 6.3 Hz, 2H), 3.89 (m, 2H), 4.07 (t, 4.64 Hz, 2H), 6.78 (d, 8.5 Hz, 2H, arom.-H), 6.86 (d, 10.69, 1H, arom.-H), 6.89 (d, 7.74 Hz, 1H, arom.-H), 7.07-6.98 (m, 6H, arom.-H).

3) Synthesis of 2-[4-(2-{4-[3-(tert-butyldimethylsilanyloxy)propyl]-2-ethyl-2-fluorobiphenyl-4-yl}ethyl)phenoxy]ethyl 2-methylacrylate J

(67) ##STR00361##

(68) 5.60 g (10.4 mmol) of alcohol M, 5.19 ml (61.5 mmol) of methacrylic acid and 62.6 mg (0.512 mmol) of 4-(dimethylamino)pyridine are dissolved in 45 ml of dichloromethane (DCM) and cooled to 0 C. 10.87 ml (61.5 mmol) of EDC (dissolved in 30 ml of DCM) are then added, and the mixture is stirred at RT for 48 h. The reaction mixture is chromatographed directly on 250 g of silica gel with DCM, and the product fractions are evaporated in vacuo, giving 5.6 g of the desired product.

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

(70) =0.00 ppm (s, 6H, Si(CH.sub.3).sub.2), 0.85 (s, 9H, Si(C(CH.sub.3).sub.3), 1.00 (t, 7.57 Hz, 3H, CH.sub.3), 1.81 (m.sub.e, 2H), 1.89 (s, 3H), 2.42 (q, 7.54 Hz, 2H), 2.64 (t, 7.94 Hz, 2H), 2.85 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.61 (t, 6.3 Hz, 2H), 4.14 (t, 4.8 Hz, 2H), 4.42 (t, 5.02 Hz, 2H), 5.51 (s, 1H), 6.07 (s, 1H), 6.78 (d, 8.6 Hz, 2H, arom.-H), 6.86 (dd, 10.57, 1.33 Hz, 1H, arom.-H), 6.89 (dd, 7.74, 1.48 Hz, 1H, arom.-H), 7.1-6.97 (m, 6H, arom.-H).

4) Synthesis of 2-(4-{2-[2-ethyl-2-fluoro-4-(3-hydroxypropyl)biphenyl-4-yl]-ethyl}phenoxy)ethyl 2-methylacrylate

(71) ##STR00362##

(72) 5.60 g (9.30 mmol) of methacrylic acid ester M are dissolved in 112 ml of tetrahydrofuran (THF), the solution is cooled to 0 C., and 5.27 ml (10.5 mmol/2 N) of hydrochloric acid are added dropwise. The reaction solution is allowed to warm to room temperature and stirred for 3 h. When the reaction is complete, the mixture is carefully neutralised using NaHCO.sub.3 solution, and the product is extracted a number of times with MTB ether. The combined organic phases are dried over sodium sulfate, filtered and evaporated. The reaction product is chromatographed on silica gel with heptane/ethyl acetate, and the product fractions are evaporated in vacuo. The product is subsequently dried at 40 C. and 1.6.Math.10.sup.4 bar for 3 hours in order to remove solvent residues, giving 3.6 g of the desired product.

(73) Phases: Tg 24 C. I

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

(75) =1.10 (t, 7.57 Hz, 3H, CH.sub.3), 1.32 (s, 1H, OH), 1.81 (m.sub.e, 2H), 1.98 (m.sub.e, 5H), 2.53 (q, 7.54 Hz, 2H), 2.77 (t, 7.92 Hz, 2H), 2.95 (s, 4H, phenyl-CH.sub.2CH.sub.2-phenyl), 3.76 (t, 6.42 Hz, 2H), 4.24 (t, 4.75 Hz, 2H), 4.52 (t, 5.0 Hz, 2H), 5.61 (s, 1H), 6.17 (s, 1H), 6.88 (d, 8.56 Hz, 2H, arom.-H), 6.96 (dd, 10.56, 1.01 Hz, 1H, arom.-H), 7.04 (d, 7.75, 1.29 Hz, 1H, arom.-H), 7.2-7.08 (m, 6H, arom.-H).

(76) The following example compounds are prepared analogously to the above examples:

(77) TABLE-US-00008 No. Structure of the example compound 5. 6. 7. 8. 9. 10. 11. 12. 0 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 0 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 0 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 00 43. 01 44. 02 45. 03 46. 04 47. 05 48. 06 49. 07 50. 08 51. 09 52. 0 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 0 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 0 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 0 83. 84. 85. 86. 87. 88. 89. 90. 91.

B) Mixture Examples

(78) LC media according to the invention are prepared using the following liquid-crystalline mixtures consisting of low-molecular-weight components in the percentage proportions by weight indicated.

(79) TABLE-US-00009 H1: Nematic host mixture ( < 0) CY-3-O2 15.50% Clearing point [ C.]: 75.1 CCY-3-O3 8.00% n [589 nm, 20 C.]: 0.098 CCY-4-O2 10.00% [1 kHz, 20 C.]: 3.0 CPY-2-O2 5.50% .sub. [1 kHz, 20 C.]: 3.4 CPY-3-O2 11.50% .sub. [1 kHz, 20 C.]: 6.4 CCH-34 9.25% K.sub.1 [pN, 20 C.]: 13.1 CCH-23 24.50% K.sub.3 [pN, 20 C.]: 13.3 PYP-2-3 8.75% .sub.1 [mPa .Math. s, 20 C.]: 113 PCH-301 7.00% V.sub.0 [20 C., V]: 2.22

(80) TABLE-US-00010 H2: Nematic host mixture ( < 0) CY-3-O4 14.00% Clearing point [ C.]: 80.0 CCY-3-O2 9.00% n [589 nm, 20 C.]: 0.090 CCY-3-O3 9.00% [1 kHz, 20 C.]: 3.3 CPY-2-O2 10.00% .sub. [1 kHz, 20 C.]: 3.4 CPY-3-O2 10.00% .sub. [1 kHz, 20 C.]: 6.7 CCY-3-1 8.00% K.sub.1 [pN, 20 C.]: 15.1 CCH-34 9.00% K.sub.3 [pN, 20 C.]: 14.6 CCH-35 6.00% .sub.1 [mPa .Math. s, 20 C.]: 140 PCH-53 10.00% V.sub.0 [20 C., V]: 2.23 CCH-301 6.00% CCH-303 9.00%

(81) TABLE-US-00011 H3: Nematic host mixture ( < 0) CC-3-V1 9.00% Clearing point [ C.]: 74.7 CCH-23 18.00% n [589 nm, 20 C.]: 0.098 CCH-34 3.00% [1 kHz, 20 C.]: 3.4 CCH-35 7.00% .sub. [1 kHz, 20 C.]: 3.5 CCP-3-1 5.50% .sub. [1 kHz, 20 C.]: 6.9 CCY-3-O2 11.50% K.sub.1 [pN, 20 C.]: 14.9 CPY-2-O2 8.00% K.sub.3 [pN, 20 C.]: 15.9 CPY-3-O2 11.00% .sub.1 [mPa .Math. s, 20 C.]: 108 CY-3-O2 15.50% V.sub.0 [20 C., V]: 2.28 PY-3-O2 11.50%

(82) TABLE-US-00012 H4: Nematic host mixture ( < 0) CC-3-V 37.50% Clearing point [ C.]: 74.8 CC-3-V1 2.00% n [589 nm, 20 C.]: 0.099 CCY-4-O2 14.50% [1 kHz, 20 C.]: 2.9 CPY-2-O2 10.50% .sub. [1 kHz, 20 C.]: 3.7 CPY-3-O2 9.50% .sub. [1 kHz, 20 C.]: 6.6 CY-3-O2 15.00% K.sub.1 [pN, 20 C.]: 12.2 CY-3-O4 4.50% K.sub.3 [pN, 20 C.]: 13.4 PYP-2-4 5.50% .sub.1 [mPa .Math. s, 20 C.]: 92 PPGU-3-F 1.00% V.sub.0 [20 C., V]: 2.28

(83) TABLE-US-00013 H5: Nematic host mixture ( < 0) CCH-23 20.00% Clearing point [ C.]: 74.8 CCH-301 6.00% n [589 nm, 20 C.]: 0.105 CCH-34 6.00% [1 kHz, 20 C.]: 3.2 CCP-3-1 3.00% .sub. [1 kHz, 20 C.]: 3.5 CCY-3-O2 11.00% .sub. [1 kHz, 20 C.]: 6.8 CPY-2-O2 12.00% K.sub.1 [pN, 20 C.]: 12.7 CPY-3-O2 11.00% K.sub.3 [pN, 20 C.]: 13.6 CY-3-O2 14.00% .sub.1 [mPa .Math. s, 20 C.]: 120 CY-3-O4 4.00% V.sub.0 [20 C., V]: 2.16 PCH-301 4.00% PYP-2-3 9.00%

(84) TABLE-US-00014 H6: Nematic host mixture ( < 0) CC-4-V 17.00% Clearing point [ C.]: 106.1 CCP-V-1 15.00% n [589 nm, 20 C.]: 0.120 CCPC-33 2.50% [1 kHz, 20 C.]: 3.6 CCY-3-O2 4.00% .sub. [1 kHz, 20 C.]: 3.5 CCY-3-O3 5.00% .sub. [1 kHz, 20 C.]: 7.0 CCY-4-O2 5.00% K.sub.1 [pN, 20 C.]: 16.8 CLY-3-O2 3.50% K.sub.3 [pN, 20 C.]: 17.3 CLY-3-O3 2.00% .sub.1 [mPa .Math. s, 20 C.]: 207 CPY-2-O2 8.00% V.sub.0 [20 C., V]: 2.33 CPY-3-O2 10.00% CY-3-O4 17.00% PYP-2-3 11.00%

(85) TABLE-US-00015 H7: Nematic host mixture ( < 0) CY-3-O2 15.00% Clearing point [ C.]: 75.5 CCY-4-O2 9.50% n [589 nm, 20 C.]: 0.108 CCY-5-O2 5.00% [1 kHz, 20 C.]: 3.0 CPY-2-O2 9.00% .sub. [1 kHz, 20 C.]: 3.5 CPY-3-O2 9.00% .sub. [1 kHz, 20 C.]: 6.5 CCH-34 9.00% K.sub.1 [pN, 20 C.]: 12.9 CCH-23 22.00% K.sub.3 [pN, 20 C.]: 13.0 PYP-2-3 7.00% .sub.1 [mPa .Math. s, 20 C.]: 115 PYP-2-4 7.50% V.sub.0 [20 C., V]: 2.20 PCH-301 7.00%

(86) TABLE-US-00016 H8: Nematic host mixture ( < 0) CY-3-O2 15.00% Clearing point [ C.]: 74.7 CY-5-O2 6.50% n [589 nm, 20 C.]: 0.108 CCY-3-O2 11.00% [1 kHz, 20 C.]: 3.0 CPY-2-O2 5.50% .sub. [1 kHz, 20 C.]: 3.6 CPY-3-O2 10.50% .sub. [1 kHz, 20 C.]: 6.6 CC-3-V 28.50% K.sub.1 [pN, 20 C.]: 12.9 CC-3-V1 10.00% K.sub.3 [pN, 20 C.]: 15.7 PYP-2-3 12.50% .sub.1 [mPa .Math. s, 20 C.]: 97 PPGU-3-F 0.50% V.sub.0 [20 C., V]: 2.42

(87) TABLE-US-00017 H9: Nematic host mixture ( < 0) CCH-35 9.50% Clearing point [ C.]: 79.1 CCH-501 5.00% n [589 nm, 20 C.]: 0.091 CCY-2-1 9.50% [1 kHz, 20 C.]: 3.6 CCY-3-1 10.50% .sub. [1 kHz, 20 C.]: 3.5 CCY-3-O2 10.50% .sub. [1 kHz, 20 C.]: 7.1 CCY-5-O2 9.50% K.sub.1 [pN, 20 C.]: 14.6 CPY-2-O2 12.00% K.sub.3 [pN, 20 C.]: 14.5 CY-3-O4 9.00% .sub.1 [mPa .Math. s, 20 C.]: 178 CY-5-O4 11.00% V.sub.0 [20 C., V]: 2.12 PCH-53 13.50%

(88) TABLE-US-00018 H10: Nematic host mixture ( < 0) BCH-32 4.00% Clearing point [ C.]: 74.8 CC-3-V1 8.00% n [589 nm, 20 C.]: 0.106 CCH-23 13.00% [1 kHz, 20 C.]: 3.5 CCH-34 7.00% .sub. [1 kHz, 20 C.]: 3.6 CCH-35 7.00% .sub. [1 kHz, 20 C.]: 7.1 CCY-3-O2 13.00% K.sub.1 [pN, 20 C.]: 14.8 CPY-2-O2 7.00% K.sub.3 [pN, 20 C.]: 15.8 CPY-3-O2 12.00% .sub.1 [mPa .Math. s, 20 C.]: 115 CY-3-O2 12.00% V.sub.0 [20 C., V]: 2.23 PCH-301 2.00% PY-3-O2 15.00%

(89) TABLE-US-00019 H11: Nematic host mixture ( < 0) CY-3-O4 22.00% Clearing point [ C.]: 86.9 CY-5-O4 12.00% n [589 nm, 20 C.]: 0.111 CCY-3-O2 6.00% [1 kHz, 20 C.]: 4.9 CCY-3-O3 6.00% .sub. [1 kHz, 20 C.]: 3.8 CCY-4-O2 6.00% .sub. [1 kHz, 20 C.]: 8.7 CPY-2-O2 10.00% K.sub.1 [pN, 20 C.]: 14.9 CPY-3-O2 10.00% K.sub.3 [pN, 20 C.]: 15.9 PYP-2-3 7.00% .sub.1 [mPa .Math. s, 20 C.]: 222 CC-3-V1 7.00% V.sub.0 [20 C., V]: 1.91 CC-5-V 10.00% CCPC-33 2.00% CCPC-35 2.00%

(90) TABLE-US-00020 H12: Nematic host mixture ( < 0) CY-3-O4 12.00% Clearing point [ C.]: 86.0 CY-5-O2 10.00% n [589 nm, 20 C.]: 0.110 CY-5-O4 8.00% [1 kHz, 20 C.]: 5.0 CCY-3-O2 8.00% .sub. [1 kHz, 20 C.]: 3.8 CCY-4-O2 7.00% .sub. [1 kHz, 20 C.]: 8.8 CCY-5-O2 6.00% K.sub.1 [pN, 20 C.]: 14.7 CCY-2-1 8.00% K.sub.3 [pN, 20 C.]: 16.0 CCY-3-1 7.00% .sub.1 [mPa .Math. s, 20 C.]: 250 CPY-3-O2 9.00% V.sub.0 [20 C., V]: 1.90 CPY-3-O2 9.00% BCH-32 6.00% PCH-53 10.00%

(91) TABLE-US-00021 H13: Nematic host mixture ( < 0) CC-3-V1 10.25% Clearing point [ C.]: 74.7 CCH-23 18.50% n [589 nm, 20 C.]: 0.103 CCH-35 6.75% [1 kHz, 20 C.]: 3.1 CCP-3-1 6.00% .sub. [1 kHz, 20 C.]: 3.4 CCY-3-1 2.50% .sub. [1 kHz, 20 C.]: 6.4 CCY-3-O2 12.00% K.sub.1 [pN, 20 C.]: 15.4 CPY-2-O2 6.00% K.sub.3 [pN, 20 C.]: 16.8 CPY-3-O2 9.75% .sub.1 [mPa .Math. s, 20 C.]: 104 CY-3-O2 11.50% V.sub.0 [20 C., V]: 2.46 PP-1-2V1 3.75% PY-3-O2 13.00%

(92) TABLE-US-00022 H14: Nematic host mixture ( < 0) CC-3-V 27.50% Clearing point [ C.]: 74.7 CC-3-V1 10.00% n [589 nm, 20 C.]: 0.104 CCH-35 8.00% [1 kHz, 20 C.]: 3.0 CCY-3-O2 9.25% .sub. [1 kHz, 20 C.]: 3.4 CLY-3-O2 10.00% .sub. [1 kHz, 20 C.]: 6.4 CPY-3-O2 11.75% K.sub.1 [pN, 20 C.]: 15.3 PY-3-O2 14.00% K.sub.3 [pN, 20 C.]: 16.2 PY-4-O2 9.00% .sub.1 [mPa .Math. s, 20 C.]: 88 PYP-2-4 0.50% V.sub.0 [20 C., V]: 2.44

(93) TABLE-US-00023 H15: Nematic host mixture ( < 0) CC-4-V 10.00% Clearing point [ C.]: 77.0 CC-5-V 13.50% n [589 nm, 20 C.]: 0.113 PGU-3-F 6.50% [1 kHz, 20 C.]: 19.2 ACQU-2-F 10.00% .sub. [1 kHz, 20 C.]: 23.8 ACQU-3-F 12.00% .sub. [1 kHz, 20 C.]: 4.6 PUQU-3-F 11.00% K.sub.1 [pN, 20 C.]: 11.5 CCP-V-1 12.00% K.sub.3 [pN, 20 C.]: 11.1 APUQU-2-F 6.00% .sub.1 [mPa .Math. s, 20 C.]: 122 APUQU-3-F 7.00% V.sub.0 [20 C., V]: 0.81 PGUQU-3-F 8.00% CPGU-3-OT 4.00%

(94) TABLE-US-00024 H16: Nematic host mixture ( < 0) PGU-2-F 3.50% Clearing point [ C.]: 77.0 PGU-3-F 7.00% n [589 nm, 20 C.]: 0.105 CC-3-V1 15.00% [1 kHz, 20 C.]: 7.2 CC-4-V 18.00% .sub. [1 kHz, 20 C.]: 10.3 CC-5-V 20.00% .sub. [1 kHz, 20 C.]: 3.1 CCP-V-1 6.00% K.sub.1 [pN, 20 C.]: 15.3 APUQU-3-F 15.00% K.sub.3 [pN, 20 C.]: 13.5 PUQU-3-F 5.50% .sub.1 [mPa .Math. s, 20 C.]: 63 PGP-2-4 3.00% V.sub.0 [20 C., V]: 1.53 BCH-32 7.00%

(95) TABLE-US-00025 H17: Nematic host mixture ( < 0) APUQU-2-F 6.00% Clearing point [ C.]: 74.0 APUQU-3-F 12.00% n [589 nm, 20 C.]: 0.120 PUQU-3-F 18.00% [1 kHz, 20 C.]: 17.4 CPGU-3-OT 9.00% .sub. [1 kHz, 20 C.]: 22.0 CCGU-3-F 3.00% .sub. [1 kHz, 20 C.]: 4.5 BCH-3F.F.F 14.00% K.sub.1 [pN, 20 C.]: 10.1 CCQU-3-F 10.00% K.sub.3 [pN, 20 C.]: 10.8 CC-3-V 25.00% .sub.1 [mPa .Math. s, 20 C.]: 111 PGP-2-2V 3.00% V.sub.0 [20 C., V]: 0.80

(96) TABLE-US-00026 H18: Nematic host mixture ( < 0) PUQU-3-F 15.00% Clearing point [ C.]: 74.3 APUQU-2-F 5.00% n [589 nm, 20 C.]: 0.120 APUQU-3-F 12.00% [1 kHz, 20 C.]: 14.9 CCQU-3-F 11.00% .sub. [1 kHz, 20 C.]: 19.1 CCQU-5-F 1.50% .sub. [1 kHz, 20 C.]: 4.3 CPGU-3-OT 5.00% K.sub.1 [pN, 20 C.]: 11.2 CCP-30CF3 4.50% K.sub.3 [pN, 20 C.]: 10.8 CGU-3-F 10.00% .sub.1 [mPa .Math. s, 20 C.]: 98 PGP-2-3 1.50% V.sub.0 [20 C., V]: 0.91 PGP-2-2V 8.00% CC-3-V 26.50%

(97) TABLE-US-00027 H19: Nematic host mixture ( < 0) CCQU-3-F 9.00% Clearing point [ C.]: 94.5 CCQU-5-F 9.00% n [589 nm, 20 C.]: 0.121 PUQU-3-F 16.00% [1 kHz, 20 C.]: 20.4 APUQU-2-F 8.00% .sub. [1 kHz, 20 C.]: 24.7 APUQU-3-F 9.00% .sub. [1 kHz, 20 C.]: 4.3 PGUQU-3-F 8.00% K.sub.1 [pN, 20 C.]: 12.1 CPGU-3-OT 7.00% K.sub.3 [pN, 20 C.]: 13.9 CC-4-V 18.00% .sub.1 [mPa .Math. s, 20 C.]: 163 CC-5-V 5.00% V.sub.0 [20 C., V]: 0.81 CCP-V-1 6.00% CCPC-33 3.00% PPGU-3-F 2.00%

(98) TABLE-US-00028 H20: Nematic host mixture ( < 0) CC-3-V 28.50% Clearing point [ C.]: 85.6 CCP-V1 3.00% n [589 nm, 20 C.]: 0.121 CCPC-33 2.00% [1 kHz, 20 C.]: 19.5 PGU-2-F 4.00% .sub. [1 kHz, 20 C.]: 23.8 CCQU-3-F 8.00% .sub. [1 kHz, 20 C.]: 4.3 CCQU-5-F 6.00% K.sub.1 [pN, 20 C.]: 11.6 CCGU-3-F 3.00% K.sub.3 [pN, 20 C.]: 12.7 PUQU-2-F 2.00% .sub.1 [mPa .Math. s, 20 C.]: 126 PUQU-3-F 10.00% V.sub.0 [20 C., V]: 0.81 APUQU-2-F 6.00% APUQU-3-F 9.00% PGUQU-3-F 5.00% PGUQU-4-F 5.00% PGUQU-5-F 4.00% CPGU-3-OT 4.00% PPGU-3-F 0.50%

(99) The following polymerisable self-alignment additives (PSAAs) are used:

(100) TABLE-US-00029 PSAA No. Structure 1 0 2 3

(101) The following polymerisable compound is used:

(102) ##STR00453##

(103) The following non-polymerisable self-alignment additives are used:

(104) ##STR00454##

Mixture Example 1

(105) Polymerisable self-alignment additive 1 (1.0% by weight) is added to a nematic LC medium H1 of the VA type (<0), and the mixture is homogenised.

(106) Use in Test cells without Pre-Alignment Layer:

(107) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(108) VA alignment layers which are used for PM-VA, PVA, MVA and analogous technologies are no longer necessary with the use of additives such as polymerisable self-alignment additive 1.

Mixture Example 2

(109) Polymerisable self-alignment additive 1 (1.0% by weight) is added to a nematic LC medium H15 of the VA-IPS type (>0), and the mixture is homogenised.

(110) Use in Test Cells without Pre-Alignment Layer:

(111) The mixture formed is introduced into a test cell (without polyimide alignment layer, layer thickness d4 m, ITO interdigital electrodes arranged on one substrate surface, glass on the opposite substrate surface, without passivation layer). The LC medium has a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cell formed can be switched reversibly by application of a voltage.

(112) VA alignment layers which are used for VA-IPS, HT-VA and analogous technologies are no longer necessary with the use of additives such as polymerisable self-alignment additive 1.

Mixture Examples 3 and 4

(113) Polymerisable self-alignment additives 2 (1.5% by weight) and 3 (2.0% by weight) are added to a nematic LC medium H1 (<0) analogously to Mixture Example 1, and the mixture is homogenised. The mixtures formed are introduced into test cells without pre-alignment layer. The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cells formed can be switched reversibly by application of a voltage.

Mixture Examples 5 and 6

(114) Polymerisable self-alignment additives 2 (1.5% by weight) and 3 (2.0% by weight) are added to a nematic LC medium H15 (>0) analogously to Mixture Example 2, and the mixture is homogenised. The mixtures formed are introduced into test cells without pre-alignment layer. The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cells formed can be switched reversibly by application of a voltage.

Mixture Examples 7-20

(115) Polymerisable self-alignment additive 1 (1.0% by weight) is added to nematic

(116) LC media H2-H14 (<0) analogously to Mixture Example 1, and the mixture is homogenised. The mixtures formed are introduced into test cells without pre-alignment layer (cf. Mixture Example 1). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cells formed can be switched reversibly by application of a voltage.

Mixture Examples 21-26

(117) Polymerisable self-alignment additive 1 (1.0% by weight) is added to nematic LC media H16-H20 (>0) analogously to Mixture Example 2, and the mixture is homogenised. The mixtures formed are introduced into test cells without pre-alignment layer (cf. Mixture Example 2). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA-IPS cells formed can be switched reversibly by application of a voltage.

Mixture Examples 27-28

(118) A polymerisable self-alignment additive 1 (0.3% by weight) and in each case a non-polymerisable self-alignment additive A-1 (1.5% by weight) or A-2 (0.3% by weight) are added to a nematic LC medium H1 of the VA type (<0), and the mixture is homogenised.

(119) Use in Test Cells without Alignment Layer:

(120) The mixture formed is introduced into a test cell (without polyimide alignment layer, cell thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC medium has a spontaneous homeotropic (vertical) alignment to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(121) VA alignment layers which are used for PM-VA, PVA, MVA and analogous technologies are no longer necessary on use of additives such as the polymerisable self-alignment additive 1 in combination with A-1 or A-2.

Mixture Examples 1a and 3a (Polymerisation of Mixture Examples 1 and 3)

(122) In each case a polymerisable self-alignment additive 1 (1.0% by weight) or 2 (1.5% by weight) is added to a nematic LC medium H1 (<0), and the mixture is homogenised.

(123) Use in Test Cells without Pre-Alignment Layer:

(124) The mixtures formed are introduced into test cells (without polyimide alignment layer, cell thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(125) While a voltage greater than the optical threshold voltage (for example 14 Vpp) is applied, the VA cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 at 20 C. or 40 C. with a 340 nm band-pass filter. This causes polymerisation of the polymerisable compounds. The homeotropic alignment is thus additionally stabilised, a pre-tilt is established, and a polymer layer forms. The PSA-VA cells obtained can be switched reversibly up to the clearing point on application of a voltage. The response times are shortened compared with the unpolymerised cell. The threshold voltages (V.sub.10) change (Table 1).

(126) The polymerisation can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilised and a polymer layer forms without a pre-tilt being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(127) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerisable self-alignment additives 1 and 2.

Mixture Example 1b (Polymer Stabilisation of Mixture Example 1a)

(128) A polymerisable compound RM-41 (0.3% by weight) and a polymerisable self-alignment additive 1 (1.0% by weight) are added to a nematic LC medium H1 (<0), and the mixture is homogenised.

(129) Use in Test cells without Alignment Layer:

(130) The mixtures formed are introduced into test cells (without polyimide alignment layer, cell thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(131) While a voltage greater than the optical threshold voltage (for example 14 Vpp) is applied, the VA cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 at 20 C. or 40 C. with a 340 nm band-pass filter. This causes polymerisation of the polymerisable compounds. The homeotropic alignment is thus additionally stabilised, a pre-tilt is established, and a polymer layer forms. The PSA-VA cells obtained can be switched reversibly up to the clearing point by application of a voltage. The response times are shortened compared with the unpolymerised cell. The threshold voltages (V.sub.10) change (Table 1).

(132) The polymerisation can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilised and a polymer layer forms without a pre-tilt being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(133) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerisable self-alignment additives 1 in combination with RM-41.

Mixture Example 28a (Polymerisation of Mixture Example 28)

(134) A polymerisable self-alignment additive 1 (0.3% by weight) and an unpolymerisable self-alignment additive A-2 (0.3% by weight) are added to a nematic LC medium H1 of the VA type (<0), and the mixture is homogenised.

(135) Use in Test Cells without Pre-Alignment Layer:

(136) The mixtures formed are introduced into test cells (without polyimide alignment layer, cell thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(137) While a voltage greater than the optical threshold voltage (for example 14 Vpp) is applied, the VA cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 at 20 C. or 40 C. with a 340 nm band-pass filter. This causes polymerisation of the polymerisable compounds. The homeotropic alignment is thus additionally stabilised, a pre-tilt is established, and a polymer layer forms. The PSA-VA cells obtained can be switched reversibly up to the clearing point on application of a voltage. The response times are shortened compared with the unpolymerised cell. The threshold voltages (V.sub.10) change (Table 1).

(138) The polymerisation can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilised and a polymer layer forms without a pre-tilt being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(139) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as polymerisable self-alignment additive 1 in combination with A-2.

Mixture Example 27b (Polymerisation of Mixture Example 27a)

(140) A polymerisable compound RM-41 (0.3% by weight), a polymerisable self-alignment additive 1 (0.3% by weight) and an unpolymerisable self-alignment additive A-1 (1.5% by weight) are added to a nematic LC medium H1 of the VA type (<0), and the mixture is homogenised.

(141) Use in Test Cells without Pre-Alignment Layer:

(142) The mixtures formed are introduced into test cells (without polyimide alignment layer, cell thickness d4.0 m, ITO coating on both sides, without passivation layer). The LC media have a spontaneous homeotropic (vertical) alignment with respect to the substrate surfaces. This alignment remains stable up to the clearing point, and the VA cell formed can be switched reversibly by application of a voltage.

(143) While a voltage greater than the optical threshold voltage (for example 14 Vpp) is applied, the VA cells are irradiated with UV light having an intensity of 100 mW/cm.sup.2 at 20 C. or 40 C. with a 340 nm band-pass filter. This causes polymerisation of the polymerisable compounds. The homeotropic alignment is thus additionally stabilised, a pre-tilt is established, and a polymer layer forms. The PSA-VA cells obtained can be switched reversibly up to the clearing point on application of a voltage. The response times are shortened compared with the unpolymerised cell. The threshold voltages (V.sub.10) change (Table 1).

(144) The polymerisation can also be carried out without application of a voltage. The homeotropic alignment is thus additionally stabilised and a polymer layer forms without a pre-tilt being established. The polymer layer acts as protective layer and improves the long-term stability of the PSA-VA cell.

(145) VA alignment layers which are used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as polymerisable self-alignment additive 1 in combination with RM-41 and A-2.

(146) TABLE-US-00030 TABLE 1 Threshold voltages V.sub.10 of VA and PSA cells. Host H1 in combination with polymerisable self-alignment additive (PSOA). Polymerisation conditions: 340 nm band-pass filter, 20 C., 0 Vpp, 10 min, 100 mW/cm.sup.2. Response Mixture Further UV Cell time/ms Example PSOA comp. irradiation type V.sub.10/V 0 V.fwdarw.5 V 1 1 No VA 2.47 27 3 2 No VA 2.47 34 27 1 A-1 No VA 2.55 25 28 1 A-2 No VA 2.50 26 1a 1 Yes PSA 4.54 15 1b 1 RM-41 Yes PSA 4.81 17 3a 2 Yes PSA 2.63 17 27b 1 A-1, Yes PSA 2.57 22 RM-41 28a 1 A-2 Yes PSA 2.58 23