Liquid crystalline medium

Abstract

The invention relates to a liquid-crystalline medium which contains at least two polymerisable compounds or reactive mesogens (RM) and at least one compound selected from the group of compounds of the formula IIA, IIB and IIC, ##STR00001##
in which R.sup.2A, R.sup.2B, R.sup.2C, L.sup.1-6, ring B, Z.sup.2, Z.sup.2, p, q and v have the meanings indicated in Claim 1,
and to the use thereof for an active-matrix display, in particular based on the VA, PSA, PS-VA, PALC, FFS, PS-FFS, IPS or PS-IPS effect, especially for the use in LC displays of the PS (polymer stabilised) or PSA (polymer sustained alignment) type.

Claims

1. A liquid-crystalline medium based on a mixture of polar compounds having negative dielectric anisotropy, comprising at least two reactive mesogens, at least two of said reactive mesogens having sufficiently different polymerization reactivity from one another allowing their polymerization by two separate polymerizations and at least one compound selected from the group of compounds consisting of the compounds of formulae IIA, IIB and IIC, ##STR00319## in which R.sup.2A, R.sup.2B and R.sup.2c each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF.sub.3 or at least monosubstituted by halogen, in which one or more CH.sub.2 groups are optionally replaced by O, S, ##STR00320## CC, CF.sub.2O, OCF.sub.2, OCO or OCO in such a way that O atoms are not linked directly to one another, ##STR00321## denotes ##STR00322## Y.sup.1-6 each, independently of one another, denote H or F, L.sup.1 and L.sup.2 each, independently of one another, denote F, Cl, CF.sub.3 or CHF.sub.2, L.sup.3-6 each, independently of one another, denote H, F, Cl, CF.sub.3 or CHF.sub.2, but at least two of L.sup.3-6 denote F, Cl, CF.sub.3 or CHF.sub.2, Z.sup.2 and Z.sup.2 each, independently of one another, denote a single bond, CH.sub.2CH.sub.2, CHCH, CC, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, COO, OCO, CFCF, or CHCHCH.sub.2O, p denotes 1 or 2, and, in the case where Z.sup.2=single bond, p also denotes 0, q denotes 0 or 1, y denotes 0 or 1, and denotes 1 to 6.

2. The liquid-crystalline medium according to claim 1, wherein the at least two reactive mesogens each having a polymerization reactivity that is different from the other of the at least two reactive mesogens are compounds of formula I
R.sup.Ma-A.sup.M1-(Z.sup.M1-A.sup.M2).sub.m1-R.sup.MbI wherein R.sup.Ma and R.sup.Mb each, independently of one another, denote P, P-Sp-, H, halogen, SF.sub.5, NO.sub.2, an alkyl, alkenyl or alkynyl group, P denotes a polymerizable group, Sp denotes a spacer group or a single bond, A.sup.M1 and A.sup.M2 each, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which optionally encompasses or contains fused rings, and which is optionally mono- or polysubstituted by L, L denotes P, P-Sp-, OH, CH.sub.2OH, F, Cl, Br, I, CN, NO.sub.2, NCO, NCS, OCN, SCN, C(O)N(Rx).sub.2, C(O)Y.sup.1, C(O)R.sup.x, N(R.sup.x).sub.2, SF.sub.5, optionally substituted silyl, optionally substituted aryl having 6 to 20 C atoms, or straight-chain or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which one or more H atoms are optionally replaced by F, Cl, P or P-Sp-, Y.sup.1 denotes halogen, Z.sup.M1 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, CHCH, COO, OCOCHCH, CR.sup.0R.sup.00 or a single bond, R.sup.0 and R.sup.00 each, independently of one another, denote H or alkyl having 1 to 12 C atoms, R.sup.x denotes P, P-Sp-, H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which one or more non-adjacent CH.sub.2 groups are optionally 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 one or more H atoms are optionally replaced by F, Cl, P or P-Sp-, 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, m1 denotes 0, 1, 2, 3 or 4, and n1 denotes 1, 2, 3 or 4, where at least one of R.sup.Ma, R.sup.Mb and L denotes P or P-Sp- or contains at least one group P or P-Sp-.

3. The liquid-crystalline medium according to claim 2, wherein one of R.sup.Ma and R.sup.Mb or both denote(s) P or P-Sp-.

4. The liquid-crystalline medium according to claim 1, which contains at least two reactive mesogens selected from the group consisting of the compounds of formulae I-1 to I-44 ##STR00323## ##STR00324## ##STR00325## ##STR00326## ##STR00327## ##STR00328## wherein P.sup.1 and P.sup.2 each, independently of one another, denote a polymerizable group, Sp.sup.1 and Sp.sup.2 each, independently of one another, denote a single bond or a spacer group, where one of the radicals P.sup.1-Sp.sup.1- and P.sup.2Sp.sup.2- optionally denotes 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 one or more non-adjacent CH.sub.2 groups are optionally each replaced, independently of one another, by C(R.sup.0)C(R.sup.00)), CC, N(R.sup.0), 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 one or more H atoms are optionally replaced by F, Cl, CN or P.sup.1-SP.sup.1-, 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, 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, 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 or alkylcarbonyloxy having 1 to 12 C atoms, L and L each, independently of one another, denote H, F, Cl or CF.sub.3, r denotes 0, 1, 2, 3 or 4, denotes 0, 1, 2 or 3, t denotes 0, 1 or 2, and x denotes 0 or 1.

5. The liquid-crystalline medium according to claim 1, which contains at least two reactive mesogens selected from the group consisting of the compounds of formulae RM-1 to RM-86: ##STR00329## ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337##

6. The liquid-crystalline medium according to claim 1, wherein the at least one compound of formulae IIA, IIB and IIC are selected from the group consisting of the compounds of formulae IIA-1 to IIC-6, ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## 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.

7. The liquid-crystalline medium according to claim 1, further containing one or more compounds of formula III, ##STR00347## in which R.sup.31 and R.sup.32 each, independently of one another, denote a straight-chain alkyl, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and ##STR00348## denotes ##STR00349## Z.sup.3 denotes a single bond, 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, C.sub.4H.sub.9, or CFCF.

8. The liquid-crystalline medium according to claim 1, further containing at least one compound of formulae L-1 to L-11, ##STR00350## ##STR00351## in which R, R.sup.1 and R.sup.2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF.sub.3 or at least monosubstituted by halogen, in which one or more CH.sub.2 groups are optionally replaced by O, S, ##STR00352## OCO or OCO in such a way that O atoms are not linked directly to one another, alkyl denotes an alkyl radical having 1-6 C atoms, and s denotes 1 or 2.

9. The liquid-crystalline medium according to claim 1, further containing one or more terphenyls of formulae T-1 to T-21, ##STR00353## ##STR00354## ##STR00355## in which R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms, n denotes 0-4, and m denotes 1-6.

10. The liquid-crystalline medium according claim 1, further containing one or more compounds of formulae O-1 to O-16, ##STR00356## ##STR00357## in which R.sup.1 and R.sup.2 each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF.sub.3 or at least monosubstituted by halogen, in which one or more CH.sub.2 groups are optionally replaced by O, S, ##STR00358## CC, CF.sub.2O, OCF.sub.2, OCO or OCO in such a way that O atoms are not linked directly to one another.

11. The liquid-crystalline medium according to claim 1, further containing one or more indane compounds of formula In, ##STR00359## in which R.sup.11, R.sup.12, R.sup.13 denote a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1-5 C atoms, R.sup.12 and R.sup.13 additionally also denote halogen, ##STR00360## denotes one of the following groups ##STR00361## i denotes 0, 1 or 2.

12. The liquid-crystalline medium according to claim 2, wherein the proportion of the compounds of formula I in the mixture as a whole is 0.1 to 5% by weight.

13. A process for preparing the liquid-crystalline medium according to claim 1, comprising mixing together the at least two reactive mesogens each having a polymerization reactivity that is different from the other of the at least two reactive mesogens with at least one compound of formula IIA, IIB or IIC, and additives are optionally added.

14. An electro-optical display having active-matrix addressing, which contains, as dielectric, the liquid-crystalline medium according to claim 1.

15. The electro-optical display according to claim 14, which is a VA, PSA, PS-VA, PALC, FFS, PS-FFS, IPS, PSIPS or flexible display.

16. The PS or PSA display according to claim 14, which contains a display cell containing two substrates and two electrodes, wherein at least one substrate is transparent to light and at least one substrate has one or two electrodes provided thereon, and a layer of an LC medium containing two polymerized components located between the substrates, wherein the polymerized components are obtainable by polymerization of the at least two reactive mesogens each having a polymerization reactivity that is different from the other of the at least two reactive mesogens between the substrates of the display cell in the LC medium, optionally while applying a voltage to the electrodes.

17. The PS or PSA display according to claim 16, which contains a display cell containing two substrates wherein one substrate is a glass substrate and the other substrate is a flexible substrate made by RM polymerization of the at least two reactive mesogens each having a polymerization reactivity that is different from the other of the at least two reactive mesogens.

18. A method for preparing a PS or PSA display, comprising providing the LC mixture according to claim 1 into a display cell containing two substrates and two electrodes, wherein at least one substrate is transparent to light and at least one substrate has one or two electrodes provided thereon, and polymerizing the at least two reactive mesogens each having a polymerization reactivity that is different from the other of the at least two reactive mesogens.

19. The method according to claim 18, wherein polymerization is achieved by exposure to UV light having a wavelength from 320 nm to 400 nm.

20. The liquid crystalline medium according to claim 1, wherein at least two of said reactive mesogens have a substantially different polymerization UV absorption spectrum from each other.

21. The liquid crystalline medium according to claim 4, comprising one or more polymerizable compounds or reactive mesogens (RM) of formulae I-2 and I-3 and one or more polymerizable compounds or reactive mesogens (RM) of formula I-13 to I-21.

22. The liquid crystalline medium according to claim 5, comprising one or more polymerizable compounds or reactive mesogens (RM) of formulae RM-1 to RM-32 and one or more polymerizable compounds or reactive mesogens (RM) of formulae RM-41 to RM-65.

23. A composite system comprising a liquid crystalline medium comprising at least one compound of formulae IIA, IIB and/or IIC, of claim 1 and two different polymeric components obtained by separate polymerization of the at least two reactive mesogens.

24. The system according to claim 23, wherein polymerization of the at least two different reactive mesogens is achieved or achievable by UV radiation, while at least two of the at least two reactive mesogens are polymerized by the application of an UV irradiation with a spectral distribution different from that one used for the polymerization of the other of said of at least two reactive mesogens and whereby a voltage is applied during at least one of said polymerizations.

25. An electro-optical display having active-matrix addressing, which contains, as dielectric, the system according to claim 23.

26. The method according to claim 18, wherein at least one of the at least two reactive mesogens is polymerized under the application of a voltage.

27. The method according to claim 19, wherein at least one of the at least two reactive mesogens is polymerized under the application of a voltage.

28. The liquid-crystalline medium according to claim 1, which further contains a polymerization initiator.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) RM-1 and RM-41 show a different UV absorption behaviour as shown in FIG. 1.

(2) The PS-VA mixture is introduced into a cell with homeotropic alignment. The polymerization of RM-1 and RM-41 is done selectively. RM-41 is polymerized first by using an UV cut filter and the RM polymer layer is formed. In the next step the PS-VA process takes place with RM-1 under 2.sup.nd UV exposure (UV light with a power of 100 mW/cm.sup.2) and the pretilt angle is generated.

Example M2

(3) To the following host mixture H1

(4) TABLE-US-00007 CY-3-O2 15.00% Clearing point [ C.]: 75.5 CCY-4-O2 9.50% n [589 nm, 20 C.]: 0.1075 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.3 [pN, 20 C.]: 13.0 CCH-23 22.00% K.sub.3/K.sub.1 [20 C.]: 1.01 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%
are added two different reactive mesogens with different reactivity:

(5) ##STR00314##

(6) According to Example M1 the mixture is introduced in to a cell and the PS-VA process is applied.

Example M3

(7) To the following host mixture H1

(8) TABLE-US-00008 CY-3-O2 15.00% Clearing point [ C.]: 75.5 CCY-4-O2 9.50% n [589 nm, 20 C.]: 0.1075 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.3 [pN, 20 C.]: 13.0 CCH-23 22.00% K.sub.3/K.sub.1 [20 C.]: 1.01 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%
are added two different reactive mesogens with different reactivity:

(9) ##STR00315##

(10) According to Example M1 the mixture is introduced in to a cell and the PS-VA process is applied.

Example M4

(11) To the following host mixture H1

(12) TABLE-US-00009 CY-3-O2 15.00% Clearing point [ C.]: 74.7 CY-5-O2 6.50% n [589 nm, 20 C.]: 0.1082 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.3 [pN, 20 C.]: 15.7 CC-3-V1 10.00% K.sub.3/K.sub.1 [20 C.]: 1.22 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
are added two different reactive mesogens with different reactivity:

(13) ##STR00316##

(14) According to Example M1 the mixture is introduced in to a cell and the PS-VA process is applied.

Example M5

(15) To the following host mixture H1

(16) TABLE-US-00010 CY-3-O2 15.00% Clearing point [ C.]: 74.7 CY-5-O2 6.50% n [589 nm, 20 C.]: 0.1082 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.3 [pN, 20 C.]: 15.7 CC-3-V1 10.00% K.sub.3/K.sub.1 [20 C.]: 1.22 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
are added two different reactive mesogens with different reactivity:

(17) ##STR00317##

(18) According to Example M1 the mixture is introduced in to a cell and the PS-VA process is applied.

Example M6

(19) To the following host mixture H1

(20) TABLE-US-00011 CY-3-O2 15.00% Clearing point [ C.]: 74.7 CY-5-O2 6.50% n [589 nm, 20 C.]: 0.1082 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.3 [pN, 20 C.]: 15.7 CC-3-V1 10.00% K.sub.3/K.sub.1 [20 C.]: 1.22 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
are added two different reactive mesogens with different reactivity:

(21) ##STR00318##

(22) According to Example M1 the mixture is introduced in to a cell and the PS-VA process is applied.