Liquid-crystalline medium and high-frequency components comprising same

Abstract

The present invention relates to liquid-crystalline media comprising one or more polymerisable compounds, preferably of formula P
P.sup.a-(Sp.sup.a).sub.s1-(A.sup.1-Z.sup.1).sub.n1-A.sup.2-Q-A.sup.3-(Z.sup.4-A.sup.4).sub.n2-(Sp.sup.b).sub.s2-P.sup.bP
and one or more compounds selected from the group of compounds of formulae I, II, and III, ##STR00001##
in which the parameters have the meaning indicated in Claim 1, and to components comprising these media for high-frequency technology, in particular phase shifters and microwave array antennas.

Claims

1. A liquid-crystal medium, comprising one or more polymerisable compounds of formula P
P.sup.a-(Sp.sup.a).sub.s1-(A.sup.1-Z.sup.1).sub.n1-A.sup.2-Q-A.sup.3-(Z.sup.4-A.sup.4).sub.n2-(Sp.sup.b).sub.s2-P.sup.bP wherein P.sup.a, P.sup.b each, independently of one another, are a polymerisable group, Sp.sup.a, Sp.sup.b each, independently of one another, denote a spacer group, s1, s2 each, independently of one another, denote 0 or 1, n1, n2 each, independently of one another, denote 0 or 1, Q denotes a single bond, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, (CO)O, O(CO), (CH.sub.2).sub.4, CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CHCH, CFCF, CFCH, (CH.sub.2).sub.3O, O(CH.sub.2).sub.3, CHCF, CC, O, CH.sub.2, (CH.sub.2).sub.3, or CF.sub.2, Z.sup.1, Z.sup.4 independently of one another, denote a single bond, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2, (CO)O, O(CO), (CH.sub.2).sub.4, CH.sub.2CH.sub.2, CF.sub.2CF.sub.2, CF.sub.2CH.sub.2, CH.sub.2CF.sub.2, CHCH, CFCF, CFCH, (CH.sub.2).sub.3O, O(CH.sub.2).sub.3, CHCF, CC, O, CH.sub.2, (CH.sub.2).sub.3, or CF.sub.2, where Z.sup.1 and Q or Z.sup.4 and Q do not simultaneously denote a group selected from CF.sub.2O and OCF.sub.2, A.sup.1, A.sup.2, A.sup.3, A.sup.4, each, independently of one another, denote a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-bicyclohexylene, in which one or more non-adjacent CH.sub.2 groups are optionally replaced by O and/or S and in which one or more H atoms are optionally replaced by F, b) 1,4-phenylene or 1,3-phenylene, in which one or two CH groups are optionally replaced by N and in which one or more H atoms are optionally replaced by L, c) 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 or selenophene-2,5-diyl, each of which is optionally mono- or polysubstituted by L, d) saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which are optionally replaced by heteroatoms, and A.sup.3, alternatively may be 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, and one or more compounds of formulae I, II or III ##STR00194## in which L.sup.11 denotes R.sup.11 or X.sup.11, L.sup.12 denotes R.sup.12 or X.sup.12, R.sup.11 and R.sup.12, independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 15 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, X.sup.11 and X.sup.12, independently of one another, denote H, F, Cl, CN, NCS, SF.sub.5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms, and ##STR00195## independently of one another, denote ##STR00196## in which L.sup.21 denotes R.sup.21 and, in the case where Z.sup.21 and/or Z.sup.22 denote trans-CHCH or trans-CFCF, alternatively denotes X.sup.21, L.sup.22 denotes R.sup.22 and, in the case where Z.sup.21 and/or Z.sup.22 denote trans-CHCH or trans-CFCF, alternatively denotes X.sup.22, R.sup.21 and R.sup.22, independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17, or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15, X.sup.21 and X.sup.22, independently of one another, denote F, Cl, CN, NCS, SF.sub.5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, one of Z.sup.21 and Z.sup.22 denotes trans-CHCH, trans-CFCF or CC and the other, independently thereof, denotes trans-CHCH, trans-CFCF or a single bond, and ##STR00197## independently of one another, denote ##STR00198## in which L.sup.31 denotes R.sup.31 or X.sup.31, L.sup.32 denotes R.sup.32 or X.sup.32, R.sup.31 and R.sup.32, independently of one another, denote H, unfluorinated alkyl or unfluorinated alkoxy having 1 to 17 C atoms or unfluorinated alkenyl, unfluorinated alkenyloxy or unfluorinated alkoxyalkyl having 2 to 15 C atoms, X.sup.31 and X.sup.32, independently of one another, denote H, F, Cl, CN, NCS, SF.sub.5, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms or fluorinated alkenyl, unfluorinated or fluorinated alkenyloxy or unfluorinated or fluorinated alkoxyalkyl having 2 to 7 C atoms, Z.sup.31 to Z.sup.33, independently of one another, denote trans-CHCH, trans CFCF, CC or a single bond, and ##STR00199## independently of one another, denote ##STR00200## and wherein the liquid-crystal medium has a clearing point of 90 C. or more.

2. The liquid-crystal medium according to claim 1, which comprises one or more mono-reactive polymerisable compounds and/or one or more direactive polymerisable compounds.

3. The liquid-crystal medium according to claim 2, which comprises one or more mono-reactive polymerisable compounds which are methacrylates and/or one or more direactive polymerisable compounds which are bisacrylates or mixed acrylate methacrylates.

4. The liquid-crystal medium according to claim 1, which comprises one or more compounds of formula I.

5. The liquid-crystal medium according to claim 1, which comprises one or more compounds of formula II.

6. The liquid-crystal medium according to claim 1, which comprises one or more compounds of formula III.

7. The liquid-crystal medium according to claim 1, which additionally comprises a polymerisation initiator which is a UV- or thermo initiator.

8. A method for stabilizing the liquid-crystal medium according to claim 1, comprising polymerising the polymerisable compounds therein.

9. A composite system comprising a polymer obtained or obtainable from the polymerisation of the polymerisable compounds in the liquid-crystal medium according to claim 1.

10. A component for high-frequency technology, which comprises the liquid-crystal medium according to claim 1 or a composite system comprising a polymer obtained or obtainable from the polymerisation of the polymerisable compounds in said liquid-crystal medium.

11. The component according to claim 10, which is suitable for operation in the microwave range.

12. The component according to claim 10, which is a phase shifter or a LC based antenna element operable in the microwave region.

13. A process for preparing the liquid-crystal medium according to claim 1, comprising mixing one or more polymerisable compounds of formula P with one or more mesogenic compounds of formulae I, II or III, and optionally with one or more further compounds and/or with one or more additives.

14. A microwave antenna array, comprising one or more components according to claim 10.

15. The liquid-crystal medium according to claim 1, wherein A.sup.1, A.sup.2, A.sup.3, A.sup.4, each, independently of one another, denote a) trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-bicyclohexylene, in which one or more non-adjacent CH.sub.2 groups are optionally replaced by O and/or S and in which one or more H atoms are optionally replaced by F, b) 1,4-phenylene or 1,3-phenylene, in which one or two CH groups are optionally replaced by N and in which one or more H atoms are optionally replaced by L, c) 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 or selenophene-2,5-diyl, each of which is optionally mono- or polysubstituted by L d) bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, ##STR00201## in which one or more H atoms are optionally replaced by L, and/or one or more double bonds are optionally replaced by single bonds, and/or one or more CH groups are optionally replaced by N, 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.03, R.sup.04 each, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which one or more H atoms are optionally replaced by F, M denotes O, S, CH.sub.2, CHY.sup.1 or CY.sup.1Y.sup.2, and Y.sup.1 and Y.sup.2 each, independently of one another, denote H, F, Cl, CN or CF.sub.3, and one of the groups Y.sup.1 and Y.sup.2 alternatively denotes OCF.sub.3, and A.sup.3 alternatively may be a single bond.

16. The liquid-crystal medium according to claim 1, wherein the compound of formula I is a compound of one of the following formulae ##STR00202## in which ##STR00203## have the meanings given for the compound of formula I, R.sup.11 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms, R.sup.12 denotes unfluorinated alkyl having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms or unfluorinated alkoxy having 1 to 7 C atoms, X.sup.11 and X.sup.12 independently of one another, denote F, Cl, OCF.sub.3, CF.sub.3, CN, NCS or SF.sub.5.

17. The liquid-crystal medium according to claim 1, wherein the compound of formula II is a compound of one of the following formulae ##STR00204## in which Z.sup.21 and Z.sup.22 denote trans-CHCH or trans-CFCF, R.sup.21 and R.sup.22 independently of one another, denote H, unfluorinated alkyl or alkoxy having 1 to 7 C atoms or unfluorinated alkenyl having 2 to 7 C atoms, X.sup.22 denotes F, Cl, CN or NCS, and one of ##STR00205## denotes ##STR00206## and the others, independently of one another, denote ##STR00207##

18. The liquid-crystal medium according to claim 1, wherein the compound of formula III is a compound of one of the following formulae ##STR00208## wherein Y.sup.31 and Y.sup.32 denotes H or F, R.sup.31 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms, R.sup.32 denotes unfluorinated alkyl or alkoxy, each having 1 to 7 C atoms, or unfluorinated alkenyl having 2 to 7 C atoms, and X.sup.32 denotes F, Cl, or OCF.sub.3.

19. The liquid-crystal medium according to claim 1, wherein the compound of formula P is a compound of one of the following formulae ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## wherein 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 denotes 0, 1, 2, 3 or 4, s denotes 0, 1, 2 or 3, and n denotes an integer between 1 and 24.

20. The liquid-crystal medium according to claim 1, wherein the compound of formula P is a compound of one of the following formulae ##STR00215## ##STR00216## ##STR00217## wherein P.sup.a, P.sup.b, Sp.sup.a, Sp.sup.b, s1 and s2 are as defined for the compound of formula P.

21. The liquid-crystal medium according to claim 1, which has a clearing point of 120 C. or more.

Description

EXAMPLES

(1) The following examples illustrate the present invention without limiting it in any way.

(2) However, it is clear to the person skilled in the art from the physical properties what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties which can preferably be achieved is thus well defined for the person skilled in the art.

Examples 1.1 to 1.3 and Comparative Example 1

Comparative Example 1

(3) A liquid-crystal mixture C-1 having the composition and properties as indicated in the following table is prepared and characterized with respect to its general physical properties and its applicability in microwave components at 19 GHz.

(4) TABLE-US-00007 Composition Compound Conc./ No. Abbreviation mass-% 1 PPTUI-3-2 20.0 2 PPTUI-3-4 36.0 3 GGP-3-CL 10.0 4 GGP-5-CL 20.0 5 CPGP-5-2 7.0 6 CPGP-5-3 7.0 100.0 Physical Properties T(N, I) = 173 C. n(20 C., 589.3 nm) = 0.335 (20 C., 1 kHz) = 4.6 .sub.1 (20 C.) = 746 mPa .Math. s tan .sub. r, (20 C., 19 GHz) = 0.0143 tan .sub. r, (20 C., 19 GHz) = 0.0038 (20 C., 19 GHz) = 0.252 (20 C., 19 GHz) = 17.6

Examples 1.1 to 1.3

(5) The mixture C-1 is divided into three parts. To each one of these three parts

(6) a) 0.2% of the photo initiator IrgaCure 819

(7) ##STR00190##
b) a certain concentration alternatively of one of the two reactive mesogenic compounds of the formulae RM-1

(8) ##STR00191##
and RM-2

(9) ##STR00192##
and
c) a certain concentration of the reactive mesogen of the formula RM-C

(10) ##STR00193##
respectively, are added.

(11) To one each of these three parts alternatively 1.67% of RM-1 and 3.33% of RM-2, 2.50% of RM-1 and 5.00% of RM-2, respectively 3.33% of RM-1 and 6.67% of RM-2, are added.

(12) The three resultant mixtures are called M-1.1 to M-1.3. These three mixtures each are filled into test cells with antiparallel rubbed glas substrates covered by PI AI3046. The test cells have a cell gap of 50 m and the polymer precursor is polymerised under UV irradiation (Dymax 3.3 mW/cm.sup.2 using a long pass filter (380 nm, Schott GG380). The irradiation time is 3 min.

(13) The filled test cells are then investigated with respect to the physical properties of the systems comprising of the liquid crystalline media and the polymerisation product of the reactive monomers.

(14) TABLE-US-00008 TABLE 1 Compositions of the mixtures investigated Material C-1 RM-1 PM-C IRG-819 Example Mixture Composition Number Concentration/mass-% C-1 100.0 0.00 0.00 0.00 1.1 95.0 1.67 3.33 0.20 1.2 92.5 2.5 5.00 0.20 1.3 90.0 3.33 6.67 0.20

(15) TABLE-US-00009 TABLE 2 Physical Properties (at 20 C.) of the mixtures investigated prior to polymerisation Mixture C-1 M-1.1 M-1.2 M-1.3 Propertye Value T(N, I)/ C. 173 t.b.d. t.b.d. t.b.d. (1 kHz) 4.51 4.05 3.94 3.71 k.sub.1/pN 17.2 16.1 15.7 14.2 k.sub.3/pN 39.9 35.2 36.5 36.4 V.sub.0/V 2.06 2.11 2.11 2.07 V.sub.0 in 50 um test cell, described above.

(16) TABLE-US-00010 TABLE 3 Physical Properties (at 20 C.) of the mixtures investigated after polymerisation Mixture C-1 M-1.1 M-1.2 M-1.3 Propertye Value T(N, I)/ C. n.a. t.b.d. t.b.d. t.b.d. (1 kHz) n.a. t.b.d. t.b.d. t.b.d. k.sub.1/pN n.a. t.b.d. t.b.d. t.b.d. k.sub.3/pN n.a. t.b.d. t.b.d. t.b.d. V.sub.0/V n.a. t.b.d. t.b.d. t.b.d. Remarks: t.b.d.: to be determined n.a.: not applicable

(17) The liquid crystalline materials showed significantly improved (i.e. shorter) response times after polymerisation of the polymer precursor.

Example 2

(18) A liquid-crystal mixture M-2 having the composition and properties as indicated in the following table is prepared.

(19) TABLE-US-00011 Composition Compound No. Abbreviation 1 GGP-5-CL 26.0 2 PGIGI-3-CL 8.0 3 PGIGI-5-CL 20.0 4 PGIGI-5-F 9.0 5 PPTY-3-4 3.0 6 PYGP-3-5 5.0 7 PYGP-5-3 5.0 8 CGPC-3-5 3.0 9 CGPC-5-5 5.0 10 CPGP-5-2 8.0 11 CPGP-5-3 8.0 100.0 Physical properties T(N, I) = 171 C. n.sub.e (20 C., 589.3 nm) = 1.7859 n (20 C., 589.3 nm) = 0.2954 .sub. (20 C., 1 kHz) = 6.4 (20 C., 1 kHz) = 2.0 .sub.1 (20 C.) = 650 mPa .Math. s

(20) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

(21) TABLE-US-00012 TABLE 4 Properties of mixture M-2 at 19 GHz T/ C. .sub.r, .sub.r,|| tan .sub.r, tan .sub.r,|| .sub.r 11.27 2.40 2.97 0.0109 0.0026 0.19 17.45 29.71 2.41 2.97 0.0159 0.0037 0.19 11.70 58.28 2.41 2.97 0.0252 0.0061 0.18 7.07 87.50 2.40 2.89 0.0372 0.0097 0.17 4.51 Note: at 20 C., the following is obtained approximately by intrapolation: .sub.r = 0.56, tan .sub.r, = 0.013 and = 14.5.

(22) For comparison, the compound 4-pentyl-4-cyanobiphenyl (also called 5CB or K15, Merck KGaA) gives tan .sub..sub.r,=0.026 and =4.3 at 20 C.

(23) TABLE-US-00013 TABLE 5 Comparison of the properties at 19 GHz and 20 C. Example Liquid crystal .sub.r .sub. r, 1 M-1 0.56 0.013 14.5 2 M-2 0.56 0.014 15 Comparison 5CB 0.026 4.3

Example 3

(24) A liquid-crystal mixture M-3 having the composition and properties as indicated in the following table is prepared.

(25) TABLE-US-00014 Composition Compound No. Abbreviation 1 GGP-5-CL 26.0 2 PGIGI-3-CL 8.0 3 PGIGI-5-CL 20.0 4 PGIGI-5-F 5.0 5 PPTY-3-4 3.0 6 PYGP-4-4 4.0 7 PYGP-5-3 5.0 8 CCZPC-3-5 3.0 9 CGPC-3-5 3.0 10 CGPC-5-5 5.0 11 CPGP-5-2 8.0 12 CPGP-5-3 8.0 100.0 Physical properties T(N, I) = 179.5 C. n.sub.e (20 C., 589.3 nm) = 1.7861 n (20 C., 589.3 nm) = 0.3118

(26) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

(27) TABLE-US-00015 TABLE 6 Properties of mixture M-3 at 19 GHz T/ C. .sub.r, .sub.r,|| tan .sub.r, tan .sub.r,|| .sub.r FoM 11.49 2.41 2.98 0.0108 0.0028 0.19 17.77 20.29 2.42 2.98 0.0130 0.0033 0.19 14.50 25.02 2.42 2.97 0.0143 0.0035 0.19 13.08 29.80 2.42 2.97 0.0155 0.0038 0.19 11.99 34.55 2.42 2.96 0.0169 0.0041 0.18 10.95 58.29 2.41 2.93 0.0246 0.0062 0.18 7.20 77.56 2.40 2.90 0.0319 0.0087 0.17 5.36 97.57 2.40 2.86 0.0406 0.0116 0.16 4.00 Note: at 20 C., the following is obtained approximately by intrapolation: .sub.r = 0.56, tan .sub.r, = 0.014 and = 15.

Example 4

(28) A liquid-crystal mixture M-4 having the composition and properties as indicated in the following table is prepared.

(29) TABLE-US-00016 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-5-CL 20.0 3 PPTUI-3-2 20.0 4 PPTUI-3-4 20.0 5 PPTUI-4-4 16.0 6 CPGP-5-2 7.0 7 CPGP-5-3 7.0 100.0 Physical properties T(N, I) = 170.1 C. n.sub.e (20 C., 589.3 nm) = 1.5267 n (20 C., 589.3 nm) = 0.2918 .sub. (20 C., 1 kHz) = 7.8 (20 C., 1 kHz) = 4.4 .sub.1 (20 C.) = 698 mPa .Math. s

(30) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 5

(31) A liquid-crystal mixture M-5 having the composition and properties as indicated in the following table is prepared.

(32) TABLE-US-00017 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-5-CL 19.0 3 PPTUI-3-2 18.0 4 PPTUI-3-4 18.0 5 PPTUI-4-4 10.0 6 PGIGP-3-5 6.00 7 PPGU-3-F 3.00 8 CPGP-5-2 8.0 9 CPGP-5-3 8.0 100.0 Physical properties T(N, I) = 183.5 C. n (20 C., 589.3 nm) = 0.283 .sub. (20 C., 1 kHz) = 8.0 (20 C., 1 kHz) = 3.5 .sub.1 (20 C.) = 753 mPa .Math. s

(33) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters.

Example 6

(34) A liquid-crystal mixture M-6 having the composition and properties as indicated in the following table is prepared.

(35) TABLE-US-00018 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-5-CL 17.0 3 PPTUI-3-2 13.0 4 PPTUI-3-4 13.0 5 PPTUI-4-4 10.0 6 PPGU-3-F 3.0 7 PPGU-4-F 3.0 8 PPGU-V2-F 3.0 9 PGIGP-3-5 7.0 10 PGIGP-5-5 7.0 11 CPGP-5-2 7.0 12 CPGP-5-3 7.0 100.0 Physical properties

(36) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 7

(37) A liquid-crystal mixture M-7 having the composition and properties as indicated in the following table is prepared.

(38) TABLE-US-00019 Composition Compound No. Abbreviation 1 GGP-5-CL 17.0 2 PPTUI-3-2 20.0 3 PPTUI-3-4 20.0 4 PPTUI-4-4 10.0 5 PPGU-3-F 3.0 6 PPGU-4-F 3.0 7 PPGU-V2-F 3.0 8 PGIGP-3-4 5.0 9 PGIGP-3-5 5.0 10 CPGP-5-2 7.0 11 CPGP-5-3 7.0 100.0 Physical properties T(N, I) = 198.0 C. .sub. (20 C., 1 kHz) = 7.7 (20 C., 1 kHz) = 3.5

(39) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 8

(40) A liquid-crystal mixture M-8 having the composition and properties as indicated in the following table is prepared.

(41) TABLE-US-00020 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-5-CL 20.0 3 PPTUI-3-2 15.0 4 PPTUI-3-4 20.0 5 PPGU-3-F 3.0 6 PPGU-4-F 3.0 7 PPGU-V2-F 3.0 8 PGIGP-3-4 5.0 9 PGIGP-3-5 5.0 10 CPGP-5-2 8.0 11 CPGP-5-3 8.0 100.0 Physical properties T(N, I) = 193.0 C. .sub. (20 C., 1 kHz) = 8.7 (20 C., 1 kHz) = 3.5

(42) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 9

(43) A liquid-crystal mixture M-9 having the composition and properties as indicated in the following table is prepared.

(44) TABLE-US-00021 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-5-CL 19.0 3 PPTUI-3-2 18.0 4 PPTUI-3-4 18.0 5 PPTUI-4-4 10.0 6 PPGU-3-F 2.0 7 PPGU-4-F 2.0 8 PPGU-V2-F 2.0 9 PGIGP-3-5 5.0 10 CPGP-5-2 7.0 11 CPGP-5-3 7.0 100.0 Physical properties

(45) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 10

(46) A liquid-crystal mixture M-10 having the composition and properties as indicated in the following table is prepared.

(47) TABLE-US-00022 Composition Compound No. Abbreviation 1 PGP-2-5 10.0 2 PGP-3-4 10.0 3 PGP-3-7 15.0 4 PGP-2-2V 5.0 5 PYP-2-2V 10.0 6 PYP-2-4 10.0 7 PYP-2-5 20.0 8 PYP-3-5 15.0 9 PGIGP-3-5 5.0 100.0 Physical properties

(48) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 11

(49) A liquid-crystal mixture M-11 having the composition and properties as indicated in the following table is prepared.

(50) TABLE-US-00023 Composition Compound No. Abbreviation 1 GGP-3-F 10.0 2 GGP-5-F 10.0 3 GGP-3-CL 10.0 4 GGP-4-CL 20.0 5 GGP-5-CL 20.0 6 GGP-6-CL 10.0 7 GGPP-5-3 5.0 8 PGGP-3-5 5.0 9 PGGP-3-6 5.0 10 PGGP-5-3 5.0 100.0 Physical properties T(N, I) = 134.5 C. n.sub.e (20 C., 589.3 nm) = 1.8036 n (20 C., 589.3 nm) = 0.2774 .sub. (20 C., 1 kHz) = 15.2 (20 C., 1 kHz) = 10.2 .sub.1 (20 C.) = 758 mPa .Math. s

(51) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 12

(52) A liquid-crystal mixture M-12 having the composition and properties as indicated in the following table is prepared.

(53) TABLE-US-00024 Composition Compound No. Abbreviation 1 GGP-3-F 5.0 2 GGP-3-CL 10.0 3 GGP-4-CL 10.0 4 GGP-5-CL 15.0 5 GGP-5-3 20.0 6 PGP-2-5 10.0 7 PGP-3-7 15.0 8 PGP-2-2V 10.0 9 PGGP-3-5 5.0 100.0 Physical properties n.sub.e (20 C., 589.3 nm) = 1.7885 n (20 C., 589.3 nm) = 0.2640 .sub. (20 C., 1 kHz) = 8.8 (20 C., 1 kHz) = 4.7 .sub.1 (20 C.) = 660 mPa .Math. s

(54) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 13

(55) A liquid-crystal mixture M-13 having the composition and properties as indicated in the following table is prepared.

(56) TABLE-US-00025 Composition Compound No. Abbreviation 1 GGP-3-CL 10.0 2 GGP-4-CL 20.0 3 GGP-5-CL 20.0 4 GGP-6-CL 10.0 5 GGP-5-3 25.0 6 PGGP-3-5 5.0 7 PGGP-3-6 5.0 8 PGGP-5-3 5.0 100.0 Physical properties T(N, I) = 124.5 C. n.sub.e (20 C., 589.3 nm) = 1.7951 n (20 C., 589.3 nm) = 0.2709 .sub. (20 C., 1 kHz) = 11.6 (20 C., 1 kHz) = 6.8 .sub.1 (20 C.) = 895 mPa .Math. s

(57) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

Example 14 a

(58) A liquid-crystal mixture M-14 a having the composition and properties as indicated in the following table is prepared.

(59) TABLE-US-00026 Composition Compound No. Abbreviation 1 GGP-3-CL 5.0 2 GGP-5-CL 19.0 3 PGU-7-F 2.0 4 PPTUI-3-2 18.0 5 PPTUI-3-4 18.0 6 PPTUI-4-4 10.0 7 PPGU-7-F 2.0 8 PGIGP-3-5 6.0 9 DPGU-3-F 2.0 10 DPGU-3-OT 2.0 11 CPGP-5-2 8.0 12 CPGP-5-3 8.0 100.0 Physical properties T(N, I) = 184.5 C.

(60) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters or LC based antenna elements in MW region.

(61) TABLE-US-00027 TABLE 4 Properties of mixture M-14 at 30 GHz T/ C. .sub.r, .sub.r,|| tan .sub.r, tan .sub.r,|| .sub.r 9.47 2.51 2.92 0.0094 0.0035 0.140 15.0 19.67 2.51 2.92 0.0115 0.0041 0.139 12.1 30.07 2.49 2.94 0.0135 0.0046 0.152 11.2 40.52 2.44 2.96 0.0169 0.0046 0.175 10.3 50.17 2.36 2.96 0.0214 0.0050 0.204 9.48 59.99 2.34 2.94 0.0246 0.0056 0.204 8.24 70.41 2.34 2.93 0.0276 0.0061 0.199 7.22 79.74 2.35 2.91 0.0291 0.0067 0.195 6.69 84.52 2.35 2.91 0.0295 0.0071 0.192 6.51 Note: at 20 C., the following is obtained approximately by intrapolation: .sub.r, = 2.51, tan .sub.r, = 0.0115, = 0.140 and = 14.5.

Example 14 b

(62) A liquid-crystal mixture M-14 b having the composition and properties as indicated in the following table is prepared.

(63) TABLE-US-00028 Composition Compound No. Abbreviation 1 GGP-5-CL 20.0 2 PGU-3-CL 2.0 3 PGU-4-OT 2.0 4 PGP-F-OT 3.0 5 PPTUI-3-2 13.0 6 PPTUI-3-4 15.0 7 PPTUI-4-4 20.0 8 PPGU-7-F 2.0 9 PGIGP-3-5 6.0 10 CPTP-3-2 3.0 11 DPGU-3-F 2.0 12 DPGU-3-OT 2.0 13 CPGP-5-2 4.0 14 CPGP-5-3 6.0 100.0 Physical properties T(N, I) = 175.5 C.

(64) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters.

Example 15

(65) A liquid-crystal mixture M-15 having the composition and properties as indicated in the following table is prepared.

(66) TABLE-US-00029 Composition Compound No. Abbreviation 1 GGP-5-CL 10.0 2 GGP-6-CL 5.0 3 PGP-3-2V 3.0 4 PGP-2-2V 3.0 5 PPTUI-3-2 15.0 6 PPTUI-3-4 18.0 7 PPTUI-4-4 21.0 8 PPGU-7-F 2.0 9 PPGU-V2-F 2.0 10 PGIGP-3-5 7.0 11 CPTP-3-2 4.0 12 CPGU-3-OT 2.0 13 CPGU-4-OT 2.0 14 DPGU-3-OT 2.0 15 CPGP-5-2 4.0 100.0 Physical properties T(N, I) = 178 C.

(67) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters.

Example 16

(68) A liquid-crystal mixture M-16 having the composition and properties as indicated in the following table is prepared.

(69) TABLE-US-00030 Composition Compound No. Abbreviation 1 GGP-5-CL 20.0 2 GGP-5-3 12.0 3 PPTUI-3-2 12.0 4 PPTUI-3-4 16.0 5 PPTUI-4-4 20.0 6 PGUQU-5-F 5.0 7 PGGP-3-5 5.0 8 PGGP-3-6 4.0 9 APGP-3-3 3.0 10 APGP-3-4 3.0 100.0 Physical properties T(N, I) = 159.5 C. .sub. (20 C., 1 kHz) = 7.9 (20 C., 1 kHz) = 4.3 .sub.1 (20 C.) = 686 mPa .Math. s

(70) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters.

Example 17

(71) A liquid-crystal mixture M-17 having the composition and properties as indicated in the following table is prepared.

(72) TABLE-US-00031 Composition Compound No. Abbreviation 1 GGP-5-3 10.0 2 PPTUI-3-F 8.0 3 PPTUI-4-F 8.0 4 PPTUI-3-2 12.0 5 PPTUI-3-4 16.0 6 PPTUI-4-4 20.0 7 PPTUI-3-A4 5.0 8 PGUQU-5-F 7.0 9 PGGP-3-5 4.0 10 PGGP-3-6 4.0 11 APGP-3-3 3.0 12 APGP-3-4 3.0 100.0 Physical properties T(N, I) = 169 C.

(73) This mixture is very highly suitable for applications in the microwave range, in particular for phase shifters.

(74) The mixtures of examples 2 to 17 are treated and investigated as described under example 1. The resultant composite systems comprising the polymerised polymer porecursors show comparably good properties. They are characterized in particular by improved response times.