Polymerizable compound having conjugated bonds, liquid crystal composition and liquid crystal display device

Abstract

Subject It is to provide a polymerizable compound having a high polymerization reactivity, a high conversion yield and a high solubility in a liquid crystal composition, a polymerizable composition including this compound, a liquid crystal composite prepared from this polymerizable composition and a liquid crystal display device containing this composite. Means for solving the Subject A compound represented by formula (1), the liquid crystal composition and the liquid crystal display device. ##STR00001##
In the formula, for example, ring A.sup.1, ring A.sup.2 and ring A.sup.4 are phenylene or cyclohexylene; Sp.sup.1 and Sp.sup.2 are a single bond or alkylene having 1 to 6 carbons; Z.sup.1 and Z.sup.2 are CHCH or CC; a is 1, b is 0; and P.sup.1 and P.sup.2 are a polymerizable group.

Claims

1. A polymerizable composition including at least one compound selected from the group of compounds represented by formula (1) and at least one compound selected from the group of compounds represented by formula (2) to formula (4): ##STR00140## in formula (1), P.sup.1 and P.sup.2 are independently a polymerizable group; Sp.sup.1 and Sp.sup.2 are independently a single bond or alkylene having 1 to 6 carbons, and in this alkylene at least one CH.sub.2 may be replaced by O, COO or OCO, and at least one CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in these groups at least one hydrogen may be replaced by fluorine; ring A.sup.1, ring A.sup.2, and ring A.sup.4 are independently a divalent group derived from benzene, naphthalene, anthracene, pyrimidine or pyridine, and in this divalent group at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by halogen or -Sp.sup.3-P.sup.3, where the definition of P.sup.3 is the same as that of P.sup.1 and P.sup.2 and the definition of Sp.sup.3 is the same as that of Sp.sup.1 and Sp.sup.2, and ring A.sup.2 may be independently a divalent group derived from cyclohexane, cyclohexene, tetrahydropyran or dioxane; Z.sup.1 and Z.sup.2 are independently CHCH or CC; and a is 1, and b is; and then ##STR00141## in formula (2) to formula (4), R.sup.11 and R.sup.12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; ring B.sup.1, ring B.sup.2, ring B.sup.3 and ring B.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; and Z.sup.11, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC or COO.

2. The polymerizable composition according to claim 1, further including at least one compound selected from the group of compounds represented by formula (5) to formula (7): ##STR00142## in formula (5) to formula (7), R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3; ring C.sup.1, ring C.sup.2 and ring C.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.14, Z.sup.15 and Z.sup.16 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC, COO, CF.sub.2O, OCF.sub.2, CH.sub.2O or (CH.sub.2).sub.4; and L.sup.11 and L.sup.12 are independently hydrogen or fluorine.

3. The polymerizable composition according to claim 1, further including at least one compound selected from the group of compounds represented by formula (8): ##STR00143## in formula (8), R.sup.14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; X.sup.12 is CN or CCCN; ring D.sup.1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.17 is a single bond, CH.sub.2CH.sub.2, CC, COO, CF.sub.2O, OCF.sub.2 or CH.sub.2O; L.sup.13 and L.sup.14 are independently hydrogen or fluorine; and i is 1, 2, 3 or 4.

4. The polymerizable composition according to claim 1, further including at least one compound selected from the group of compounds represented by formula (9) to formula (15): ##STR00144## in formula (9) to formula (15), R.sup.15 and R.sup.16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; R.sup.17 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl at least one CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; ring E.sup.1, ring E.sup.2, ring E.sup.3 and ring E.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; ring E.sup.5 and ring E.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z.sup.18, Z.sup.19, Z.sup.20 and Z.sup.21 are independently a single bond, CH.sub.2CH.sub.2, COO, CH.sub.2O, OCF.sub.2 or OCF.sub.2CH.sub.2CH.sub.2; L.sup.15 and L.sup.16 are independently fluorine or chlorine; S.sup.11 is hydrogen or methyl; X is CHF or CF.sub.2; and j, k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 1 or 2, the sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

5. A liquid crystal composite formed by the polymerization of the polymerizable composition according to claim 1.

6. A liquid crystal display device containing the polymerizable composition according to claim 1.

7. A compound represented by any one of formula (1-1) to formula (1-6): ##STR00145## in formula (1-1) to formula (1-6), P.sup.1 and P.sup.2 are independently a polymerizable group; Sp.sup.1 and Sp.sup.2 are independently a single bond, CH.sub.2O, OCH.sub.2, COO, OCO, CHCH, CC, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2, CHCHO or OCHCH; ring A.sup.1 and ring A.sup.4 are independently a divalent group derived from benzene, pyrimidine or pyridine; ring A.sup.2 is independently a divalent group derived from benzene, pyrimidine, pyridine, cyclohexane, cyclohexene, tetrahydropyran or dioxane; and in the divalent groups derived from benzene, pyrimidine or pyridine at least one hydrogen may be replaced by halogen, alkyl having 1 carbon, alkyl having 1 carbon in which at least one hydrogen has been replaced by halogen or -Sp.sup.3-P.sup.3, where the definition of P.sup.3 is the same as that of P.sup.1 and P.sup.2 and the definition of Sp.sup.3 is the same as that of Sp.sup.1 and Sp.sup.2; Z.sup.1 and Z.sup.2 are independently CHCH or CC; and ; a is 1, and b is 0.

8. The compound according to claim 7, wherein in formula (1-1) to formula (1-6), P.sup.1 is OCO-(M.sup.1)CCH(M.sup.2), vinyloxy or oxiranyl, and P.sup.2 is OCO-(M.sup.3)CCH(M.sup.4), vinyloxy or oxiranyl, where M.sup.1, M.sup.2, M.sup.3 and M.sup.4 are independently hydrogen, fluorine, methyl or trifluoromethyl; Sp.sup.1 and Sp.sup.2 are independently a single bond, CH.sub.2O, OCH.sub.2, COO, OCO, CHCH, CC, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2, CHCHO or OCHCH; ring A.sup.1 and ring A.sup.4 are independently a divalent group derived from benzene; ring A.sup.2 is independently a divalent group derived from benzene, pyrimidine, pyridine, cyclohexane, tetrahydropyran or dioxane; and in the divalent group derived from benzene at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 carbon or alkyl having 1 carbon in which at least one hydrogen has been replaced by fluorine; Z.sup.1 and Z.sup.2 are independently CHCH or CC; -; and a is 1, and b is 0.

9. The compound according to claim 7, wherein in formula (1-1) to formula (1-6), P.sup.1 is OCO-(M.sup.1)CCH(M.sup.2), and P.sup.2 is OCO-(M.sup.3)CCH(M.sup.4), where M.sup.1 and M.sup.3 are independently hydrogen or methyl, M.sup.2 and M.sup.4 are hydrogen; Sp.sup.1 and Sp.sup.2 are independently a single bond; ring A.sup.1, ring A.sup.2, and ring A.sup.4 are independently a divalent group derived from benzene, and in this divalent group one or two hydrogens may be replaced by fluorine, chlorine, methyl, difluoromethyl or trifluoromethyl; Z.sup.1 and Z.sup.2 are independently CHCH or CC; and a is 1, and b is 0.

10. A compound represented by either formula (1-11) or (1-12) ##STR00146## wherein in formula (1-11) or formula (1-12), P.sup.4 is OCO-(M.sup.5)CCH.sub.2 and P.sup.5 is OCO-(M.sup.6)CCH.sub.2, where M.sup.5 and M.sup.6 are independently hydrogen, fluorine, methyl or trifluoromethyl; Sp.sup.4 and Sp.sup.5 are independently a single bond, CH.sub.2O, OCH.sub.2, COO, OCO, CHCH, CC, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2, CHCHO or OCHCH; ring A.sup.5, ring A.sup.6, ring A.sup.7 and ring A.sup.8 are independently 1,4-phenylene, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in this divalent group at least one hydrogen may be replaced by fluorine, methyl, difluoromethyl or trifluoromethyl; ring A.sup.6 and ring A.sup.7 may be independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl; and Z.sup.4, Z.sup.5 and Z.sup.6 are independently CHCH or CC.

11. The compound according to claim 10, wherein in formula (1-11) or formula (1-12), P.sup.1 is OCO-(M.sup.5)CCH.sub.2 and P.sup.2 is OCO-(M.sup.6)CCH.sub.2, where M.sup.5 and M.sup.6 are independently hydrogen or methyl; Sp.sup.4 and Sp.sup.5 are independently a single bond, CH.sub.2O, OCH.sub.2, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2, CHCHO or OCHCH; ring A.sup.5, ring A.sup.6, ring A.sup.7 and ring A.sup.8 are independently 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2-difluoromethyl-1,4-phenylene or 2-trifluoromethyl-1,4-phenylene; and Z.sup.4, Z.sup.5 and Z.sup.6 are independently CHCH or CC.

12. A compound represented by either formula (1-111) or (1-112): ##STR00147## wherein in formula (1-111) or formula (1-112), P.sup.6 and P.sup.7 are independently OCOHCCH.sub.2 or OCO(CH.sub.3)CCH.sub.2; Sp.sup.6 and Sp.sup.7 are independently a single bond, CH.sub.2O, OCH.sub.2, CHCHO or OCHCH; ring A.sup.9 and ring A.sup.10 are independently 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; and Z.sup.7, Z.sup.8 and Z.sup.9 are independently CHCH or CC.

13. The compound according to claim 12, wherein in formula (1-111) or formula (1-112), Sp.sup.1 and Sp.sup.2 are a single bond.

14. A compound represented by formula (1-1111), formula (1-1112) or (1-1113): ##STR00148## wherein in formula (1-1111), (1-1112) or formula (1-1113), P.sup.8 and P.sup.9 are independently OCOHCCH.sub.2 or OCO(CH.sub.3)CCH.sub.2, and ring A.sup.11 is 2-fluoro-1,4-phenylene.

15. A polymerizable composition including at least one compound according to claim 7.

16. An optically anisotropic material formed by polymerization of the polymerizable composition according to claim 15.

Description

EXAMPLES

(1) The invention will be explained in more detail by way of examples. The invention is not limited to the examples.

1. Examples for Compound (1)

(2) Compound (1) was prepared by the method described below. Compounds prepared herein were identified by NMR analysis and so forth. The physical properties of the compounds were measured by the methods described below.

(3) NMR Analysis

(4) A model DRX-500 apparatus made by Bruker BioSpin Corporation was used for measurement. In the measurement of .sup.1H-NMR, a sample was dissolved in a deuterated solvent such as CDCl.sub.3, and the measurement was carried out under the conditions of room temperature, 500 MHz and the accumulation of 16 scans. Tetramethylsilane (TMS) was used as an internal standard. In the measurement of .sup.19F-NMR, CFCl.sub.3 was used as the internal standard, and 24 scans were accumulated. In the explanation of the nuclear magnetic resonance spectra, the symbols s, d, t, q, quin, sex, m and br stand for a singlet, a doublet, a triplet, a quartet, a quintet, a sextet, a multiplet and line-broadening, respectively.

(5) HPLC Analysis

(6) Model Prominence (LC-20AD; SPD-20A) made by Shimadzu Corporation was used for measurement. A column YMC-Pack ODS-A (length 150 mm, bore 4.6 mm, particle size 5 m) made by YMC Co., Ltd. was used. Acetonitrile and water were suitably mixed and used as an eluent. A UV detector, a RI detector, a Corona detector and so forth were suitably used as a detector. A wavelength for the UV detector was 254 nm. A sample was dissolved in acetonitrile to give a 0.1% by weight solution, and then 1 microliter of the solution was injected into the sample injector. Model C-R7Aplus made by Shimadzu Corporation was used as a recorder.

(7) Ultraviolet and Visible Spectrophotometric Analysis

(8) Model PharmaSpec UV-1700 made by Shimadzu Corporation was used for measurement. Wavelengths in the range of 190 nm to 700 nm were used for the detection. A sample was dissolved in acetonitrile, giving a 0.01 mmol/L solution, which was placed in a quartz cell (optical path length: 1 cm) and measured.

(9) Samples for Measurement

(10) A compound itself was used as a sample when the phase structure and the transition temperature (a clearing point, a melting point, a starting temperature of polymerization and so forth) were measured. A mixture of the compound and mother liquid crystals was used as a sample when physical properties such as the maximum temperature of a nematic phase, viscosity, optical anisotropy and dielectric anisotropy were measured.

(11) Measurement Methods

(12) The physical properties of compounds were measured according to the following methods. Most were methods described in the JEITA standards (JEITA-ED-2521B) which was deliberated and established by Japan Electronics and Information Technology Industries Association (abbreviated to JEITA), or the modified methods. No thin film transistors (TFT) were attached to a TN device used for measurement

(13) (1) Phase Structures

(14) A sample was placed on a hot plate of a melting point apparatus (Hot Stage Model FP-52 made by Mettler Toledo International Inc.) equipped with a polarizing microscope. The phase conditions and their changes were observed with the polarizing microscope while the sample was heated at the rate of 3 C. per minute, and the kinds of phases were specified.

(15) (2) Transition Temperature ( C.)

(16) A differential scanning calorimeter, Diamond DSC System, made by Perkin-Elmer Inc. or a high sensitivity differential scanning analyzer, X-DSC7000, made by SII NanoTechnology Inc. was used for measurement. A sample was heated and then cooled at the rate of 3 C. per minute. The starting point of an endothermic peak or an exothermic peak caused by the phase change of the sample was obtained by extrapolation, and thus the transition temperature was determined. The melting point and the starting temperature of polymerization of a compound were also measured by use of this apparatus. The transition temperature of a compound from solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated to the minimum temperature of a liquid crystal phase. The transition temperature of a compound from a liquid crystal phase to liquid may be abbreviated to a clearing point.

(17) The symbol C stood for crystals, which were expressed as C.sub.1 and C.sub.2 when the kinds of crystals were distinguishable. The symbols S and N stood for a smectic phase and a nematic phase, respectively. When a smectic A phase, a smectic B phase, a smectic C phase or a smectic F was distinguishable in the smectic phases, it was expressed as S.sub.A, S.sub.B, S.sub.C or S.sub.F, respectively. The symbol I stood for a liquid (isotropic). Transition temperatures were expressed as, for example, C 50.0 N 100.0 Iso, which means that the transition temperature from crystals to a nematic phase was 50.0 C., and the transition temperature from the nematic phase to a liquid was 100.0 C.

(18) (3) Maximum Temperature of a Nematic Phase (T.sub.NI or NI; C.)

(19) A sample was placed on a hot plate of a melting point apparatus equipped with a polarizing microscope and was heated at the rate of 1 C. per minute. The temperature was measured when a part of the sample began to change from a nematic phase to an isotropic liquid. A higher limit of the temperature range of a nematic phase may be abbreviated to the maximum temperature. The symbol T.sub.NI means that the sample was a mixture of compound (1) and mother liquid crystals. The symbol NI means that the sample was a mixture of compound (1) and compounds such as components B, C, D and E.

(20) (4) Minimum Temperature of a Nematic Phase (T.sub.C; C.)

(21) A sample having a nematic phase was kept in freezers at temperatures of 0 C., 10 C., 20 C., 30 C. and 40 C. for 10 days, and then the liquid crystal phases were observed. For example, when the sample maintained the nematic phase at 20 C. and changed to crystals or a smectic phase at 30 C., T.sub.C was expressed as 20 C. A lower limit of the temperature range of a nematic phase may be abbreviated to the minimum temperature.

(22) (5) Viscosity (Bulk Viscosity; ; Measured at 20 C.; mPa.Math.s)

(23) The viscosity was measured by use of an E-type viscometer made by Tokyo Keiki Inc.

(24) (6) Optical Anisotropy (Refractive Index Anisotropy; n; Measured at 25 C.)

(25) The measurement was carried out using an Abbe refractometer with a polarizing plate attached to the ocular, using light at a wavelength of 589 nanometers. The surface of the main prism was rubbed in one direction, and then a sample was placed on the main prism. The refractive index (n) was measured when the direction of the polarized light was parallel to that of rubbing. The refractive index (n) was measured when the direction of polarized light was perpendicular to that of rubbing. The value of the optical anisotropy (n) was calculated from the equation: n=nn.

(26) (7) Specific Resistance (; Measured at 25 C.; cm):

(27) A sample of 1.0 milliliter was poured into a vessel equipped with electrodes. DC voltage (10 V) was applied to the vessel, and the DC current was measured after 10 seconds. The specific resistance was calculated from the following equation. (specific resistance)=[(voltage)(electric capacity of vessel)]/[(DC current)(dielectric constant in vacuum)].

(28) (8) Voltage Holding Ratio (VHR-1; measured at 25 C.; %)

(29) A TN device used for measurement had a polyimide-alignment film, and the distance between the two glass substrates (cell gap) was 5 micrometers. A sample was poured into the device, and then this device was sealed with a UV-curable adhesive. A pulse voltage (60 microseconds at 5 V) was applied to this device and the device was charged. A decreasing voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was obtained. Area B was an area without the decrease. The voltage holding ratio was expressed as a percentage of area A to area B.

(30) (9) Voltage Holding Ratio (VHR-2; Measured at 80 C.; %)

(31) The voltage holding ratio was measured by the method described above, except that it was measured at 80 C. instead of 25 C. The results were shown by using the symbol VHR-2.

(32) The measurement method of physical properties for a sample having positive dielectric anisotropy is sometimes different from that for a sample having negative dielectric anisotropy. Measurement methods are described in items (10a) to (14a) when the dielectric anisotropy is positive. When the dielectric anisotropy is negative, they are shown in items (10b) to (14b).

(33) (10a) Viscosity (Rotational Viscosity; 1; Measured at 25 C.; mPa.Math.s)

(34) Positive dielectric anisotropy: The measurement was carried out according to the method described in M. Imai, et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was poured into a TN device in which the twist angle was 0 degrees and the distance between the two glass substrates (cell gap) was 5 micrometers. A voltage with an increment of 0.5 volt in the range of 16 to 19.5 volts was applied stepwise to this device. After a period of 0.2 second with no voltage, a voltage was applied repeatedly under the conditions of a single rectangular wave alone (rectangular pulse; 0.2 second) and of no voltage (2 seconds). The peak current and the peak time of the transient current generated by the applied voltage were measured. The value of rotational viscosity was obtained from these measured values and the calculating equation (8) on page 40 of the paper presented by M. Imai, et al. The value of dielectric anisotropy necessary for this calculation was obtained by use of the device that had been used for the measurement of rotational viscosity, according to the method that will be described below.

(35) (10b) Viscosity (Rotational Viscosity; 1; Measured at 25 C.; mPa.Math.s)

(36) Negative dielectric anisotropy: The measurement was carried out according to the method described in M. Imai, et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was poured into a VA device in which the distance between the two glass substrates (cell gap) was 20 micrometers. A voltage in the range of 39 V to 50 V was applied stepwise with an increment of 1 volt to this device. After a period of 0.2 second with no voltage, a voltage was applied repeatedly under the conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds). The peak current and the peak time of the transient current generated by the applied voltage were measured. The value of rotational viscosity was obtained from these measured values and the calculating equation (8) on page 40 of the paper presented by M. Imai, et al. The value of the dielectric anisotropy necessary for the present calculation was obtained by the method that will be described below, under the heading Dielectric anisotropy.

(37) (11a) Dielectric Anisotropy (; Measured at 25 C.)

(38) Positive dielectric anisotropy: A sample was poured into a TN device in which the distance between the two glass substrates (cell gap) was 9 micrometers and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to this device, and the dielectric constant () in the major axis direction of liquid crystal molecules was measured after 2 seconds. Sine waves (0.5 V, 1 kHz) were applied to this device and the dielectric constant () in the minor axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy was calculated from the equation: =.

(39) (11b) Dielectric Anisotropy (; measured at 25 C.)

(40) Negative dielectric anisotropy: The value of dielectric anisotropy was calculated from the equation: =. Dielectric constants ( and ) were measured as follows.

(41) 1) Measurement of a dielectric constant (): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to thoroughly cleaned glass substrates. The glass substrates were rotated with a spinner, and then heated at 150 C. for one hour. A sample was poured into a VA device in which the distance between the two glass substrates (cell gap) was 4 micrometers, and then this device was sealed with a UV-curable adhesive. Sine waves (0.5 V, 1 kHz) were applied to this device, and the dielectric constant () in the major axis direction of liquid crystal molecules was measured after 2 seconds.
2) Measurement of a dielectric constant (): A polyimide solution was applied to thoroughly cleaned glass substrates. The glass substrates were calcined, and then the resulting alignment film was subjected to rubbing. A sample was poured into a TN device in which the distance between the two glass substrates (cell gap) was 9 micrometers and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and the dielectric constant () in the minor axis direction of liquid crystal molecules was measured after 2 seconds.
(12a) Elastic Constants (K; Measured at 25 C.; pN)

(42) Positive dielectric anisotropy: A LCR meter Model HP 4284-A made by Yokokawa Hewlett-Packard, Ltd. was used for measurement. A sample was poured into a homogeneous device in which the distance between the two glass substrates (cell gap) was 20 micrometers. An electric charge of 0 volts to 20 volts was applied to this device, and the electrostatic capacity and the applied voltage were measured. The measured values of the electric capacity (C) and the applied voltage (V) were fitted to the equation (2.98) and the equation (2.101) in page 75 of the Ekisho Debaisu Handobukku (Liquid Crystal Device Handbook, in English; The Nikkan Kogyo Shimbun, Ltd., Japan) and the values of K.sub.11 and K.sub.33 were obtained from the equation (2.99). Next, the value of K.sub.22 was calculated from the equation (3.18) in page 171 and the values of K.sub.11 and K.sub.33 thus obtained. The elastic constant K was expressed as an average value of K.sub.11, K.sub.22 and K.sub.33.

(43) (12b) Elastic Constants (K.sub.11 and K.sub.33; Measured at 25 C.; pN)

(44) Negative dielectric anisotropy: An elastic constant measurement system Model EC-1 made by Toyo Corporation was used for measurement. A sample was poured into a homeotropic device in which the distance between the two glass substrates (cell gap) was 20 micrometers. An electric charge of 20 volts to 0 volts was applied to this device, and electrostatic capacity and applied voltage were measured. The values of the electrostatic capacity (C) and the applied voltage (V) were fitted to the equation (2.98) and the equation (2.101) in page 75 of the Ekisho Debaisu Handobukku (Liquid Crystal Device Handbook, in English; The Nikkan Kogyo Shimbun, Ltd., Japan), and the value of the elastic constant was obtained from the equation (2.100).

(45) (13a) Threshold Voltage (Vth; Measured at 25 C.; V)

(46) Positive dielectric anisotropy: The measurement was carried out with an LCD evaluation system Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. A sample was poured into a TN device having a normally white mode, in which the distance between the two glass substrates (cell gap) was 4.45/n (micrometers) and the twist angle was 80 degrees. Voltage to be applied to this device (32 Hz, rectangular waves) was stepwise increased in 0.02 V increments from 0 V up to 10 V. During the increase, the device was irradiated with light in the perpendicular direction, and the amount of light passing through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponded to 100% transmittance and the minimum amount of light corresponded to 0% transmittance. The threshold voltage was expressed as a voltage at 90% transmittance.

(47) (13b) Threshold Voltage (Vth; Measured at 25 C.; V)

(48) Negative dielectric anisotropy: The measurement was carried out with an LCD evaluation system Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. A sample was poured into a PVA device having a normally black mode, in which the distance between the two glass substrates (cell gap) was 4 micrometers and the rubbing direction was antiparallel, and then this device was sealed with a UV-curable adhesive. The voltage to be applied to this device (60 Hz, rectangular waves) was stepwise increased in 0.02 V increments from 0 V up to 20 V. During the increase, the device was irradiated with light in the perpendicular direction, and the amount of light passing through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponded to 100% transmittance and the minimum amount of light corresponded to 0% transmittance. The threshold voltage was expressed as a voltage at 10% transmittance.

(49) (14a) Response Time (; Measured at 25 C.; Millisecond)

(50) Positive dielectric anisotropy: The measurement was carried out with an LCD evaluation system Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter was set at 5 kHz. A sample was poured into a TN device having a normally white mode, in which the cell gap between the two glass substrates was 5.0 micrometers and the twist angle was 80 degrees. Rectangular waves (60 Hz, 5 V, 0.5 second) were applied to this device. The device was simultaneously irradiated with light in the perpendicular direction, and the amount of light passing through the device was measured. The transmittance was regarded as 100% when the amount of light reached a maximum. The transmittance was regarded as 0% when the amount of light reached a minimum. Rise time (r; millisecond) was the time required for a change from 90% to 10% transmittance. Fall time (f; millisecond) was the time required for a change from 10% to 90% transmittance. The response time was expressed as the sum of the rise time and the fall time thus obtained.

(51) (14b) Response Time (; Measured at 25 C.; Millisecond)

(52) Negative dielectric anisotropy: The measurement was carried out with an LCD evaluation system Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter was set at 5 kHz. A sample was poured into a VA device having a normally black mode, in which the cell gap between two glass substrates was 3.2 micrometers, and the rubbing direction was antiparallel. This device was sealed with a UV-curable adhesive. A voltage that was a little more than the threshold voltage was applied to this device for 1 minute, and then the device was irradiated with ultraviolet light of 23.5 mW/cm.sup.2 for 8 minutes while a voltage of 5.6 V was applied. Rectangular waves (60 Hz, 10 V, 0.5 second) were applied to this device. The device was simultaneously irradiated with light in the perpendicular direction, and the amount of light passing through the device was measured. The transmittance was regarded as 100% when the amount of light reached a maximum. The transmittance was regarded as 0% when the amount of light reached a minimum. The response time was expressed as the period of time required for the change from 90% to 10% transmittance (fall time: millisecond).

Example 1

(53) Compound (1-1-1) was prepared according to the following scheme.

(54) ##STR00061##
First Step: Preparation of Compound (T-2)

(55) Compound (T-1) (60.2 g), 2-methyl-3-butyn-2-ol (74.0 g), triphenylphosphine (1.1 g), dichlorobis(triphenylphosphine)palladium (2.8 g), copper iodide (2.3 g), triethylamine (247 g) and 2,6-t-butyl-4-methylphenol (0.5 g) were placed in a 1 liter flask, and the mixture was heated under reflux for 20 hours under a stream of argon. The reaction mixture was returned to room temperature and filtered. The filtrate was concentrated under reduced pressure to give a crude product (38.6 g, 74.2% yield) of compound (T-2) as a red oil.

(56) Second Step: Preparation of Compound (T-3)

(57) Compound (T-2) (38 g) prepared in the above step was placed in a 500 ml flask and dissolved in toluene (150 ml). Sodium hydride (21.65 g) was added and the mixture was heated at 80 C. for 18 hours under a stream of argon. The reaction mixture was returned to room temperature and filtered. The residue was washed with toluene (500 ml), and the washings were combined with the filtrate and then concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane) to give compound (T-3; 11.4 g, 54.2% yield) as yellow crystals.

(58) Third Step: Preparation of Compound (T-5)

(59) 4-Bromophenol (T-4) (69.2 g) was placed in a 500 ml flask and dissolved in methylene chloride (250 ml). Triethylamine (48.6 g) was added and the mixture was cooled on an ice-salt bath. Acetyl chloride (34.54 g) was added dropwise at 5 C. to 5 C. during a period of 1 hour. After 2 hours of stirring at room temperature, water (200 ml) was added and the stirring was continued for 30 minutes. After the organic layer had been separated from the aqueous layer, the organic layer was washed with water (200 ml). The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give compound (T-5; 76.4 g, 88.8% yield) as a red brown oil.

(60) Fourth Step: Preparation of Compound (T-6)

(61) Compound (T-5) (24 g) prepared in the above step, compound (T-3) (8 g) prepared in the above step, triphenylphosphine (0.3 g), dichlorobis(triphenylphosphine)palladium (0.79 g), copper iodide (0.64 g), triethylamine (79 g) and 2,6-t-butyl-4-methylphenol (0.1 g) were placed in a 250 ml flask, and the mixture was heated under reflux for 17 hours under a stream of argon. The reaction mixture was returned to room temperature and filtered. The filtrate was concentrated under reduced pressure and recrystallized from ethanol to give compound (T-6; 5.4 g, 12% yield) as yellow crystals.

(62) Fifth Step: Preparation of Compound (T-7)

(63) Compound (T-6) (5.4 g) prepared in the above step was placed in a 250 ml flask and dissolved in methanol (10 g). A 25%-sodium hydride aqueous solution (6.05 g) was added and the mixture was stirred for 17 hours. The reaction mixture was quenched with 30% hydrochloric acid and extracted with methyl t-butyl ether (100 ml2). The extract was washed with water (200 ml), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give crude yellow crystals (6.4 g). These crude crystals were recrystallized from hexane/ethyl acetate (20/1 by volume) to give compound (T-7; 4.2 g, 97.7% yield) as yellow crystals.

(64) Sixth Step: Preparation of Compound (1-1-1)

(65) Compound (T-7) (3.2 g) prepared in the above step, methacrylic acid (2.58 g), 4-dimethylaminopyridine (0.6 g), and 2,6-t-butyl-4-methylphenol (0.05 g) were placed in a 100 ml flask and dissolved in a mixed solvent of methylene chloride (30 ml) and THF (30 ml). N,N-Dicyclohexylcarbodiimide (6.18 g) in a methylene chloride (10 ml) solution was added dropwise at temperatures below 25 C. during a period of 30 minutes. After 5 hours of stirring at room temperature, the reaction mixture was quenched with water (0.8 g) and filtered. The residue was washed with methylene chloride (100 ml), and the washings were combined with the filtrate and then concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane/ethyl acetate=15/1 by volume) to give compound (1-1-1; 4.2 g, 74% yield) as yellow crystals.

(66) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.62 (d, J=8.7 Hz, 2H), 7.59 (d, J=8.7 Hz, 2H), 7.51 (dd, J=8.1, 7.6 Hz, 1H), 7.32 (dd, J=8.1, 1.2 Hz, 1H), 7.29 (dd, J=9.7, 1.2 Hz, 1H), 7.18 (d, J=8.7 Hz, 2H2), 6.39 (s, 1H2), 5.81 (d, J=1.1 Hz, 1H2) and 2.10 (s, 3H2). .sup.19F-NMR ( ppm; CDCl.sub.3): 115.52 (dd, J=9.7, 7.6 Hz, 1F).

(67) The physical properties of compound (1-1-1) were as follows. Melting point: 134.9 C., starting temperature of polymerization: 157 C.

Example 2

(68) Compound (1-1-67) was prepared according to the following scheme.

(69) ##STR00062##
First Step: Preparation of Compound (T-8)

(70) A suspension of palladium/barium sulfate (0.8 g), quinoline (2.0 g) and methanol (20 ml) was placed in a 500 ml autoclave and stirred for 20 minutes. Compound (T-7) (4.0 g) prepared in the above step in a methanol (200 ml) solution was added and the mixture was stirred at 50 C. to 60 C. for 60 hours under pressure of hydrogen (0.3 Mpa). The reaction mixture was returned to room temperature and filtered. The filtrate was concentrated under reduced pressure. A methylene chloride (100 ml) solution of the residue was washed with brine, 10% hydrochloric acid and a saturated aqueous solution of sodium hydrogencarbonate. This solution was dried and concentrated under reduced pressure to give compound (T-8; 3.2 g, 79% yield) as yellow crystals.

(71) Second Step: Preparation of Compound (1-1-67)

(72) Compound (T-8) (3.0 g) prepared in the above step and methacrylic acid (1.86 g) were placed in a 100 ml flask and dissolved in THF (50 ml). 4-Dimethylaminopyridine (0.22 g) and 2,6-t-butyl-4-methylphenol (0.05 g) were added. N,N-Dicyclohexylcarbodiimide (4.47 g) in a THF (20 ml) solution was added dropwise at 20 C. to 25 C. during a period of 30 minutes, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was quenched with water (0.8 g) and filtered. The residue was washed with methylene chloride (100 ml), and the washings were combined with the filtrate and then concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane/ethyl acetate=20/1 by volume) to give compound (1-1-67; 2.2 g, 52% yield) as yellow crystals.

(73) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.27 (d, J=8.6 Hz, 2H), 7.25 (d, J=8.5 Hz, 2H), 7.09 (dd, J=8.1, 7.6 Hz, 1H), 7.01 (d, J=8.6 Hz, 2H), 6.99 (d, J=8.5 Hz, 2H), 6.94 (dd, J=11.3, 1.0 Hz, 1H), 6.84 (dd, J=8.1, 0.9 Hz, 1H), 6.67 (d, J=12.2 Hz, 1H), 6.60 (d, J=12.2 Hz, 1H), 6.63 (d, J=12.2 Hz, 1H), 6.50 (d, J=12.2 Hz, 1H), 6.33 (s, 1H), 6.32 (s, 1H), 5.75-5.74 (m, 2H) and 2.05 (s, 3H2). .sup.19F-NMR ( ppm; CDCl.sub.3): 115.52 (dd, J=11.3, 7.6 Hz, 1F).

(74) The physical properties of compound (1-1-67) were as follows. Melting point: 98.7 C., starting temperature of polymerization: 189 C.

(75) Compounds (1-1-2) to (1-1-66), compounds (1-1-67) to (1-1-137), compounds (1-2-1) to (1-2-40), compounds (1-3-1) to (1-3-40), compounds (1-4-1) to (1-4-40), compounds (1-5-1) to (1-5-40), compounds (1-6-1) to (1-6-40) described below can be prepared by the same method as the method described in Examples 1 and 2.

(76) ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111##

Comparative Example 1

(77) Compound (R-1) was prepared for comparison according to the following scheme.

(78) ##STR00112##
First Step: Preparation of Compound (T-9)

(79) A mixed solvent (360 ml; toluene:2-propanol:water=1:1:1) was added to compound (T-1) (40.0 g), 4-methoxyphenylboronic acid (42.42 g), 5% Pd/C (1.2 g; N.E. Chemcat Corporation), tetrabutylammonium bromide (17.4 g) and potassium carbonate (73.49 g), and the mixture was heated under reflux. After 32 hours, Pd/C was filtered and the filtrate was extracted with toluene. The extract was washed with brine, dried and concentrated under reduced pressure. The residue was purified by silica gel chromatography (toluene/ethyl acetate=19/1 by volume) to give compound (T-9; 3 g, 7.2% yield) as colorless crystals.

(80) Second Step: Preparation of Compound (T-10)

(81) Compound (T-9) (8.62 g) was dissolved in methylene chloride (100 ml) and boron tribromide (70.0 ml; a 1.0 mol/liter methylene chloride solution) was added dropwise at 20 C. or lower. The mixture was stirred at room temperature overnight. The reaction mixture was poured into ice-water (100 ml) and extracted with methylene chloride (100 ml). The extract was washed with brine, dried and concentrated under reduced pressure. The residue was purified by silica gel chromatography (ethyl acetate) to give compound (T-10; 4.2 g, 53.6% yield) as brown crystals.

(82) Third Step: Preparation of (R-1)

(83) The reaction of compound (T-10) (4.0 g) was carried out in the same manner as in Example 1 gave colorless crystals of the comparative compound (R-1).

(84) .sup.1H-NMR ( ppm; CDCl.sub.3): 7.64-7.64 (m, 4H), 7.50 (dd, J=8.1, 8.0 Hz, 1H), 7.43 (dd, J=8.0, 1.7 Hz, 1H), 7.38 (dd, J=11.9, 1.7 Hz, 1H), 7.23 (d, J=8.5 Hz, 2H2), 6.38 (s, 1H2), 5.79-5.78 (m, 1H2) and 2.09 (s, 3H2). .sup.19F-NMR ( ppm; CDCl.sub.3): 118.10 (dd, J=11.9, 8.1 Hz, 1F).

(85) The physical properties of the comparative compound (R-1) were as follows. Melting point: 179.11 C., starting temperature of polymerization: 184.15 C.

(86) Comparative Experiment

(87) The following liquid crystal composition A was used for a comparative experiment.

(88) TABLE-US-00001 3-H2B(2F,3F)-O2 (9-4) 18% 5-H2B(2F,3F)-O2 (9-4) 17% 3-HH1OCro(7F,8F)-5 (13-6) 6% 3-HBB(2F,3F)-O2 (10-7) 10% 4-HBB(2F,3F)-O2 (10-7) 6% 5-HBB(2F,3F)-O2 (10-7) 6% 2-HH-3 (2-1) 14% 3-HH-4 (2-1) 8% 3-HHB-1 (3-1) 5% 3-HHB-3 (3-1) 6% 3-HHB-O1 (3-1) 4%

(89) A polymerizable compound was added to this liquid crystal composition A in the ratio of 0.3% by weight. This composition was irradiated with ultraviolet light of 75 mW/cm.sup.2 for 200 seconds (15,000 mJ). A mercury-xenon lamp, Execure 4000-D made by Hoya Candeo Optronics Corp. was used for the irradiation with ultraviolet light. The amount of the polymerizable compound remained in the composition was measured with HPLC. Table 1 summarizes the results, together with the results on the irradiation with ultraviolet light for 400 seconds (30,000 mJ). Unreacted reactant was expressed as a ratio of the unreacted polymerizable compound to the added polymerizable compound. 2% or less shows that the unreacted polymerizable compound could not be detected. It was found from the table that two compounds of the invention were consumed by the polymerization although the unreacted reactant was remained with regard to the comparative compound (R-1). Accordingly, it is concluded that the compound of the invention is excellent in view of a high reactivity.

(90) TABLE-US-00002 TABLE 1 Amount of unreacted polymerizable compound Unreacted reactant Polymerizable (% by weight) compound Structural formula 15,000 mJ 30,000 mJ Compound (1-1-1) 2% or less 2% or less Compound (1-1-67) 2% or less 2% or less Comparative compound (R-1) 41% 26%

2. Examples for the Polymerizable Composition

(91) The compounds described in Examples were expressed in terms of symbols based on the definition in Table 2 described below. In Table 2, the configuration of 1,4-cyclohexylene is trans. The parenthesized number next to a symbolized compound in Example indicates the number of the compound. The symbol () means any other liquid crystal compound. The content (percentage) of liquid crystal compounds means the percentages by weight (% by weight) based on the weight of the liquid crystal composition. Last, the values of physical properties of the composition were summarized. The physical properties were measured according to the method described above, and the measured values were reported without extrapolation.

(92) TABLE-US-00003 TABLE 2 Method of Description of Compounds using Symbols R(A.sub.1)Z.sub.1 . . . Z.sub.n(A.sub.n)R 1) Left-terminal Group R Symbol C.sub.nH.sub.2n+1 n- C.sub.nH.sub.2n+1O nO C.sub.mH.sub.2m+1OC.sub.nH.sub.2n mOn CH.sub.2CH V C.sub.nH.sub.2n+1CHCH nV CH.sub.2CHC.sub.nH.sub.2n Vn C.sub.mH.sub.2m+1CHCHC.sub.nH.sub.2n mVn CF.sub.2CH VFF CF.sub.2CHC.sub.nH.sub.2n VFFn 2) Right-terminal Group R Symbol C.sub.nH.sub.2n+1 -n OC.sub.nH.sub.2n+1 On COOCH.sub.3 EMe CHCH.sub.2 V CHCHC.sub.nH.sub.2n+1 Vn C.sub.nH.sub.2nCHCH.sub.2 nV C.sub.mH.sub.2mCHCHC.sub.nH.sub.2n+1 mVn CHCF.sub.2 VFF F F Cl CL OCF.sub.3 OCF3 OCF.sub.2H OCF2H CF.sub.3 CF3 CFCHCF.sub.3 FVCF3 CN C 3) Bonding Group Z.sub.n Symbol C.sub.nH.sub.2n n COO E CHCH V CH.sub.2O 1O OCH.sub.2 O1 CF.sub.2O X CC T 4) Ring Structure A.sub.n Symbol H B B(F) B(2F) 0 B(F,F) B(2F,5F) B(2F,3F) B(2F,3CL) G dh Dh Cro(7F,8F) 5) Examples of Description Example 1. 3-BB(F,F)XB(F,F)F Example 2. 3-HBB(2F,3F)O2 Example 3. 3-HH-4 0 Example 4. 3-HBB(F,F)F

Example 3

(93) TABLE-US-00004 2-HB-C (5-2) 5% 3-HB-C (5-2) 12% 3-HB-O2 (2-5) 15% 2-BTB-1 (2-10) 3% 3-HHB-F (6-1) 4% 3-HHB-1 (3-1) 6% 3-HHB-O1 (3-1) 7% 3-HHB-3 (3-1) 14% 3-HHEB-F (6-10) 4% 5-HHEB-F (6-10) 4% 2-HHB(F)-F (6-2) 7% 3-HHB(F)-F (6-2) 7% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 5%

(94) Compound (1-1-1) was added to the preceding composition in the ratio of 0.2% by weight.

(95) ##STR00132##
NI=101.0 C.; n=0.100; =4.6; =18.1 mPa.Math.s.

Example 4

(96) TABLE-US-00005 5-HB-CL (5-2) 16% 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 4% 3-HHB-F (6-1) 4% 3-HHB-CL (6-1) 3% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6-2) 10% 4-HHB(F)-F (6-2) 9% 5-HHB(F)-F (6-2) 9% 7-HHB(F)-F (6-2) 8% 5-HBB(F)-F (6-2) 4% 1O1-HBBH-5 (4-1) 5% 3-HHBB(F,F)-F (7-6) 2% 4-HHBB(F,F)-F (7-6) 3% 5-HHBB(F,F)-F (7-6) 3% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3%

(97) Compound (1-1-108) was added to the preceding composition in the ratio of 0.3% by weight.

(98) ##STR00133##
NI=118.8 C.; n=0.094; =3.9; =20.9 mPa.Math.s.

Example 5

(99) TABLE-US-00006 3-HH-4 (2-1) 15% 3-HH-5 (2-1) 4% 3-HH-V (2-1) 3% 3-HB-O2 (2-5) 12% 3-H2B(2F,3F)-O2 (9-4) 15% 5-H2B(2F,3F)-O2 (9-4) 15% 3-HHB(2F,3CL)-O2 (10-12) 5% 2-HBB(2F,3F)-O2 (10-7) 3% 3-HBB(2F,3F)-O2 (10-7) 9% 5-HBB(2F,3F)-O2 (10-7) 9% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 4% 3-HHB-O1 (3-1) 3%

(100) Compound (1-1-67) was added to the preceding composition in the ratio of 0.2% by weight.

(101) ##STR00134##
NI=75.6 C.; n=0.093; =4.0; =18.8 mPa.Math.s.

Example 6

(102) TABLE-US-00007 2-HH-3 (2-1) 21% 3-HH-4 (2-1) 9% 1-BB-3 (2-8) 9% 3-HB-O2 (2-5) 2% 3-BB(2F,3F)-O2 (9-3) 9% 5-BB(2F,3F)-O2 (9-3) 6% 2-HH1OB(2F,3F)-O2 (10-5) 13% 3-HH1OB(2F,3F)-O2 (10-5) 19% 3-HHB-1 (3-1) 5% 3-HHB-O1 (3-1) 3% 5-B(F)BB-2 (3-8) 4%

(103) Compound (B1) was added to the preceding composition in the ratio of 0.3% by weight.

(104) ##STR00135##
NI=73.8 C.; n=0.100; =3.0; =15.0 mPa.Math.s.

Example 7

(105) TABLE-US-00008 2-HH-3 (2-1) 16% 7-HB-1 (2-5) 10% 5-HB-O2 (2-5) 8% 3-HB(2F,3F)-O2 (9-1) 17% 5-HB(2F,3F)-O2 (9-1) 16% 3-HHB(2F,3CL)-O2 (10-12) 3% 4-HHB(2F,3CL)-O2 (10-12) 3% 5-HBB(2F,3F)-O2 (10-7) 2% 3-HH1OCro(7F,8F)-5 (13-6) 5% 5-HBB(F)B-2 (4-5) 10% 5-HBB(F)B-3 (4-5) 10%

(106) Compound (1-1-106) was added to the preceding composition in the ratio of 0.4% by weight.

(107) ##STR00136##
NI=76.3 C.; n=0.106; =2.5; =22.6 mPa.Math.s.

Example 8

(108) TABLE-US-00009 1-BB-3 (2-8) 10% 3-HH-V (2-1) 27% 3-BB(2F,3F)-O2 (9-3) 15% 2-HH1OB(2F,3F)-O2 (10-5) 20% 3-HH1OB(2F,3F)-O2 (10-5) 14% 3-HHB-1 (3-1) 8% 5-B(F)BB-2 (3-8) 6%

(109) Compound (1-1-1) was added to the preceding composition in the ratio of 0.3% by weight.

(110) ##STR00137##
NI=73.8 C.; n=0.109; =3.1; =15.6 mPa.Math.s.

Example 9

(111) TABLE-US-00010 5-HB(F)B(F,F)XB(F,F)-F (7-41) 5% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 7% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 3-HH-V (2-1) 39% 3-HH-V1 (2-1) 9% 3-HHEH-5 (3-13) 3% 3-HHB-1 (3-1) 4% V-HHB-1 (3-1) 5% V2-BB(F)B-1 (3-6) 5% 1V2-BB-F (5-1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 11% 3-HHBB(F,F)-F (7-6) 3%

(112) Compound (1-1-106) was added to the preceding composition in the ratio of 0.15% by weight.

(113) ##STR00138##
NI=82.6 C.; n=0.105; =6.3; =12.2 mPa.Math.s.

Example 10

(114) TABLE-US-00011 3-GB(F)B(F,F)XB(F,F)-F (7-57) 5% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 7% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 3% 3-HH-V (2-1) 41% 3-HH-V1 (2-1) 7% 3-HHEH-5 (3-13) 3% 3-HHB-1 (3-1) 6% V-HHB-1 (3-1) 3% V2-BB(F)B-1 (3-7) 5% 1V2-BB-F (5-1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 6% 3-GB(F,F)XB(F,F)-F (6-113) 5% 3-HHBB(F,F)-F (7-6) 3%

(115) Compound (1-1-67) was added to the preceding composition in the ratio of 0.2% by weight.

(116) ##STR00139##
NI=81.5 C.; n=0.102; =7.3; =12.8 mPa.Math.s.

(117) Although the invention has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the invention.

INDUSTRIAL APPLICABILITY

(118) A liquid crystal display device having a mode such as PSA can be made by the polymerization of a polymerizable composition including compound (1) and a liquid crystal composition. This device has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio and a long service life. Accordingly, compound (1) can be used for liquid crystal display projectors, liquid crystal display televisions and so forth. Compound (1) can also be used as a starting material for an optically anisotropic material.