LIQUID CRYSTAL COMPOUND HAVING DIFLUOROMETHYLENEOXY GROUP, LIQUID CRYSTAL COMPOSITION, AND LIQUID CRYSTAL DISPLAY DEVICE
20180030347 ยท 2018-02-01
Assignee
Inventors
Cpc classification
C09K19/04
CHEMISTRY; METALLURGY
C09K2019/3425
CHEMISTRY; METALLURGY
C09K19/322
CHEMISTRY; METALLURGY
C09K19/3003
CHEMISTRY; METALLURGY
International classification
C09K19/30
CHEMISTRY; METALLURGY
Abstract
Provided are a liquid crystal compound satisfying at least one of physical properties such as high stability heat and light, a high clearing point (or high maximum temperature), low minimum temperature of the liquid crystal phase, small viscosity, suitable optical anisotropy, large dielectric anisotropy, large dielectric constant in a minor axis direction, a suitable elastic constant and excellent compatiblity with other liquid crystal compounds; a liquid crystal composition containing the liquid crystal compound; and a liquid crystal display device including the composition.
The compound is represented by formula (1).
##STR00001##
In formula (1), for example R.sup.1 is alkyl having 1 to 12 carbons; ring A.sup.1 is 1,4-cyclohexylene; ring B.sup.1 is 1,4-phenylene; Z.sup.1, Z.sup.2 and 7.sup.3 are a single bond; L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8 and L.sup.9 are hydrogen or halogen; X.sup.1 is fluorine; a is 1 to 3; and n.sup.1 and n.sup.2 are independently 0 or 1.
Claims
1. A compound, represented by formula ##STR00106## wherein, in formula (1), R.sup.1 is alkyl having 1 to 12 carbons, and in the R.sup.1, at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O are adjacent is excluded, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; ring A.sup.1 is 1,4-cyclohexylene or 1,4-cyclohexenylene; ring B.sup.1 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by halogen, and in the rings, at least one hydrogen may be replaced halogen; Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, CH.sub.2CH.sub.2, CC, CFCH, CFCF, CF.sub.2O, OCF.sub.2, CH.sub.2O or OCH.sub.2; L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8 and L.sup.9 are independently hydrogen or halogen; X.sup.1 is fluorine, chlorine, CF.sub.3, CHF.sub.2, CH.sub.2F, OCHF.sub.2, OCH.sub.2F or OCF.sub.3; a is 1, 2 or 3; and n.sup.1 is 0 or n.sup.2 is 0 or 1, and a sum of n.sup.1 and n.sup.2 is 0 or 1.
2. The compound according to claim 1, wherein, in formula (1), R.sup.1 is alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxyalkyl having 1 to 11 carbons or alkenyloxyalkyl having 2 to 11 carbons.
3. The compound according to claim 1, wherein, in formula (1) Z.sup.1, Z.sup.2 and Z.sup.3 are independently a single bond, CH.sub.2CH.sub.2, CC, CHCH or CF.sub.2O.
4. The compound according to claim 1, represented by any one of formulas (1-1) to (1-3): ##STR00107## wherein, in formulas (1-1) to (1-3), R.sup.1 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring A.sup.1 is 1,4-cyclohexylene or 1,4-cyclohexenylene; ring B.sup.1 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by halogen, and at least one hydrogen to be directly bonded to the rings may be replaced by fluorine; Z.sup.1, Z .sup.2 and Z.sup.3 are independently a single bond, CH.sub.2CH.sub.2, CC, CHCH or CF.sub.2O; L.sup.1, L.sup.2, L.sup.3, L.sup.4, L.sup.5, L.sup.6, L.sup.7, L.sup.8 and L.sup.9 are independently hydrogen or fluorine; X.sup.1 is fluorine, CF.sub.3 or OCF.sub.3; and a is 1 or 2.
5. The compound according to claim 1, represented by any one of formulas (1-4) to (1-6): ##STR00108## wherein, in formulas (1-4) to (1-6), R.sup.1 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring A.sup.1 is 1,4-cyclohexylene or 1,4-cyclohexenylene; ring B.sup.1 is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene, and at least one hydrogen directly bonded to the rings may be, replaced by fluorine; L.sup.1, L.sup.2, L.sup.4, L.sup.6, L.sup.7, L.sup.8 and L.sup.9 are independently hydrogen or fluorine; X.sup.1 is fluorine, CF.sub.3 or OCF.sub.3; and a is 1 or 2.
6. The compound according to claim 1, represented by any one of formulas (1-7) to (1-14): ##STR00109## wherein, in formulas (1-7) to (1-14), R.sup.1 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; L.sup.1, L.sup.4, L.sup.7, L.sup.9 and L.sup.10 are independently hydrogen or fluorine; X.sup.1 is fluorine, CF.sub.3 or OCF.sub.3; and a is 1 or 2.
7. The compound according to claim 1, represented by any one of formulas (1-15) to (1-18): ##STR00110## wherein, in formulas (1-15) to (1-18), R.sup.1 is alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; L.sup.1, L.sup.4 , L.sup.7, L.sup.9 and L.sup.10 are independently hydrogen or fluorine; and X.sup.1 is fluorine, CF.sub.3 or OCF.sub.3.
8. A liquid. crystal composition, containing at least one compound according to claim 1.
9. The liquid crystal composition according to claim 8, further containing at least one compound selected from the group of compounds represented by formulas (2) to (4): ##STR00111## wherein, in formulas (2) to (4), R.sup.11 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the R.sup.11, at least one hydrogen may be replaced by fluorine, and in the groups, at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O are adjacent is excluded; X.sup.11 is fluorine, chlorine, OCF.sub.3, OCR.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3; ring B.sup.1, ring B.sup.2 and ring B.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced. by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.11, Z.sup.12 and Z.sup.13 independently represent 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, in which, when at least one of Z.sup.11, Z.sup.12 and Z.sup.13 is CF.sub.2O, R.sup.11 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy haying 1 to 9 carbons or alkenyloxy haying 2 to 9 carbons, and in the groups, at least one hydrogen may be replaced by fluorine.
10. The liquid crystal composition according to claim 8, further containing at least one compound selected from the group of compounds represented by formula (5): ##STR00112## wherein, in formula (5), R.sup.12 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the R.sup.I2, at least one hydrogen maybe replaced by fluorine, and at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O are adjacent is excluded; X.sup.2 is CN or CCCN; ring C.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.14 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.
11. The liquid crystal composition according to claim 8, further containing at least one compound selected from the group of compounds represented by formulas (6) to (12): ##STR00113## wherein, in formulas (6) to (12), R.sup.13 and R.sup.14 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the groups, at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O are adjacent is excluded, and at least one hydrogen may be replaced by fluorine; R.sup.15 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the R.sup.15, at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O is adjacent is excluded, and at least one hydrogen may be replaced by fluorine; S.sup.11 is hydrogen or methyl; X is CF.sub.2, O or CHF; ring D.sup.1, ring D.sup.2, ring D.sup.3 and ring D.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahythpyran-2,5-diyl or decahydronaphthalene-2,6-diyl; ring D.sup.5 and ring D.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z.sup.15, Z.sup.16, Z.sup.17 and Z.sup.18 are independently a single bond, CH.sub.2CH.sub.2, COO, CH.sub.2O or OCF.sub.2CH.sub.2CH.sub.2; L.sup.15 and L.sup.16 are independently fluorine or chlorine; and j, k, m, n, p, q, r and s are independently 0 or 1, a sum of k, m, n and p is 1 or 2, a sum of q, r and s is 0, 1, 2 or 3 and t is 1, 2 or 3.
12. The liquid crystal composition according to claim 8, further containing at least one compound selected from the group of compounds represented bv formulas (13) to (15): ##STR00114## wherein, in formulas (13) to (15), R.sup.16 and R.sup.17 are independently alkyl having 1 to 10 carbons or aikenvl having 2 to 10 carbons, and in the groups, at least one piece of CH.sub.2 may be replaced by O, in which a case where two pieces of O are adjacent is excluded, and in the groups, 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-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyramidine-2,5-diyl; and Z.sup.19, Z.sup.20 and Z.sup.21 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC or COO.
13. The liquid crystal composition according to claim 8, further containing at least one selected from the group of a polymerizable compound, an optically active compound, an antioxidant, an ultraviolet light absorber, allght stabilizer, a heat stabilizer and an antifoaming agent.
14. A liquid crystal display device, including the liquid crystal composition according to claim 8.
Description
EXAMPLES
1. Examples of Compound (1)
[0171] The invention will be described in more detail by way of Examples. Examples are described as typical examples, and therefore the invention is limited by the Examples. Compound (1) was synthesized according to procedures described below. The thus synthesized compound was identified by a method such as an NMR analysis. Physical properties of a compound or a composition, and characteristics of a device were measured by the methods described below.
[0172] NMR analysis: For measurement, DRX-500 made by Bruker BioSpin Corporation was used. In .sup.1H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl.sub.3, and measurement was carried out under conditions of room temperature, 500 MHz and 16 times of accumulation. Tetramethylsilane was used as an internal standard. In .sup.19F-NMR measurement, CFCl.sub.3 was used as an internal standard, and measurement was carried out under conditions of 24 times of accumulation. In explaining nuclear magnetic resonance spectra obtained, s, d, t, q, quip, sex and m stand for a singlet, a doublet, a triplet, a quartet, a quintet, a sextet and a multiplet, and br being broad, respectively.
[0173] Gas chromatographic analysis: For measurement, GC-2010 Gas Chromatograph made by Shimadzu Corporation was used. As a column, a capillary column DB-1 (length 60 m, bore 0.25 mm, film thickness 0.25 m) made by Agilent Technologies, Inc. was used. As a carrier gas, helium (1 mL/minute) was used. A temperature of a sample vaporizing chamber and a temperature of a detector (FID) were set to 300 C. and 300 C., respectively. A sample was dissolved in acetone and prepared to be a 1 wt % solution, and then 1 microliter of the solution obtained was injected into the sample vaporizing chamber. As a recorder, GC Solution System made by Shimadzu Corporation or the like was used.
[0174] Gas chromatography mass spectrometry: For measurement, GCMS-QP2010 Ultra Gas Chromatograph Mass Spectrometer made by Shimadzu Corporation was used. As a column, a capillary column DB-1 (length 60 m, bore 0.25 mm, film thickness 0.25 m) made by Agilent Technologies, Inc. was used. As a carrier gas, helium (1 mL/minute) was used. A temperature of a sample vaporizing chamber, a temperature of an ion source, ionization voltage and emission current were set to 300 C., 200 C., 70 eV, 150 uA, respectively. A sample was dissolved in acetone and prepared to be a 1 wt % solution, and then 1 microliter of the solution obtained was injected into the sample vaporizing chamber. As a recorder, GCMS Solution System made by Shimadzu Corporation or the like was used.
[0175] HPLC analysis: For measurement, Prominence (LC-20AD; SPD-20A) made by Shimadzu Corporation was used. As a column, YMC-Pack ODS-A (length 150 mm, bore 4.6 mm, particle diameter 5 m) made by YMC Co., Ltd. was used. As an eluate, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector or the like was appropriately used. When the UV detector was used, a detection wavelength was set at 254 nm. A sample was dissolved in acetonitrile and prepared to be a 0.1 wt % solution, and then 1 microliter of the solution was injected into a sample chamber. As a recorder, C-R7Aplus made by Shimadzu Corporation was used.
[0176] Ultraviolet-Visible Spectrophotometry: For measurement, PharmaSpec UV-1700 made by Shimadzu Corporation was used. A detection wavelength was adjusted in the range of 190 nm to 700 nm. A sample was dissolved in acetonitrile and prepared to be a 0.01 mmol/L solution, and measurement was carried out by putting the solution in a quartz cell (optical path length: 1 cm).
[0177] Sample for mEasurEment: Upon measuring phase structure and a transition temperature (a clearing point, a melting point, a polymerization starting temperature or the like), a compound itselfwasusedasasample. Upon measuring physical properties such as maximum temperature of a nematic phase, viscosity, optical anisotropy and dielectric anisotropy, a mixture of a compound and a base liquid crystal was used as a sample.
[0178] When the sample prepared by mixing the compound with the base liquid crystal was used, an extrapolated value was calculated according to the following formula and a calculated value was described: [extrapolated value]=(100[measured value of a sample][% by weight of a base liquid crystal][measured value of the base liquid crystal])/[% by weight of a compound].
[0179] Base liquid crystal (A): When the dielectric anisotropy of the compound was zero or positive, base liquid crystal (A) described below was used. A proportion of each component was expressed in terms of % by weight.
TABLE-US-00002
[0180] A ratio of the compound to base liquid crystal (A) was adjusted to (15% by weight: 85% by weight). When crystals (or a smectic phase) precipitated at 25 C. at the ratio, a ratio of the compound to base liquid crystal (A) was changed in the order of (10% by weight: 90% by weight), (5% by weight: 95% by weight) and (1% by weight: 99% by weight), and the sample was measured at a ratio at which no crystal (or no smectic phase) precipitated at 25 C. In addition, unless otherwise noted, the ratio of the compound to base liquid crystal (A) was (15% by weight: 85% by weight).
[0181] Measuring method: Physical properties were measured according to methods described below. Most of the methods are described in the Standard. of Japan E:ectronics and Information Technology industries Association (JEITA) discussed and established in JEITA (JEITA ED-2521B). A modified method was also applied. No thin film transistor (TFT) was attached to a TN device used for measurement.
[0182] (1) Phase structure: A sample was placed on a hot plate in a melting point apparatus (FP-52 Hot Stage made by Mettler-Toledo International Inc.) equipped with a polarizing microscope. A state of phase and a change thereof were observed with the polarizing microscope while the sample was heated at a rate of 3 C. per minute, and a kind of the phase was specified.
[0183] (2) Transition temperature ( C.): For measurement, a differential scanning calorimeter, Diamond DSC System, made by PerkinElmer, Inc. or a high sensitivity differential scanning calorimeter, X-DSC7000, made by SII NanoTechnology Inc. was used. A sample was heated and then cooled at a rate of 3 C. per minute, and a starting point of an endothermic peak or an exothermic peak caused by a phase change of the sample was determined by extrapolation, and thus a transition temperature was determined. A melting point and a polymerization starting temperature of a compound were also measured using the apparatus. Temperature at which a compound undergoes transition from a solid to a liquid crystal phase such as the smectic phase and the nematic phase may be occasionally abbreviated as minimum temperature of the liquid crystal phase. Temperature at which the compound undergoes transition from the liquid crystal phase to liquid may be occasionally abbreviated as clearing point.
[0184] A crystal was expressed as C. When the crystals were distinguishable in two kinds, each was expressed as C.sub.1 or C.sub.2. The smectic phase or the nematic phase was expressed as S or N. When smectic A phase, smectic B phase, smectic C phase or smectic F phase was distinguishable among the smectic phases, the phases were expressed as S.sub.A, S.sub.B, S.sub.C or S.sub.F, respectively. A liquid (isotropic) was expressed as I. A transition temperature was expressed as C50.0 N 100.0 I, for example. The expression indicates that a transition temperature from the crystals to the nematic phase is 50.0 C., and a transition temperature from the nematic phase to the liquid is 100.0 C.
[0185] (3) Compatibility of compounds: Samples in which the base liquid crystal and the compound were mixed for proportions of the compounds to be 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight and 1% by weight were prepared. The samples were put in glass vials, and the glass vials were kept in freezers at 20 C. or 30 C. for a predetermined period of time. Whether or not a nematic phase was kept or whether or not crystals or a smectic phase precipitated was observed. Conditions under which the nematic phase was kept were applied as a measure of compatlbility. The proportion of the compound and the temperature of the freezer may be changed when necessary.
[0186] (4) Maximum temperature of nematic phase (T.sub.NI or NI; C.): A sample was placed on a hot plate in a melting point apparatus equipped with a polarizing microscope, and heated at a rate of 1 C. per minute. Temperature when part of the sample began to change from a nematic phase to an isotropic liquid was measured. When the sample was a mixture of compound (1) and the base liquid crystal, the maximum temperature was expressed in terms of a symbol T.sub.NI. When the sample was a mixture of compound (1) and a compound selected from compound (2) to compound (15), the maximum temperature was expressed as a symbol NI. A maximum temperature of the nematic phase maybe occasionally abbreviated as maximum temperature.
[0187] (5) Minimum temperature of nematic phase (T.sub.C; C.) : Samples each having a nematic phase were put in glass vials and kept in freezers at temperatures of 0 C., 10 C., 20 C., 30 C. and 40 C. for 10 days, and then 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 T.sub.c<20 C. A minimum temperature of the nematic phase may be occasionally abbreviated as minimum temperature.
[0188] (6) Viscosity (bulk viscosity; ; measured at 20 C.; mPa.Math.s): For measurement, a cone-plate (E type) rotational viscometer made by Tokyo Keiki Inc. was used.
[0189] (7) Viscosity (rotational viscosity; 1; measured at 25 C.; mPa.Math.s): Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was put in a TN device in which a twist angle was 0 degrees and a distance (cell gap) between two glass substrates was 5 m. Voltage was applied stepwise to the device in the range of 16 V to 19.5 V at an increment of 0.5 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. A value of dielectric anisotropy required for the calculation was determined using the device by which the rotational viscosity was measured and by a method described below.
[0190] (8) Optical anisotropy (refractive index anisotropy; measured at 25 C.; n): Measurement was carried out by an Abbe refractometer with a polarizing plate mounted on an ocular, using light at a wavelength of 589 nm. A surface of a main prism was rubbed in one direction, and then a sample was added dropwise onto the main prism. A refractive index (n) was measured when a direction of polarized light was parallel to a direction of rubbing. A refractive index (n) was measured when the direction of polarized light was perpendicular to the direction of rubbing. A value of optical anisotropy (n) was calculated from an equation: n=nn.
[0191] (9) Dielectric anisotropy (; measured at 25 C.): A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 pm and a twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured. A value of dielectric anisotropy was calculated from an equation: =.
[0192] (10) Elastic constant (K; measured at 25 C.; pN): For measurement, HP 4 2 8 4A LCR Meter made by Yokogawa-Hewlett-Packard Co. was used. A sample was put in a horizontal alignment device in which a distance (cell gap) between two glass substrates was 20 m. An electric charge of 0 V to 20 V was applied to the device, and electrostatic capacity (C) and applied voltage (V) were measured. The measured values were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku in Japanese; Nikkan Kogyo Shimbun, Ltd.) and values of K.sub.11 and K.sub.33 were obtained from equation (2.99). Next, K.sub.22 was calculated using the previously determined values of K.sub.11 and K.sub.33 in equation (3.18) on page 171. Elastic constant K was expressed in terms of a mean value of the thus determined K.sub.11, K.sub.22 and K.sub.33.
[0193] (11) Threshold voltage (Vth; measured at 25 C.; V): For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 0.45/n (m) and a twist angle was 80 degrees. A voltage (32 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 10 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of a voltage at 90% transmittance.
[0194] (12) Change in heating current values (dH; measured. at 25 C.; A): Then, dH was determined according to the following formula (A):
dH(A)=Iha(A)Ihb(A) (A)
where, Iha in formula (A) denotes a value of the current passing through the liquid crystal. composition after heating, and. Ihb denotes a value of the current passing through the liquid crystal composition before heating. The liquid crystal composition was heated at 150 C. for 1 hour in atmospheric air. A TN device used for the measurement was prepared by facing two glass substrates obliquely vapor-deposited with silicon dioxide, in which a distance (cell gap) between the two glass substrates was 10 m and an electrode area was 1 cm.sup.2. A current value was determined by applying a rectangular wave of 3 V and 32 Hz to the device at 25 C.
[0195] (13) Voltage holding ratio (VHR-1; measured at 25 C.; %): A TN device used for measurement had a polyimide alignment film, and a distance (cell gap) between two glass substrates was 5 m. A sample was put in the device, and then the device was sealed with an ultraviolet-curable adhesive. The device was charged by applying a pulse voltage (60 microseconds at 5 V) at 25 C. A decaying 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 determined. Area B is an area without decay. A voltage holding ratio is expressed in terms of a percentage of area A to area B.
[0196] (14) Voltage holding ratio (VHR-2; measured at 80 C.; %): A voltage holding ratio was measured by a method described above except that the voltage holding ratio was measured at 80 C. in place of 25 C. The results were expressed in terms of a symbol VHR-2.
[0197] (15) Specific resistance (p; measured at 25 C.; cm): Into a vessel equipped with electrodes, 1.0 mL of sample was injected. A direct current voltage (10 V) was applied to the vessel, and a direct current after 10 seconds was measured. Specific resistance was calculated from the following equation: (specific resistance)={(voltage)(electric capacity of a vessel)}/{(direct current)(dielectric constant of vacuum)}.
[0198] (16) Response time (i; measured at 25 C.; ms): For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A low-pass filter was set to 5 kHz. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 5.0 pm and a twist angle was 80 degrees. A voltage (rectangular waves; 60 Hz, 5 V, 0.5 second) was applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. A rise time (r; millisecond) was expressed in terms of time required for a change from 90% transmittance to 10% transmittance. A fall time (f; millisecond) was expressed in terms of time required for a change from 10% transmittance to 90% transmittance. A response time was expressed by a sum of the rise time and the fall time thus obtained.
[0199] (17) Flicker rate (measured at 25 C.; %): For measurement, 3298F Multimedia Display Tester made by Yokogawa Electric Corporation was used. A light source was LED. A sample was put in a normally black mode FFS device in which a distance (cell gap) between two glass substrates was 3.5 m and a rubbing direction was anti-parallel. The device was sealed with an ultraviolet-curable adhesive. Voltage was applied to the device, and a voltage having a maximum amount of light transmitted through the device was measured. A flicker rate displayed thereon was read by bringing a sensor unit close to the device while voltage was applied to the device.
[0200] Raw material: Solmix (registered. trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and. was purchased from Japan Alcohol Trading Co., Ltd.
Synthesis Example 1
Synthesis of compound (No 1-3-7)
[0201] ##STR00070##
First Step
[0202] Under a nitrogen atmosphere, an isopropylmagnes ium chloride-lithium chloride complex (1.3 M, THF (tetrahydrofuran) solution, 281 mL) and THF (500 mL) were put in a reaction vessel, and the resulting' mixture was cooled to 0 C. Compound (T-1) (67.96 g) was slowly added thereto, and the resulting mixture was stirred until compound (T-1) disappeared. Next, compound (T-2) (50.00 g) was slowly added thereto, and the resulting mixture was stirred for 8 hours while returning to room temperature. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride, and an aqueous layer thereof was subjected to extraction with toluene. A combined organic layer was washed with brine. The resulting material was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain compound (T-3) (79.00 g, yield: 91%).
Second Step
[0203] Under a nitrogen atmosphere, compound (T-3) (79.00 g), ethylene glycol (3.95 g), PISA (paratoluenesulfonic acid monohydrate, 2.37 g) and toluene (790 mL) were put in a reaction vessel, and the resulting mixture was heated under reflux for 4 hours while distilled-off water was removed. The reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate, and an aqueous layer thereof was subjected to extraction with toluene. A combined. organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified. by sca gel chromatography (toluene/ethyl acetate=10/1 in a volume ratio) to obtain compound (T-4). Compound (T-4) obtained, 5% palladium on carbon (2.37 g) and IPA (790 ml,) were put in a reaction vessel, and the resulting mixture was stirred for 8 hours under a hydrogen atmosphere. The catalyst was removed by filtration, and the resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (heptane/toluene=10/1 in a volume ratio), and further purified through recrystallization in Solml (registered trademark) A-11 to obtain compound (T-5) (54.90 g, Yield: 73%).
Third Step
[0204] Under a nitrogen atmosphere, compound (T-5) (54.90 g) and THF (549 mL) were put in a reaction vessel, and the resulting mixture was cooled to 60 C. Then, n-butyl lithium (1.65 M, n-hexane solution, 157 mL) was slowly added thereto, and the resulting mixture was stirred for 2 hours, Next, dibromodifluoromethane (54.36 g) was slowly added thereto and the resulting mixture was stirred for 8 hours while returning to room temperature. The resulting reaction mixture was poured into water, and an aqueous layer thereof was subjected to extraction with. toluene, Then, a combined. organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure and the resulting residue was purified by qilica gel chromatography (toluene/ethyl acetate-10/1 in a volume ratio) to obtain compound (T-6) (65.7 g; yield: 48%).
Fourth Step
[0205] Compound (T-6) (20.00 g), compound (T-7) (9.24 g) synthesized according to the method described in WO 2008/105286 A1, potassium carbonate (5.27 g), tetrabutylphosphonium bromide (TBPB) (6.47 g), heptane (12 mL) and water (110 mL) were put in a reaction vessel, and the resulting mixture was heated under reflux for 20 hours. The reaction mixture was poured into water, and an aqueous layer thereof was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (toluene/ethyl.sub. acetate=10/1 in a volume ratio), and further purified through recrystailization in Solmix (registered trademark) A-11 to obtain compound (T-8) (18.80 g, yield: 74%).
Fifth Step
[0206] Under a nitrogen atmosphere, compound (T-8) (18.80 g), formic acid (38.4 mL), TBAB (2.27 g) and toluene (128 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water, and returned to neutrality with sodium bicarbonate. An aqueous layer thereof was subjected to extraction with toluene, and a combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified through. recrystallization in heptane to obtain compound (T-9) (9.00 g, yield: 76%).
Sixth Step
[0207] Under a nitrogen atmosphere, (methoxymethyl)triphenylphosphonium chloride (8.02 g) and THF (90 mL) were put in a reaction vessel, and the resulting mixture was cooled to 40 C. Potassium t-butoxide (2.62 g) was added thereto, and the resulting mixture was stirred for 1 hour while maintaining 40 C. Next, a THF (90 mL) solution of compound (T-9) (9.00 g) was slowly added dropwise thereto, and after dropwise addition, the resulting mixture was stirred for 3 hours while returning to room, temperature. The reaction mixture was poured into water, and an aqueous layer thereof was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (tolueneiheptane=2/1 in a volume ratio) to obtain compound (T-10). Compound (T-10) obtained and Raney nickel (0.9 g) were put in a reaction vessel, and the resulting mixture was stirred for 30 hours under a hydrogen atmosphere.
[0208] The catalyst was removed by filtration, and then the resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (toluene/heptane=2/1 in a volume ratio), and further purified through recrystallization in Solmix (registered trademark) A-11 to obtain compound (No. 1-3-7) (1.86 g, yield: 19%)
[0209] .sup.1H-NMR (ppm; CDCl.sub.3): 7.38-7.34 (m, 1H), 7.17-7.12 (m, 4H), 6.86-6.83 (m, 2H), 3.35 (s, 3H), 3.24 (d, J=6.3 Hz, 2H), 2.54-2.47 (m, 1H), 1.95-1.93 (m, 4H), 1.69-1.61 (m, 1H), 1.47-1.38 (m, 2H), 1.17-1.08 (m, 2H)
[0210] Transition temperature: C 80.2 N 96.4 I.
[0211] Maximum temperature (T.sub.NT)=59.7 C.; dielectric anisotropy ()=40.2; dielectric constant () in the minor axis direction=8.5; optical anisotropy (n)=0.137; viscosity ()=81.6 mPa.Math.s.
Synthesis Example 2
Synthesis of Compound (No. 1-1-4)
[0212] ##STR00071##
First Step
[0213] Under a nitrogen atmosphere, compound (T-6) (25.00 g), compound (T-11) (6.164 g), potassium carbonate (12.08 g), tetrabutylammonium bromide (TBAB) (4.03 g) and 1,4-dioxane (200 mL) were put in a reaction vessel, and the resulting mixture was heated under reflux for 8 hours. The reaction mixture was poured into water, and an aqueous layer thereof was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (toluene/ethyl acetate-10/1 in a volume ratio), and further purified by recrystallization in Solmix (registered trademark) A-11 to obtain compound (T-12) (12.82 g, yield: 62%).
Second Step
[0214] Under a nitrogen atmosphere, compound (T-12) (12.82 g) formic acid (38.4 mL), TBAB (2.27 g) and toluene (128 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and returned to neutrality with sodium. bicarbonate. An aqueous layer thereof was subjected to extraction with toluene, and a combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (toluene/ethyl acetate=10/1 in a volume ratio) to obtain compound (T-13) (11.17 g, yield: 99%).
Third Step
[0215] Under a nitrogen atmosphere, (methoxymethyl) triphenylphosphoni=chloride (12.30 g) and THF (100 mL) were put in a. reactor, and the resulting mixture was cooled to 40 C. Potassium t-butoxide (4.03 g) was added thereto, and the resulting mixture was stirred for 1 hour wile maintaining 40 C. Next, a THF (40 mL) solution of compound (T-13) (10.41 g) was slowly added dropwise thereto, and. after dropwise addition, the resuitinq mixture was stirred for 3 hours while returning to room temperature. The reaction mixture was poured into water, and an aqueous layer thereof was subjected to extraction with toluene. A combined organic layer was washed with brine and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (toluene/heptane=2/1 in a volume ratio) to obtain compound (T-14). Compound (T-14) obtained, 5% palladium on carbon (0.31 g), toluene (100 mL) and IPA (100 mL) were put in a reaction vessel, and the resulting mixture was stirred for 12 hours under a hydrogen atmosphere. The catalyst was removed by filtration, and then the resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (ethyl acetateptane=1/10 in a volume ratio), and further purified. through recrystallization in in Solmix (registered trademark) A-11 to obtain compound (1-1-4) (3.71 g, yield: 33%).
[0216] .sup.1H-NMR. (ppm; CDCl.sub.3) : 6.98-6.92 (m, 2H), 6.85-6.82 (m, 2H), 3.35 (s, 3H), 3.24 (J =6.3 Hz, 2H.), 2.50 (tt, J =12.2 Hz, J =3.1 Hz, 1H), 1.97-1.90 (m, 4H), 1.69-1.60 (m, 1H), 1.46-1.37 (m, 2H), 1.17-1.08 (m, 2)
[0217] Transition temperature: C 57.1 I.
[0218] Maximum temperature (T.sub.NT)=19.6 C.; dielectric anisotropy ()31.1; dielectric constant in a minor axis direction ()=9.1; optical anisotropy (n)=0 .070; viscosity ()=49.8 mPa.Math.s.
Comparative Example 1
Comparison of Physical Properties
[0219] Compound (S-1) below was selected as a comparative compound. The reason is that the compound is described in JP H10-251186 A and is similar to the compound of the invention.
##STR00072##
[0220] .sup.1H-NMR (ppm; CDCl.sub.3): 6.98-6.92 (m, 2H), 6.85-6.82 (m, 2H), 2.49 (tt, J =12.2 Hz, J =3.1 Hz, 1H), 1.90-1.88 (m, 4H), 1.44-1.19 (m, 7H), 1.08-1.00 (m, 2H), 0.90 (J =7.5 Hz, 3H)
[0221] Transition temperature: C 40.2 I.
[0222] Maximum temperature (T.sub.NT)=11.0 C.; dielectric anisotropy ()=20,3; dielectric constant in a minor axis direction ()=7.2; optical anisotropy (n)=0.064; viscosity ()=38.9 mPa.Math.s
TABLE-US-00003 TABLE 2 Physical properties of compound (No. 1-1-4) and comparative compound (S-1) Compound (No. 1-1-4) Comparative compound (S-1)
[0223] Physical properties of compound (No. 1-1-4) and comparative compound (S-1) obtained. in Synthesis Example 2 are summarized in Table 2. Table 2 shows that compound (No. 1-1-4) is superior to comparative compound (S-1) in view of larger dielectric anisotropy and further a larger dielectric constant in the minor axis direction.
Comparative Example 2
[0224] Compound (S-2) below was selected as a comparative compound. The reason is that the compound is similar to the compound of the invention. The compound was synthesized according to the method described in JP H10-251186 A.
##STR00075##
[0225] .sup.1H-NMR (ppm; CDCl.sub.3): 7.37-7.34 (m, 1H), 7.17-7.12 (m, 4H), 6.85-6.83 (m, 2H), 2.51-2.46 (m, 1H), 1.90-1.88 (m, 4H), 1.44-1.19 (m, IH), 1.09-1.00 (m, 2H), 0.90 (t, J =7.5 Hz, 3H)
[0226] Transition temperature: C 14.5 N 118.5 I.
[0227] Maximum temperature (T.sub.NT)=69.0 C.; dielectric anisotropy ()=28.3; dielectric constant in a minor axis direction ()=6.5; optical anisotropy (n)=0.130; viscosity ()=65.7 mPa.Math.s
TABLE-US-00004 TABLE 3 Physical properties of compound (No. 1-3-7) and comparative compound (S-2) Compound (No. 1-3-7) Comparative compound (S-2)
[0228] Physical. properties of compound (No. 1-3-7) and comparative compound (S-2) obtained in Synthesis Example 1 are summarized in Table 3. Table 3 shows that compound (No. 1-3-7) superior to comparative compound (S-2) in view of larger dielectric anisotropy and further a larger dielectric constant in the minor axis direction.
2. Synthesis of Compound (1)
[0229] Compound (1) is synthesized. according to 2. Synthesis of compound (1) and Synthesis Example described above. Specific examples of such a compound include compounds (No. 1-1-1) to (No. 1-130), compounds (No. 1-2-1) to (No. 1-2-48) and compounds (No. 1-3-1) to (No. 1-3-31) described below.
##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088##
3. Examples of Compositions
[0230] The invention will be described in more detail by way of Examples. Examples are described as typical examples, and therefore the invention is limited by the Examples. For example, the invention includes a composition in Use Example, and also a mixture of a composition in Use Example 1 and a composition in. Use Example 2. The invention also includes a mixture prepared by mixing at least two compositions in Use Examples . The compounds in Use Examples were expressed using symbols according to definitions in Table 3 below. In Table 3, a configuration with regard to 1,4-cyclohexylene is trans. A parenthesized number after the symbol in Use Example expresses a chemical formula to which the compound belongs. A symbol () means a liquid crystal compound. different from. compounds (1) to (15). A proportion (percentage) of the liquid crystal compound is expressed in. terms of weight percent (% by weight) based on. the weight of the liquid crystal composition without containing an additive. Values of physicalpropertiesofecornpositionwere summarized in a. last part. The physical properties were measured. according to the methods described above, and measured values were directly described (without extrapolation).
TABLE-US-00005 TABLE 4 Method for Description of Compounds using Symbols R-(A1)-Z1- ... - Zn-(An)-R 1) Left-terminal Group R Symbol C.sub.nH.sub.2n+1 n C.sub.nH.sub.2n+1O nO C.sub.m H.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 OCHCHCF.sub.3 OVCF3 CN C 3) Bonding Group Zn 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 An Symbol
Use Example 1
[0231]
TABLE-US-00006 1O1-HB(F,F)XB(F,F)-F (No. 1-1-4) 8% 2-HB-C (8-1) 4% 3-HB-C (8-1) 10% 3-HB-O2 (2-5) 14% 2-BTB-1 (2-10) 4% 3-HHB-F (6-1) 5% 3-HHB-1 (3-1) 7% 3-HHB-O1 (3-1) 4% 3-HHB-3 (3-1) 13% 3-HHEB-F (6-10) 3% 5-HHEB-F (6-10) 3% 2-HHB(F)-F (6-2) 6% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 6% 3-HHB(F,F)-F (6-3) 5% NI = 88.8 C.; = 18.9 mPa .Math. s; n = 0.098; = 6.5.
Use Example 2
[0232]
TABLE-US-00007 1O1-HBBXB(F,F)-F (No. 1-2-1) 5% 3-HB-CL (5-2) 15% 3-HB-O2 (2-5) 10% 3-HHB(F,F)-F (6-3) 5% 3-HBB(F,F)-F (6-24) 30% 5-HBB(F,F)-F (6-24) 25% 5-HBB(F)B-2 (4-5) 5% 5-HBB(F)B-3 (4-5) 5% NI = 71.8 C.; = 24.0 mPa .Math. s; n = 0.127; = 7.3.
Use Example 3
[0233]
TABLE-US-00008 1O1-HB(F,F)XB(F)B(F,F)-F (No. 1-3-7) 6% 7-HB(F,F)-F (5-4) 3% 3-HB-O2 (2-5) 6% 2-HHB(F)-F (6-2) 10% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 10% 2-HBB(F)-F (6-23) 10% 3-HBB(F)-F (6-23) 8% 5-HBB(F)-F (6-23) 13% 2-HBB-F (6-22) 5% 3-HBB-F (6-22) 5% 5-HBB-F (6-22) 3% 3-HBB(F,F)-F (6-24) 4% 5-HBB(F,F)-F (6-24) 9% NI = 84.5 C.; = 28.1 mPa .Math. s; n = 0.117; = 7.7
Use Example 4
[0234]
TABLE-US-00009 2O1-chB(F,F)XB(F,F)-F (No. 1-1-23) 6% 5-HB-CL (5-2) 18% 3-HHB-F (6-1) 6% 3-HHB-CL (6-1) 5% 4-HHB-CL (6-1) 5% 3-HHB(F)-F (6-2) 9% 4-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 10% 7-HHB(F)-F (6-2) 9% 5-HBB(F)-F (6-23) 6% 1O1-HBBH-5 (4-1) 3% 3-HHBB(F,F)-F (7-6) 3% 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%
Use Example 5
[0235]
TABLE-US-00010 2O1-HB(2F,3F)XB(F,F)-F (No. 1-1-7) 4% 3-HHB(F,F)-F (6-3) 9% 3-H2HB(F,F)-F (6-15) 10% 4-H2HB(F,F)-F (6-15) 7% 5-H2HB(F,F)-F (6-15) 7% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F)-F (6-24) 18% 3-H2BB(F,F)-F (6-27) 8% 5-HHBB(F,F)-F (7-6) 3% 5-HHEBB-F (7-17) 3% 3-HH2BB(F,F)-F (7-15) 3% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 5%
Use Example 6
[0236]
TABLE-US-00011 2O2-HB(F,F)XB(F,F)-F (No. 1-1-18) 7% 5-HB-F (5-2) 10% 6-HB-F (5-2) 9% 7-HB-F (5-2) 6% 2-HHB-OCF3 (6-1) 6% 3-HHB-OCF3 (6-1) 6% 4-HHB-OCF3 (6-1) 6% 5-HHB-OCF3 (6-1) 6% 3-HH2B-OCF3 (6-4) 4% 5-HH2B-OCF3 (6-4) 3% 3-HHB(F,F)-O (6-3) 3% 3-HHB(F,F)-O (6-3) 5% 3-HH2B(F)-F (6-5) 3% 3-HBB(F)-F (6-23) 10% 5-HBB(F)-F (6-23) 10% 5-HBBH-3 (4-1) 3% 3-HB(F)BH-3 (4-2) 3%
Use Example 7
[0237]
TABLE-US-00012 2O1-HBB(F,F)XB(F,F)-F (No. 1-2-9) 5% 5-HB-CL (5-2) 13% 3-HHB-1 (3-1) 6% 3-HHB(F,F)-F (6-3) 9% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F)-F (6-24) 13% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F)-F (6-12) 4% 5-HHEB(F,F)-F (6-12) 4% 2-HBEB(F,F)-F (6-39) 4% 3-HBEB(F,F)-F (6-39) 4% 5-HBEB(F,F)-F (6-39) 3% 3-HHBB(F,F)-F (7-6) 5%
Use Example 8
[0238]
TABLE-US-00013 2O1-HB(F,F)XB(F,F)-CF3 (No. 1-1-9) 6% 3-HB-CL (5-2) 4% 5-HB-CL (5-2) 5% 3-HHB-OCF3 (6-1) 4% 3-H2HB-OCF3 (6-13) 4% 5-H4HB-OCF3 (6-19) 13% V-HHB(F)-F (6-2) 5% 3-HHB(F)-F (6-2) 3% 5-HHB(F)-F (6-2) 6% 3-H4HB(F,F)-CF3 (6-21) 8% 5-H4HB(F,F)-CF3 (6-21) 8% 5-H2HB(F,F)-F (6-15) 6% 5-H4HB(F,F)-F (6-21) 8% 2-H2BB(F)-F (6-26) 5% 3-H2BB(F)-F (6-26) 10% 3-HBEB(F,F)-F (6-39) 5%
Use Example 9
[0239]
TABLE-US-00014 1O1-HB(F,F)XB(F)B(F,F)-F (No. 1-3-7) 7% 5-HB-CL (5-2) 17% 7-HB(F,F)-F (5-4) 5% 3-HB-O2 (2-5) 17% 3-HHB-1 (3-1) 11% 3-HHB-O1 (3-1) 7% 2-HHB(F)-F (6-2) 6% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 7% 3-HHB(F,F)-F (6-3) 6% 3-H2HB(F,F)-F (6-15) 4% 4-H2HB(F,F)-F (6-15) 5% NI = 72.0 C.; = 21.8 mPa .Math. s; n = 0.085; = 5.8.
Use Example 10
[0240]
TABLE-US-00015 1O1-HB(F,F)XB(F,F)-F (No. 1-1-4) 6% 1O1-HBBXB(F,F)-F (No. 1-2-1) 4% 5-HB-CL (5-2) 3% 7-HB(F)-F (5-3) 6% 3-HB-O2 (2-5) 15% 3-HHEB-F (6-10) 10% 5-HHEB-F (6-10) 9% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F)-F (6-12) 6% 3-GHB(F,F)-F (6-109) 4% 4-GHB(F,F)-F (6-109) 7% 5-GHB(F,F)-F (6-109) 8% 2-HHB(F,F)-F (6-3) 5% 3-HHB(F,F)-F (6-3) 7% NI = 70.7 C.; = 29.1 mPa .Math. s; n = 0.079; = 9.6.
Use Example 11
[0241]
TABLE-US-00016 2O1-HB(F,F)XB(F)B(F,F)-OCF3 (No. 1-3-23) 4% 3-HB-O1 (2-5) 12% 3-HH-4 (2-1) 4% 3-HB(2F,3F)-O2 (9-1) 11% 5-HB(2F,3F)-O2 (9-1) 12% 2-HHB(2F,3F)-1 (10-1) 12% 3-HHB(2F,3F)-1 (10-1) 13% 3-HHB(2F,3F)-O2 (10-1) 12% 5-HHB(2F,3F)-O2 (10-1) 13% 3-HHB-1 (3-1) 7%
Use Example 12
[0242]
TABLE-US-00017 2O1-chB(F,F)XB(F,F)-F (No. 1-1-23) 7% 2-HH-5 (2-1) 3% 3-HH-4 (2-1) 13% 3-HH-5 (2-1) 3% 3-HB-O2 (2-5) 11% 3-H2B(2F,3F)-O2 (9-4) 14% 5-H2B(2F,3F)-O2 (9-4) 14% 3-HHB(2F,3CL)-O2 (10-12) 4% 2-HBB(2F,3F)-O2 (10-7) 5% 3-HBB(2F,3F)-O2 (10-7) 7% 5-HBB(2F,3F)-2 (10-7) 9% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 4% 3-HHB-O1 (3-1) 3%
Use Example 13
[0243]
TABLE-US-00018 2O1-HB(2F,3F)XB(F,F)-F (No. 1-1-7) 8% 2-HH-3 (2-1) 21% 3-HH-4 (2-1) 8% 1-BB-3 (2-8) 8% 3-HB-O2 (2-5) 3% 3-BB(2F,3F)-O2 (9-3) 7% 5-BB(2F,3F)-O2 (9-3) 4% 2-HH1OB(2F,3F)-O2 (10-5) 11% 3-HH1OB(2F,3F)-O2 (10-5) 17% 3-HBB(2F,3CLF)-O2 (10-13) 3% 3-HHB-1 (3-1) 5% 3-HHB-O1 (3-1) 3% 5-B(F)BB-2 (3-8) 2%
Use Example 14
[0244]
TABLE-US-00019 2O2-HB(F,F)XB(F,F)-F (No. 1-1-18) 4% 2O1-HBB(F,F)XB(F,F)-F (No. 1-2-9) 3% 2-HH-3 (2-1) 15% 7-HB-1 (2-5) 8% 5-HB-O2 (2-5) 8% 3-HB(2F,3F)-O2 (9-1) 15% 5-HB(2F,3F)-O2 (9-1) 15% 3-HHB(2F,3CL)-O2 (10-12) 3% 4-HHB(2F,3CL)-O2 (10-12) 3% 5-HHB(2F,3CL)-O2 (10-12) 4% 3-HH1OCro(7F,8F)-5 (13-6) 6% 5-HBB(F)B-2 (4-5) 8% 5-HBB(F)B-3 (4-5) 8%
Use Example 15
[0245]
TABLE-US-00020 2O1-HB(F,F)XB(F,F)-CF3 (No. 1-1-9) 6% 3-HH-4 (2-1) 5% 1-BB-3 (2-8) 6% 3-HH-V (2-1) 20% 3-BB(2F,3F)-O2 (9-3) 11% 5-BB(2F,3F)-O2 (9-3) 5% 2-HH1OB(2F,3F)-O2 (10-5) 20% 3-HH1OB(2F,3F)-O2 (10-5) 13% 3-HHB-1 (3-1) 8% 5-B(F)BB-2 (3-8) 6%
Use Example 16
[0246]
TABLE-US-00021 2O1-HB(F,F)XB(F)B(F,F)-OCF3 (No. 1-3-23) 5% 2-HH-3 (2-1) 5% 3-HH-V1 (2-1) 8% 1V2-HH-1 (2-1) 8% 1V2-HH-3 (2-1) 5% 3-BB(2F,3F)-O2 (9-3) 8% 5-BB(2F,3F)-O2 (9-3) 5% 3-H1OB(2F,3F)-O2 (9-5) 7% 2-HH1OB(2F,3F)-O2 (10-5) 7% 3-HH1OB(2F,3F)-O2 (10-5) 19% 3-HDhB(2F,3F)-O2 (10-3) 7% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 2% 2-BB(2F,3F)B-3 (11-1) 11%
Use Example 17
[0247]
TABLE-US-00022 1O1-HB(F,F)XB(F,F)-F (No. 1-1-4) 4% 1V2-BEB(F,F)-C (8-15) 6% 3-HB-C (8-1) 17% 2-BTB-1 (2-10) 9% 5-HH-VFF (2-1) 23% 3-HHB-1 (3-1) 5% VFF-HHB-1 (3-1) 10% VFF2-HHB-1 (3-1) 12% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 5% 3-H2BTB-4 (3-17) 4% NI = 84.1 C.; = 15.4 mPa .Math. s; n = 0.133; = 7.7.
Use Example 18
[0248]
TABLE-US-00023 1O1-HBBXB(F,F)-F (No. 1-2-1) 3% 2O1-chB(F,F)XB(F,F)-F (No. 1-1-23) 4% 3-HB-O1 (2-5) 10% 3-HH-4 (2-1) 5% 3-HH-VFF (2-1) 5% 3-HB(2F,3F)-O2 (9-1) 9% 5-HB(2F,3F)-O2 (9-1) 10% 2-HHB(2F,3F)-1 (10-1) 11% 3-HHB(2F,3F)-1 (10-1) 12% 3-HHB(2F,3F)-O2 (10-1) 10% 5-HHB(2F,3F)-O2 (10-1) 11% 3-HHB-1 (3-1) 6% 1-BB-5 (2-8) 4%
Use Example 19
[0249]
TABLE-US-00024 1O1-HB(F,F)XB(F)B(F,F)-F (No. 1-3-7) 4% 2O1-HB(F,F)XB(F,F)-CF3 (No. 1-1-9) 4% 2-HH-3 (2-1) 13% 7-HB-1 (2-5) 8% 5-HB-O2 (2-5) 8% 3-HB(2F,3F)-O2 (9-1) 13% 5-HB(2F,3F)-O2 (9-1) 13% 3-HHB(2F,3CL)-O2 (10-12) 4% 4-HHB(2F,3CL)-O2 (10-12) 3% 2-H1OB(2F,3F)-O2 (9-5) 3% 3-H1OB(2F,3F)-O2 (9-5) 3% 3-HH1OCro(7F,8F)-5 (13-6) 5% 5-HBB(F)B-2 (4-5) 9% 5-HBB(F)B-3 (4-5) 10%
Use Example 20
[0250]
TABLE-US-00025 2O1-HB(2F,3F)XB(F,F)-F (No. 1-1-7) 5% 2-HH-5 (2-1) 3% 3-HH-4 (2-1) 15% 3-HH-5 (2-1) 4% 3-HB-O2 (2-5) 12% 3-H2B(2F,3F)-O2 (9-4) 10% 5-H2B(2F,3F)-O2 (9-4) 10% 3-HHB(2F,3CL)-O2 (10-12) 5% 2-HBB(2F,3F)-O2 (10-7) 5% 3-HBB(2F,3F)-O2 (10-7) 7% 5-HBB(2F,3F)-O2 (10-7) 6% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 4% 3-HHB-O1 (3-1) 3% 3-HH2B(2F,3F)-O2 (10-4) 5% 3-DhB(2F,3F)-O2 (9-2) 3%
Use Example 21
[0251]
TABLE-US-00026 2O2-HB(F,F)XB(F,F)-F (No. 1-1-18) 6% 2-HH-3 (2-1) 5% 3-HH-V1 (2-1) 7% 1V2-HH-1 (2-1) 5% 1V2-HH-3 (2-1) 4% 3-BB(2F,3F)-O2 (9-3) 6% 5-BB(2F,3F)-O2 (9-3) 3% 3-H1OB(2F,3F)-O2 (9-5) 4% 2-HH1OB(2F,3F)-O2 (10-5) 8% 3-HH1OB(2F,3F)-O2 (10-5) 17% 3-HDhB(2F,3F)-O2 (10-3) 5% 3-dhBB(2F,3F)-O2 (10-9) 3% V-HHB-1 (3-1) 5% V2-HHB-1 (3-1) 5% 3-HHB-1 (3-1) 3% 3-HHB-3 (3-1) 3% 2-BB(2F,3F)B-3 (11-1) 11%
Use Example 22
[0252]
TABLE-US-00027 2O1-HBB(F,F)XB(F,F)-F (No. 1-2-9) 7% 2-HH-3 (2-1) 18% 3-HH-4 (2-1) 7% 1-BB-3 (2-8) 8% 3-HB-O2 (2-5) 3% 3-BB(2F,3F)-O2 (9-3) 8% 5-BB(2F,3F)-O2 (9-3) 5% 2-HH1OB(2F,3F)-O2 (10-5) 10% 3-HH1OB(2F,3F)-O2 (10-5) 18% 3-HHB-1 (3-1) 5% 3-HHB-O1 (3-1) 3% 5-B(F)BB-2 (3-8) 2% V-HBB-2 (3-4) 6%
INDUSTRIAL APPLICABILITY
[0253] A liquid crystal compound of the invention has excellent physical properties. A liquid crystal composition containing the compound can be widely utilized in a liquid crystal display device to be used in a personal computer, a television or the like.