CN111253953A - Liquid crystal composition and element for phase control of electromagnetic wave signals - Google Patents
Liquid crystal composition and element for phase control of electromagnetic wave signals Download PDFInfo
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- CN111253953A CN111253953A CN201910852540.5A CN201910852540A CN111253953A CN 111253953 A CN111253953 A CN 111253953A CN 201910852540 A CN201910852540 A CN 201910852540A CN 111253953 A CN111253953 A CN 111253953A
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- 239000000203 mixture Substances 0.000 title claims abstract description 169
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 139
- 150000001875 compounds Chemical class 0.000 claims abstract description 200
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 112
- 125000003342 alkenyl group Chemical group 0.000 claims description 43
- -1 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl Chemical group 0.000 claims description 41
- 125000003545 alkoxy group Chemical group 0.000 claims description 37
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 29
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 29
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 26
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 26
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 13
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 claims description 12
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 11
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 7
- 125000005732 2,6-difluoro-1,4-phenylene group Chemical group [H]C1=C(F)C([*:1])=C(F)C([H])=C1[*:2] 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000012071 phase Substances 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 125000004093 cyano group Chemical group *C#N 0.000 description 23
- 239000000523 sample Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000007824 aliphatic compounds Chemical class 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- APGNXGIUUTWIRE-UHFFFAOYSA-N 4-Pentylphenylacetylene Chemical compound CCCCCC1=CC=C(C#C)C=C1 APGNXGIUUTWIRE-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
- G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
- G01S7/02—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S13/00
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
- G01S7/00—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00
- G01S7/48—Details of systems according to groups G01S13/00, G01S15/00, G01S17/00 of systems according to group G01S17/00
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Radar, Positioning & Navigation (AREA)
- Remote Sensing (AREA)
- Computer Networks & Wireless Communication (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a liquid crystal composition and a device for phase control of electromagnetic wave signals. The liquid crystal composition has good characteristicsHas an excellent balance of characteristics, and is useful as a material for an element for controlling the phase of an electromagnetic wave signal having a frequency of 1MHz to 400 THz. The liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (1), and is used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz. In the formula (1), ring A1Ring A2Ring A3And ring A4A group represented by any one of (I) to (XV) below; z1And Z3For example, a single bond; p and q are 0, 1, or 2; r1For example, alkyl; r2For example, is said R1or-CN.
Description
Technical Field
The present invention relates to an element for controlling the phase of an electromagnetic wave signal having a frequency of 1MHz to 400THz and a liquid crystal composition used for the element. The composition has a nematic phase, and positive or negative dielectric constant anisotropy.
Background
Examples of the element for controlling the phase of the electromagnetic wave signal having a frequency of 1MHz to 400THz include a millimeter wave band, a microwave band antenna, and an infrared laser element. Various methods have been studied for these elements, but a method using a liquid crystal which is considered to have few failures due to the absence of a mechanically movable portion has been attracting attention.
The orientation of the molecules of the liquid crystal changes according to an external bias electric field, and the dielectric constant changes. By utilizing such properties, for example, a microwave device capable of electrically controlling the transmission characteristics of a high-frequency transmission line from the outside can be realized. As such a device, a voltage-controlled millimeter-wave band variable phase shifter in which a waveguide is filled with nematic liquid crystal, a microwave/millimeter-wave band variable phase shifter using nematic liquid crystal as a dielectric substrate of a microstrip line, and the like have been reported (patent documents 1 and 2).
Such an element for controlling the phase of an electromagnetic wave signal desirably has characteristics such as a wide usable temperature range, high gain, and low loss. Therefore, the characteristics of the liquid crystal composition require a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, a large optical anisotropy in a frequency range used for phase control, a large dielectric constant anisotropy, a small dielectric loss, a large specific resistance in a drive frequency range, stability against heat, and the like.
Conventional compositions are disclosed in the following patent documents 3 to 4.
[ Prior art documents ]
[ patent document ]
[ patent document 1] International publication No. 2017/201515
[ patent document 2] specification of U.S. patent publication No. 2018/0239213
[ patent document 3] Japanese patent laid-open No. 2004-285085
[ patent document 4] Japanese patent laid-open publication No. 2011-
Disclosure of Invention
[ problems to be solved by the invention ]
The present invention has an object to provide a liquid crystal composition having the above-mentioned required characteristics and an excellent balance of characteristics as a material for use in an element for controlling the phase of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
[ means for solving problems ]
The inventors have found that a liquid crystal composition containing a liquid crystal compound having a specific structure solves the above problems, and have completed the present invention.
The present invention has the following configuration.
[1] A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component and used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
In the formula (1), the reaction mixture is,
R1is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms, and one or two or more CH groups present in the alkyl group, the alkoxy group, the alkylthio group, the alkenyl group or the alkenyloxy group2As O atoms which are not bonded directly to one another, may be substituted by-O-, -CO-, or-COO-, R2Is the said R1、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H、-NCS、-SF5or-NO2；
Ring A1Ring A2Ring A3And ring A4Independently a group represented by any one of the following formulae (I) to (XV), ring A2And ring A3At least one of the above groups is a group represented by any one of the formulae (I) to (XII);
in the radicals of the formulae (I) to (XII),
at least one hydrogen may pass through-CH3、-CH2CH3、-CH2CH2CH3、-OCH3、-OCH2CH3、-SCH3or-F; z1And Z3Independently a single bond, -CH2CH2-、-CF2O-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH2-, -O-, or-CO-, Z2is-C ≡ C-C ≡ C-;
p and q are independently 0, 1 or 2, and when p and q are 2, a plurality of rings A are present1、Z1、Z3And ring A4May be the same or different.
[2] The liquid crystal composition according to [1], which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) relative to the total weight of the composition, and contains 5 to 90% by weight of at least one compound selected from the group of compounds represented by formula (2) relative to the total weight of the composition as a second component.
In formula (2), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20And ring A23May be the same or different; r20Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
[3] The liquid crystal composition according to [1], which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) relative to the total weight of the composition, and contains 5 to 90% by weight of at least one compound selected from the group of compounds represented by formula (3) relative to the total weight of the composition as a second component.
In formula (3), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl,Or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z20and Z22Independently a single bond, -CH2CH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH2-, -O-, or-CO-, Z21is-C ≡ C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20Ring A23、Z20And Z22May be the same or different.
R20Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
[4] The liquid crystal composition according to [1], which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) relative to the total weight of the composition, and contains 5 to 90% by weight of at least one compound selected from the group of compounds represented by formula (4) relative to the total weight of the composition as a second component.
In formula (4), ring A30Ring A31And ring A32Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z30、Z31And Z32Independently a single bond, -CH2CH2-、-CH＝CH-、-CH2O-、-COO-、-CF2CF2-, -C.ident.C-, or-CF2O-，Z30、Z31And Z32At least one of which is-CF2O-；X30、X31And X32Independently hydrogen or fluorine;
m1 represents 0, 1 or 2, and when m1 represents 2, a plurality of rings A are present31And Z31May be the same or different;
R20is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
[5] The liquid crystal composition according to [2], which comprises at least one compound selected from the group of compounds represented by formulae (2-1) to (2-32) as a second component.
In the formulae, R20Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
[6] The liquid crystal composition according to [3], which comprises at least one compound selected from the group of compounds represented by formulae (3-1) to (3-14) as a second component.
In the formulae, R20Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
[7] The liquid crystal composition according to [4], which comprises at least one compound selected from the group of compounds represented by formulae (4-1) to (4-15) as a second component.
In the formulae, R20Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
[8] The liquid crystal composition according to [4], which comprises at least one compound selected from the group of compounds represented by formulae (4-16) to (4-26) as a second component.
In the formulae, R20Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
[9]According to [5]]The liquid crystal composition, wherein the compound represented by the formula (1) is a compound represented by the following formula (1), based on the weight of the liquid crystal compositionIn the range of 10 to 90% by weight, R in the compounds represented by the formulae (2-1) to (2-32)21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5The proportion of the compound (b) is in the range of 10 to 90% by weight.
[10]According to [5]]Or [6]]The liquid crystal composition, wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition, and R in the compounds represented by the formulae (2-1) to (2-32)21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5In the range of 5 to 80% by weight, R in the compounds represented by the formulae (3-1) to (3-14)21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight.
[11] The liquid crystal composition according to [7], wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, and the proportion of the compound represented by the formula (4-1) to the formula (4-15) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition.
[12] The liquid crystal composition according to [8], wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, and the proportion of the compound represented by the formula (4-16) to the formula (4-26) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition.
[13]According to [5]]Or [6]]The liquid crystal composition, wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition, and R in the compounds represented by the formulae (2-1) to (2-32)21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5The proportion of the compound of (1) to (3-14) is in the range of 5 to 80% by weight, and the proportion of the compound of the formula (3-1) to (3-14) is 5% by weightTo 80 wt%.
[14]According to [6]Or [7]]The liquid crystal composition, wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition, and R in the compounds represented by the formulae (3-1) to (3-14)21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight, and the proportion of the compound represented by the formula (4-1) to the formula (4-15) is in the range of 5 to 80% by weight.
[15]According to [6]Or [8]]The liquid crystal composition, wherein the proportion of the compound represented by the formula (1) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition, and R in the compounds represented by the formulae (3-1) to (3-14)21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight, and the proportion of the compound represented by the formula (4-16) to the formula (4-26) is in the range of 5 to 80% by weight.
[16] The liquid crystal composition according to any one of [1] to [4], wherein the proportion of the liquid crystal compound other than the components selected from the group consisting of the formula (2), the formula (3), and the formula (4) is in the range of 1% by weight to 20% by weight based on the weight of the liquid crystal composition.
[17] The liquid crystal composition according to any one of [1] to [16], wherein the refractive index anisotropy (measured at 25 ℃) at a wavelength of 589nm is in the range of 0.18 to 0.35, and the dielectric constant anisotropy (measured at 25 ℃) at a frequency of 1kHz) is in the range of 7 to 40.
[18] The liquid crystal composition according to any one of [1] to [16], wherein the refractive index anisotropy (measured at 25 ℃) of a frequency of 50GHz is in the range of 0.15 to 0.40.
[19] The liquid crystal composition according to any one of [1] to [18], which comprises an acrylic monomer.
[20] The liquid crystal composition according to any one of [1] to [19], which comprises a photopolymerization initiator.
[21] The liquid crystal composition according to any one of [1] to [20], which comprises an optically active compound.
[22] An element which contains the liquid crystal composition according to any one of [1] to [21] and is used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
[ Effect of the invention ]
The composition of the present invention has a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a large optical anisotropy in a frequency region used for phase control, a small dielectric loss, and stability to heat. Therefore, an element using the material has excellent characteristics in terms of practical use.
Detailed Description
The liquid crystal composition of the present invention is sometimes simply referred to as "composition". In the device of the present invention, the phase in the "composition" may be not only a nematic phase but also another liquid crystal phase or an isotropic liquid. When used as an element, the element may be in a liquid crystal phase, and a nematic phase is preferred.
Examples of elements used for phase control of electromagnetic wave signals having frequencies of 1MHz to 400THz include millimeter-wave band variable phase shifters and LiDAR (Light Detection and Ranging) elements.
The term "liquid crystalline compound" refers to a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase but being useful as a component of a composition. The useful compounds contain a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene and have a linear molecular structure. An optically active compound is sometimes added to the composition. Even if the compound is a liquid crystalline compound, it is classified as an additive herein.
The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature". The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".
The "large specific resistance" means that the composition has a large specific resistance not only at room temperature but also at high temperature in the initial stage, and also has a large specific resistance not only at room temperature but also at high temperature after long-term use. In describing the properties such as optical anisotropy, values measured by the method described in examples were used. The "proportion of the first component" means a weight percentage (wt%) based on the total weight of the liquid crystalline compound. The same applies to the ratio of the second component and the like. The proportion of the additive mixed into the composition means a weight percentage (wt%) based on the total weight of the liquid crystalline compound.
The compound of formula (1) as the first component of the present invention will be described in more detail. Z of formula (1) of the present invention2Compounds which are-C.ident.C-in contrast to, for example, Z2The compound having a single bond tends to have poor stability to ultraviolet light. Therefore, it is difficult to practically apply the composition comprising the compound to display applications using visible light including ultraviolet light or near ultraviolet light. However, since the compound of formula (1) of the present invention has high refractive index anisotropy, it is preferable to use a composition comprising the compound of formula (1) for phase control of electromagnetic wave signals having a frequency of 1MHz to 400THz, which are lower in energy than ultraviolet and visible light.
In this case, in order to expand the liquid crystal temperature range or increase the response speed while maintaining the optical anisotropy of the composition, it is preferable to select an alkyl group, an alkoxy group, or an alkenyl group as R of the compound of formula (1)2. R of the Compound of formula (1)1And R2In order to expand the temperature range of the nematic phase of the composition, the preferred alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. Further preferred alkyl groups for reducing the viscosity are ethyl, propyl, butyl, pentyl or heptyl.
R of the Compound of formula (1)1And R2In order to expand the temperature range of the nematic phase of the composition, the preferred alkoxy group is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. Further preferred alkoxy groups for reducing the viscosity are methoxy or ethoxy.
R of the Compound of formula (1)1And R2Among them, in order to widen the temperature range of the nematic phase of the composition, preferable alkenyl groups are vinyl and 1-propeneA phenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, or a 5-hexenyl group. Further preferable alkenyl groups for reducing the viscosity are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred steric configuration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. For reasons of viscosity reduction and the like, the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, a straight-chain alkenyl group is preferable to a branched alkenyl group.
In order to improve the dielectric anisotropy while maintaining the optical anisotropy of the composition, R is2Preferably, -CN, -NCS, and-NO are selected2More preferably, -CN and-NCS are selected. In addition, in order to improve the dielectric anisotropy while maintaining the response speed of the element, R is2Preferably selected from-F, -CF3、-OCF3、-CF2H、-OCF2H. and-SF5More preferably, -F, -CF3and-OCF3。
In p and q in formula (1), p + q > 2 is preferred in order to increase the upper temperature limit of the composition. In order to lower the lower limit temperature of the composition and increase the response speed, p + q is preferably < 1, and p + q is more preferably 0.
Z1And Z3Independently a single bond, -CH2CH2-、-CF2O-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH2-, -O-, or-CO-. In order to improve the optical anisotropy of the composition, as Z1And Z3Preferably, a single bond, -CH ═ CH-, -CF ═ CF-, -CH ≡ CF-, -C ≡ C-, or-C ≡ C-, is more preferably selected from a single bond or-C ≡ C-, for the reasons of preventing deterioration of a material over time, suppressing cost, and the like.
Ring A1Ring A2Ring A3Or ring A4Independently a group represented by the formulae (I) to (XV). In this case, in order to increase the optical anisotropy or the dielectric anisotropy, it is preferable to select the groups represented by the formulae (I) to (VII). In these ring structures, in order to increase the response speed of the element, it is preferable to select the groups represented by the formulae (I), (II), and (VI). In order to reduce the dielectric loss of the device, it is preferable to select the groups represented by the formulae (V), (VII), and (VIII). Further, for the purpose of expanding the driving temperature range of the element, it is preferable to select the groups represented by formula (XIII), formula (XIV), and formula (XV).
In the radicals of the formulae (I) to (XII), at least one hydrogen may pass through the-CH3、-CH2CH3、-CH2CH2CH3、-OCH3、-OCH2CH3、-SCH3or-F substitution. In particular in the selection of-CN, -NCS, and-NO2As R2In the case of (2), introduction of these groups is preferable because compatibility of the composition is improved by reducing intermolecular interaction of the compounds. In this case, it is more preferable to select-CH for improving the compatibility of the composition2CH3、-CH2CH2CH3、-OCH3、-OCH2CH3、-SCH3To reduce the response speed of the element, it is more preferable to select-CH3and-F. On the other hand, in order to further reduce the response speed of the element, it is preferable not to substitute these groups.
Preferred compounds of the general formula (1) of the present invention are compounds represented by the following formulae (1-1) to (1-104).
In the compounds represented by the formulae (1-1) to (1-104), R11Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; r12Is the said R11、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H、-NCS、-SF5or-NO2(ii) a R is alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 4 carbon atoms or alkenyl with 2 to 5 carbon atoms.
Among the compounds represented by the above-mentioned formulae (1-1) to (1-104), in order to impart greater optical anisotropy to the composition for the purpose of improving the efficiency of phase control in the element, the structure selected from (1-1), (1-10), (1-15), (1-17), (1-21), (1-25), (1-27), (1-29), (1-31), (1-33), (1-42), (1-47), (1-57), (1-66), (1-71), (1-81), (1-89), (1-93), (1-97), (1-101) and (1-103) is preferable, and the structure selected from (1-1), (1-10) and (1-103) is more preferable, (1-15), (1-17), (1-29), (1-33), (1-42), (1-47), (1-57), (1-66), (1-89), and (1-97).
In addition, for the purpose, R is12Preferably selected from-CN, -NCS, or-NO2Particularly preferred is the selection of-CN or-NCS. On the other hand, if these radicals are chosen as R12The intermolecular interaction becomes large, and the crystallinity of the compound increases. This decreases the compatibility of the composition and increases the lower limit temperature. In order to prevent such deterioration of characteristics, among the compounds represented by the formulae (1-1) to (1-104), a structure in which (1-10), (1-16), (1-25) to (1-28), (1-42) to (1-48), (1-66) to (1-72), (1-81) to (1-88), (1-97) to (1-104) is selected is more preferable.
Of the compounds represented by the formulae (1-1) to (1-104), for the purpose of lowering the drive voltage of the element, it is preferable to select (1-6) to (1-8), (1-14), (1-19), (1-23), (1-24), (1-28), (1-38) to (1-40), (1-44), (1-46), (1-53) to (1-56), (1-62) to (1-64), (1-68), (1-77) to (1-80), (1-86) to (1-88), (1-90) to (1-92), (1-96), (1-99) to (1-100), (1-102) and (1-104). In addition, for the purpose, R is12More preferably, -CN, -F, -CF3、-OCF3、-CF2H、-OCF2H、-NCS、-SF5or-NO2Most preferably, -CN, -F, -CF3、-OCF3、-NCS。
Among the compounds represented by the above formulae (1-1) to (1-104), for example, in a millimeter wave band variable phase shift element, the structures of (1-29) to (1-32) are preferably selected for the purpose of maintaining the intensity of the wave and reducing the loss of the composition.
When the content of the compound represented by the general formula (1) is 5% by weight or more, it contributes to improvement of the properties of the composition. However, in order to obtain the desired characteristics, the content is preferably 10% by weight or more. On the other hand, the composition of the present invention may contain only the compound represented by the general formula (1), but from the viewpoint of an increase in the lower limit temperature or an increase in the viscosity, it preferably contains not less than 5% by weight of the compound other than the compound represented by the general formula (1), and more preferably contains not less than 10% by weight.
As the second component used in the composition of the present invention, compounds represented by formulae (2) to (4) can be preferably used in order to obtain the desired properties.
In formula (2), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20And ring A23May be the same or different;
R20is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
In formula (3), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z20and Z22Independently a single bond, -CH2CH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH2-, -O-, or-CO-, Z21is-C ≡ C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20Ring A23、Z20And Z22May be the same or different.
R20Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
In formula (4), ring A30Ring A31And ring A32Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z30、Z31And Z32Independently a single bond, -CH2CH2-、-CH＝CH-、-CH2O-、-COO-、-CF2CF2-, -C.ident.C-, or-CF2O-，Z30、Z31And Z32At least one of which is-CF2O-；X30、X31And X32Independently hydrogen or fluorine;
m1 represents 0, 1 or 2, and when m1 represents 2, a plurality of rings A are present31And Z31May be the same or different;
R20independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
Among the compounds represented by formula (2), compounds that can be preferably used in the present invention are compounds represented by formulae (2-1) to (2-32).
In the formulae, R20Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
Among the compounds represented by the formulae (2-1) to (2-32), in order to obtain the desired properties, it is particularly preferable to select the compounds represented by the formulae (2-1), (2-2), (2-8), (2-9), (2-10), (2-11), (2-15), (2-17), (2-18), (2-22), (2-28), (2-29), (2-30), (2-31), and (2-32).
Among the compounds represented by formula (3), compounds that can be preferably used in the present invention are compounds represented by formulae (3-1) to (3-14).
In the formulae, R20Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
Among the compounds represented by the formulae (3-1) to (3-14), the compounds (3-1), (3-4), (3-5), (3-6) and (3-12) are particularly preferably selected in order to obtain the desired properties.
Among the compounds represented by formula (4), compounds that can be preferably used in the present invention are compounds represented by formulae (4-1) to (4-15).
In the formulae, R20Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
Among the compounds represented by the formulae (4-1) to (4-15), in order to obtain the desired properties, it is particularly preferable to select (4-1), (4-2), (4-4), (4-5), (4-6), (4-7), (4-10), (4-11), and (4-12).
Among the compounds represented by the formula (4), compounds represented by the formulae (4-16) to (4-26) can be mentioned as compounds preferably usable in the present invention.
In the formulae, R20Independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
Among the compounds represented by the formulae (4-16) to (4-26), the compound (4-16) is particularly preferably selected in order to obtain the desired properties.
The composition of the present invention may contain additives such as a light stabilizer, an antioxidant, an optically active compound, a pigment, a polymerizable compound, and a photopolymerization initiator in order to improve the properties.
In order to reduce deterioration of the liquid crystal composition due to heat or light, a light stabilizer, an antioxidant, and the like may be added to the composition of the present invention. Such a light stabilizer and antioxidant are preferably a compound represented by the following formula (AI) because they have high effects and can prevent the liquid crystal temperature range of the composition from being narrowed.
RA1-RA2(Al)
Here, RA1Is a radical of the formula (AI-1) or (AI-2), in which R isA3Is hydrogen or C1-5 alkyl, RA4Independently an alkyl group having 1 to 5 carbon atoms, which represents a linking site. RA2Is an organic group having 1 to 18 carbon atoms, and one to three-H of the organic group may be reacted with RA1The same group of formula (AI-1) or formula (AI-2).
Among the compounds (AI), the compound having the group (AI-1) is a light stabilizer, and the compound having the group (AI-2) is an antioxidant. As the antioxidant, a compound represented by the following formula (AI-2-1) is preferably selected. In the formula (AI-2-1), k is an integer of 1 to 12.
In particular, since the compound (AI-2-1) having k of 1 has high volatility, a decrease in specific resistance due to heating in the atmosphere can be effectively prevented. The compound (AI-2-1) having k of 7 has a small volatility, and therefore, after the high-frequency antenna is used for a long time, reliability is effectively maintained not only at room temperature but also at a higher temperature.
The preferable proportion of the light stabilizer is 100ppm or more in order to obtain the above-mentioned effects, and the preferable proportion of the light stabilizer is 0.5% or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. Further, the preferable ratio is 100ppm to 1000 ppm. In order to obtain the above-mentioned effects, the preferable ratio of the antioxidant is 50ppm or more, and the preferable ratio of the antioxidant is 600ppm or less so that the upper limit temperature is not lowered or the lower limit temperature is not raised. Further, the preferable ratio is 100ppm to 300 ppm.
The composition of the present invention may further contain an optically active compound. The compound is mixed into the composition for the purpose of imparting a twist angle by causing a helical structure of the liquid crystal. Examples of such compounds are compounds (C-1) to (C-5). The preferable proportion of the optically active compound is 5% or less. Further, the preferable ratio is in the range of 0.01% to 2%.
In the formula (C-5), RC1Independently a hydrocarbon having up to 30 carbon atoms comprising a ring structure. Denotes asymmetric carbon.
The composition of the present invention may contain a dye such as azo dye, carotenoid dye, flavonoid dye, quinone dye or porphyrin dye in order to improve the anisotropy at frequencies of 1MHz to 400 THz.
The composition of the present invention may contain a polymerizable compound for improving the properties. For this purpose, examples of the characteristic improvement of the antenna element using the polymer dispersed liquid crystal include IEEJ basic and Materials (ieejtranductions on metals and Materials), vol.137, No.6, pp.356(2017), and the like. In the composition of the present invention, for the purpose of such improvement, a polymerizable compound may be added to the composition. As such a polymerizable compound, a radical polymerizable compound is preferable in order to maintain the electrical characteristics of the device, and a (meth) acrylic group is more preferably selected from the viewpoints of reactivity at the time of polymerization and solubility in a liquid crystal.
As such a polymerizable compound, a (meth) acrylic acid derivative having a skeleton similar to a liquid crystal can be preferably used. These compounds do not cause a significant decrease in the phase transfer point of the composition, and therefore can be preferably used in the case where the composition is used while being oriented in one direction. As such a compound, compounds represented by the following formulae (M-1) to (M-3) can be preferably mentioned.
In the formulae (M-1), (M-2), and (M-3), ring G is each independently 1, 4-cyclohexylene, 1, 4-phenylene, 1, 3-dioxane-2, 5-diyl, naphthalene-2, 6-diyl, or fluorene-2, 7-diyl, where at least one hydrogen may be substituted with fluorine, trifluoromethyl, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, or an alkanoyl group having 1 to 12 carbon atoms; zm1Each independently is a single bond, -OCH2-, -COO-, or-OCOO-; zm2Is a single bond, -O-, -OCH2-, or-COO-; xm1Is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of carbon number 1 to 20, alkenyl of carbon number 2 to 20, alkoxy of carbon number 1 to 20, or alkoxycarbonyl of carbon number 1 to 20; e is an integer from 1 to 4; f. and g is independently an integer from 0 to 3; the sum of f and g is 1 to 4; i is 0 or 1, h is each independently an integer from 0 to 20; rm1Are each independently hydrogen or CH3。
As the polymerizable compound, a (meth) acrylic acid derivative having no skeleton similar to a liquid crystal can be preferably used. These compounds can be preferably used when the driving voltage of the element is reduced. As such a compound, a compound represented by the following formula (M-4) can be preferably mentioned.
In the formula (M-4), Zm3Is a single bond or an alkylene group having 1 to 80 carbon atoms, in which at least one hydrogen may be substituted by an alkyl group having 1 to 20 carbon atoms, fluorine, or a group of the following formula (7), and at least one-CH2May be substituted by-O-, -CO-, -COO-, or-OCO-, -NH-, or-N (R)m3) -substituted, in case of substitution with a plurality of-O-, these-O-are not contiguous, Rm3Is alkyl with 1 to 12 carbon atoms; at least one-CH2-CH2-may be substituted by-CH ═ CH-, or-C ≡ C-;
Rm2is an alkyl group having 1 to 20 carbon atoms, at least one hydrogen of which may be substituted by fluorine, at least one-CH2May be substituted by-O-, -CO-, -COO-, or-OCO-, in the case of multiple-O-substitutions these-O-are not adjacent, at least one-CH2May be substituted with a divalent group generated by removing two hydrogens from a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, or a heterocyclic unsaturated aliphatic compound, in which the carbon number is 5 to 35, at least one hydrogen may be substituted with an alkyl group of a carbon number of 1 to 12, of which one-CH2-may be substituted by-O-, -CO-, -COO-, or-OCO-; rm1Is hydrogen or-CH3。
In the formula (7), Zm4Is alkylene of 1 to 12 carbon atoms, Rm1Is hydrogen or-CH3Denotes the link position.
Preferred examples of the compounds represented by the formulae (M-1) to (M-4) are the following formulae.
In the formula, Rm1Independently is hydrogen or-CH3And h is independently an integer from 1 to 20.
In the formula, Rm2Is an alkyl group having 5 to 20 carbon atoms, in which at least one-CH group2-may be substituted by-O-, -CO-, -COO-, or-OCO-, Rm3Each independently is an alkyl group having 3 to 10 carbon atoms, in which at least one-CH group is present2-may be substituted by-O-, -CO-, -COO-, or-OCO-.
In the formula (M-4-7), n is an integer of 1 to 10,
in the formula (M-4-8), M is an integer of 2 to 20,
in the formula (M-4-9), Rm3Each independently is an alkyl group having 1 to 5 carbon atoms, Rm4Each independently is an alkyl group having 1 to 20 carbon atoms, in which at least one-CH group is present2R in the same formula which may be substituted by-O-, -CO-, -COO-, or-OCO-m3And Rm4Can be the same or different from each other,
Zm5is alkylene with 10 to 30 carbon atoms, in which at least one-CH2May be substituted by-O-, -CO-, -COO-, or-OCO-, alkylene also includes those having branched alkyl groups,
in the formula (M-4-10), p is an integer of 3 to 10, Rm5And Rm6Is hydrogen or-CH3Either is-CH3，
In the formula (M-4-11), Rm7is-OH, (meth) acryloyl, or R of formula (M-4-11)m7Other residues being bound via-O-bondsTo a structure of Rm1Are each independently hydrogen or-CH3. Hereinafter, R is representedm7R having the formula (M-4-11)m7The other residues are bonded through-O-bond (M-4-11-1).
The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of an initiator such as a photopolymerization initiator. Suitable conditions, suitable types of initiators, and suitable amounts to carry out the polymerization are known to those skilled in the art and are described in the literature. For example, brilliant good solid (Irgacure)651 (registered trademark; Basf), brilliant good solid (Irgacure)184 (registered trademark; Basf), or Delocure (Darocure)1173 (registered trademark; Basf) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator ranges from about 0.1 part by weight to about 5 parts by weight based on 100 parts by weight of the polymerizable compound. Still more preferred is a range of about 1 part by weight to about 3 parts by weight.
When the liquid crystal composition of the present invention is applied to a device, an alignment film made of polyimide or the like is used to align the liquid crystal composition. On the other hand, an alignment control agent is also added to the liquid crystal in order to align the liquid crystal composition. As such an alignment controlling agent, compounds described in WO2017-057162, WO2012-104008, WO2016-129490, and the like can be preferably used.
Finally, the use of the composition is illustrated. Most of the compositions have a lower limit temperature of-10 ℃ or lower, an upper limit temperature of 70 ℃ or higher, and an optical anisotropy of 0.16 to 0.35.
The dielectric constant of a dielectric material such as a liquid crystal changes depending on frequency and temperature. Therefore, the frequency dependence of the dielectric constant is referred to as the dielectric characteristics of the dielectric body. When an ac electric field is applied to the liquid crystal, as the frequency f increases, an internal electric dipole (electric dipole) follows the change of the electric field, so that the dielectric constant ∈ 'decreases, while the conductivity σ' increases, and the dielectric loss ∈ ″ shows a peak, which is a dielectric relaxation (dielectric relaxation).
In the microwave and millimeter wave region, the method of mounting the device or the sample is completely different depending on the frequency region to be measured. For the reason that analysis of an electromagnetic field is easy up to 10GHz, a probe is often assembled with a measurement system centered on a network analyzer using an open-end coaxial type unit, and a spectrum of a complex dielectric constant (dielectric relaxation spectrum) of a sample is obtained by scanning the frequency. Above several 10GHz, it is desirable to use waveguides rather than coaxial cables. In order to calculate the dielectric constant, it is necessary to appropriately determine the boundary condition when the electromagnetic wave is incident on the sample, and if the wavelength is shortened, it is necessary to perform precise processing accordingly. In a low frequency region, a cell to be a capacitor was produced, a sample was inserted into the cell, and the dielectric constant was determined from the change in capacitance.
Examples
The present invention will be further described in detail by way of examples. The present invention is not limited by these examples. Unless otherwise specified, examples were carried out at room temperature (25 ℃).
< determination method >
The measurement and verification were carried out by the following methods. Unless otherwise specified, the measurement method not described in the present specification is based on Japanese electronic information technology Industries Association (JEITA) ED-2521B.
< Nuclear Magnetic Resonance (NMR) >
NMR was measured using DRX-500 manufactured by Bruker BioSpin.1In the measurement of H-NMR, a sample was dissolved in CDCl3And deuterated solvents. The measurement was carried out at room temperature at 500 MHz. At this time, the number of times of integration was 16. The internal standard was tetramethylsilane. In the symbols of NMR, s is a singlet (singlet), d is a doublet (doublt), t is a triplet (triplet), q is a quartet (quatet), quin is a quintet (quintet), sex is a sextant (sextet), m is a multiplet (multiplex), br is a doubletRefers to broad peak (broad).
< Differential Scanning Calorimetry (DSC) measurement >)
The measurement was performed using a differential scanning calorimeter (damond DSC from Perkin Elmer). The transition temperature is expressed by the temperature in degrees celsius between the expressions representing the phases. In the expression of phases, C is a crystalline layer, N is a nematic phase, S is a smectic phase, and I is an isotropic liquid. In the expression indicating the phase, the description of the phase in parentheses indicates a liquid crystal phase of a single transition (monotropic).
< gas chromatography >
For measurement, a GC-2014 type gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporizer was set at 280 ℃ and the detector (flame ionization detector, FID) was set at 300 ℃. The separation of the component compounds was carried out using a capillary column DB-1 (length 30m, inner diameter 0.32mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; non-polar) manufactured by Agilent technologies Inc. After preparing the sample into an acetone solution (0.1 wt%), 1. mu.L thereof was injected into the sample vaporization chamber. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.
< High Performance Liquid Chromatography (HPLC) analysis >
The measurement was carried out using HPLC LC-2000Plus manufactured by Japan Spectroscopy Co., Ltd. at a flow rate of the solvent of 1 ml/min. The peak value of each component was detected at a wavelength of 254nm using a UV-Vis detector.
< upper limit temperature of nematic phase >
In the embodiment, "NI" is an "upper limit temperature".
The upper limit temperature is a measured value of the temperature at which a sample is placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ℃/min to cause a part of the sample to undergo a self-nematic phase transition into an isotropic liquid.
< lower limit temperature of nematic phase >
In the examples, "Tc" is a "lower limit temperature".
The lower limit temperature is determined by placing a sample having a nematic phase in a glass bottle, keeping the bottle in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, and observing the phase.
Refractive index anisotropy in visible light
In the examples, the refractive index anisotropy is expressed as "Δ n".
Δ n was measured by an abbe refractometer having a polarizing plate attached to an eyepiece lens.
After rubbing the surface of the main prism in one direction, a sample was dropped onto the main prism, and the refractive index of the polarized light in the direction perpendicular to the rubbing direction was measured as n ⊥, and the refractive index of the polarized light in the direction parallel to the rubbing direction was measured as n/. DELTA.n was calculated from the value of DELTA.n/n ⊥.
At this time, light having a wavelength of 589nm was used, and the measurement temperature was 25 ℃.
Dielectric anisotropy at < 1kHz
The value of dielectric anisotropy was calculated from the formula of Δ ∈ epsilon/epsilon ⊥, and the dielectric constants (epsilon/and epsilon ⊥) were measured as follows.
(A) Measurement of dielectric constant (. epsilon. /): a solution of octadecyltriethoxysilane (0.16mL) in ethanol (20mL) was coated on the well-cleaned glass substrate. The glass substrate was rotated by a rotator and then heated at 150 ℃ for 1 hour. A sample was placed in a Vertical Alignment (VA) cell having a gap of 4 μm between two glass substrates, and the cell was sealed with an adhesive cured with ultraviolet rays. A sine wave (0.5V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds.
(B) Measurement of dielectric constant (. epsilon. ⊥) A polyimide solution was applied to a well-cleaned glass substrate, the glass substrate was fired, and the obtained alignment film was rubbed, a sample was injected into a Twisted Nematic (TN) cell having a gap of 9 μm between two glass substrates and a twist angle of 80 degrees, a sine wave (0.5V, 1kHz) was applied to the cell, and the dielectric constant (. epsilon. ⊥) in the short axis direction of liquid crystal molecules was measured after 2 seconds.
< Voltage Holding Ratio (VHR) >)
The unit for measurement has the following structure. That is, an Indium Tin Oxide (ITO) electrode and a rubbed polyimide alignment film are sequentially disposed on each substrate. Two of the substrates were bonded with the alignment film surface on the inner side so that the angle of the rubbing direction between the upper and lower substrates was 80 degrees. The gap between the two glass substrates (cell gap) was 5 μm. A liquid crystal composition is put into the cell, and then sealed with an adhesive hardened with ultraviolet rays. The TN cell was charged by applying a pulse voltage (5V, 60 μ sec). The decayed voltage was measured by a high-speed voltmeter for a period of 16.7 milliseconds, and the area a between the voltage curve and the horizontal axis in the unit cycle was determined. The area B is the area when not attenuated. The voltage holding ratio is expressed by a percentage of the area a to the area B.
Refractive index anisotropy and dielectric loss at & lt 50GHz
The refractive index anisotropy was measured by the method disclosed in Applied Optics (Applied Optics), vol.44, No.7, p1150(2005), in which a variable short-circuit waveguide of a V-band to which a window material was attached was filled with a liquid crystal and held in a static magnetic field of 0.3T for 3 minutes, a microwave of 50GHz was input to the waveguide, the amplitude ratio of a reflected wave to an incident wave was measured, the direction of the static magnetic field and the length of the short-circuit were changed to measure the direction, and the refractive index (ne, no) and the loss parameter (α e, α o) were determined, and the refractive index anisotropy (Δ n) was calculated from ne-no.
The complex dielectric constant (s ', s ") was used and calculated as the dielectric loss (tan δ) ═ s"/s'. The calculated refractive index, loss parameter and the following relational expression are used for calculating the complex dielectric constant.
Here, c is the light velocity of the vacuum. The dielectric loss is also anisotropic, and thus the numerical value is large.
ε′＝n2-κ2
ε”＝2nκ
α＝2ωc/κ
< bulk viscosity >
In the examples, the bulk viscosity of the compositions is expressed as "η".
The bulk viscosity was measured using an E-type rotational viscometer manufactured by tokyo metrological corporation. The measurement temperature was 20 ℃.
< Compound >
As the compound represented by formula (1), the following formula (1-1-1), (1-1-2), (1-1-3), (1-17-1), (1-1-4), (1-1-5), (1-1-6), (1-1-7), (1-1-8), (1-1-9), or (1-29-1) is used. Compound (1-1-1) is one of the book "Kun Shi Kui Phys" (J.appl.Phys.),65(11) 4372(1989) is synthesized in the same manner as described in Japanese patent laid-open No. 2012-167068.
[ example 1]
Synthesis of Compound represented by the formula (1-1-2)
10.0g (34.8mmol) of a compound represented by the formula (1-1-2a) synthesized according to Liquid crystal (Liquid Crystals), 27(6),801(2000), and 1,4-diazabicyclo [2.2.2 ]]Octane (1,4-Diazabicyclo [ 2.2.2)]octane, DABCO)23.4g (208mmol) of Tetrahydrofuran (THF) 100ml solution CS was added221ml (349mmol) were stirred overnight at room temperature under a stream of nitrogen. The resulting precipitate was filtered. The powder obtained was transferred to a flask and CHCl was added3100ml and stirring was carried out. Slowly add bis (tris) to the mixed solution at room temperatureChloromethyl) carbonate (triphosgene)3.8g (12.8mmol) of CHCl350ml of solution. Then, the mixture was refluxed for 3 hours in a nitrogen stream. After the reaction solution was cooled, 100ml of pure water was added. The organic layer was separated, washed with an equal amount of pure water and MgSO4And drying the mixture. After filtration and evaporation of the solvent under reduced pressure, the obtained product was recrystallized by column chromatography (silica gel, heptane/toluene 2/1) and a mixed solvent of toluene/ethanol, thereby obtaining (1-1-2). Yield 7.1g (62% yield). Gas Chromatography (GC) purity: 100 percent. Phase transition temperature (. degree. C.): c.141.0. N.147.4. I.
[ example 2]
Synthesis of Compound represented by the formula (1-17-1)
Using the same method as in Synthesis (Synthesis), (10),1541(2011), according to Synthesis (Synthesis), (5),816(2011), 3.5g (13.4mmol) of the compound represented by the formula (1-17-1a), 3.1g (18.0mmol) of 1-ethynyl-4-pentylbenzene, 260mg (13.6mmol) of CuI, 820mg (2.7mmol) of tri (o-tolyl) phosphine, and K2CO31.9g (13.7mmol) of the mixture are refluxed in ethanol (50ml) under a stream of nitrogen for 12 hours. After the reaction mixture was cooled, 100ml of toluene and 100ml of pure water were added. The organic layer was separated and MgSO4And drying the mixture. After filtration and evaporation of the solvent under reduced pressure, the obtained product was recrystallized using a column chromatography (silica gel, heptane/toluene 2/1) and a toluene/ethanol mixed solvent, thereby obtaining (1-17-1). Yield 1.3g (28% yield). GC purity: 100 percent. Phase transition temperature (. degree. C.): c91.2. N199.5. I.
[ examples 2-2]
Synthesis of Compound represented by formula (1-29-1)
The compound represented by the formula (1-29-1a) was used in place of the compound represented by the formula (1-17-1a), and the synthesis was performed in the same manner as in example 2. The obtained product was recrystallized using column chromatography (silica gel, heptane/toluene ═ 2/1) and ethanol, thereby obtaining (1-29-1). Yield 2.2g (47% yield). HPLC purity (dissolution solvent acetonitrile): 100 percent. Phase transition temperature (. degree. C.): c101.3. I.
The compound represented by the formula (1-29-1a) was synthesized as follows. To 100ml of a solution of 10.0g (29.2mmol) of a compound represented by formula (1-29-1b) synthesized according to Synthesis (Synthesis), (12),2040(2009) and N, N-Dimethylformamide (DMF)4NF 50g (70% -75% aqueous solution), and stirred at 60 deg.C for 1 hour. After the reaction mixture was cooled, 100ml of toluene and 100ml of pure water were added. The organic layer was separated and MgSO4And drying the mixture. After filtration and evaporation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, heptane/toluene 2/1), whereby (1-29-1a) was obtained. Yield 7.6g (78% yield).
< liquid crystal composition >
A composition is prepared by using the above-mentioned formulas (1-1-1), (1-1-2), (1-1-3), (1-17-1), (1-1-4), (1-1-5), (1-1-6), (1-1-7), (1-1-8), (1-1-9) and (1-29-1) in combination with a liquid crystal of the second component. The liquid crystal compound of the second component is represented by the expression in table 1. Unless otherwise specified, the divalent group of the six-membered ring in table 1 is in the trans configuration. The number in parentheses after the marked compound in the liquid crystal composition indicates the chemical formula to which the compound belongs. The symbol (-) indicates other liquid crystal compounds. The proportion of the liquid-crystalline compounds is the weight percentage based on the weight of the liquid-crystalline composition without additives.
[ example 3]
Preparation and physical Properties of liquid Crystal composition 1
NI＝90.0℃；Tc＜-20℃；Δn＝0.253；Δε＝14.1；η＝48.4mPa·s；VHR＝98.7％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.15
Dielectric loss; 0.016
[ example 4]
Preparation and Properties of liquid Crystal composition 2
NI＝90.0℃；Tc＜-20℃；Δn＝0.257；Δε＝14.8；η＝55.4mPa·s；VHR＝98.7％.
The liquid crystal composition 2 had a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.15
Dielectric loss; 0.015
[ example 5]
Preparation and Properties of liquid Crystal composition 3
NI＝90.4℃；Tc＜-20℃；Δn＝0.263；Δε＝14.2；η＝56.2mPa·s；VHR＝98.5％.
The liquid crystal composition 2 had a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.16
Dielectric loss; 0.015
[ example 6]
Preparation and Properties of liquid Crystal composition 4
NI＝90.6℃；Tc＜-20℃；Δn＝0.264；Δε＝14.0；η＝49.0mPa·s；VHR＝98.8％.
The liquid crystal composition 2 had a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.17
Dielectric loss; 0.015
[ example 7]
Preparation and Properties of liquid Crystal composition 5
NI＝92.4℃；Tc＜-20℃；Δn＝0.262；Δε＝7.7；η＝41.2mPa·s；VHR＝98.7％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
[ example 8]
Preparation and Properties of liquid Crystal composition 6
NI＝108.8℃；Tc＜-20℃；Δn＝0.292；Δε＝7.9；η＝48.2mPa·s；VHR＝98.1％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.25
Dielectric loss; 0.010
[ example 9]
Preparation and Properties of liquid Crystal composition 7
NI＝92.5℃；Tc＜-20℃；Δn＝0.270；Δε＝7.8；η＝42.6mPa·s；VHR＝98.9％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.22
Dielectric loss; 0.013
[ example 10]
Preparation and Properties of liquid Crystal composition 8
NI＝89.7℃；Tc＜-20℃；Δn＝0.254；Δε＝7.9；η＝44.5mPa·s；VHR＝98.2％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.20
Dielectric loss; 0.009
[ example 11]
Preparation and Properties of liquid Crystal composition 9
NI＝104.3℃；Tc＜-20℃；Δn＝0.288；Δε＝7.8；η＝47.8mPa·s；VHR＝98.3％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.24
Dielectric loss; 0.010
[ example 12]
Preparation and physical Properties of liquid Crystal composition 10
NI＝98.2℃；Tc＜-20℃；Δn＝0.280；Δε＝7.8；η＝46.4mPa·s；VHR＝98.1％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
[ example 13]
Preparation and Properties of liquid Crystal composition 11
NI＝91.2℃；Tc＜-20℃；Δn＝0.272；Δε＝9.4；η＝43.2mPa·s；VHR＝98.9％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
[ example 14]
Preparation and Properties of liquid Crystal composition 12
NI＝110.5℃；Tc＜-20℃；Δn＝0.318；Δε＝11.0；η＝46.1mPa·s；VHR＝99.0％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.28
Dielectric loss; 0.009
[ example 15]
Preparation and Properties of liquid Crystal composition 13
NI＝119.0℃；Tc＜-20℃；Δn＝0.322；Δε＝11.3；η＝48.1mPa·s；VHR＝98.9％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.29
Dielectric loss; 0.009
Comparative example 1 preparation and physical Properties of liquid Crystal composition ref.1
The following comparative compound (ref.1) was synthesized according to Japanese patent No. 5859189. Using the above compound, the following liquid crystal composition ref.1 was prepared in the same manner as in example 1. The physical properties of the liquid crystal composition are shown below.
NI＝93.9℃；Tc＜-20℃；Δn＝0.267；Δε＝7.6；η＝54.7mPa·s；VHR＝98.0％.
The liquid crystal composition 1 has a refractive index anisotropy and a dielectric loss at 50GHz of not more than.
Refractive index anisotropy; 0.23
Dielectric loss; 0.011
The liquid crystal compositions 5 and 7 of examples 7 and 9 had approximately the same refractive index anisotropy as the liquid crystal composition ref.1 of comparative example 1, but had a low viscosity. Thus, it is found that the liquid crystal composition of the present invention is a material having an excellent balance of properties as a material for an element used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
[ industrial applicability ]
The liquid crystal composition of the present invention can be preferably used as a material for an element for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
Claims (22)
1. A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component and used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400THz,
in the formula (1), the reaction mixture is,
R1is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkenyloxy group having 2 to 12 carbon atoms, and one or two or more CH groups present in the alkyl group, the alkoxy group, the alkylthio group, the alkenyl group or the alkenyloxy group2The O atoms, which are not bonded directly to each other, may be substituted by-O-, -CO-, or-COO-; r2Is the said R1、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H、-NCS、-SF5or-NO2(ii) a Ring A1Ring A2Ring A3And ring A4Independently a group represented by any one of the following formulae (I) to (XV), ring A2And ring A3At least one of the above groups is a group represented by any one of the formulae (I) to (XII);
in the radicals of the formulae (I) to (XII),
at least one hydrogen may pass through-CH3、-CH2CH3、-CH2CH2CH3、-OCH3、-OCH2CH3、-SCH3or-F; z1And Z3Independently a single bond, -CH2CH2-、-CF2O-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH2-, -O-, or-CO-, Z2is-C ≡ C-C ≡ C-;
p and q are independently 0, 1 or 2, and when p and q are 2, a plurality of rings A are present1、Z1、Z3And ring A4May be the same or different.
2. The liquid crystal composition according to claim 1, which contains, as a second component, 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) relative to the total weight of the composition, and 5 to 90% by weight of at least one compound selected from the group of compounds represented by formula (2) relative to the total weight of the composition,
in formula (2), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20And ring A23May be the same or different; r20Is alkyl of carbon number 1 to 12, carbonAlkoxy of number 1 to 12, or alkenyl of carbon number 2 to 12, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
3. The liquid crystal composition according to claim 1, which contains, as a second component, 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) relative to the total weight of the composition, and 5 to 90% by weight of at least one compound selected from the group of compounds represented by formula (3) relative to the total weight of the composition,
in formula (3), ring A20And ring A23Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A21And ring A22Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z20and Z22Independently a single bond, -CH2CH2-、-CH2O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH2-, -O-, or-CO-, Z21is-C ≡ C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present20Ring A23、Z20And Z22May be the same or different;
R20is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
4. The liquid crystal composition according to claim 1, which contains, as a second component, 95 to 10% by weight, relative to the total weight of the composition, of at least one compound selected from the group of compounds represented by formula (1), and 5 to 90% by weight, relative to the total weight of the composition, of at least one compound selected from the group of compounds represented by formula (4),
in formula (4), ring A30Ring A31And ring A32Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl; z30、Z31And Z32Independently a single bond, -CH2CH2-、-CH＝CH-、-CH2O-、-COO-、-CF2CF2-, -C.ident.C-, or-CF2O-，Z30、Z31And Z32At least one of which is-CF2O-；X30、X31And X32Independently hydrogen or fluorine;
m1 represents 0, 1 or 2, and when m1 represents 2, a plurality of rings A are present31And Z31May be the same or different;
R20is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
5. The liquid crystal composition according to claim 2, which contains at least one compound selected from the group of compounds represented by formulae (2-1) to (2-32) as a second component,
in the formulae, R20Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
6. The liquid crystal composition according to claim 3, which contains at least one compound selected from the group of compounds represented by formulae (3-1) to (3-14) as a second component,
in the formulae, R20Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms; r21Is the said R20、-CN、-F、-Cl、-CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5。
7. The liquid crystal composition according to claim 4, which contains at least one compound selected from the group of compounds represented by formulae (4-1) to (4-15) as a second component,
in the formulae, R20Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
8. The liquid crystal composition according to claim 4, which contains at least one compound selected from the group of compounds represented by formulae (4-16) to (4-26) as a second component,
in the formulae, R20Is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.
9. The liquid crystal composition according to claim 5, wherein the proportion of the compound represented by the formula (1) in which R is present in the compounds represented by the formulae (2-1) to (2-32) is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5The proportion of the compound (b) is in the range of 10 to 90% by weight.
10. The liquid crystal composition of claim 5 or 6, wherein the amount of the liquid crystal composition is less than the weight of the liquid crystal compositionThe proportion of the compound represented by the formula (1) in which R is present in the compound represented by the formula (2-1) to the formula (2-32) is in the range of 10% by weight to 90% by weight21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5In the range of 5 to 80% by weight, R in the compounds represented by the formulae (3-1) to (3-14)21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight.
11. The liquid crystal composition according to claim 7, wherein the proportion of the compound represented by formula (1) is in the range of 10 to 90% by weight, and the proportion of the compound represented by formula (4-1) to formula (4-15) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition.
12. The liquid crystal composition according to claim 8, wherein the proportion of the compound represented by formula (1) is in the range of 10 to 90% by weight, and the proportion of the compound represented by formula (4-16) to formula (4-26) is in the range of 10 to 90% by weight, based on the weight of the liquid crystal composition.
13. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the compound represented by the formula (1) in which R is present in the compounds represented by the formulae (2-1) to (2-32) is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition21is-CN, -F, -Cl, -CF3、-OCF3、-CF2H、-OCF2H. -NCS, or-SF5The proportion of the compound of formula (2) is in the range of 5 to 80% by weight, and the proportion of the compound represented by formula (3-1) to formula (3-14) is in the range of 5 to 80% by weight.
14. The liquid crystal composition according to claim 6 or 7, wherein the proportion of the compound represented by the formula (1) is based on the weight of the liquid crystal compositionIn the range of 10 to 90% by weight, R in the compounds represented by the formulae (3-1) to (3-14)21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight, and the proportion of the compound represented by the formula (4-1) to the formula (4-15) is in the range of 5 to 80% by weight.
15. The liquid crystal composition according to claim 6 or 8, wherein the proportion of the compound represented by formula (1) in which R is present in the compounds represented by formulae (3-1) to (3-14) is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition21The proportion of the compound which is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms is in the range of 5 to 80% by weight, and the proportion of the compound represented by the formula (4-16) to the formula (4-26) is in the range of 5 to 80% by weight.
16. The liquid crystal composition according to any one of claims 1 to 4, wherein the proportion of the liquid crystal compound other than the components selected from the group consisting of the formula (2), the formula (3), and the formula (4) is in the range of 1 to 20% by weight based on the weight of the liquid crystal composition.
17. The liquid crystal composition according to any one of claims 1 to 4, wherein the refractive index anisotropy measured at 25 ℃ of a wavelength of 589nm is in the range of 0.18 to 0.35, and the dielectric constant anisotropy measured at 25 ℃ of a frequency of 1kHz is in the range of 7 to 40.
18. A liquid crystal composition according to any one of claims 1 to 4, wherein the refractive index anisotropy measured at 25 ℃ at a frequency of 50GHz is in the range of 0.15 to 0.40.
19. The liquid crystal composition according to any one of claims 1 to 4, comprising an acrylic monomer.
20. The liquid crystal composition according to any one of claims 1 to 4, which comprises a photopolymerization initiator.
21. The liquid crystal composition according to any one of claims 1 to 4, which comprises an optically active compound.
22. An element comprising the liquid crystal composition according to any one of claims 1 to 21 and used for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
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| US6312618B1 (en) * | 2000-04-03 | 2001-11-06 | Hrl Laboratories | Polar diphenyldiacetylene liquid crystals |
| US20170362507A1 (en) * | 2016-06-15 | 2017-12-21 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
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| US6312618B1 (en) * | 2000-04-03 | 2001-11-06 | Hrl Laboratories | Polar diphenyldiacetylene liquid crystals |
| US20170362507A1 (en) * | 2016-06-15 | 2017-12-21 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
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