CN111253953B - Liquid crystal composition and element for phase control of electromagnetic wave signal - Google Patents
Liquid crystal composition and element for phase control of electromagnetic wave signal Download PDFInfo
- Publication number
- CN111253953B CN111253953B CN201910852540.5A CN201910852540A CN111253953B CN 111253953 B CN111253953 B CN 111253953B CN 201910852540 A CN201910852540 A CN 201910852540A CN 111253953 B CN111253953 B CN 111253953B
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- liquid crystal
- phenylene
- ring
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 151
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 122
- 150000001875 compounds Chemical class 0.000 claims abstract description 175
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 108
- -1 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridin-2, 5-diyl Chemical group 0.000 claims description 44
- 125000003342 alkenyl group Chemical group 0.000 claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 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 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 11
- 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 11
- 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 10
- 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
- 239000003999 initiator Substances 0.000 claims description 8
- 238000000034 method Methods 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
- 238000006467 substitution reaction Methods 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 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 9
- 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
- 230000000704 physical effect Effects 0.000 description 15
- 239000000523 sample Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 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
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 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
- 238000000926 separation method Methods 0.000 description 3
- 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
- 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
- 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
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 238000003556 assay 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 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
- 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 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 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
- 239000004215 Carbon black (E152) Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- KFDKSWDECHPONU-UHFFFAOYSA-N bis(trichloromethyl) carbonate Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl.ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl KFDKSWDECHPONU-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000001589 carboacyl group Chemical group 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
- 238000013329 compounding Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000012973 diazabicyclooctane 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
- 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
- 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
- 230000001939 inductive effect 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 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
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group 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
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 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)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Computer Networks & Wireless Communication (AREA)
- Organic Chemistry (AREA)
- Radar, Positioning & Navigation (AREA)
- Remote Sensing (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention provides a liquid crystal composition and an element for controlling the phase of an electromagnetic wave signal. The liquid crystal composition has good characteristics and excellent characteristic balance, and can be used as a material for controlling the phase of electromagnetic wave signals with the frequency of 1 MHz-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 controlling the phase of electromagnetic wave signals having a frequency of 1MHz to 400 THz. In formula (1), ring A 1 Ring A 2 Ring A 3 Ring A 4 A group represented by any one of the following (I) to (XV); z is Z 1 Z is as follows 3 For example a single bond; p and q are 0, 1, or 2; r is R 1 For example alkyl; r is R 2 For example, as said R 1 or-CN.
Description
Technical Field
The present invention relates to an element for phase control of an electromagnetic wave signal having a frequency of 1MHz to 400THz and a liquid crystal composition used in the element. The composition has a nematic phase and a 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 millimeter wave band, microwave band antenna, and infrared laser element. Various methods have been studied for these elements, but a method using a liquid crystal which is considered to have less failure due to the absence of a mechanically movable part has been attracting attention.
The alignment of the molecules of the liquid crystal changes according to the externally applied bias electric field, and the dielectric constant changes. By utilizing such a property, for example, a microwave device capable of electrically controlling the transmission characteristics of the 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 a nematic liquid crystal, a microwave-millimeter-wave band variable phase shifter using a nematic liquid crystal as a dielectric substrate of a microstrip line, or the like has been reported (patent document 1 and patent document 2).
Such an element for phase control of an electromagnetic wave signal desirably has characteristics of a wide usable temperature range, high gain, low loss, and the like. 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, low viscosity, large optical anisotropy in a frequency region used in phase control, large dielectric anisotropy, small dielectric loss, large specific resistance in a driving frequency region, stability to heat, and the like.
The conventional compositions are disclosed in patent documents 3 to 4 below.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2017/201115
[ patent document 2] U.S. patent publication No. 2018/0239213 specification
[ patent document 3] Japanese patent laid-open No. 2004-285085
Patent document 4 Japanese patent laid-open publication No. 2011-74074
Disclosure of Invention
[ problem to be solved by the invention ]
The present invention aims to provide a liquid crystal composition which is excellent in the characteristics required to have excellent characteristics and excellent in the balance of characteristics, and which is used as a material for an element for controlling the phase of an electromagnetic wave signal having a frequency of 1MHz to 400 THz.
[ means of solving the problems ]
The inventors have found that a liquid crystal composition containing a liquid crystal compound having a specific structure solves the above-described problems, and have completed the present invention.
The present invention has the following constitution.
[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 electromagnetic wave signals having a frequency of 1MHz to 400 THz.
In the formula (1), the components are as follows,
R 1 is 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 group 2 As the case where O atoms are not directly bonded to each other, can be substituted by-O-, -CO-, or-COO-, R 2 For the R 1 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H、-NCS、-SF 5 or-NO 2 ；
Ring A 1 Ring A 2 Ring A 3 Ring A 4 Independently a group represented by any one of the following formulas (I) to (XV), ring A 2 Ring A 3 At least one of which is a group represented by any one of the formulas (I) to (XII);
in the radicals of the formulae (I) to (XII),
at least one hydrogen may pass through-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-OCH 3 、-OCH 2 CH 3 、-SCH 3 or-F substitution; z is Z 1 Z is as follows 3 Independently a single bond, -CH 2 CH 2 -、-CF 2 O-、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH 2 -, -O-, or-CO-, Z 2 is-C.ident.C-;
p and q are independently 0, 1 or 2, and in the case where these p and q are 2, there are a plurality of rings A 1 、Z 1 、Z 3 Ring A 4 May 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 the formula (1) with respect 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 the formula (2) with respect to the total weight of the composition as a second component.
In formula (2), ring A 20 Ring A 23 Is independently 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, pyridin-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A 21 Ring A 22 Independently 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, whereIn the case where m1 and m2 are 2, there are plural rings A 20 Ring A 23 May be the same or different from each other; r is R 20 Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
[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 the formula (1) with respect 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 the formula (3) with respect to the total weight of the composition as a second component.
In formula (3), ring A 20 Ring A 23 Is independently 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, pyridin-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A 21 Ring A 22 Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z 20 Z is as follows 22 Independently a single bond, -CH 2 CH 2 -、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH 2 -, -O-, or-CO-, Z 21 is-C.ident.C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present 20 Ring A 23 、Z 20 And Z 22 May be the same or different.
R 20 Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
[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 the formula (1) with respect 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 the formula (4) with respect to the total weight of the composition as a second component.
In formula (4), ring A 30 Ring A 31 Ring A 32 Independently 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; z is Z 30 、Z 31 And Z 32 Independently a single bond, -CH 2 CH 2 -、-CH＝CH-、-CH 2 O-、-COO-、-CF 2 CF 2 -, -C.ident.C-, or-CF 2 O-，Z 30 、Z 31 And Z 32 At least one of them is-CF 2 O-；X 30 、X 31 And X 32 Independently hydrogen or fluorine;
m1 is 0, 1 or 2, and in the case where m1 is 2, there are a plurality of rings A 31 Z is as follows 31 May be the same or different;
R 20 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
[5] The liquid crystal composition according to [2], which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-32) as a second component.
In these formulae, R 20 Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
[6] The liquid crystal composition according to [3], which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-14) as a second component.
In these formulae, R 20 Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
[7] The liquid crystal composition according to [4], which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-15) as a second component.
In these formulae, R 20 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.
[8] The liquid crystal composition according to [4], which contains at least one compound selected from the group of compounds represented by the formulas (4-16) to (4-26) as a second component.
In these formulae, R 20 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.
[9]According to [5 ]]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, R in the compounds represented by the formulas (2-1) to (2-32) 21 is-CN, -F, -Cl, -CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 The proportion of the compounds of (2) 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, R in the compounds represented by the formulas (2-1) to (2-32) 21 is-CN, -F,-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 The ratio of the compounds represented by the formulae (3-1) to (3-14) is in the range of 5 to 80% by weight 21 The proportion of the compound that 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 wt%.
[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 formulas (4-16) to (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, R in the compounds represented by the formulas (2-1) to (2-32) 21 is-CN, -F, -Cl, -CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 The proportion of the compound represented by the formula (3-1) to the formula (3-14) is in the range of 5 to 80% by weight, and the proportion of the compound represented by the formula (3-1) to the formula (3-14) is in the range of 5 to 80% by weight.
[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, R in the compounds represented by the formulas (3-1) to (3-14) 21 The proportion of the compound that 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 wt%, 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 wt%.
[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, R in the compounds represented by the formulas (3-1) to (3-14) 21 The proportion of the compound that 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 wt%, and the proportion of the compound represented by the formulas (4-16) to (4-26) is in the range of 5 to 80 wt%.
[16] The liquid crystal composition according to any one of [1] to [4], wherein a proportion of the liquid crystal compound other than the component selected from the group consisting of the formula (2), the formula (3), and the formula (4) is in a 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 [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 ℃) 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 [1] to [18], which comprises an acrylic monomer.
[20] The liquid crystal composition according to any one of [1] to [19], which contains 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 containing the liquid crystal composition according to any one of [1] to [21], and 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 in phase control, a small dielectric loss, and stability to heat. Therefore, the element using the material has a practically excellent characteristic.
Detailed Description
The liquid crystal composition of the present invention is sometimes simply referred to as "composition". In the element of the present invention, the phase in the "composition" is not limited to nematic, but may be other liquid crystal phases or isotropic liquids. When used as an element, the liquid crystal phase is preferably a nematic phase.
Examples of the element for controlling the phase of an electromagnetic wave signal having a frequency of 1MHz to 400THz include a millimeter-wave band variable phase shifter, a laser radar (Light Detection and Ranging, liDAR) element, and the like.
The "liquid crystalline compound" refers to a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound which does not have a liquid crystal phase but is useful as a component of the composition. The useful compounds contain six-membered rings such as 1, 4-cyclohexylene or 1, 4-phenylene and have a linear molecular structure. Optically active compounds are 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 is sometimes simply referred to as "upper limit temperature". The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".
By "large specific resistance" is meant that the composition has a large specific resistance not only at room temperature but also at a high temperature in the initial stage, and also has a large specific resistance not only at room temperature but also at a high temperature after a long period of use. In describing the characteristics such as optical anisotropy, values measured by the method described in examples are 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 proportion of the second component. The proportion of the additive to be 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 invention 2 Compounds which are-C.ident.C-are relative to, for example, Z 2 Is a single bondThe compounds of (2) tend 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 comprising 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 the composition containing the compound of formula (1) for phase control of electromagnetic wave signals having frequencies 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 improve the response speed while maintaining the optical anisotropy of the composition, it is preferable to select alkyl, alkoxy, or alkenyl as R of the compound of formula (1) 2 . R of the compound of the formula (1) 1 R is R 2 In order to expand the temperature range of the nematic phase of the composition, the preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl groups. Further preferred alkyl groups are ethyl, propyl, butyl, pentyl or heptyl in order to reduce the viscosity.
R of the compound of formula (1) 1 R is R 2 In order to expand the temperature range of the nematic phase of the composition, preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy groups. Further preferred alkoxy groups are methoxy or ethoxy groups for reducing the viscosity.
R of the compound of formula (1) 1 R is R 2 In order to expand the temperature range of the nematic phase of the composition, preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. Further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for viscosity reduction. The preferred stereochemistry of-ch=ch-in these alkenyl groups depends on the position of the double bond. Among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl, the trans configuration is preferable for the purpose of reducing viscosity and the like. In alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl and the likeThe cis configuration is preferred. Of these alkenyl groups, the straight chain alkenyl group is superior to the branched alkenyl group.
In order to improve the dielectric anisotropy in a state where the optical anisotropy of the composition is maintained, R is as 2 Preferably, -CN, -NCS, and-NO are selected 2 More preferably, -CN and-NCS are selected. In addition, in order to improve dielectric anisotropy in a state where the response speed of the element is maintained, R is as follows 2 Preferably selected from the group consisting of-F, -CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -SF 5 More preferably, the selection is-F, -CF 3 and-OCF 3 。
In p and q of the formula (1), p+q > 2 is preferable in order to raise the upper limit temperature of the composition. In order to reduce the lower limit temperature of the composition and increase the response speed, p+q < 1 is preferable, and p+q=0 is more preferable.
Z 1 Z is as follows 3 Independently a single bond, -CH 2 CH 2 -、-CF 2 O-、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH 2 -, -O-, or-CO-. In order to improve the optical anisotropy of the composition, Z is 1 Z is as follows 3 The single bond, -ch=ch-, -cf=cf-, -ch=cf-, -c≡c-, or-c≡c-is preferably selected, and the single bond or-c≡c-is more preferably selected from the viewpoints of preventing the material from being degraded with time, suppressing the cost, and the like.
Ring A 1 Ring A 2 Ring A 3 Or ring A 4 Independently a group represented by the formula (I) to the formula (XV). In this case, in order to increase the optical anisotropy or the dielectric anisotropy, the groups represented by the formulas (I) to (VII) are preferably selected. Of these ring structures, groups represented by the formulas (I), (II), and (VI) are preferably selected in order to increase the response speed of the element. In order to reduce dielectric loss of the element, the groups represented by the formulas (V), (VII) and (VIII) are preferably selected. Further, for the purpose of expanding the driving temperature range of the element, the groups represented by the formulas (XIII), (XIV), and (XV) are preferably selected.
Radicals of the formulae (I) to (XII)At least one hydrogen may be reacted via-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-OCH 3 、-OCH 2 CH 3 、-SCH 3 or-F substitution. In particular in the selection of-CN, -NCS, and-NO 2 As R 2 In the case of (a), the introduction of these groups is preferable because the compatibility of the composition is improved by reducing the intermolecular interaction of the compounds. In this case, in order to improve the compatibility of the composition, it is more preferable to select-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-OCH 3 、-OCH 2 CH 3 、-SCH 3 In order to reduce the response speed of the element, it is more preferable to select-CH 3 -F. On the other hand, in order to further reduce the response speed of the element, it is preferable not to be substituted with these groups.
As the compound represented by the general formula (1) of the present invention, preferred compounds are compounds represented by the following formulas (1-1) to (1-104).
In the compounds represented by the formulas (1-1) to (1-104), R 11 Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, an alkylthio group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms; r is R 12 For the R 11 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H、-NCS、-SF 5 or-NO 2 The method comprises the steps of carrying out a first treatment on the surface of the R is alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 4 carbon atoms, or alkenyl of 2 to 5 carbon atoms.
Among the compounds represented by the formulas (1-1) to (1-104), in order to impart greater optical anisotropy to the composition, the structures of (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) are preferably selected, and the structures of (1-1), (1-10), (1-15), (1-17), (1-29), (1-33), (1-42), (1-47), (1-57), (1-66), (1-89) and (1-97) are more preferably selected, for the purpose of improving the efficiency of phase control in the element.
In addition, for the purpose, R is 12 Preferably, the selection is-CN, -NCS, or-NO 2 Particular preference is given to selecting-CN or-NCS. On the other hand, if these groups are selected as R 12 The intermolecular interaction becomes large and the crystallinity of the compound increases. With this, the compatibility of the composition decreases, and the lower limit temperature increases. In order to prevent such deterioration of characteristics, among the compounds represented by the formulas (1-1) to (1-104), the structures of (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) are more preferably selected.
Among the compounds represented by the formulas (1-1) to (1-104), in order to impart a larger dielectric anisotropy to the composition for the purpose of reducing the driving voltage of the element, the structures of (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) are preferably selected. In addition, for the purpose, R is 12 More preferably, -CN, -F, -CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H、-NCS、-SF 5 or-NO 2 Most preferably-CN, -F, -CF 3 、-OCF 3 、-NCS。
Among the compounds represented by the formulae (1-1) to (1-104), for example, in the millimeter wave band variable phase shift element, the structures (1-29) to (1-32) are preferably selected for the purpose of reducing the loss of the composition for the purpose of maintaining the intensity of the wave.
When the content of the compound represented by the general formula (1) is 5% by weight or more, the improvement of the properties of the composition can be facilitated. 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 the rise in the lower limit temperature or the rise in the viscosity, it is preferable to contain 5% by weight or more of the compound other than the compound represented by the general formula (1), and more preferable to contain 10% by weight or more.
As the second component used in the composition of the present invention, in order to obtain the desired characteristics, compounds represented by formulas (2) to (4) may be preferably used.
In formula (2), ring A 20 Ring A 23 Independently is 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 A 21 Ring A 22 Independently 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 present 20 Ring A 23 May be the same or different from each other;
R 20 is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
In formula (3), ring A 20 Ring A 23 Independently 1, 4-cyclohexylene1, 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 A 21 Ring A 22 Independently 1, 4-phenylene, 2, 6-naphthylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z 20 z is as follows 22 Independently a single bond, -CH 2 CH 2 -、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH 2 -, -O-, or-CO-, Z 21 is-C.ident.C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present 20 Ring A 23 、Z 20 And Z 22 May be the same or different.
R 20 Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
In formula (4), ring A 30 Ring A 31 Ring A 32 Independently 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; z is Z 30 、Z 31 And Z 32 Independently a single bond, -CH 2 CH 2 -、-CH＝CH-、-CH 2 O-、-COO-、-CF 2 CF 2 -, -C.ident.C-, or-CF 2 O-，Z 30 、Z 31 And Z 32 At least one of them is-CF 2 O-；X 30 、X 31 And X 32 Independently hydrogen or fluorine;
m1 is 0, 1 or 2, and in the case where m1 is 2, there are a plurality of rings A 31 Z is as follows 31 May be the same or different;
R 20 independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
Among the compounds represented by the formula (2), compounds which can be preferably used in the present invention are compounds represented by the formulas (2-1) to (2-32).
In these formulae, R 20 Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
Of these compounds represented by the formulae (2-1) to (2-32), 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) are particularly preferable in order to obtain the desired characteristics.
Among the compounds represented by the formula (3), compounds which can be preferably used in the present invention are compounds represented by the formulas (3-1) to (3-14).
In these formulae, R 20 Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
Of these compounds represented by the formulae (3-1) to (3-14), the selection of (3-1), (3-4), (3-5), (3-6), and (3-12) is particularly preferable in order to obtain the desired characteristics.
Among the compounds represented by the formula (4), compounds which can be preferably used in the present invention are compounds represented by the formulas (4-1) to (4-15).
In these formulae, R 20 Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms.
Of these compounds represented by the formulae (4-1) to (4-15), 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) in order to obtain the desired characteristics.
Among the compounds represented by the formula (4), the compounds represented by the formulas (4-16) to (4-26) may be preferably used in the present invention.
In these formulae, R 20 Independently is an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12 carbon atoms, or an alkenyl group of 2 to 12 carbon atoms.
Of these compounds represented by the formulae (4-16) to (4-26), the choice (4-16) is particularly preferable in order to obtain the desired characteristics.
In order to improve the 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 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 an antioxidant are preferable to be a compound represented by the following formula (AI) because they have a high effect and prevent the liquid crystal temperature range of the composition from being narrowed.
R A1 -R A2 (Al)
Here, R is A1 Is a radical of the formula (AI-1) or (AI-2), in which R is a radical of the formula (AI-1) or (AI-2) A3 Is hydrogen or alkyl with 1-5 carbon atoms, R A4 Independently an alkyl group having 1 to 5 carbon atoms, and represents a linking position. R is R A2 An organic group having 1 to 18 carbon atoms, one to three-H of the organic group being optionally substituted with R A1 The same radical of formula (AI-1) or formula (AI-2).
Of the compounds (AI), the compound having the group of (AI-1) is a light stabilizer, and the compound having the group of (AI-2) is an antioxidant. As the antioxidant, a compound of 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, the decrease in specific resistance due to heating in the atmosphere can be effectively prevented. Since the compound (AI-2-1) having k of 7 has low volatility, reliability is effectively maintained not only at room temperature but also at a high temperature after a long-term use of the high-frequency antenna.
In order to obtain the above-mentioned effect, the preferable proportion of the light stabilizer is 100ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of the light stabilizer is 0.5% or less. Further, the preferable ratio is 100ppm to 1000ppm. In order to obtain the above-mentioned effect, the preferable proportion of the antioxidant is 50ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of the antioxidant is 600ppm or less. Further, the preferable ratio is 100ppm to 300ppm.
Optically active compounds may also be added to the compositions of the present invention. The compound is mixed into the composition for the purpose of imparting a twist angle by inducing 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), R C1 Independently a hydrocarbon having a ring structure and up to 30 carbon atoms. * Representing asymmetric carbons.
Pigments such as azo-based, carotenoid-based, flavonoid-based, quinone-based, porphyrin-based and the like may also be contained in the composition of the present invention in order to improve the anisotropy at a frequency of 1MHz to 400 THz.
In order to improve the properties, the composition of the present invention may contain a polymerizable compound. For this purpose, examples of the improvement of the characteristics of the antenna element using the polymer dispersed liquid crystal include IEEJ basic and materials journal (IEEJ Transactions on Fundamentals and Materials), vol.137, no.6, pp.356 (2017), and the like. In the composition of the present invention, the polymerizable compound may be added to the composition for the purpose of such improvement. As such a polymerizable compound, a radical polymerizable compound is preferable for maintaining the electrical characteristics of the element, and a (meth) acrylic group is more preferable from the viewpoints of reactivity at the time of polymerization and solubility in liquid crystal.
As a preferable polymerizable compound, there can be mentioned (meth) acrylic acid derivatives having a skeleton similar to that of a liquid crystal. These compounds do not significantly lower the phase transfer point of the composition, and thus can be preferably used in the case of orienting the composition in one direction. As preferable examples of such compounds, compounds represented by the following formulas (M-1) to (M-3) can be cited.
In the formula (M-1), the formula (M-2), and the formula (M-3), the 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, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, or alkanoyl having 1 to 12 carbon atoms; z is Z m1 Are each independently a single bond, -OCH 2 -, -COO-, or-OCOO-; z is Z m2 Is a single bond, -O-, -OCH 2 -, or-COO-; x is X m1 Is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or alkoxycarbonyl of 1 to 20 carbon atoms; 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 independently the integer from 0 to 20A number; r is R m1 Each independently is hydrogen or CH 3 。
Further, as the polymerizable compound, there may be mentioned (meth) acrylic acid derivatives having no skeleton similar to that of liquid crystals. These compounds can be preferably used in lowering the driving voltage of the element. As preferable examples of such a compound, a compound represented by the following formula (M-4) may be given.
In the formula (M-4), Z m3 Is a single bond or an alkylene group having 1 to 80 carbon atoms, in which at least one hydrogen may be substituted with an alkyl group having 1 to 20 carbon atoms, fluorine, or a group of the following formula (7), at least one-CH 2 -can be prepared by-O-, -CO-, -COO-or-OCO-, -NH-, or-N (R) m3 ) -substitution, in the case of substitution by a plurality of-O-groups, which are not contiguous, R m3 Alkyl of 1 to 12 carbon atoms; at least one-CH 2 -CH 2 -may be substituted by-ch=ch-, or-c≡c-;
R m2 an alkyl group having 1 to 20 carbon atoms, wherein at least one hydrogen may be substituted with fluorine, at least one-CH 2 -can be substituted by-O-, -CO-, -COO-, or-OCO-, in which case the-O-groups are not contiguous, at least one-CH 2 Substituted by a divalent radical which is formed by removing two hydrogens from a saturated aliphatic compound of the carbocyclic formula, a saturated aliphatic compound of the heterocyclic formula, an unsaturated aliphatic compound of the carbocyclic formula, or an unsaturated aliphatic compound of the heterocyclic formula, in which divalent radicals the number of carbons is 5 to 35, at least one hydrogen may be substituted by an alkyl radical of the number of carbons 1 to 12, of which alkyl radical one-CH 2 -may be substituted by-O-, -CO-, -COO-, or-OCO-; r is R m1 Is hydrogen or-CH 3 。
In the formula (7), Z m4 Of carbon number 1 to 12 Alkylene group, R m1 Is hydrogen or-CH 3 Indicating the connection location.
Preferred examples of the compounds represented by the formulas (M-1) to (M-4) are the formulas shown below.
In the formula, R m1 Independently hydrogen or-CH 3 H is independently an integer from 1 to 20.
In the formula, R m2 Alkyl of 5 to 20 carbon atoms, of which at least one-CH 2 -can be substituted by-O-, -CO-, -COO-, or-OCO-, R m3 Each independently is an alkyl group having 3 to 10 carbon atoms, at least one of which is-CH 2 -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), R m3 Each independently is an alkyl group of 1 to 5 carbon atoms, R m4 Each independently is an alkyl group having 1 to 20 carbon atoms, at least one of which is-CH 2 -can be substituted by-O-, -CO-, -COO-, or-OCO-, R in the same formula m3 And R is R m4 The two may be the same or different,
Z m5 an alkylene group having 10 to 30 carbon atoms, at least one of the alkylene groups being-CH 2 -can be prepared by-O-, -CO-, COO-, or OCO-, substitution, the alkylene group also includes those having a branched alkyl group,
in the formula (M-4-10), p is an integer of 3 to 10, R m5 R is R m6 Is hydrogen or-CH 3 Either of them is-CH 3 ，
In the formula (M-4-11), R m7 R is-OH, (meth) acryl, or of the formula (M-4-11) m7 Other than residues bonded via-O-, R m1 Each independently is hydrogen or-CH 3 . Hereinafter, R is represented by m7 R having the formula (M-4-11) m7 The other residues are bonded via-O-bond to form a structure of formula (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 for carrying out the polymerization, suitable types of initiators, and suitable amounts are known to the person skilled in the art and are described in the literature. For example, brilliant best (Irgacure) 651 (registered trademark; BASF), brilliant best (Irgacure) 184 (registered trademark; BASF), or Darocure 1173 (registered trademark; BASF)) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator is in the range of about 0.1 parts by weight to about 5 parts by weight based on 100 parts by weight of the polymerizable compound. Further preferred ratios are in the 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 an element, an alignment film made of polyimide or the like is used for aligning the liquid crystal composition. On the other hand, in order to orient the liquid crystal composition, an orientation controlling agent is also added to the liquid crystal. As such an orientation controlling agent, a compound described in WO2017-057162, WO2012-104008, WO2016-129490 or the like can be preferably used.
Finally, the use of the composition will be described. 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 body such as a liquid crystal varies according to frequency and temperature. Therefore, the frequency dependence of these dielectric constants is referred to as the dielectric properties of the dielectric body. When an alternating electric field is applied to the liquid crystal, as the frequency f increases, an internal electric dipole (electric dipole) can follow the change of the electric field, and thus the dielectric constant epsilon 'decreases while the conductivity sigma' increases, and the dielectric loss epsilon "shows a peak, which is dielectric relaxation (dielectric relaxation).
In the microwave and millimeter wave region, the method of mounting the device or sample is quite different depending on the measured frequency region. For the reason that electromagnetic field analysis is easy up to 10GHz, in many cases, a probe uses an open-end coaxial type cell, and a measurement system centering on a network analyzer is assembled and the frequency is scanned to obtain a spectrum of complex permittivity (dielectric relaxation spectrum) of a sample. At frequencies above 10GHz, waveguides are required rather than coaxial cables. In order to calculate the dielectric constant, the boundary condition when the electromagnetic wave is incident on the sample must be appropriately determined, and if the wavelength becomes short, precise processing is required accordingly. In a low frequency region, a capacitor cell is fabricated, a sample is inserted therein, and the dielectric constant is obtained from the change in capacitance.
Examples
The present invention will be further described in detail by examples. The present invention is not limited by these examples. Examples were carried out at room temperature (25 ℃) unless otherwise specified.
< assay >)
The measurement and verification were performed by the following method. Unless otherwise stated, the measurement method not described in the present specification is based on Japanese society of electronic information technology and technology (Japan Electronics and Information Technology Industries Association, JEITA). ED-2521B.
< Nuclear magnetic resonance (nuclear magnetic resonance, NMR) >
NMR was measured using DRX-500 manufactured by Bruker Biospin, inc. 1 In the measurement of H-NMR, a sample was dissolved in CDCl 3 And in an isotonic deuterated vehicle. The measurement was performed at 500MHz at room temperature. At this time, the cumulative number of times was 16. The internal standard is tetramethylsilane. In the notation of NMR, s denotes a single peak (single), d denotes a double peak (doublet), t denotes a triple peak (triplet), q denotes a quadruplet (quatert), quintet (quintet), sex denotes a hexa peak (setet), m denotes a multiple peak (multiplet), br denotes a broad peak (broad).
Differential scanning calorimetry (differential scanning calorimetry, DSC) assay
The measurement was performed using a differential scanning calorimeter (Dai Meng (Diamond) DSC from Perkin Elmer). The transition temperature is expressed by describing the temperature in degrees celsius between expressions of the phases. In the expression phase, C is a crystalline layer, N is a nematic phase, S is a smectic phase, and I is an isotropic liquid. In the expression of the phase, the expression of the phase with brackets indicates a liquid crystal phase of a single phase change (monotropic).
< gas chromatography analysis >)
For measurement, a GC-2014 type gas chromatograph manufactured by Shimadzu corporation was used. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set at 280℃and the detector (flame ionization detector (flame ionization detector, FID)) was set at 300 ℃. The separation of the component compounds was carried out using a capillary column DB-1 (30 m in length, 0.32mm in inside diameter, 0.25 μm in thickness; dimethylpolysiloxane as the stationary liquid phase; nonpolar) manufactured by Agilent technologies Co., ltd. (Agilent Technologies Inc.). After preparing the sample into an acetone solution (0.1 wt%), 1. Mu.L of the acetone solution was injected into the sample vaporization chamber. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compound and the area of the peak.
< high Performance liquid chromatography (high performance liquid chromatography, HPLC) analysis >
The measurement was performed using HPLC LC-2000Plus manufactured by Japanese spectroscopic 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 an embodiment, "NI" is "upper temperature".
The upper limit temperature is a measured value of the temperature at which a part of the sample changes from a nematic phase to an isotropic liquid by placing the sample on a hot plate provided with a melting point measuring device of a polarized light microscope and heating the sample at a rate of 1 ℃/min.
< lower limit temperature of nematic phase >
In an embodiment, "Tc" is the "lower limit temperature".
The lower limit temperature is determined by placing a sample having a nematic phase into a glass bottle, keeping the sample in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, and observing the phase.
< refractive index anisotropy under visible light >)
In the examples, the refractive index anisotropy is expressed as "Δn".
Δn is measured by an abbe refractometer having a polarizing plate attached to an eyepiece.
After rubbing the surface of the main prism in one direction, a sample was dropped onto the main prism, the refractive index perpendicular to the direction of the polarized light and the rubbing direction was measured with n+.t, and the refractive index parallel to the direction of the polarized light and the rubbing direction was measured with n/. Δn is calculated using Δn=n/-n≡..
At this time, the measurement temperature was 25℃using light having a wavelength of 589 nm.
< dielectric constant anisotropy at 1kHz >)
The value of the dielectric anisotropy is calculated from the equation of Δε=ε/- ε. The dielectric constant (. Epsilon. T) was measured as follows.
(A) Determination of dielectric constant (ε): a well-cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). After the glass substrate was rotated by a rotator, the glass substrate was heated at 150℃for 1 hour. Samples were placed in vertically oriented (vertical alignment, VA) elements of two glass substrates spaced 4 μm apart, and the elements were sealed with an adhesive that was cured with ultraviolet light. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon./V) of the liquid crystal molecules was measured in the long axis direction after 2 seconds.
(B) Determination of dielectric constant (ε+.T): a polyimide solution was coated on the sufficiently cleaned glass substrate. After the glass substrate is calcined, the obtained alignment film is subjected to a rubbing treatment. Samples were injected into a Twisted Nematic (TN) cell having a 9 μm gap between two glass substrates and a twist angle of 80 degrees. A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon. DELTA.T.) of the liquid crystal molecules was measured in the short axis direction after 2 seconds.
Voltage holding ratio (voltage holding ratio, VHR) >
The units used for the measurement were of the following configuration. That is, an Indium Tin Oxide (ITO) electrode and a rubbed polyimide alignment film are sequentially disposed on each substrate. The two substrates were bonded to each other with the alignment film surface as the inner side so that the angle of the rubbing direction between the upper and lower substrates was 80 degrees. The interval (cell gap) between the two glass substrates was 5. Mu.m. The liquid crystal composition was put into the cell, and then sealed with an adhesive that was cured with ultraviolet rays. Pulse voltages (5V, 60 μs) were applied to the TN cells to charge them. The decaying voltage was measured with 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 obtained. Area B is the area when unattenuated. The voltage holding ratio is expressed by the percentage of the area a to the area B.
Refractive index anisotropy and dielectric loss at < 50GHz >)
The measurement was performed by the method disclosed in Applied Optics, vol.44, no.7, p1150 (2005). Regarding refractive index anisotropy, liquid crystal was filled in a V-band variable-length waveguide to which a window material was attached, and held in a static magnetic field of 0.3T for 3 minutes. A microwave of 50GHz was input to the waveguide, and the amplitude ratio of the reflected wave to the incident wave was measured. The direction of the static magnetic field and the tube length of the short-circuiting device are changed to measure, and the refractive index (ne, no) and the loss parameters (αe, αo) are determined. Refractive index anisotropy (Δn) is calculated from ne-no.
The complex dielectric constant (ε ', ε ") was used and calculated as dielectric loss (tan δ) =ε"/ε'. The complex permittivity is calculated using the calculated refractive index, loss parameter, and the following relational expression.
Here, c is the light velocity of the vacuum. Dielectric loss also exhibits anisotropy, and thus the recorded value is large.
ε′＝n 2 -κ 2
ε”＝2nκ
α＝2ωc/κ
< bulk viscosity >
In the examples, the bulk viscosity of the composition is expressed as "η".
The bulk viscosity was measured using an E-type rotary viscometer manufactured by Tokyo counter Co., ltd. The measured temperature was 20 ℃.
< Compounds >
As the compound represented by the formula (1), the following 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) are used. The compound (1-1-1) is described in "application physics express (J.Appl.Phys.),65(11) 4372 (1989) was synthesized in the same manner as described in Japanese patent application laid-open No. 2012-167068, and (1-1-3) was synthesized in the same manner as described in Japanese patent application laid-open No. 2012.
Example 1
Synthesis of Compound represented by the formula (1-1-2)
To 10.0g (34.8 mmol) of a compound represented by the formula (1-1-2 a) synthesized according to Liquid Crystals (27 (6), 801 (2000), 1, 4-diazabicyclo [2.2.2 ]Octane (1, 4-Diazabicyclo [2.2.2 ]]octane, DABCO) 23.4g (208 mmol)CS was added to 100ml of Tetrahydrofuran (THF) 2 21ml (349 mmol) were stirred overnight at room temperature under a nitrogen flow. The resulting precipitate was filtered. The obtained powder was transferred to a flask and CHCl was added 3 100ml, and stirring. To the mixed solution was slowly added 3.8g (12.8 mmol) of bis (trichloromethyl) carbonate (triphosgene) CHCl at room temperature 3 50ml of solution. Then, reflux was performed in a nitrogen stream for 3 hours. After the reaction solution was cooled, 100ml of pure water was added. After separating the organic layer, the mixture was washed with an equal amount of pure water and with MgSO 4 Drying. After filtration and distillation of the solvent under reduced pressure, the obtained product was recrystallized by column chromatography (silica gel, heptane/toluene=2/1) and toluene/ethanol mixed solvent, thereby obtaining (1-1-2). Yield 7.1g (62% yield). Gas chromatography (gas chromatography, GC) purity: 100%. Phase transition temperature (deg.c): c.141.0.n.147.4.i.
Example 2
Synthesis of Compound represented by the formula (1-17-1)
3.5g (13.4 mmol), 3.1g (18.0 mmol) of 1-ethynyl-4-pentylbenzene, 260mg (13.6 mmol) of CuI, 820mg (2.7 mmol) of tris (o-tolyl) phosphine, and K of the compound represented by the formula (1-17-1 a) synthesized according to Synthesis (10), 1541 (2011) in the same manner as in Synthesis (5), 816 (2011) 2 CO 3 1.9g (13.7 mmol) of the mixture are refluxed in ethanol (50 ml) under nitrogen flow for 12 hours. After the reaction mixture was cooled, 100ml of toluene and 100ml of pure water were added. After separation of the organic layer, mgSO was used 4 Drying. After filtration and distillation of the solvent under reduced pressure, the obtained product was recrystallized by column chromatography (silica gel, heptane/toluene=2/1) and toluene/ethanol mixed solvent, thereby obtaining (1-17-1). Yield 1.3g (28% yield). GC purity: 100%. Phase transition temperature (deg.c): c.91.2.n.199.5.i.
Examples 2 to 2
Synthesis of Compound represented by the formula (1-29-1)
The synthesis was performed in the same manner as in example 2 using the compound represented by the formula (1-29-1 a) instead of the compound represented by the formula (1-17-1 a). The obtained product was recrystallized by column chromatography (silica gel, heptane/toluene=2/1) and ethanol, thereby obtaining (1-29-1). Yield 2.2g (47% yield). HPLC purity (solvent acetonitrile dissolution): 100%. Phase transition temperature (deg.c): c.101.3.i.
The compounds represented by the formula (1-29-1 a) were synthesized as follows. To 100ml of a solution of 10.0g (29.2 mmol) of N, N-Dimethylformamide (DMF) of a compound represented by the formula (1-29-1 b) synthesized according to Synthesis (12), 2040 (2009) 4 NF 50g (70% -75% aqueous solution) was stirred at 60℃for 1 hour. After the reaction mixture was cooled, 100ml of toluene and 100ml of pure water were added. After separation of the organic layer, mgSO was used 4 Drying. After filtration and distillation of the solvent under reduced pressure, the obtained product was purified by column chromatography (silica gel, heptane/toluene=2/1), whereby (1-29-1 a) was obtained. Yield 7.6g (78% yield).
< liquid Crystal composition >
The liquid crystal of the second component is used to prepare a composition by compounding the above-mentioned formulae (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). The liquid crystal compound of the second component is represented by the expression of table 1. Unless otherwise specified, the divalent radical of the six-membered ring of table 1 is in the trans configuration. The numbers in brackets after the marked compounds in the liquid crystal composition represent the chemical formulas to which the compounds belong. The symbol of (-) refers to other liquid crystal compounds. The proportion of the liquid crystal compound is a weight percentage based on the weight of the liquid crystal 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.15
Dielectric loss; 0.016
Example 4
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 2 at 50GHz were as follows.
Refractive index anisotropy; 0.15
Dielectric loss; 0.015
Example 5
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 2 at 50GHz were as follows.
Refractive index anisotropy; 0.16
Dielectric loss; 0.015
Example 6
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 2 at 50GHz were as follows.
Refractive index anisotropy; 0.17
Dielectric loss; 0.015
Example 7
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
Example 8
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.25
Dielectric loss; 0.010
Example 9
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.22
Dielectric loss; 0.013
Example 10
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.20
Dielectric loss; 0.009
Example 11
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
Example 13
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.23
Dielectric loss; 0.010
Example 14
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.28
Dielectric loss; 0.009
Example 15
Preparation and physical 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
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 publication No. 5859189. Using the compound, the following liquid crystal composition ref.1 was prepared in the same manner as in example 1. 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 refractive index anisotropy and dielectric loss of the liquid crystal composition 1 at 50GHz were as follows.
Refractive index anisotropy; 0.23
Dielectric loss; 0.011
The liquid crystal compositions 5 and 7 of examples 7 and 9 have refractive index anisotropies substantially the same as that of the liquid crystal composition ref.1 of comparative example 1, but have a small viscosity. Thus, it was found that the liquid crystal composition of the present invention is excellent in balance of characteristics as a material for an element for controlling the phase 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 (14)
1. A liquid crystal composition comprising at least one compound selected from the group of compounds represented by the formula (1) as a first component and at least one compound selected from the group of compounds represented by the formula (3) as a second component, and being used for phase control of electromagnetic wave signals having a frequency of 1MHz to 400THz,
In the formula (1), the components are as follows,
R 1 alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atomsAlkylthio of 1 to 12 carbon atoms or alkenyloxy of 2 to 12 carbon atoms, with respect to one or more CH present in said alkyl, said alkoxy, said alkylthio or said alkenyloxy 2 As the case where O atoms are not directly bonded to each other, can be substituted by-O-, -CO-, or-COO-; r is R 2 For the R 1 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H、-NCS、-SF 5 or-NO 2 The method comprises the steps of carrying out a first treatment on the surface of the Ring A 1 Ring A 2 Ring A 3 Ring A 4 Independently a group represented by any one of the following formulas (I) to (XV), ring A 2 Ring A 3 At least one of which is a group represented by any one of the formulas (I) to (XII);
in the radicals of the formulae (I) to (XII),
at least one hydrogen may pass through-CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-OCH 3 、-OCH 2 CH 3 、-SCH 3 or-F substitution; z is Z 1 Z is as follows 3 Independently a single bond, -CH 2 CH 2 -、-CF 2 O-、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-C≡C-C≡C-、-COO-、-CH 2 -, -O-, or-CO-, Z 2 is-C.ident.C-;
p and q are independently 0, 1 or 2, and in the case where these p and q are 2, there are a plurality of rings A 1 、Z 1 、Z 3 Ring A 4 Which may be the same or different from each other,
in formula (3), ring A 20 Ring A 23 Is independently 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, pyridin-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A 21 Ring A 22 Independently 1, 4-phenylene, 2, 6-phenyleneNaphthyl, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene, or 2, 6-difluoro-1, 4-phenylene;
Z 20 z is as follows 22 Independently a single bond, -CH 2 CH 2 -、-CH 2 O-、-CH＝CH-、-CF＝CF-、-CH＝CF-、-C≡C-、-COO-、-CH 2 -, -O-, or-CO-, Z 21 is-C.ident.C-;
m1 and m2 are independently 0, 1 or 2, and when m1 and m2 are 2, a plurality of rings A are present 20 Ring A 23 、Z 20 And Z 22 May be the same or different from each other;
R 20 is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
2. The liquid crystal composition according to claim 1, which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) with respect to the total weight of the composition, and further contains at least one compound selected from the group of compounds represented by formula (2),
in formula (2), ring A 20 Ring A 23 Is independently 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, pyridin-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, or tetrahydropyran-2, 5-diyl, ring A 21 Ring A 22 Independently 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 present 20 Ring A 23 May be the same or different from each other; r is R 20 Is alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms, R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
3. The liquid crystal composition according to claim 1, which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) with respect 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) with respect to the total weight of the composition as a second component.
4. The liquid crystal composition according to claim 1, which contains 95 to 10% by weight of at least one compound selected from the group of compounds represented by formula (1) with respect to the total weight of the composition, and further contains at least one compound selected from the group of compounds represented by formula (4),
in formula (4), ring A 30 Ring A 31 Ring A 32 Independently 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; z is Z 30 、Z 31 And Z 32 Independently a single bond, -CH 2 CH 2 -、-CH＝CH-、-CH 2 O-、-COO-、-CF 2 CF 2 -, -C.ident.C-, or-CF 2 O-，Z 30 、Z 31 And Z 32 At least one of them is-CF 2 O-；X 30 、X 31 And X 32 Independently hydrogen or fluorine;
m1 is 0, 1 or 2, and in the case where m1 is 2, there are a plurality of rings A 31 Z is as follows 31 May be the same or different;
R 20 is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
5. The liquid crystal composition according to claim 2, which contains at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-32),
in these formulae, R 20 Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
6. The liquid crystal composition according to claim 3, which contains at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-14) as a second component,
in these formulae, R 20 Is alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or alkenyl of 2 to 12 carbon atoms; r is R 21 For the R 20 、-CN、-F、-Cl、-CF 3 、-OCF 3 、-CF 2 H、-OCF 2 H. -NCS, or-SF 5 。
7. The liquid crystal composition according to claim 4, which contains at least one compound selected from the group of compounds represented by the formulas (4-1) to (4-15),
In these formulae, R 20 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.
8. The liquid crystal composition according to claim 4, which contains at least one compound selected from the group of compounds represented by the formulas (4-16) to (4-26),
in these formulae, R 20 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.
9. The liquid crystal composition according to any one of claims 1 to 4, 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.
10. The 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.
11. The liquid crystal composition according to any one of claims 1 to 4, comprising an acrylic monomer.
12. The liquid crystal composition according to any one of claims 1 to 4, comprising a photopolymerization initiator.
13. The liquid crystal composition according to any one of claims 1 to 4, comprising an optically active compound.
14. An element containing the liquid crystal composition according to any one of claims 1 to 13 and used for phase control of electromagnetic wave signals having a frequency of 1MHz to 400 THz.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-226262 | 2018-12-03 | ||
| JP2018226262 | 2018-12-03 | ||
| JP2019-150310 | 2019-08-20 | ||
| JP2019150310A JP2020094175A (en) | 2018-12-03 | 2019-08-20 | Liquid crystal composition for use in phase control of electromagnetic wave signal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111253953A CN111253953A (en) | 2020-06-09 |
| CN111253953B true CN111253953B (en) | 2024-02-23 |
Family
ID=70923987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910852540.5A Active CN111253953B (en) | 2018-12-03 | 2019-09-10 | Liquid crystal composition and element for phase control of electromagnetic wave signal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111253953B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2022048990A (en) * | 2020-09-15 | 2022-03-28 | Jnc株式会社 | Liquid crystal composition used in element for phase control of electromagnetic wave signal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312618B1 (en) * | 2000-04-03 | 2001-11-06 | Hrl Laboratories | Polar diphenyldiacetylene liquid crystals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6696312B2 (en) * | 2016-06-15 | 2020-05-20 | Jnc株式会社 | Liquid crystal composition and liquid crystal display device |
-
2019
- 2019-09-10 CN CN201910852540.5A patent/CN111253953B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312618B1 (en) * | 2000-04-03 | 2001-11-06 | Hrl Laboratories | Polar diphenyldiacetylene liquid crystals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111253953A (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI672332B (en) | Liquid crystal composition, use thereof, and liquid crystal display device | |
| JP6809459B2 (en) | Liquid crystal composition and liquid crystal display element | |
| TW538118B (en) | Chiral compounds I | |
| TWI719139B (en) | Liquid crystal composition and liquid crystal display element | |
| TWI630263B (en) | Liquid crystal composition, use thereof, and liquid crystal display device | |
| CN111732569B (en) | Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element | |
| KR20180090257A (en) | Liquid crystal composition and liquid crystal display element | |
| KR20180052608A (en) | Polymerizable polar compounds, liquid crystal compositions and liquid crystal display elements | |
| CN101302145A (en) | Stilbene derivatives, liquid crystal mixture and electrooptical display | |
| CN109762577B (en) | Liquid crystal compound based on cyclopentanobenzofuran framework, composition and preparation method of compound | |
| TWI663251B (en) | Liquid crystal composition,use of liquid crystal conposition and liquid crystal display device | |
| TWI694140B (en) | Polymerizable polar compound, liquid crystal composition and liquid crystal display element | |
| CN106565652B (en) | Compound having tetrahydropyran ring, liquid crystal composition, and liquid crystal display element | |
| CN114181713A (en) | Liquid crystal composition and phase control element | |
| CN111253953B (en) | Liquid crystal composition and element for phase control of electromagnetic wave signal | |
| TWI599641B (en) | Liquid crystal composition and its use, and liquid crystal display element | |
| CN111278800B (en) | Polymerizable polar compound, liquid crystal composition, and liquid crystal display element | |
| TWI728101B (en) | Polymerizable polar compound, liquid crystal composition and liquid crystal display element | |
| US11155753B2 (en) | Liquid crystal composition used for phase control of electromagnetic wave signal | |
| CN110914233B (en) | Polymerizable polar compound, liquid crystal composition, and liquid crystal display element | |
| CN107868665B (en) | Liquid crystal compound, liquid crystal composition, and liquid crystal display element | |
| CN112979471B (en) | Liquid crystal molecule horizontal alignment agent, liquid crystal composition and liquid crystal display element | |
| CN111587237A (en) | Compound, liquid crystal composition and liquid crystal display element | |
| TWI633177B (en) | Liquid crystal composition and use thereof, liquid crystal display element, and polymerization Stable alignment type liquid crystal display element | |
| CN112368260B (en) | Compound, liquid crystal composition and liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |