CN111373017B - Liquid crystal composition and liquid crystal display element - Google Patents
Liquid crystal composition and liquid crystal display element Download PDFInfo
- Publication number
- CN111373017B CN111373017B CN201880075272.4A CN201880075272A CN111373017B CN 111373017 B CN111373017 B CN 111373017B CN 201880075272 A CN201880075272 A CN 201880075272A CN 111373017 B CN111373017 B CN 111373017B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- carbon atoms
- group
- general formula
- crystal composition
- 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
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 161
- 239000000203 mixture Substances 0.000 title claims abstract description 114
- 150000001875 compounds Chemical class 0.000 claims abstract description 169
- 125000004432 carbon atom Chemical group C* 0.000 claims description 141
- 125000000217 alkyl group Chemical group 0.000 claims description 52
- 125000003342 alkenyl group Chemical group 0.000 claims description 43
- 125000003545 alkoxy group Chemical group 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 125000001153 fluoro group Chemical group F* 0.000 claims description 36
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 19
- -1 4-cyclohexenyl Chemical group 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 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 5
- 239000011159 matrix material Substances 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000013307 optical fiber Substances 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 15
- 239000000758 substrate Substances 0.000 description 29
- 239000000126 substance Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 16
- 239000010408 film Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- 125000005451 3-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C([H])=C(F)C([*:2])=C1[H] 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 125000005450 2,3-difluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C(F)=C(F)C([*:1])=C1[H] 0.000 description 1
- 125000005449 2-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(F)C([*:1])=C1[H] 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- 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
- C09K19/38—Polymers
-
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- 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
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/3009—Cy-Ph
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
- C09K2019/301—Cy-Cy-Ph
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The object of the present invention is to provide a liquid crystal composition having negative dielectric anisotropy delta epsilon and T NI High, large Δn, small γ1; and a VA-type, FFS-type or IPS-type liquid crystal display element which is free from or little in display failure, uses the liquid crystal composition, has a high response speed and a high VHR, and further provides a PSA element using a polymerizable compound. The liquid crystal composition of the present invention solves the above problems by a liquid crystal composition containing a compound of the general formula (i).
Description
Technical Field
The present invention relates to a liquid crystal composition and a liquid crystal display element using the same.
Background
Liquid crystal display devices have been used for watches, electronic calculators, and various electric devices for home use, measuring instruments, automotive panels, word processors, electronic notepads, printers, computers, televisions, and the like. As a liquid crystal display system, a TN (twisted nematic) system, an STN (super twisted nematic) system, a DS (dynamic light scattering) system, a GH (guest host) system, an IPS (in-plane switching) system, an OCB (optically compensated birefringence) system, an ECB (voltage controlled birefringence) system, a VA (vertical alignment) system, a CSH (color supervertical) system, a FLC (ferroelectric liquid crystal) system, or the like can be exemplified. The driving method may be a static driving method, a multiplex driving method, a simple matrix method, or an Active Matrix (AM) method using a TFT (thin film transistor), a TFD (thin film diode), or the like. Among these display modes, IPS type, ECB type, VA type, CSH type, and the like have a characteristic that a liquid crystal composition exhibiting a negative value using Δε (dielectric anisotropy) is used. Among these, the VA display system using AM driving is used for applications such as a display element, for example, a television or a monitor, which requires high-speed response and a wide viewing angle.
As a liquid crystal composition having a negative Δ∈, liquid crystal compositions using the following liquid crystal compounds (a) to (E) having a 2, 3-difluorophenylene skeleton and the like are disclosed (see patent document 1).
[ chemical 1]
However, neither liquid crystal composition can satisfy both the response speed and reliability required for a large-sized liquid crystal display element in particular.
Patent document 2 discloses that the response speed of a homeotropic alignment liquid crystal cell is improved by using a liquid crystal material having a large index (FoM) expressed by the following expression, but it cannot be said that the requirement is satisfied sufficiently.
[ number 1]
FoM＝K 33 ·Δn 2 /γ1
In view of the aboveIn a liquid crystal composition requiring high-speed response and high reliability such as a liquid crystal television, the nematic phase-isotropic liquid phase transition temperature (T NI ) And refractive index anisotropy (Δn), requires rotational viscosity (γ) 1 ) Small spring constant (K) 33 ) Large, gamma 1 /K 33 Small, and the voltage holding ratio VHR is high.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-216747
Patent document 2: japanese patent laid-open No. 2006-301643
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a liquid crystal composition having a negative dielectric anisotropy (delta epsilon) and appropriately adjusting T NI And Δn, and γ1 is small, and a VA-type, FFS-type, or IPS-type liquid crystal display device having a high response speed, a high VHR, and no or little display failure using the liquid crystal composition is provided.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by a liquid crystal composition containing a compound having a specific chemical structure, and have completed the present application.
Further, the above-described problems can be solved by using a polymerizable compound together with the liquid crystal composition, and the present application has been completed.
ADVANTAGEOUS EFFECTS OF INVENTION
The present application provides a liquid crystal composition having negative dielectric anisotropy (delta epsilon) and T NI The present application can provide a VA-type, FFS-type, or IPS-type liquid crystal display device having high Δn and small γ1, which has no or little display failure, uses the liquid crystal composition, has a high response speed, and has a high VHR.
Detailed Description
The liquid crystal composition of the present application contains a compound having negative dielectric anisotropy (delta epsilon) represented by the general formula (i); the present application is a liquid crystal composition further comprising a polymerizable compound, and a liquid crystal display element using the liquid crystal composition.
[ chemical 2]
Wherein X is i1 And X i2 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group,
Y i1 and Y i2 Each independently represents-O-, -CF 2 -、-CO-、-CX i3 X i4 -，Y i1 And Y i2 Any one of above represents-O-, X i3 、X i4 Respectively and independently represent X i1 The meaning of the same is that,
L i1 、L i2 、L i3 、L i4 and L i5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or a general formula (L) i -1) a group represented by formula (i),
[ chemical 3]
(wherein R is i1 Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms,
A i1 a group selected from the group consisting of:
(a) 1, 4-Cyclohexylene (1-CH present in this group) 2 -or not more than 2-CH 2 Can be substituted by-O-or-S-,
(b) 1, 4-phenylene (1-ch=or non-contiguous 2 or more-ch=present in the group may be substituted with-n=and 1 hydrogen atom present in the group may be substituted with a fluorine atom),
(c) 1, 4-cyclohexenyl, naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl (the hydrogen atoms present in this group may be substituted by fluorine atoms, in addition, 1-ch=or more than 2-ch=that are not adjacent in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-n=),
Z i1 represents-CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -、-COO-、-OCO-、-CH 2 CH 2 -、-CF 2 CF 2 -, -CH=CH-, -CF=CF-, C.ident.C-or a single bond,
n i1 represents 1 or 2, at n i1 Represents 2 and there are a plurality of A i1 And Z i1 When they are the same or different);
W i1 the general formula (W) i1 -1)、(W i1 -2) or (W) i1 -3) a group represented by formula (i),
[ chemical 4]
(wherein, represents a group represented by the formula L i2 Or Y i2 Is a bond point, and is represented by L i5 Bonding points, L, of bonded carbon atoms adjacent to each other i6 、L i7 And L i8 Respectively and independently represent and L i1 The same meaning),
W i2 represents a single bond or-CL i9 L i10 -，
(L i9 And L i10 Respectively and independently represent and L i1 The same meaning),
L i1 、L i2 、L i3 、L i4 、L i5 、L i6 、L i7 、L i8 、L i9 and L i10 1-CH present in (B) 2 -or not more than 2-CH 2 Can be substituted by-C.ident.C-, -O-, -COO-, -an OCO-or-CO-substitution, in addition, hydrogen is present in alkyl or alkenyl groupsAtoms may be substituted with fluorine atoms).
The content of the compound of the general formula (i) in the liquid crystal composition of the present invention is preferably 0.1 mass%, preferably 0.2 mass%, preferably 0.3 mass%, preferably 0.5 mass%, preferably 1 mass%, preferably 2 mass%, preferably 3 mass%, preferably 4 mass%, as the lower limit value, more preferably 20 mass%, more preferably 15 mass%, more preferably 13 mass%, more preferably 10 mass%, and the content range is preferably 0.1 to 25 mass%, more preferably 0.1 to 20 mass%, more preferably 0.1 to 15 mass%, and particularly preferably 1 to 15 mass%. Hereinafter, mass% is described as%.
Attach importance to T NI In this case, the content is preferably reduced to a small level, and the gamma is preferably improved 1 /K 33 When the response speed is important, the preferable content is set to be large.
In the general formula (i), X is preferable i1 And X i2 At least one of them is a fluorine atom, and preferably both are fluorine atoms.
Y i1 And Y i2 Preferably one is O-and the other is-CH 2 -a compound, and a compound in which both are-O-, preferably a compound in which both are-O-.
Preferably L i1 And L i2 Independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, in order to reduce gamma 1 The alkyl group having 1 to 8 carbon atoms or the alkenyl group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is particularly preferable. In addition, a linear shape is preferable. In order to increase |Δε| is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, particularly preferably an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. In order to improve the miscibility with other liquid crystal components, L is preferable i1 And L i2 Different, preferably L i1 And L i2 Any of (2) is an alkoxy or alkenyloxy group, particularly preferably L i1 Is an alkoxy group. At L i1 And L i2 The hydrogen atoms present in (a) may be substituted by fluorine atoms, preferably not substituted by fluorine atoms.
In addition, L i1 And L i2 The following are preferred:
[ chemical 5]
In order to make gamma 1 Reduction, R i1 The alkyl group having 1 to 8 carbon atoms or the alkenyl group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms or the alkenyl group having 2 to 5 carbon atoms is particularly preferable. In addition, a linear shape is preferable. In order to increase |Δε| is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferably an alkoxy group having 1 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. There are a plurality of R i1 In this case, R is preferable for improving the miscibility with other liquid crystal components i1 Mutually different, preferably a plurality of R's present i1 Either of them is an alkoxy or alkenyloxy group, particularly preferably L i1 R in (a) i1 Is alkoxy or alkenyloxy. R is R i1 The hydrogen atoms present in (a) may be substituted by fluorine atoms, preferably not substituted by fluorine atoms.
Preferably A i1 Represents a group selected from the following.
[ chemical 6]
Specifically, in order to make γ 1 Reduction, preferably A 1 Is trans-1, 4-cyclohexylene, unsubstituted 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene, particularly preferably trans-1, 4-cyclohexylene. In order to improve the miscibility with other liquid crystal components, trans-1, 4-cyclohexylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene is preferable. To increase T ni Unsubstituted 1, 4-phenylene, unsubstituted 1, 4-cyclohexylene, 1, 4-cyclohexenyl or unsubstituted naphthalene-2, 6-diyl are preferred. In order to exhibit a large negative Δε, it is preferably 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene or 2, 3-difluoro-1, 4-phenylene. For the purpose ofA is a liquid crystal material which exhibits a large negative Δε and exhibits miscibility with other liquid crystal components i1 The total number of fluorine atoms present in the catalyst is preferably 1 to 4, particularly preferably 1 to 3.
In order to make gamma 1 Lowering Z i1 Preferably a single bond, -CH 2 CH 2 -、-CH 2 O-or-OCH 2 -, more preferably a single bond or-CH 2 CH 2 -. To increase T ni Preferably a single bond, -COO-, -OCO-, -CH=CH-, or-C.ident.C-, more preferably a single bond, -CH=CH-, or-C.ident.C-. In order to improve the miscibility with other liquid crystal components, it is preferably a single bond, -CH 2 CH 2 -、-CH 2 O-or-OCH 2 -. In order to improve the long-term reliability when forming a liquid crystal display element, a single bond is preferable.
n i1 When 2 is represented, a plurality of Z's are preferably present i1 Any one or more of (2) represents a single bond. In paying attention to gamma 1 When n is i1 Preferably 1. Attach importance to T ni In this case, 2 is preferable.
W i1 Preferably of the general formula (W i1 -1) or (W) i1 -3)。
W i2 Preferably a single bond.
L i3 Preferably represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms, in order to cause γ 1 The reduction is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. In addition, a linear shape is preferable.
Preferably L i1 、L i2 And L i3 At least one of (C) is a hydrogen atom, preferably L i1 Or L i3 Is a hydrogen atom. Preferably L i1 Is C1-8 alkyl or C1-8 alkoxy, L i2 Is a hydrogen atom, L i3 Is an alkyl group having 1 to 8 carbon atoms, preferably L i1 Is a hydrogen atom, L i2 Is C1-8 alkyl or C1-8 alkoxy, L i3 Is an alkyl group having 1 to 8 carbon atoms.
Preferably L i4 And L i5 Each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and preferably represents a hydrogen atom.
Preferably L i6 And L i7 Each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms, and is preferably a hydrogen atom.
Preferably L i8 Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms, and is preferably a hydrogen atom.
Preferably L i9 And L i10 Represents a hydrogen atom.
In the compound represented by the general formula (i), the hetero atoms are not directly bonded to each other.
Among the compounds represented by the general formula (i), the compounds represented by the following general formulae (i-1) to (i-48) are preferable. Among them, particularly preferred compounds are compounds represented by the general formulae (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), (i-7), (i-8), (i-9), (i-10), (i-11) and (i-12), compounds represented by the general formulae (i-1), (i-2), (i-3) and (i-4), compounds represented by the general formulae (i-1) and (i-3), and compounds represented by the general formula (i-1).
[ chemical 7]
(wherein R is i1 And R is i2 R in the general formula (i) i1 The same meaning)
[ chemical 8]
(wherein R is i1 And R is i2 R in the general formula (i) i1 The same meaning)
[ chemical 9]
(wherein R is i1 And R is i2 R in the general formula (i) i1 The same meaning)
[ chemical 10]
(wherein R is i1 And R is i2 R in the general formula (i) i1 The same meaning)
The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group of compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05), in addition to the compound represented by the general formula (i). These compounds correspond to compounds having an anisotropy that is negative in dielectric properties. The sign of these compounds Δε is negative and its absolute value shows a value greater than 2. Further, Δε of the compound was the following value: extrapolated values from measured values of dielectric anisotropy of compositions in which the compound was added to compositions having a dielectric property of approximately neutral at 25 ℃.
[ chemical 11]
Wherein R is 21 And R is 22 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, 1 or not adjacent to each other of the groups being-CH 2 Can be independently and individually substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-or-OCO-substitution, Z is Z 1 Respectively and independently represent a single bond, -CH 2 CH 2 -、-OCH 2 -、-CH 2 O-、-COO-、-OCO-、-OCF 2 -、-CF 2 O-, -ch=ch-, -cf=cf-or-c≡c-,m each independently represents 1 or 2.
R 21 The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Wherein Z is 1 When other than a single bond, R 21 Alkyl groups having 1 to 3 carbon atoms are preferable.
R 22 The alkyl group having 1 to 8 carbon atoms or the alkoxy group having 1 to 8 carbon atoms is preferable, the alkyl group having 1 to 5 carbon atoms or the alkoxy group having 1 to 4 carbon atoms is more preferable, and the alkoxy group having 1 to 4 carbon atoms is still more preferable.
R 21 And R is 22 Can be alkenyl, preferably is a group represented by any one selected from the formulae (R1) to (R5) (wherein the black point in the formulae represents a carbon atom in the ring structure), preferably is a group represented by the formula (R1) or (R2), R 21 And R is 22 The content of the alkenyl group-containing compound is preferably as small as possible, and it is preferable that the alkenyl group-containing compound is not contained in a large amount.
[ chemical 12]
Z 1 Respectively and independently represent a single bond, -CH 2 CH 2 -、-OCH 2 -、-CH 2 O-、-COO-、-OCO-、-OCF 2 -、-CF 2 O-, -CH=CH-, -CF=CF-, or-C≡C-, preferably a single bond, -CH 2 CH 2 -、-OCH 2 -、-CH 2 O-, more preferably a single bond or-CH 2 O-。
When m is 1, Z is preferable 1 Is a single bond.
When m is 2, Z is preferable 1 is-CH 2 CH 2 -、-CH 2 O-。
The fluorine atom of the compound represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted with a chlorine atom which is a halogen group. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and it is preferably not contained.
The hydrogen atom present on the ring of the compound represented by the general formula (N-01), (N-02), (N-03), (N-04) and (N-05) may be further substituted with a fluorine atom or a chlorine atom. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not.
The compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably those having a negative Δε and an absolute value of Δε of 3 or more. Specifically, R 22 Preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.
The compound represented by the general formula (N-01) preferably contains one or more compounds selected from the group consisting of the compounds represented by the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3) and the general formula (N-01-4).
[ chemical 13]
(wherein R is 21 Meaning the same as above, R 23 Each independently represents an alkoxy group having 1 to 4 carbon atoms).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1) and a compound represented by the general formula (N-01-4).
When high VHR is necessary, that is, when high reliability is necessary, it is preferable that the compound represented by the general formula (N-01-3) is not contained in order to give a liquid crystal display element which is free from display failure.
The compound represented by the general formula (N-02) preferably contains one or more compounds selected from the group consisting of the compounds represented by the general formula (N-02-1), the general formula (N-02-2) and the general formula (N-02-3).
[ chemical 14]
(wherein R is 21 Meaning the same as above, R 23 Each independently represents an alkoxy group having 1 to 4 carbon atoms).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i) and a compound represented by the general formula (N-02-1).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i) and a compound represented by the general formula (N-02-3).
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1) at the same time.
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-3) at the same time.
As the compound represented by the general formula (N-03), it is preferable to contain one or more compounds represented by the general formula (N-03-1).
[ 15]
(wherein R is 21 Meaning the same as above, R 23 An alkoxy group having 1 to 4 carbon atoms).
The liquid crystal composition of the present invention preferably combines a compound represented by the general formula (i) with a compound represented by the general formula (N-03-1).
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-03-1) at the same time.
As the compound represented by the general formula (N-04), it is preferable to contain one or more compounds represented by the general formula (N-04-1).
[ 16]
/>
(wherein R is 21 Meaning the same as above, R 23 An alkoxy group having 1 to 4 carbon atoms).
The liquid crystal composition of the present invention particularly preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-04-1) at the same time.
The compound represented by the general formula (N-05) is preferably a compound selected from the group of compounds represented by the formulas (N-05-1) to (N-05-3).
[ chemical 17]
The lower limit value of the preferable content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit value of the preferable content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit value of the preferable content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit value of the preferable content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% with respect to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.
The lower limit value of the preferable content of the compound represented by the formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17% and 20% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%.
The liquid crystal composition of the present invention particularly preferably contains 0.1% to 15% of the compound represented by the general formula (i), 1% to 20% of the compound represented by the general formula (N-01-1), 1% to 30% of the compound represented by the general formula (N-01-4), and 1% to 20% of the compound represented by the general formula (N-04-1).
The liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06).
[ chemical 18]
(wherein R is 21 And R is 22 Meaning the same as before
When it is desired to adjust various physical properties, the compound represented by the general formula (N-06) is effective in obtaining a large refractive index anisotropy (. DELTA.n) and a high T ni As the large Δε, a compound represented by the general formula (N-06) can be used.
The lower limit value of the preferable content of the compound represented by the formula (N-06) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17% and 20% relative to the total amount of the liquid crystal composition of the present invention. The upper limit of the preferable content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 5%.
The liquid crystal composition of the present invention contains one or more compounds selected from the group of compounds represented by the general formulae (NU-01) to (NU-06).
[ chemical 19]
(wherein R is NU11 、R NU12 、R NU21 、R NU22 、R NU31 、R NU32 、R NU41 、R NU42 、R NU51 、R NU52 、R NU61 、R NU62 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, 1 or not adjacent to 2 or more-CH groups in the groups 2 Each independently can be substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-substitution. )
In further detail, R NU11 、R NU12 、R NU21 、R NU22 、R NU31 、R NU32 、R NU41 、R NU42 、R NU51 、R NU52 、R NU61 、R NU62 Preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. In the case where the response speed is important, at least 1R is preferable NU11 、R NU21 、R NU31 、R NU41 、R NU51 And R is NU61 Alkenyl groups having 2 to 3 carbon atoms. The compound having such an alkenyl group is preferably 10% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, relative to the total amount of the liquid crystal composition of the present invention. In the case of high VHR importanceThe compound having an alkenyl group is preferably 40% or less, more preferably 35% or less, and still more preferably 30% or less.
In order to achieve both high speed and high reliability, it is preferable to use only the general formula (NU-01) as the compound having an alkenyl group, and R is particularly preferable in this case NU11 Is alkyl of 2 to 4 carbon atoms, R NU12 Alkenyl groups having 2 to 3 carbon atoms.
In order to achieve both high speed and high reliability, it is preferable to use the general formulae (NU-01) and (NU-05) as the compound having an alkenyl group, and in this case, R is particularly preferable NU11 Is alkyl of 2 to 4 carbon atoms, R NU12 Alkenyl having 2 to 3 carbon atoms, preferably R NU51 Alkenyl of 2 to 3 carbon atoms, R NU52 Is an alkyl group having 2 to 3 carbon atoms.
In order to achieve both high speed and high reliability, it is preferable to use the general formula (NU-01) and the general formulae (NU-05) and (NU-04) as the compound having an alkenyl group, and in this case, R is particularly preferable NU11 Is alkyl of 2 to 4 carbon atoms, R NU12 Alkenyl having 2 to 3 carbon atoms, preferably R NU51 R is R NU41 Alkenyl of 2 to 3 carbon atoms, R NU52 R is R NU42 Is an alkyl group having 2 to 3 carbon atoms.
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-02).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-03).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-04) and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-05) and a compound represented by the general formula (NU-06).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-05).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-06).
The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01), the general formula (NU-05) and the general formula (NU-06).
The content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 25 to 45% by mass.
The content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass.
The content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably 0 to 10% by mass.
The content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.
The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.
The liquid crystal composition of the present invention may contain one or two or more kinds of polymerizable compounds.
The liquid crystal composition of the present invention may contain one or two or more polymerizable compounds represented by the general formula (RM) as polymerizable compounds.
[ chemical 20]
(wherein R is 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 And R is 108 Respectively and independently represent P 13 -S 13 -, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, P 11 、P 12 And P 13 Each independently represents the formula (Re-1) to (Re-1)A polymerizable group represented by the formula (Re-9),
[ chemical 21]
(wherein R is 11 、R 12 、R 13 、R 14 And R is 15 Each independently represents any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m r5 、m r7 、n r5 And n r7 Each independently represents 0, 1, or 2, m r5 、m r7 、n r5 And/or n r7 When 0 is represented, a single bond is represented),
S 11 、S 12 and S is 13 Each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, 1-CH in the alkylene group 2 -or not more than 2-CH 2 -can be substituted by-O-, -OCO-or-COO-, there are a plurality of P 13 And S is 13 Each of which may be the same or different).
The liquid crystal composition containing the polymerizable compound represented by the general formula (RM) is suitable for producing a PSA-type or PSVA-type liquid crystal display element. It is also suitable for manufacturing NPS type liquid crystal display elements. In addition, it is also preferable to manufacture a PI-less type liquid crystal display element characterized by having no alignment film.
The liquid crystal composition comprising the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (RM) has a suitably high polymerization rate, and thus can impart a pretilt angle to a target in a short ultraviolet irradiation time. Further, the residual amount of the polymerizable compound after polymerization can be reduced. This can improve the production efficiency of the PSA-type or PSVA-type liquid crystal display device. In addition, display failure (e.g., a failure such as burn-in) due to a change in the pretilt angle is not generated or such an effect that display failure is rarely generated can be achieved. In the present specification, the term "display failure" means a display failure caused by a change in the pretilt angle with time, a display failure caused by a residual amount of an unreacted polymerizable compound, and a display failure caused by a decrease in the voltage holding ratio.
In the above formula (RM), R 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 And R is 108 Respectively and independently represent P 13 -S 13 Any one of an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom is preferably 1 to 16 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms when the alkyl group and the alkoxy group are used. The alkyl group and the alkoxy group may be linear or branched, and particularly linear is preferred.
In the above formula (RM), R 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 And R is 108 Preferably represents P 13 -S 13 -, an alkoxy group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, and further preferably represents P 13 -S 13 -any one of an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom. The alkoxy group preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
In addition, P 11 、P 12 And P 13 The polymerizable groups (formula (Re-1) to (Re-9)) may be the same or different.
In the above formula (RM), P 11 、P 12 And P 13 Each independently is preferably formula (Re-1), formula (Re-2), formula (Re-3), formula (Re-4), formula (Re-5) or formula (Re-7), more preferably formula (Re-1), formula (Re-2), formula (Re-3) or formula (Re-4), still more preferably formula (Re-1), and still more preferably an acrylic group or a methacrylic group.
P 11 And P 12 At least one of them is preferably of the formula (Re-1), more preferably an acrylic group or a methacrylic group, still more preferably a methacrylic group, particularly preferably P 11 And P 12 Is methyl groupAn acrylic group.
In the above general formula (RM), S 11 、S 12 And S is 13 Each independently is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. S is S 11 、S 12 And S is 13 When the compound is a single bond, the amount of the polymerizable compound remaining after ultraviolet irradiation is sufficiently small, and display failure due to a change in pretilt angle is less likely to occur, and display failure of a PSA-type or PSVA-type liquid crystal display element is not likely to occur, or is less likely to occur. At S 11 、S 12 And S is 13 In the case of 1 to 3 carbon atoms, the liquid crystal display element is suitable for NPS type liquid crystal display elements.
The lower limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 0.01 mass%, preferably 0.02 mass%, preferably 0.03 mass%, preferably 0.04 mass%, preferably 0.05 mass%, preferably 0.06 mass%, preferably 0.07 mass%, preferably 0.08 mass%, preferably 0.09 mass%, preferably 0.1 mass%, preferably 0.12 mass%, preferably 0.15 mass%, preferably 0.17 mass%, preferably 0.2 mass%, preferably 0.22 mass%, preferably 0.25 mass%, preferably 0.27 mass%, preferably 0.3 mass%, preferably 0.32 mass%, preferably 0.35 mass%, preferably 0.37 mass%, preferably 0.4 mass%, preferably 0.42 mass%, preferably 0.45 mass%, preferably 0.5 mass%, preferably 0.55 mass%. The upper limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 5 mass%, preferably 4.5 mass%, preferably 4 mass%, preferably 3.5 mass%, preferably 3 mass%, preferably 2.5 mass%, preferably 2 mass%, preferably 1.5 mass%, preferably 1 mass%, preferably 0.95 mass%, preferably 0.9 mass%, preferably 0.85 mass%, preferably 0.8 mass%, preferably 0.75 mass%, preferably 0.7 mass%, preferably 0.65 mass%, preferably 0.6 mass%, preferably 0.55 mass%, preferably 0.5 mass%, preferably 0.45 mass%, preferably 0.4 mass%.
More specifically, in order to obtain a sufficient pretilt angle or a small residual amount of the polymerizable compound or a high Voltage Holding Ratio (VHR), the content thereof is preferably 0.2 to 0.6 mass%, and when suppression of precipitation at low temperature is important, the content thereof is preferably 0.01 to 0.4 mass%. In particular, when a rapid response speed is obtained, the content thereof is preferably increased to 2 mass%.
In the case where a plurality of polymerizable compounds represented by the general formula (RM) are contained, the content of each is preferably 0.01 to 0.4 mass%. Accordingly, in order to solve all these technical problems, it is particularly preferable to adjust the polymerizable compound represented by the general formula (RM) to a range of 0.1 to 0.6 mass%.
The polymerizable compound represented by the general formula (RM) according to the present invention, specifically, the compounds represented by the general formulae (RM-1) to (RM-10) are preferable, and PSA-type liquid crystal display elements using these compounds are used, and the polymerizable compound has a small residual amount, a sufficient pretilt angle, and no or little occurrence of defects such as alignment defects and display defects due to a change in pretilt angle or the like.
[ chemical 22]
[ chemical 23]
Wherein R is M1 And R is M2 Each independently represents any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and more preferably represents an alkyl group having 1 carbon atom or a hydrogen atom.
The liquid crystal composition of the present invention may contain one or two or more compounds having a terphenyl structure or a tetrabenzene structure and having a dielectric anisotropy Δεof greater than +2, that is, compounds having positive dielectric anisotropy. The Δεof the compound is a value obtained by extrapolating a measured value of dielectric anisotropy of a composition obtained by adding the compound to a composition having a substantially neutral dielectric property at 25 ℃. The compound is used in combination with desired properties such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, and the like, and in particular, the reactivity of the polymerizable compound in the liquid crystal composition containing the polymerizable compound can be accelerated.
The lower limit of the preferable content of the compound having a terphenyl structure or a tetrabiphenyl structure and having a dielectric constant anisotropy Δεof more than +2 relative to the total amount of the liquid crystal composition of the present invention is 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 10%. The upper limit of the preferable content is, for example, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3% with respect to the total amount of the liquid crystal composition of the present invention in one embodiment of the present invention.
The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a usual nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a light stabilizer, an infrared absorber, or the like.
Examples of the antioxidant include hindered phenols (hindered phenol) represented by the general formulae (H-1) to (H-4).
[ chemical 24]
In the general formulae (H-1) to (H-3), R H1 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms, 1-CH present in the groups 2 -or not more than 2-CH 2 Each independently of the others can be substituted by-O-or-S-and, in addition, 1 or more than 2 hydrogen atoms present in the radical can each independently be substituted by fluorine or chlorine atoms. More specifically, it is preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms, and it is more preferably an alkyl group having 3 to 7 carbon atoms or a carbon atomAlkenyl groups having 2 to 7 atoms.
In the general formula (H-4), M H4 Represents an alkylene group having 1 to 15 carbon atoms (1 or 2 or more of the alkylene groups-CH 2 -may be substituted by-O-, -CO-, -COO-, -OCO-in such a way that the oxygen atoms are not directly adjacent. ) -OCH 2 -、-CH 2 O-、-COO-、-OCO-、-CF 2 O-、-OCF 2 -、-CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -C.ident.C-, a single bond 1, 4-phenylene (any hydrogen atom in the 1, 4-phenylene group may be substituted with a fluorine atom) or trans-1, 4-cyclohexylene, an alkylene group having 1 to 14 carbon atoms is preferable, and if volatility is taken into consideration, the number of carbon atoms is preferably a large number, and in view of the viscosity, the number of carbon atoms is preferably not excessively large, and therefore, is more preferably 2 to 12 carbon atoms, still more preferably 3 to 10 carbon atoms, still more preferably 4 to 10 carbon atoms, still more preferably 5 to 10 carbon atoms, and still more preferably 6 to 10 carbon atoms.
In the general formulae (H-1) to (H-4), 1 or not adjacent or more than 2-ch=groups in the 1, 4-phenylene groups may be substituted with-n=groups. In addition, the hydrogen atoms in the 1, 4-phenylene group may each independently be substituted with a fluorine atom or a chlorine atom.
1 or not adjacent ones of 1, 4-cyclohexylene groups of the general formula (H-2) and the general formula (H-4) -CH of more than 2 2 -may be substituted by-O-or-S-. In addition, the hydrogen atoms in the 1, 4-cyclohexylene group may each independently be substituted with a fluorine atom or a chlorine atom.
More specifically, the following formulas (H-11) to (H-15) are exemplified.
[ chemical 25]
When the liquid crystal composition of the present invention contains an antioxidant, it is preferably 10 mass ppm or more, more preferably 20 mass ppm or more, and still more preferably 50 mass ppm or more. The upper limit of the content of the antioxidant is 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, and more preferably 100 mass ppm.
Nematic phase-isotropic liquid phase transition temperature (T) of the liquid crystal composition of the present invention Ni ) From 60℃to 120℃and more preferably from 70℃to 100℃and particularly preferably from 70℃to 85 ℃. In the present invention, T is expressed as 60℃or higher Ni High.
In the case of liquid crystal television applications, T Ni Preferably 70 to 80 ℃, T in the case of mobile applications Ni Preferably from 80 to 90 ℃, T in the case of outdoor display applications such as PID (public information display ) Ni Preferably from 90 to 110 ℃.
The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) at 20 ℃ of 0.08 to 0.14, more preferably 0.09 to 0.13, particularly preferably 0.09 to 0.12. In further detail, it is preferably 0.10 to 0.13 when corresponding to a thin cell gap, and preferably 0.08 to 0.10 when corresponding to a thick cell gap. In the present invention, Δn is greater than 0.09.
The liquid crystal composition of the present invention has a rotational viscosity (. Gamma.) at 20 ℃ 1 ) 50 to 160 mPas, preferably 55 to 160 mPas, preferably 60 to 160 mPas, preferably 80 to 150 mPas, preferably 90 to 140 mPas, preferably 90 to 130 mPas, preferably 100 to 130 mPas.
The liquid crystal composition of the present invention has a dielectric anisotropy (. DELTA.. Di-elect cons.) of from-2.0 to-8.0, preferably from-2.0 to-6.0, more preferably from-2.0 to-5.0, still more preferably from-2.5 to-4.0, particularly preferably from-2.5 to-3.5, at 20 ℃.
The upper limit value of the total content of the compounds having alkenyl groups in the compounds constituting the liquid crystal composition of the present invention is preferably 10%, preferably 8%, preferably 6%, preferably 5%, preferably 4%, preferably 3%, preferably 2%, preferably 1%, preferably 0%, and the total content of the compounds having alkenyl groups is preferably in the range of 0 to 10%, preferably 0 to 8%, preferably 0 to 5%, preferably 0 to 4%, preferably 0 to 3%, preferably 0 to 2%. Except that the compound represented by the general formula (NU-01) was not contained.
The liquid crystal composition of the present invention preferably contains, as an essential component, one or more compounds selected from the group consisting of the compounds represented by the general formula (N-01), the general formula (N-02), the general formula (N-03), the general formula (N-04), the general formula (N-05) and the general formula (N-06), and one or more compounds selected from the group consisting of the compounds represented by the general formulae (NU-01) to (NU-06), and the upper limit value of the total of these contents is preferably 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, and the lower limit value of the total of these contents is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 96 mass%, 95 mass%, 96 mass%, 98 mass%, 99% and 99 mass%.
The liquid crystal display element using the liquid crystal composition of the present invention is useful particularly for an active matrix driving liquid crystal display element, and can be suitably used for a liquid crystal display element such as VA, FFS, IPS, PSA, PSVA, PS-IPS or PS-FFS, NPS, PI-less.
The liquid crystal display device according to the present invention preferably includes a first substrate and a second substrate disposed to face each other, a common electrode provided on the first substrate or the second substrate, a pixel electrode provided on the first substrate or the second substrate and having a thin film transistor, and a liquid crystal layer provided between the first substrate and the second substrate and containing a liquid crystal composition. If necessary, an alignment film for controlling the alignment direction of the liquid crystal molecules may be provided on the opposite surface side of at least one of the first substrate and the second substrate so as to be in contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected in accordance with the driving mode of the liquid crystal display element, and a known alignment film such as a rubbing alignment film (for example, polyimide) or a photo-alignment film (for example, decomposed polyimide) can be used. Further, a color filter may be provided on the first substrate or the second substrate as appropriate, and a color filter may be provided on the pixel electrode or the common electrode.
The two substrates of the liquid crystal cell used in the liquid crystal display element according to the present invention may be made of glass, a transparent material having flexibility such as plastic, or an opaque material such as silicon. The transparent substrate having the transparent electrode layer can be obtained by, for example, sputtering Indium Tin Oxide (ITO) on a transparent substrate such as a glass plate.
The color filter may be manufactured by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method, etc. A method of manufacturing a color filter by a pigment dispersion method will be described as an example: the curable coloring composition for color filters is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. This step is performed for each of red, green, and blue 3 colors, whereby a pixel portion for a color filter can be formed. In addition, a pixel electrode including an active element such as a TFT, a thin film diode, or a metal-insulator-metal (soi) resistivity element may be provided on the substrate.
The first substrate and the second substrate are preferably opposed to each other such that the common electrode and the pixel electrode layer are positioned inward.
The interval between the first substrate and the second substrate can be adjusted via the spacer. In this case, the thickness of the light control layer to be obtained is preferably adjusted to be 1 to 100. Mu.m. Further preferably 1.5 to 10 μm, and when a polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is preferably adjusted so that the contrast ratio becomes maximum. In addition, when two polarizing plates are present, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast become good. Further, a retardation film for enlarging the viewing angle may be used. Examples of the spacers include glass particles, plastic particles, alumina particles, and photoresist materials. Then, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates in a form provided with a liquid crystal injection port, the substrates are bonded to each other, and the sealant is heated and thermally cured.
As a method for sandwiching the liquid crystal composition between two substrates, a general vacuum injection method, an ODF method, or the like can be used.
In order to form the alignment state of the liquid crystal display element of the present invention, the liquid crystal display element can be produced by using a liquid crystal composition containing a polymerizable compound in a liquid crystal composition and polymerizing the polymerizable compound in the liquid crystal composition.
As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, polymerization at an appropriate polymerization rate is desired in order to obtain good alignment performance of the liquid crystal, and a method of polymerizing by irradiation of active energy rays such as ultraviolet rays or electron rays alone or in combination or sequentially is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. In addition, when polymerization is performed in a state in which the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency with respect to active energy rays. In addition, the following means may be used: when irradiation is performed with light, only a specific portion is polymerized using a mask, and then conditions such as an electric field, a magnetic field, or a temperature are changed to change the orientation state of the unpolymerized portion, and further irradiation with active energy rays is performed to polymerize the unpolymerized portion. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the liquid crystal composition. The applied alternating electric field is preferably alternating current with a frequency of 10Hz to 10kHz, more preferably with a frequency of 60Hz to 10kHz, the voltage being selected in dependence on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the liquid crystal display element of the PSVA type, the pretilt angle is preferably controlled to 80 degrees to 89.9 degrees from the viewpoints of alignment stability and contrast.
The temperature at which the active energy rays such as ultraviolet rays and electron rays are irradiated for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate with an alignment film, the liquid crystal composition is preferably in a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. It is preferable to polymerize it at a temperature close to room temperature, i.e., typically, at 15 to 35 ℃.
On the other hand, for example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate without an alignment film, the liquid crystal composition may have a temperature range wider than the temperature range at the time of irradiation applied to the liquid crystal display element having a substrate with an alignment film.
As the lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used. The wavelength of the irradiated ultraviolet light is preferably ultraviolet light whose irradiation wavelength region is not in the absorption wavelength region of the liquid crystal composition, and if necessary, ultraviolet light is preferably filtered out and used. The intensity of the irradiated ultraviolet rays is preferably 0.1mW/cm 2 ～100W/cm 2 Further preferably 2mW/cm 2 ～50W/cm 2 . The energy of the irradiated ultraviolet rays can be suitably adjusted, and is preferably 10mJ/cm 2 To 500J/cm 2 Further preferably 100mJ/cm 2 To 200J/cm 2 . When irradiated with ultraviolet rays, the intensity may be changed. The time for irradiating ultraviolet rays may be appropriately selected depending on the intensity of the irradiated ultraviolet rays, and is preferably 10 seconds to 3600 seconds, and more preferably 10 seconds to 600 seconds.
Examples
The present invention will be further described in detail with reference to the following examples, but the present invention is not limited to these examples. In the compositions of the following examples and comparative examples, "%" means "% by mass". The following abbreviations are used for the description of the compounds in the examples.
Unless otherwise specified, the physical property values are measured based on methods described in the electronic information technology industry association standard JEITA ED-2521B, modified 3 months in 2009, and released by the corporate society of electronic information technology industry.
(side chain)
-n -C n H 2n+1 Straight-chain alkyl of carbon number n
n- C n H 2n+1 Linear alkyl of carbon number n
-On -OC n H 2n+1 Straight-chain alkoxy of carbon number n
nO- C n H 2n+1 Linear alkoxy of O-carbon number n
-V -CH＝CH 2
V- CH 2 ＝CH-
-V1 -CH＝CH-CH 3
1V- CH 3 -CH＝CH-
-F -F
-OCF3 -OCF 3
(linker)
-CF2O- -CF 2 -O-
-OCF2- -O-CF 2 -
-1O- -CH 2 -O-
-O1- -O-CH 2 -
-2- -CH 2 -CH 2 -
-COO- -COO-
-OCO- -OCO-
-single bond
(Ring structure)
[ chemical 26]
The characteristics measured in the examples are as follows.
T Ni : nematic phase-isotropic liquid phase transition temperature (. Degree. C.)
T →N : solid-nematic phase transition temperature (. Degree. C.)
An: refractive index anisotropy at 20 DEG C
Δε: dielectric constant anisotropy at 20 DEG C
γ 1 : rotational viscosity at 20 ℃ (mPa. S)
K 11 : elastic constant K at 20 DEG C 11 (pN)
K 33 : elastic constant K at 20 DEG C 33 (pN)
VHR: voltage holding ratio at 1V, 60Hz, 60 ℃ (%)
(results of preparation and evaluation of liquid Crystal composition)
The liquid crystal compositions of example 1 and comparative example 1 were prepared, and physical properties were measured. In addition, T is taken as the physical property value Ni The composition ratios are designed in such a way that Δn and Δε become the same. The composition ratios and physical property values of these liquid crystal compositions are shown in table 1.
TABLE 1
| Example 1 | Comparative example 1 | |
| T Ni | 83.9 | 84.6 |
| T →N | G-22 | G-27 |
| Δn | 0.1033 | 0.1018 |
| Δε | -2.97 | -2.95 |
| γ1 | 99 | 102 |
| 3-Cy-Cy-2 | 22 | 19 |
| 3-Cy-Cy-4 | 6 | 7 |
| 3-Cy-Ph-O1 | 13 | 11 |
| 3-Cy-Ph-Ph-2 | 7 | 6 |
| 3-Cy-Ph-Ph5-O2 | 8 | 9 |
| 3-Cy-Ph-Ph5-O3 | 8 | 9 |
| 3-Cy-Ph-Ph5-O4 | 8 | 9 |
| 3-Cy-Ph5-O2 | 9 | 15 |
| 3-Cy-Cy-Ph5-O2 | 15 | 15 |
| 2O-Bd-3 | 4 |
The effects of the present application were confirmed by the same preparation as in examples 2 to 4 and comparative examples 2 to 4.
TABLE 2
| Example 2 | Comparative example 2 | |
| T NI | 82.9 | 83.6 |
| T →N | G-22 | G-25 |
| Δn | 0.1022 | 0.1002 |
| Δε | -3.04 | -3.06 |
| γ1 | 99 | 105 |
| 3-Cy-Cy-2 | 22 | 19 |
| 3-Cy-Cy-4 | 8 | 7 |
| 3-Cy-Ph-O1 | 14 | 15 |
| 3-Cy-1O-Ph5-O1 | 6 | 7 |
| 3-Cy-1O-Ph5-O2 | 3 | |
| 3-Cy-Ph-Ph-2 | 9 | 9 |
| 3-Cy-Ph-Ph5-O2 | 8 | 8 |
| 3-Cy-Ph-Ph5-O3 | 8 | 8 |
| 3-Cy-Ph-Ph5-O4 | 8 | 8 |
| 3-Cy-Cy-1O-Ph5-O2 | 13 | 16 |
| 2O-Bd-3 | 4 |
TABLE 3
| Example 3 | Comparative example 3 | |
| T NI | 85.1 | 84.0 |
| T →N | G-43 | G-56 |
| Δn | 0.1059 | 0.1051 |
| Δε | -3.21 | -3.01 |
| γ1 | 94 | 96 |
| 3-Cy-Cy-V | 38 | 31 |
| V-Cy-Ph-Ph-3 | 6 | 6 |
| 3-Cy-Ph-Ph-2 | 5 | 6 |
| 3-Cy-Ph-Ph-5 | 4 | 6 |
| 2-Cy-Cy-1O-Ph5-O2 | 12 | 12 |
| 3-Cy-Cy-1O-Ph5-O2 | 12 | 12 |
| 2-Ph-2-Ph-Ph5-O2 | 6 | 6 |
| 3-Ph-2-Ph-Ph5-O2 | 6 | 6 |
| 3-Cy-Ph5-O2 | 6 | 15 |
| 2O-Bd-3 | 5 |
TABLE 4
| Example 4 | Comparative example 4 | |
| T NI | 87.5 | 86.9 |
| T →N | G-18 | G-23 |
| Δn | 0.1044 | 0.1046 |
| Δε | -3.12 | -3.13 |
| γ1 | 107 | 116 |
| 3-Cy-Cy-2 | 20 | 16 |
| 3-Cy-Cy-4 | 8 | 5 |
| 3-Cy-Cy-V1 | 9 | 10 |
| V-Cy-Ph-Ph-3 | 5 | 5 |
| 3-Cy-Ph-Ph-2 | 6 | 6 |
| 3-Cy-Ph-Ph-5 | 6 | 6 |
| 2-Cy-Cy-1O-Ph5-O2 | 11 | 12 |
| 3-Cy-Cy-1O-Ph5-O2 | 11 | 12 |
| 2-Ph-2-Ph-Ph5-O2 | 6 | 6 |
| 3-Ph-2-Ph-Ph5-O2 | 5 | 7 |
| 3-Cy-Ph5-O2 | 8 | 15 |
| 2O-Bd-3 | 5 |
[ chemical 27]
As described above, the liquid crystal composition of the present application has negative dielectric anisotropy (. DELTA.. Epsilon.) and T Ni High, delta n is large, gamma 1 Small, K 33 Large, gamma 1 /K 33 Is small.
It can be seen that: the values of Δn and Δε are almost the same as those of examples 1 and 2, but the liquid crystal compositions of comparative examples 1 and 2 containing no compound represented by the general formula (i) were deteriorated by large γ1. Thus, it was confirmed that: if the compositions of examples 1 and 2 are used to manufacture VA-type and FFS-type liquid crystal display devices, the response time is short and VHR is high. At this time, it was also confirmed that no display failure was observed. In contrast, the compositions of the comparative examples were also prepared as VA-type and FFS-type liquid crystal display devices, and the response time was measured, but the response time was deteriorated as compared with the compositions of the examples.
Further, from T Ni The results for the compositions of examples 3 and 4, which are high and have an increased Δε, are also known: not only improve T Ni And Δε, also inhibit γ1 from rising.
In example 3, the value of Δε in comparative example 3 was reduced, and the low-voltage driving was not suitable. In addition, in comparison of example 4 and comparative example 4, it is found that: in the liquid crystal composition of the present application, γ1 is improved by about 8%.
A polymerizable compound represented by the formula (RM-2) (wherein R is represented by the formula) was added in an amount of 0.5% by mass based on 99.5% by mass of the liquid crystal composition of example 1 M1 And R is M2 Methyl) and a polymerizable compound, and a PSA-type liquid crystal display element is produced.
[ chemical 28]
In addition, in the production of PSA-type liquid crystal display elements, ultraviolet rays having peaks at 313nm and 365nm were irradiated. Measurement conditions of response speed: von was 5. 5V, voff V and the measurement temperature was 20 ℃, and the measurement machine used DMS703 from AUTRONIC-MELCHERS corporation.
And (3) confirming: t (T) Ni High, delta n is large, gamma 1 Small, K 33 Large, gamma 1 Small, and high-speed response.
As described above, the present application has excellent effects.
Claims (9)
1. A liquid crystal composition comprising 1 or more than 2 compounds represented by the general formula (i),
Wherein X is i1 And X i2 Each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group,
Y i1 represents-O-, -CO-, -CX i3 X i4 -，Y i2 represents-O-, -CO-, Y i1 And Y i2 Any one or more of them represents-O-, X i3 、X i4 Respectively and independently represent X i1 The meaning of the same is that,
L i1 、L i2 、L i3 、L i4 and L i5 Each independently represents a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or a general formula (L) i -1) a group represented by formula (i),
wherein R is i1 Represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms or an alkenyloxy group having 2 to 15 carbon atoms,
A i1 a group selected from the group consisting of:
(a) 1, 4-cyclohexylene, 1-CH present in this radical 2 -or not more than 2-CH 2 -may be substituted by-O-or-S-;
(b) 1, 4-phenylene, wherein 1-ch=or non-adjacent 2 or more-ch=groups present in the group may be substituted with-n=and 1 hydrogen atom present in the group may be substituted with a fluorine atom;
(c) 1, 4-cyclohexenyl, naphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, decahydronaphthalene-2, 6-diyl, the hydrogen atoms present in these groups may be substituted by fluorine atoms, in addition, 1-ch=or more than 2-ch=that are not adjacent in naphthalene-2, 6-diyl or 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl may be substituted by-n=,
Z i1 represents-CH 2 O-、-OCH 2 -、-CF 2 O-、-OCF 2 -、-COO-、-OCO-、-CH 2 CH 2 -、-CF 2 CF 2 -, -CH=CH-, -CF=CF-, C.ident.C-or a single bond,
n i1 represents 1 or 2, at n i1 Represents 2 and there are a plurality of A i1 And Z i1 When they are identical or different,
W i1 the general formula (W) i1 -1)、(W i1 -2) or (W) i1 -3) a group represented by formula (i),
wherein, represents and L i2 Or Y i2 Is a bond point of (C), a sum of (L) i5 Bonding points, L, of bonded carbon atoms adjacent to each other i6 、L i7 And L i8 Respectively and independently represent and L i1 The meaning of the same is that,
W i2 represents a single bond or-CL i9 L i10 -，
L i9 And L i10 Respectively and independently represent and L i1 The meaning of the same is that,
L i1 、L i2 、L i3 、L i4 、L i5 、L i6 、L i7 、L i8 、L i9 and L i10 1-CH present in (B) 2 -or not more than 2-CH 2 Can be replaced by-C.ident.C-, -O-, -COO-, -an OCO-or-CO-substitution, in addition, in the case of the optical fiber, the hydrogen atoms present in the alkyl or alkenyl groups may be substituted by fluorine atoms,
further comprising 1 or 2 or more compounds represented by the general formula (NU-05),
wherein R is NU51 And R is NU52 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms,
of which 1 or not adjacent 2 or more-CH' s 2 Each independently can be substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-substitution.
2. The liquid crystal composition according to claim 1, wherein the liquid crystal composition comprises 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formula (N-01), the general formula (N-02), the general formula (N-03), the general formula (N-04) and the general formula (N-05),
Wherein R is 21 And R is 22 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, 1 or not adjacent to each other of which is at least 2-CH 2 Each independently can be substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-or-OCO-substitution, Z is Z 1 Each independently represents a single bond, -CH 2 CH 2 -、-OCH 2 -、-CH 2 O-、-COO-、-OCO-、-OCF 2 -、-CF 2 O-, -ch=ch-, -cf=cf-, or-c≡c-, each m independently represents 1 or 2.
3. The liquid crystal composition according to claim 2, wherein the liquid crystal composition comprises 1 or 2 or more compounds selected from the group consisting of compounds represented by the general formula (NU-01), the general formula (NU-02), the general formula (NU-03), the general formula (NU-04) and the general formula (NU-06),
wherein R is NU11 、R NU12 、R NU21 、R NU22 、R NU31 、R NU32 、R NU41 、R NU42 、R NU61 、R NU62 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, 1 or not adjacent to each other of which is at least 2-CH 2 Each independently can be substituted by-CH=CH-, -C≡C-, -O-, -CO-, -COO-, or-OCO-substitution.
4. The liquid crystal composition according to claim 3, wherein the compound represented by the general formula (NU-01) has an alkenyl group in an amount of 0 to 50% by mass in total.
5. The liquid crystal composition according to claim 3, wherein the total content of the compound represented by the general formula (i), the compound selected from the group of compounds represented by the general formulae (N-01) to (N-05), and the compound selected from the group of compounds represented by the general formulae (NU-01) to (NU-06) is 95% by mass to 100% by mass.
6. The liquid crystal composition according to claim 1 or 2, wherein the liquid crystal composition comprises 1 or 2 or more polymerizable compounds represented by the general formula (RM),
wherein R is 101 、R 102 、R 103 、R 104 、R 105 、R 106 、R 107 And R is 108 Respectively and independently represent P 13 -S 13 -, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, P 11 、P 12 And P 13 Each independently represents a polymerizable group represented by the formula (Re-1) to the formula (Re-9),
wherein R is 11 、R 12 、R 13 、R 14 And R is 15 Each independently represents any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m r5 、m r7 、n r5 And n r7 Each independently represents 0, 1, or 2, at m r5 、m r7 、n r5 And/or n r7 In the case of 0, a single bond is represented,
S 11 、S 12 and S is 13 Independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, wherein1-CH of (2) 2 -or not more than 2-CH 2 -can be substituted by-O-, -OCO-or-COO-, there are a plurality of P 13 And S is 13 When they are different, they may be the same or different.
7. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 6.
8. A liquid crystal display element for active matrix driving, using the liquid crystal composition according to any one of claims 1 to 6.
9. A VA-type, IPS-type, FFS-type, PSA-type or PSVA-type liquid crystal display element using the liquid crystal composition of any one of claims 1 to 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-240599 | 2017-12-15 | ||
| JP2017240599 | 2017-12-15 | ||
| PCT/JP2018/043958 WO2019116904A1 (en) | 2017-12-15 | 2018-11-29 | Liquid-crystal composition and liquid-crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111373017A CN111373017A (en) | 2020-07-03 |
| CN111373017B true CN111373017B (en) | 2023-09-26 |
Family
ID=66819612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880075272.4A Active CN111373017B (en) | 2017-12-15 | 2018-11-29 | Liquid crystal composition and liquid crystal display element |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6575735B1 (en) |
| KR (1) | KR20200098501A (en) |
| CN (1) | CN111373017B (en) |
| TW (1) | TWI763954B (en) |
| WO (1) | WO2019116904A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527522B (en) * | 2018-05-25 | 2022-07-29 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound, liquid crystal composition and liquid crystal display device |
| JP7392434B2 (en) * | 2019-12-02 | 2023-12-06 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| CN115746871A (en) * | 2022-11-16 | 2023-03-07 | Tcl华星光电技术有限公司 | Liquid crystal composition and liquid crystal display panel |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097258A (en) * | 2003-08-01 | 2005-04-14 | Clariant Internatl Ltd | Fluorinated polycyclic compound and its use in liquid crystal mixture |
| CN1942461A (en) * | 2004-04-14 | 2007-04-04 | 默克专利股份有限公司 | Dibenzofuran-, dibenzothiophene- and fluorene derivatives |
| CN103459552A (en) * | 2011-04-06 | 2013-12-18 | Dic株式会社 | Nematic liquid crystal composition, liquid crystal display element using same |
| JP2015108127A (en) * | 2013-10-23 | 2015-06-11 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| CN105121598A (en) * | 2013-10-03 | 2015-12-02 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN110461852A (en) * | 2017-06-06 | 2019-11-15 | Dic株式会社 | Liquid-crystal compounds and combinations thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10115955B4 (en) * | 2001-03-30 | 2017-10-19 | Merck Patent Gmbh | Fluorinated fluorene derivatives |
| DE10336023B4 (en) * | 2003-08-01 | 2017-10-19 | Merck Patent Gmbh | Fluorinated heterocycles and their use in liquid crystal mixtures |
| US20060238696A1 (en) | 2005-04-20 | 2006-10-26 | Chien-Hui Wen | Method of aligning negative dielectric anisotropic liquid crystals |
| JP2014516366A (en) | 2011-03-29 | 2014-07-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal medium |
| DE102017002925A1 (en) * | 2016-04-21 | 2017-10-26 | Merck Patent Gmbh | Liquid crystalline medium |
-
2018
- 2018-11-29 TW TW107142653A patent/TWI763954B/en active
- 2018-11-29 KR KR1020207015047A patent/KR20200098501A/en unknown
- 2018-11-29 WO PCT/JP2018/043958 patent/WO2019116904A1/en active Application Filing
- 2018-11-29 JP JP2019531842A patent/JP6575735B1/en active Active
- 2018-11-29 CN CN201880075272.4A patent/CN111373017B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097258A (en) * | 2003-08-01 | 2005-04-14 | Clariant Internatl Ltd | Fluorinated polycyclic compound and its use in liquid crystal mixture |
| CN1942461A (en) * | 2004-04-14 | 2007-04-04 | 默克专利股份有限公司 | Dibenzofuran-, dibenzothiophene- and fluorene derivatives |
| CN103459552A (en) * | 2011-04-06 | 2013-12-18 | Dic株式会社 | Nematic liquid crystal composition, liquid crystal display element using same |
| CN105121598A (en) * | 2013-10-03 | 2015-12-02 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| JP2015108127A (en) * | 2013-10-23 | 2015-06-11 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| CN110461852A (en) * | 2017-06-06 | 2019-11-15 | Dic株式会社 | Liquid-crystal compounds and combinations thereof |
Non-Patent Citations (1)
| Title |
|---|
| 稠环衍生物类液晶的合成进展;高嫒嫒;安忠维;;液晶与显示(第02期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20200098501A (en) | 2020-08-20 |
| TW201930566A (en) | 2019-08-01 |
| JPWO2019116904A1 (en) | 2019-12-19 |
| TWI763954B (en) | 2022-05-11 |
| JP6575735B1 (en) | 2019-09-18 |
| CN111373017A (en) | 2020-07-03 |
| WO2019116904A1 (en) | 2019-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6245211B2 (en) | Nematic liquid crystal composition and liquid crystal display device using the same | |
| KR102117336B1 (en) | Nematic liquid-crystal composition and liquid-crystal display element obtained using same | |
| CN108779395B (en) | Nematic liquid crystal composition and liquid crystal display element using same | |
| JP6369663B1 (en) | Liquid crystal composition and liquid crystal display element | |
| JP7024254B2 (en) | Liquid crystal composition and liquid crystal display element | |
| WO2019021838A1 (en) | Liquid crystal composition and liquid crystal display device | |
| CN111373017B (en) | Liquid crystal composition and liquid crystal display element | |
| JP6452019B1 (en) | Liquid crystal composition and liquid crystal display element | |
| TWI786218B (en) | Liquid crystal composition and liquid crystal display element | |
| JP7243170B2 (en) | Liquid crystal composition and liquid crystal display element | |
| CN113265261A (en) | Liquid crystal composition and liquid crystal display | |
| CN112980465B (en) | Liquid crystal composition and liquid crystal display element | |
| JP2020097678A (en) | 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240523 Address after: 606 Huai'an East Road, Shijiazhuang City, Hebei Province Patentee after: Shijiazhuang Chengzhi Yonghua Display Materials Co.,Ltd. Country or region after: China Address before: Tokyo, Japan Patentee before: DIC Corp. Country or region before: Japan |