CN116622384A - Liquid crystal composition, liquid crystal element liquid crystal lens, and birefringent lens for stereoscopic image display - Google Patents
Liquid crystal composition, liquid crystal element liquid crystal lens, and birefringent lens for stereoscopic image display Download PDFInfo
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- CN116622384A CN116622384A CN202310053372.XA CN202310053372A CN116622384A CN 116622384 A CN116622384 A CN 116622384A CN 202310053372 A CN202310053372 A CN 202310053372A CN 116622384 A CN116622384 A CN 116622384A
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- 239000000203 mixture Substances 0.000 title claims abstract description 231
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 199
- 150000001875 compounds Chemical class 0.000 claims abstract description 237
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 76
- 239000001257 hydrogen Substances 0.000 claims abstract description 76
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 43
- -1 tetrahydropyran-2, 5-diyl Chemical group 0.000 claims description 42
- 229910052736 halogen Inorganic materials 0.000 claims description 39
- 150000002367 halogens Chemical class 0.000 claims description 39
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 9
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 7
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 6
- 239000002216 antistatic agent Substances 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 5
- 125000003275 alpha amino acid group Chemical group 0.000 claims description 4
- 210000002858 crystal cell Anatomy 0.000 claims 3
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000010287 polarization Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000000654 additive Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 8
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- 239000002518 antifoaming agent Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ZKJNETINGMOHJG-GGWOSOGESA-N (e)-1-[(e)-prop-1-enoxy]prop-1-ene Chemical compound C\C=C\O\C=C\C ZKJNETINGMOHJG-GGWOSOGESA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- G02F1/29—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 position or the direction of light beams, i.e. deflection
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B30/00—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images
- G02B30/20—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes
- G02B30/26—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type
- G02B30/27—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type involving lenticular arrays
- G02B30/28—Optical systems or apparatus for producing three-dimensional [3D] effects, e.g. stereoscopic images by providing first and second parallax images to an observer's left and right eyes of the autostereoscopic type involving lenticular arrays involving active lenticular arrays
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to a liquid crystal composition, a liquid crystal element liquid crystal lens and a birefringent lens for stereoscopic image display. The invention provides a liquid crystal composition and a component comprising the same, wherein the liquid crystal composition is used as a frequency bandA material used for an electromagnetic wave signal control element having a rate in the range of 1GHz to 10THz, which satisfies at least one of the characteristics of a wide temperature range of a nematic phase, a large refractive index anisotropy and a small dielectric loss tangent (tan delta) in a frequency region used for control, and has excellent balance of characteristics. A liquid crystal composition comprising at least one compound selected from the group of compounds represented by formula (1). For example, R 1 Alkyl of 1 to 12 carbon atoms; z is Z 11 Is a single bond; l (L) 11 、L 12 、L 13 L and L 18 Is hydrogen; l (L) 17 Is methyl; y is Y 11 Y and Y 22 Is hydrogen; a is 0, b is 1, and c is 0.
Description
Technical Field
The present invention relates to a liquid crystal composition having a nematic phase and positive dielectric anisotropy, and an element comprising the same. In particular, the present invention relates to a liquid crystal composition, a liquid crystal element liquid crystal lens, and a birefringent lens for stereoscopic image display, which are used for electromagnetic wave control in the frequency range of 1GHz to 10 THz.
Background
Many novel applications of liquid crystal compositions for display applications are attracting attention as applications in high-frequency technology such as antennas for transmitting and receiving electromagnetic waves using the liquid crystal compositions.
Specifically, as an element for electromagnetic wave control in the frequency range of 1GHz to 10THz, there are a millimeter wave band or a microwave band antenna, an infrared laser element, and the like. Various methods have been studied for these elements, but a method using a liquid crystal composition which is considered to have less failure due to the absence of a mechanically movable part has been attracting attention.
The liquid crystal composition having dielectric anisotropy has a dielectric constant in the vertical direction and the horizontal direction different from each other with respect to the alignment direction of the liquid crystal composition at a frequency (about several tens kHz to several hundreds MHz or less) lower than the frequency (relaxation frequency) at which the alignment polarization is relaxed.
Even in the range from microwave to terahertz wave (about 10 THz), which is a frequency higher than the relaxation frequency, the value becomes small, but a difference in dielectric constant between the vertical direction and the horizontal direction with respect to the alignment direction of the liquid crystal composition is observed, and thus there is dielectric constant anisotropy (non-patent document 1). Therefore, the liquid crystal composition changes the orientation direction of molecules according to an external field (electric field), and thus the dielectric constant in one direction can be changed.
By utilizing this property, the liquid crystal composition changes the orientation of molecules according to an electric field from the outside, and thus the dielectric constant can be changed. For example, a microwave device in which the transmission characteristics of a high-frequency transmission line can be controlled electrically from the outside can be realized. As such a device, a voltage-controlled millimeter-wave band variable phase shifter in which a waveguide is filled with a nematic liquid crystal composition, a microwave/millimeter-wave band broadband variable phase shifter using a nematic liquid crystal composition as a dielectric substrate of a microstrip line, or the like has been reported (patent document 1 and patent document 2).
In recent years, a technology of a meta material (meta) technology that displays a behavior that an electromagnetic wave including light does not have in nature has been studied. Various electromagnetic wave control elements have been proposed according to their characteristics, which are applied to the technical fields of high-frequency devices, microwave devices, antennas, and the like. As a capacitance control material for a transmission line using a metamaterial, a liquid crystal composition in which the dielectric constant is changed by changing the orientation of molecules according to an electric field from the outside is also considered.
Such an element for electromagnetic wave control desirably has characteristics such as high gain and low loss. When phase control of a high-frequency signal is considered, regarding characteristics required for a liquid crystal composition, it is required that dielectric anisotropy capable of large phase control is large and dielectric loss tangent (tan δ) proportional to absorption energy of an electromagnetic wave signal of the liquid crystal composition is small in a frequency region used for phase control (non-patent document 1).
The liquid crystal composition being a dielectricAnd thus produces polarization (dielectric polarization) with respect to an external field (electric field). The dielectric constant is a physical property quantity indicating the response of a dielectric to an electric field, and the magnitude of the dielectric constant is related to dielectric polarization. The mechanism by which dielectric polarization occurs can be broadly divided into three types. Is electron polarization, ion polarization, and orientation polarization. The polarization of the orientation is polarization accompanying the orientation of dipole moment (dipole moment), and as described above, the polarization of the orientation is relaxed at a frequency of about several hundred kHz to several hundred MHz, and the polarization of the orientation is reduced. As a result, dielectric polarization at high frequencies (microwave to terahertz wave (about 10 THz) range) is only related to electron polarization and ion polarization. Furthermore, in a lossless dielectric, there is epsilon=n in dielectric constant and refractive index 2 Considering that the ionic polarization of the liquid crystal composition is small, it is considered that the larger the refractive index anisotropy (Δn) under visible light due to the electron polarization is, the larger the dielectric constant anisotropy (Δε) in the high-frequency region is (non-patent document 2). Therefore, the liquid crystal composition preferably has a large refractive index anisotropy.
In order to achieve the switching characteristics and high energy efficiency of the element, the driving voltage is desirably low. Therefore, the liquid crystal composition preferably has a large dielectric anisotropy even at a low frequency (a frequency lower than the relaxation frequency).
In addition, the element used for electromagnetic wave control is required to have a wide usable temperature range, a short response time of the element, and the like, and as the characteristics of the liquid crystal composition, there are also required to have a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a low stability to heat, a low viscosity, and the like.
The liquid crystal compositions used in the above-mentioned devices are disclosed in patent documents 3 and 4 below.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2017/201115
[ patent document 2] International publication No. 2017/208996
[ patent document 3] Japanese patent laid-open No. 2004-285085
Patent document 4 Japanese patent laid-open publication No. 2011-74074
[ non-patent literature ]
[ non-patent document 1] [ liquid crystal (EKISHO) ] 23, volume (No. 1), (2019), pages 51-55
[ non-patent document 2] [ dielectric theory of phenomena ] society of electric society of sciences (ohm sha) stock Co., ltd., 7 months, 25 days, 92 pages to 95 pages in 1973
Disclosure of Invention
[ problem to be solved by the invention ]
As a material for an element used for electromagnetic wave control, a liquid crystal composition is required to have not only a high upper limit temperature of a nematic phase and a low lower limit temperature of the nematic phase, but also a large dielectric anisotropy (large refractive index anisotropy), a small dielectric loss tangent (tan δ) and a large dielectric anisotropy at a low frequency for reducing a driving voltage in a frequency region where electromagnetic wave control is performed, and further preferably to have a small viscosity, a large specific resistance in a driving frequency region and stability to heat.
However, as a liquid crystal composition used for such an element used for electromagnetic wave control, a liquid crystal composition used for a conventional display application or the like is insufficient in terms of characteristics. The reason is that for high frequency control applications such as high insertion loss (insertion loss) and/or insufficient phase shift, their characteristics are insufficient.
The development of liquid crystal materials for electromagnetic wave controlled elements is still under development, and in order to improve the characteristics of high frequency control, attempts have been made to develop novel compounds capable of optimizing such elements. In addition, a special liquid crystal medium is required for use as a material for an element used for electromagnetic wave control.
An object of the present invention is to provide a liquid crystal composition used as a material for an element for electromagnetic wave control having a frequency in the range of 1GHz to 10THz, and which exhibits good and excellent balance of required characteristics, and an element containing the liquid crystal composition.
[ means of solving the problems ]
The inventors have made an intensive study and as a result, have found that a liquid crystal composition containing, as a first component, at least one compound selected from the group of compounds represented by formula (1) as a liquid crystal compound having a specific structure solves the above-mentioned problems, and have completed the present invention.
The present invention is the following items.
The liquid crystal composition according to item 1 contains at least one compound selected from the group of compounds represented by formula (1).
In the formula (1), the components are as follows,
R 1 is hydrogen, halogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen;
ring A 1 Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, 2,6, 7-trioxabicyclo [ 2.2.2.2]Octane-1, 4-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 11 z is as follows 12 Is a single bond, -ch=ch-, -cf=cf-, -c≡c-, or-c≡c-;
L 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 l and L 18 Is hydrogen, halogen, alkyl of 1 to 3 carbon atoms or cycloalkyl of 3 to 5 carbon atoms;
Y 11 hydrogen, halogen or alkyl of 1 to 3 carbon atoms;
Y 12 hydrogen or halogen;
L 14 、L 15 、L 16 、L 17 、L 18 y and Y 11 At least one of which is an alkyl group having 1 to 3 carbon atoms;
a and c are 0 or 1, b is 0, 1 or 2, the sum of a, b and c is 1 or more and 3 or less, a is 0, b is 1, c is 0, Z 11 Is a single bond, L 11 、L 12 、L 13 、L 17 、L 18 Y and Y 12 When hydrogen is Y 11 And not methyl.
The liquid crystal composition according to item 1, which contains at least one compound selected from the group of compounds represented by formula (2) and formula (3).
In the formula (2), the amino acid sequence of the compound,
R 2 is hydrogen, halogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen;
ring A 2 Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, 2,6, 7-trioxabicyclo [ 2.2.2.2]Octane-1, 4-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 21 z is as follows 22 Is a single bond, -C.ident.C-or-C.ident.C-;
L 21 、L 22 、L 23 l and L 24 Is hydrogen, halogen, alkyl of 1 to 3 carbon atoms or cycloalkyl of 3 to 5 carbon atoms;
X 2 is-C.ident.C-CF 3 or-C.ident.C-C.ident.N;
Y 21 y and Y 22 Hydrogen, halogen or alkyl of 1 to 3 carbon atoms;
d is 0 or 1, e is 0, 1, 2 or 3, and the sum of d and e is 1 or more and 3 or less;
in the formula (3), the amino acid sequence of the compound,
R 31 is hydrogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
R 32 Is R 31 Or-n=c=s;
ring A 3 Is pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 31 z is as follows 32 Is a single bond, -C.ident.C-or-C.ident.C-;
L 31 、L 32 、L 33 、L 34 、L 35 、L 36 、L 37 、L 38 l and L 39 Hydrogen or halogen;
f is 0 or 1, g is 0, 1 or 2, and the sum of f and g is 0 or more and 2 or less.
Item 3. The liquid crystal composition according to item 1 or item 2 contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-6) as the compound represented by formula (1).
In the formulae (1-1) to (1-6),
R 1 ' is an alkyl group of 1 to 12 carbon atoms, at least one of which is- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
L 11 '、L 12 '、L 13 '、L 14 '、L 15 '、L 16 '、L 17 ' and L 18 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 11 ' is hydrogen, fluorine, chlorine, methyl or ethyl;
Y 12 ' is hydrogen, fluorine or chlorine;
L 14 '、L 15 '、L 16 '、L 17 '、L 18 ' and Y 11 At least one of' is methyl or ethyl;
here, in the formula (1-1), L 11 '、L 12 '、L 13 '、L 17 '、L 18 ' and Y 12 When' is hydrogen, Y 11 ' not methyl.
Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the compound represented by formula (1) is in the range of 5 to 80% by weight based on the weight of the liquid crystal composition.
The liquid crystal composition according to any one of items 2 to 4, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-8) as the compound represented by formula (2).
In the formulae (2-1) to (2-8),
R 2 ' is an alkyl group of 1 to 12 carbon atoms, at least one of which is- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
L 21 '、L 22 '、L 23 ' and L 24 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 21 ' and Y 22 ' is hydrogen, fluorine, chlorine, methyl or ethyl.
The liquid crystal composition according to any one of items 2 to 5, wherein the proportion of the compound represented by formula (2) is in the range of 5 to 50% by weight based on the weight of the liquid crystal composition.
The liquid crystal composition according to any one of items 2 to 6, which contains at least one compound selected from the group of compounds represented by formulas (3-1) to (3-6) as the compound represented by formula (3).
In the formulae (3-1) to (3-6),
R 31 ' is an alkyl group of 1 to 12 carbon atoms, of which at least one-CH 2 -optionally substituted by-O-at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-; r is R 32 ' is R 31 ' or-n=c=s; l (L) 32 '、L 34 '、L 35 '、L 36 '、L 37 '、L 38 ' and L 39 ' is hydrogen, fluorine or chlorine;
in the formula (3-6), in L 35 '、L 36 '、L 38 ' and L 39 When' is hydrogen, R 32 ' is-n=c=s.
The liquid crystal composition according to any one of items 2 to 7, wherein the proportion of the compound represented by formula (3) is in the range of 5 to 50% by weight based on the weight of the liquid crystal composition.
The liquid crystal composition according to any one of items 1 to 8, wherein the refractive index anisotropy at 25℃at a wavelength of 589nm is 0.35 or more.
The liquid crystal composition according to any one of items 1 to 9, wherein the dielectric anisotropy of 25 ℃ in the frequency range of less than 1MHz is 5 or more.
Item 11. The liquid crystal composition according to any one of items 1 to 10, wherein the dielectric constant anisotropy of 25 ℃ at least one frequency of 1GHz to 10THz is in the range of 0.50 to 3.0.
Item 12. The liquid crystal composition according to any one of item 1 to item 11, comprising an optically active compound.
The liquid crystal composition according to any one of items 1 to 12, comprising a polymerizable compound.
The liquid crystal composition according to any one of items 1 to 13, which contains at least one of an antioxidant, an ultraviolet absorber, an antistatic agent and a dichroic dye.
Item 15. An element containing the liquid crystal composition according to any one of items 1 to 14, and which is used for switching such that switching of dielectric constant can be controlled reversibly by changing the orientation direction of liquid crystal molecules reversibly.
Item 16. An element containing the liquid crystal composition according to any one of items 1 to 14 and used for electromagnetic wave control in a frequency range of 1GHz to 10 THz.
The liquid crystal lens or the birefringent lens for stereoscopic image display according to item 17, which contains the liquid crystal composition according to any one of items 1 to 14.
[ Effect of the invention ]
According to the present invention, not only the high upper limit temperature of the nematic phase and the low lower limit temperature of the nematic phase but also at least one of the characteristics of the composition such as large dielectric anisotropy, small dielectric loss tangent (tan δ), and large dielectric anisotropy at low frequency for reducing the driving voltage in the frequency region where electromagnetic wave control is performed can be sufficiently satisfied. Further, it is possible to provide a more preferable liquid crystal composition which further satisfies at least one of the characteristics of the composition such as low viscosity, high specific resistance in the driving frequency region, and stability to heat. The element using the liquid crystal composition of the present invention can exhibit excellent characteristics of being capable of electromagnetic wave control over a wide temperature range.
Detailed Description
The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "electromagnetic wave control element" are sometimes abbreviated as "composition" and "element", respectively. The "electromagnetic wave control element" is a generic term for an electromagnetic wave control panel and an electromagnetic wave control module. The "liquid crystalline compound" is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound which does not have a liquid crystal phase but is mixed in a composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the liquid crystal phase. The compound has a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and its molecule (liquid crystal molecule) is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having alkenyl groups are not classified as polymerizable compounds in their meaning.
The liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. The proportion (content) of the liquid crystalline compound is expressed by a weight percentage (wt%) based on the weight of the liquid crystal composition. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a stabilizer for ultraviolet light and heat, a matting agent, a pigment (dichroic dye), an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an antistatic agent, and a magnetic compound are added to the liquid crystal composition as necessary. The proportion (amount) of the additive is represented by a weight percentage (wt%) based on the weight of the liquid crystal composition, as in the proportion of the liquid crystal compound. Weight parts per million (ppm) are also sometimes used. The proportions of the polymerization initiator and the polymerization inhibitor are expressed based on the weight of the polymerizable compound.
The "upper limit temperature of the nematic phase" is sometimes simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as "lower limit temperature". The expression "increasing the dielectric constant anisotropy" means that the value thereof increases positively when the composition having positive dielectric constant anisotropy and that the value thereof increases negatively when the composition having negative dielectric constant anisotropy.
At least one compound selected from the group of compounds represented by the formula (1) is sometimes referred to simply as "compound (1)". "Compound (1)" means one compound or two or more compounds represented by formula (1). The same is true for the compounds represented by other formulas. By "at least one" in relation to "substitutable" is meant not only the position but also the number thereof can be selected without limitation.
The compound (1 z) is described as an example. In the formula (1 z), the symbols of α and β surrounded by hexagons correspond to the rings α and β, respectively, and represent rings such as a six-membered ring and a condensed ring. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or may be different. The rule applies to a plurality of rings a when the subscript 'x' is greater than 2. The rules also apply to other notations such as bond Z. The diagonal line intersecting one side of ring beta indicates that any hydrogen on ring beta may be substituted with a substituent (-Sp-P). The subscript 'y' represents the number of substituents substituted. When the subscript 'y' is 0, no such substitution is present. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on the ring beta. In that case, the rule "may be the same or may be different" also applies. The rule applies to the case where the symbol Ra is used for a plurality of compounds.
In the formula (1 z), for example, the expression "Ra and Rb are alkyl, alkoxy or alkenyl" means that Ra and Rb are independently selected from the group consisting of alkyl, alkoxy and alkenyl. Here, the group represented by Ra and the group represented by Rb may be the same or may be different. The rules also apply to the case where the notation of Ra is used for a variety of compounds. The rules also apply in the case of using a plurality of Ra for one compound.
At least one compound selected from the compounds represented by the formula (1 z) is sometimes referred to simply as "compound (1 z)". "Compound (1 z)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1 z). The same is true for the compounds represented by other formulas. The expression "at least one compound selected from the group consisting of the compounds represented by the formula (1 z) and the formula (2 z)" means at least one compound selected from the group consisting of the compound (1 z) and the compound (2 z).
The expression "at least one 'a'" means that the number of 'a' is arbitrary. In the expression "at least one of the" a's "may be substituted with the" B ", the positions of the" a's "are arbitrary when the number of the" a's "is one, and the positions of the" a's "may be selected without limitation when the number of the" a's "is two or more. Sometimes use "at least one-CH 2 -can be expressed by-O-substitution ". In that case, -CH 2 -CH 2 -CH 2 By non-contiguous-CH 2 -conversion to-O-CH by-O-substitution 2 -O-. However, there is no adjacency-CH 2 -O-substituted case. The reason is that the substitution generates-O-O-CH 2 - (peroxides).
The alkyl group of the liquid crystalline compound is a linear alkyl group or a branched alkyl group, and unless otherwise specified, a cycloalkyl group is not included. Straight chain alkyl groups are preferred over branched alkyl groups. The same is true for terminal groups such as alkoxy, alkenyl, and the like. For the configuration related to 1, 4-cyclohexylene, the trans configuration is superior to the cis configuration in order to raise the upper temperature. 2-fluoro-1, 4-phenylene means the following two divalent groups. In the chemical formula, fluorine can be directed to the left (L) or to the right (R). The same applies to divalent radicals of asymmetric rings such as 2, 5-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, tetrahydropyran-2, 5-diyl. In order to raise the upper limit temperature, the preferred tetrahydropyran-2, 5-diyl group is oriented to the right (R).
The benzo [ b ] thiophene-2, 5-diyl and the benzo [ b ] thiophene-2, 6-diyl are each represented by the following structural formula.
In the case where at least one hydrogen on these rings is substituted with halogen or an alkyl group having 1 to 3 carbon atoms, the following structure is preferable in terms of ease of synthesis.
R is halogen or alkyl with 1 to 3 carbon atoms.
The bonding group such as a carbonyloxy group may be-COO-or-OCO-.
In the chemical formula of the component compound, the terminal group R 1 The notations of (2) are for a variety of compounds. Of these compounds, any two R 1 The radicals represented may be identical or different. For example, R in the presence of the compound (1-1) 1 ' methyl group, R of Compound (1-2) 1 ' in the case of ethyl. R of the compound (1-1) is also present 1 ' is ethyl, R of the compound (1-2) 1 ' in the case of propyl. The rule also applies to R 2 、R 31 、R 32 Etc.
The present invention also includes the following items. (a) The composition further comprises at least one additive selected from optically active compounds, antioxidants, ultraviolet absorbers, stabilizers for ultraviolet rays and heat, matting agents, pigments (dichroic pigments), antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, antistatic agents, magnetic compounds, and the like. (b) an element comprising said composition. (c) A component comprising the composition and for controlling electromagnetic wave signals at least one frequency of 1GHz to 10 THz. (d) The composition further comprises a polymerizable compound and a member comprising the composition. (e) The use of said composition as a composition having a nematic phase. (f) Are used as optically active compositions by adding optically active compounds to the compositions.
The liquid crystal composition of the present invention has a large dielectric anisotropy and a small dielectric loss tangent (tan delta) in a frequency region of an electromagnetic wave signal in a range of 1GHz to 10 THz. Therefore, it can be suitably used not only as an element associated with electromagnetic waves (microwaves) in the range of 1GHz to 10THz, but also as an element associated with electromagnetic waves (microwaves) in the range of 1GHz to 50 GHz.
The composition of the present invention is described in the following order. First, the structure of the component compounds in the composition will be described. Second, the main characteristics of the constituent compounds and the main effects of the compounds on the composition will be described. Third, the combination of components in the composition, preferred proportions of the components, and their basis will be described. Fourth, preferred modes of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.
First, the structure of the component compounds in the composition will be described. The compositions of the present invention are classified as composition a and composition B. The composition A may contain a liquid crystalline compound selected from the group consisting of the compound (1), the compound (2) and the compound (3), and may further contain other liquid crystalline compounds, additives and the like. The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (1), the compound (2) and the compound (3). Such compounds are mixed in the composition for the purpose of further adjusting the properties. The additives are optically active compounds, antioxidants, ultraviolet absorbers, stabilizers against ultraviolet rays and heat, matting agents, pigments (dichroic pigments), antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, antistatic agents, polar compounds, and the like.
The composition B contains substantially only the liquid crystalline compound selected from the group consisting of the compound (1), the compound (2) and the compound (3). By "substantially" is meant that the composition may contain additives but no other liquid crystalline compounds. The amount of the components of composition B is small compared to composition a. From the viewpoint of cost reduction, composition B is superior to composition a. Composition a is superior to composition B in that the characteristics can be further adjusted by mixing other liquid crystalline compounds.
Second, the main characteristics of the constituent compounds and the main effects of the compounds on the characteristics of the composition will be described. Based on the effects of the present invention, the main characteristics of the constituent compounds are summarized in table 1. In the notation of table 1, L means large or high, M means medium, and S means small or low. The symbols L, M, S are classifications based on qualitative comparisons between component compounds, and 0 (zero) means a value of substantially zero or near zero.
Properties of the Compounds of Table 1
| Compounds of formula (I) | (1) | (2) | (3) |
| Upper limit temperature | S to L | S to L | S to L |
| Viscosity of the mixture | S to M | M to L | S to M |
| Refractive index anisotropy | L | L | L |
| Dielectric constant anisotropy | S to M | M to L | 0 to M |
When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows.
The compound (1) has mainly an effect of improving the refractive index anisotropy of the liquid crystal composition and improving the dielectric constant anisotropy. The upper limit temperature and viscosity can be controlled to some extent by selecting the sum of a, b and c of the compound (1). That is, if the sum of a, b, and c is reduced, the upper limit temperature tends to be low and the viscosity tends to be low. When the sum of a, b and c is increased, the upper limit temperature tends to be high and the viscosity tends to be high. The specific resistance of the compound (1) tends to be low as a whole.
The compound (2) has mainly an effect of improving the refractive index anisotropy of the liquid crystal composition and improving the dielectric constant anisotropy as compared with the compound (1). In order to achieve high conversion characteristics and high energy efficiency, the dielectric constant anisotropy is preferably large. The relationship between the number of rings (the sum of d and e in the formula (2)) contained in the compound and the upper limit temperature and viscosity is the same as that of the compound (1).
The compound (3) has mainly an effect of increasing the temperature range of the nematic phase while improving the refractive index anisotropy. In addition, at R 32 When-n=c=s, there is an effect of improving the dielectric anisotropy. The relationship between the number of rings (sum of f and g in formula (3)) and the upper limit temperature and viscosity in the compound is the same as that in the compound (1) and the compound (2), but the compound (3) tends to be as follows: the effect of raising the upper limit temperature, lowering the lower limit temperature and lowering the viscosity is greater than that of the compound (1) and the compound (2).
Third, the combination of the components in the composition, the preferable ratio of the component compounds, and the basis thereof will be described. Preferred combinations of the components in the composition are compound (1) +compound (2), compound (1) +compound (3) or compound (1) +compound (2) +compound (3). In addition to this, a composition containing only the compound (1) can also be prepared. From the viewpoint of further improving the refractive index anisotropy and the dielectric constant anisotropy and reducing the viscosity, a particularly preferred combination is compound (1) +compound (2) +compound (3).
In order to expand the temperature range of the nematic phase while increasing the refractive index anisotropy and increasing the dielectric constant anisotropy, the preferable proportion of the compound (1) is in the range of about 5 to about 80% by weight based on the weight of the liquid crystal composition. Further preferred proportions are in the range of about 10% to about 70% by weight. Particularly preferred proportions range from about 20% to about 60% by weight.
The preferable proportion of the compound (2) is in the range of about 5% by weight to about 50% by weight, based on the weight of the liquid crystal composition, in order to improve the dielectric constant anisotropy and to improve the refractive index anisotropy while suppressing the rise of the lower limit temperature. Further preferred proportions are in the range of about 10% to about 45% by weight. Particularly preferred proportions range from about 15% to about 40% by weight.
The preferable proportion of the compound (3) is about 5% by weight or more in order to increase the refractive index anisotropy and to expand the temperature range of the nematic phase, and the preferable proportion of the compound (3) is about 50% by weight or less in order to increase the dielectric constant anisotropy, based on the weight of the liquid crystal composition. Further preferred proportions are in the range of about 10% to about 45% by weight. Particularly preferred proportions range from about 15% to about 40% by weight.
Fourth, preferred modes of the component compounds will be described.
R 1 R is R 2 Is hydrogen, halogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen.
R 31 R is R 32 Is hydrogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-.
In addition, R 32 Or-n=c=s.
In order to improve stability against ultraviolet light or heat, R is preferably 1 、R 2 、R 31 R is R 32 Preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy or ethoxy. For reducing the viscosity, methyl, ethyl, propyl, butyl, pentyl, methoxy or ethoxy groups are preferred.
In addition, R is for improving refractive index anisotropy or dielectric constant anisotropy 32 Also preferred is-n=c=s.
a and c are 0 or 1, b is 0, 1 or 2, and the sum of a, b and c is 1 or more and 3 or less. In order to increase the refractive index anisotropy and to reduce the viscosity, a is preferably 0, and in order to reduce the lower limit temperature, a is preferably 1. B is preferably 1 for lowering the lower limit temperature and for lowering the viscosity, and b is preferably 2 for increasing the refractive index anisotropy and for increasing the upper limit temperature. In order to lower the lower limit temperature and to lower the viscosity, c is preferably 0, in order to increase the refractive index anisotropy and in order to increase the upper limit temperature, c is preferably 1. In order to increase the refractive index anisotropy and in order to increase the upper limit temperature, the sum of a, b and c is preferably 2 or 3.
Where a is 0, b is 1, c is 0, Z 11 Is a single bond, L 11 、L 12 、L 13 、L 17 、L 18 Y and Y 12 When hydrogen is Y 11 And not methyl.
d is 0 or 1, e is 0, 1, 2 or 3, and the sum of d and e is 1 or more and 3 or less. In order to increase the refractive index anisotropy and to reduce the viscosity, d is preferably 0, and in order to reduce the lower limit temperature, d is preferably 1. In order to lower the lower limit temperature and to lower the viscosity, e is preferably 1, in order to increase the refractive index anisotropy and in order to increase the upper limit temperature, e is preferably 2 or 3. In order to increase the refractive index anisotropy and in order to increase the upper limit temperature, the sum of d and e is preferably 2 or 3.
f is 0 or 1, g is 0, 1 or 2, and the sum of f and g is 0 or more and 2 or less. In order to increase the refractive index anisotropy and to reduce the viscosity, f is preferably 0. In order to lower the lower limit temperature and to lower the viscosity, g is preferably 0, in order to increase the refractive index anisotropy and in order to increase the upper limit temperature, g is preferably 1 or 2. In order to increase the refractive index anisotropy and in order to increase the upper limit temperature, the sum of f and g is preferably 1 or 2.
Z 11 Z is as follows 12 Is a single bond, -CH=CH-, -CF=CF-, -C.ident.C-or-C.ident.C-. To reduce the viscosity, Z is preferably 11 Z is as follows 12 Is a single bond, Z is preferable for improving refractive index anisotropy 11 Z is as follows 12 is-CH=CH-or-C≡C-.
Z 21 Z is as follows 22 Is a single bond, -C.ident.C-or-C.ident.C-. To reduce the viscosity, preference is given toSelected Z 21 Z is as follows 22 Is a single bond, Z is preferable for improving refractive index anisotropy 21 Z is as follows 22 is-C.ident.C-or-C.ident.C-.
Z 31 Z is as follows 32 Is a single bond, -C.ident.C-or-C.ident.C-. To reduce the viscosity, Z is preferably 31 Z is as follows 32 Is a single bond, Z is preferable for improving refractive index anisotropy 31 Z is as follows 32 is-C.ident.C-or-C.ident.C-.
Ring A 1 Ring A 2 Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, 2,6, 7-trioxabicyclo [ 2.2.2.2 ]Octane-1, 4-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being substituted by halogen or alkyl having 1 to 3 carbon atoms.
Preferred ring A 1 Ring A 2 Is 1, 4-cyclohexylene, pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl. Further, 1, 4-cyclohexylene is preferable.
Ring A 3 Is pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, and at least one hydrogen in these rings may be substituted by halogen or alkyl having 1 to 3 carbon atoms.
L 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 、L 18 、L 21 、L 22 、L 23 L and L 24 Is hydrogen, halogen, alkyl of 1 to 3 carbon atoms or cycloalkyl of 3 to 5 carbon atoms. In order to raise the upper limit temperature, L is preferably 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 、L 18 、L 21 、L 22 、L 23 L and L 24 Is hydrogen, L is preferable in order to improve dielectric anisotropy 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 、L 18 、L 21 、L 22 、L 23 L and L 24 In order to lower the lower limit temperature, L is preferably fluorine or chlorine 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 、L 18 、L 21 、L 22 、L 23 L and L 24 Is fluorine, chlorine, methyl, ethyl or cyclopropyl. In order to increase the dielectric anisotropy of the entire liquid crystal composition, L is preferable 11 L and L 12 、L 13 L and L 14 Or L 21 L and L 22 Not both halogen.
L 31 、L 32 、L 33 、L 34 、L 35 、L 36 、L 37 、L 38 L and L 39 Is hydrogen or halogen. In order to raise the upper limit temperature, L is preferably 31 、L 32 、L 33 、L 34 、L 35 、L 36 、L 37 、L 38 L and L 39 Is hydrogen, L is preferable for improving dielectric anisotropy and for lowering the lower limit temperature 31 、L 32 、L 33 、L 34 、L 35 、L 36 、L 37 、L 38 L and L 39 Is fluorine or chlorine. In order to increase the dielectric anisotropy of the entire liquid crystal composition, L is preferable 31 L and L 32 、L 34 L and L 35 Or L 37 L and L 38 Not both halogen.
Y 11 Is hydrogen, halogen or alkyl of 1 to 3 carbon atoms. In order to improve the refractive index anisotropy, Y is preferably 11 Is hydrogen, preferably Y in order to lower the lower limit temperature 11 Is methyl or ethyl. Y is Y 12 Is hydrogen or halogen. In order to improve the refractive index anisotropy, Y is preferably 12 Is hydrogen, preferably Y in order to improve dielectric anisotropy 12 Is fluorine or chlorine.
Y 21 Y and Y 22 Is hydrogen, halogen or alkyl of 1 to 3 carbon atoms. In order to improve the refractive index anisotropy, Y is preferably 21 Y and Y 22 Is hydrogen, preferably Y in order to improve dielectric anisotropy 21 Y and Y 22 In order to lower the lower limit temperature, Y is preferably fluorine or chlorine 21 Y and Y 22 Is methyl or ethyl.
X 2 is-C.ident.C-CF 3 or-C.ident.C-C.ident.N. In order to improve refractive index anisotropy, X is preferably selected 2 is-C.ident.C-C.ident.N.
Fifth, preferred component compounds are shown.
Preferred compounds (1) are compounds (1-1) to (1-6).
In the formulae (1-1) to (1-6),
R 1 ' is an alkyl group of 1 to 12 carbon atoms, at least one of which is- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
L 11 '、L 12 '、L 13 '、L 14 '、L 15 '、L 16 '、L 17 ' and L 18 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 11 ' is hydrogen, fluorine, chlorine, methyl or ethyl;
Y 12 ' is hydrogen, fluorine or chlorine;
L 14 '、L 15 '、L 16 '、L 17 '、L 18 ' and Y 11 At least one of' is methyl or ethyl;
here, in the formula (1-1), L 11 '、L 12 '、L 13 '、L 17 '、L 18 ' and Y 12 When' is hydrogen, Y 11 ' not methyl.
Preferably, at least one of the compounds (1) is the compound (1-1), the compound (1-2), the compound (1-4) or the compound (1-5).
Preferred compounds (2) are compounds (2-1) to (2-8).
In the formulae (2-1) to (2-8),
R 2 ' is an alkyl group of 1 to 12 carbon atoms, at least one of which is- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-; l (L) 21 '、L 22 '、L 23 ' and L 24 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 21 ' and Y 22 ' is hydrogen, fluorine, chlorine, methyl or ethyl.
Preferably, at least one of the compounds (2) is the compound (2-1), the compound (2-3) or the compound (2-4). Preferred compounds (3) are compounds (3-1) to (3-6).
In the formulae (3-1) to (3-6),
R 31 ' is an alkyl group of 1 to 12 carbon atoms, of which at least one-CH 2 -optionally substituted by-O-at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-; r is R 32 ' is R 31 ' or-n=c=s; l (L) 32 '、L 34 '、L 35 '、L 36 '、L 37 '、L 38 ' and L 39 ' is hydrogen, fluorine or chlorine;
in the formula (3-6), in L 35 '、L 36 '、L 38 ' and L 39 When' is hydrogen, R 32 ' is-n=c=s.
Preferably, at least one of the compounds (3) is the compound (3-2), the compound (3-3), the compound (3-4) or the compound (3-5). More preferably, at least two of the compounds (3) are the compound (3-2) and the compound (3-4), or the combination of the compound (3-3) and the compound (3-4).
Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, stabilizers against ultraviolet rays and heat, matting agents, pigments (dichroic pigments), antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, antistatic agents, polar compounds, and the like. Hereinafter, unless otherwise specified, the mixing ratio of these additives is a ratio (weight) based on the weight of the liquid crystal composition.
The combination of additives used is arbitrary, and for example, different kinds of antioxidants can be used in combination. For example, different types of additives may be used in combination as in the case of using an antioxidant in combination with an ultraviolet absorber and a stabilizer.
The optically active compound is added to the composition for the purpose of inducing a helix structure of the liquid crystal to impart a twist angle. Examples of such compounds are compounds (4-1) to (4-5). The preferred proportion of the optically active compound is about 5% by weight or less. Further preferred ratios are in the range of about 0.01% to about 2% by weight.
Antioxidants are added to the compositions in order to prevent a decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use of the element. Preferred examples of the antioxidant are compound (5) wherein t is an integer of 1 to 9, and the like.
In the compound (5), t is preferably 1, 3, 5, 7 or 9. Further preferably t is 7. Since the compound (5) having t of 7 has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use of the element. In order to obtain the effect, the preferable proportion of the antioxidant is about 50ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of the antioxidant is about 600ppm or less. Further preferred ratios are in the range of about 100ppm to about 300 ppm.
Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. In addition, light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer are compounds (6-1) to (6-16) and the like. In order to obtain the effect, the preferable proportion of these absorbents or stabilizers is about 50ppm or more, and in order not to lower the upper limit temperature or in order not to raise the lower limit temperature, the preferable proportion of these absorbents or stabilizers is about 10000ppm or less. Further preferred ratios are in the range of about 100ppm to about 10000 ppm.
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Preferred additives for stabilizers against ultraviolet light and heat are amino-trans compounds represented by the compound (7) (U.S. registered patent No. 6495066).
In the formula (7), R m R is R n Is alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, alkenyl group with 2 to 12 carbon atoms or alkenyloxy group with 2 to 12 carbon atoms; x is X a is-NO 2 -c≡n, -n=c=s, fluoro or-OCF 3 ；Y a Y and Y b Is hydrogen or fluorine. In order to obtain the effect, the preferable proportion of these stabilizers is in the range of 1 to 20% by weight, and more preferably in the range of 5 to 10% by weight.
The matting agent is a compound that receives light energy absorbed by the liquid crystalline compound and converts the light energy into heat energy to prevent the decomposition of the liquid crystalline compound. In order to obtain the above-mentioned effect, the preferable proportion of these matting agents is about 50ppm or more, and in order to lower the lower limit temperature, the preferable proportion of these matting agents is about 20000ppm or less. Further preferred ratios are in the range of about 100ppm to about 10000 ppm.
In order to adapt to a Guest Host (GH) mode element, a dichroic dye (dichromatic dye) such as an azo dye, an anthraquinone dye, or the like is added to the composition. The preferred proportion of pigment is in the range of about 0.01% to about 10% by weight. To prevent foaming, defoamers such as simethicone, methyl phenyl silicone oil, and the like are added to the composition. In order to obtain the above effect, the preferable proportion of the antifoaming agent is about 1ppm or more, and in order to prevent the display failure, the preferable proportion of the antifoaming agent is about 1000ppm or less. Further preferred ratios are in the range of about 1ppm to about 500 ppm.
The polymerizable compound is added to the composition so as to be suitable for the polymer-stabilized element. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, ethyleneoxy compound, propenyl ether, epoxy compound (oxetane ) and vinyl ketone. Further preferred examples are derivatives of acrylic or methacrylic esters. In order to obtain the above-mentioned effect, the preferable proportion of the polymerizable compound is about 0.05% by weight or more, and in order to prevent the driving temperature from rising, the preferable proportion of the polymerizable compound is about 20% by weight or less. Further preferred ratios are in the range of about 0.1% to about 10% by weight. The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of a polymerization initiator such as a photopolymerization initiator. Suitable conditions for the polymerization, suitable types and suitable amounts of initiator are known to the person skilled in the art and are described in the literature. For example, brilliant best (Irgacure) 651 (registered trademark; BASF), brilliant best (Irgacure) 184 (registered trademark; BASF), or Darocure 1173 (registered trademark; BASF)) as a photopolymerization initiator is suitable for radical polymerization. The preferable proportion of the photopolymerization initiator is in the range of about 0.1 parts by weight to about 5 parts by weight based on 100 parts by weight of the polymerizable compound. Further preferred ratios are in the range of about 1 part by weight to about 3 parts by weight.
In order to prevent polymerization when the polymerizable compound is stored, a polymerization inhibitor may be added. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, etc.
In the present specification, the polar compound is an organic compound having polarity, and does not include a compound having an ionic bond. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. The polarity is caused by the unequal distribution of partial charges among atoms of different species in the compound. For example, the polar compounds have the formula-OH, -COOH, -SH, -NH 2 At least one of the partial structures, > NH, > N-, and the like.
Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by the methods described in the following books: organic Synthesis (Organic Syntheses, john Wiley father and son publishing company (John Wiley & Sons, inc.)), organic reactions (Organic Reactions, john Wiley father and son, inc.), "comprehensive organic Synthesis (Comprehensive Organic Synthesis, pergamon Press))," (New laboratory lecture, bolus)), and the like. The compositions are prepared by known methods from the compounds obtained in the manner described. For example, the constituent compounds are mixed and then dissolved in each other by heating.
Finally, the use of the composition will be described. The composition of the present invention has a lower limit temperature of about-10 ℃ or lower and an upper limit temperature of about 70 ℃ or higher, and therefore can be used not only as a composition having a nematic phase but also as an optically active composition by adding an optically active compound.
The dielectric constants of the aligned liquid crystal compositions in the vertical direction and the horizontal direction are different. Therefore, the dielectric anisotropy is characteristic.
The element using the liquid crystal composition generally includes, not limited to an antenna element, an element in which two substrates sandwich the liquid crystal composition in a layer form, and liquid crystal molecules are aligned (oriented) in one direction by an orientation film located at an interface thereof. In the case where no external field is applied, the liquid crystal molecules in the element are aligned in one direction by the alignment regulating force of the alignment film, and when the external field is applied, the liquid crystal molecules in the element are deviated from the alignment of the alignment film and are directed in the direction of the external field. When the external field is again removed, the alignment is restored to the original alignment state in one direction by the alignment regulating force of the alignment film. In this way, the direction of the liquid crystal molecules in the element can be controlled according to the direction or magnitude of the external field, whereby the inclination (angle) of the liquid crystal molecules in the element with respect to one direction can be controlled. Since the liquid crystal composition has dielectric anisotropy, the angle of the liquid crystal molecules in the element with respect to one direction is controlled, so that the dielectric constant of the liquid crystal composition layer in the element with respect to one direction can be controlled. For example, the dielectric constant of the liquid crystal composition layer in the element in one direction without an external field is the dielectric constant in the vertical direction of the liquid crystal composition, and by applying an external field to it perpendicularly to one direction, it can be changed to the dielectric constant in the horizontal direction of the liquid crystal composition.
As described above, the liquid crystal composition of the present application can be used as a switching element capable of reversibly controlling the dielectric constant by reversibly changing the alignment direction of liquid crystal molecules.
The angle of the liquid crystal molecules within the element can be controlled using the electric field as an external field. The voltage required to drive the liquid crystal molecules is a driving voltage. In order to control the angle of the liquid crystal molecules, it is required that the dielectric constant anisotropy of the liquid crystal composition at 25 ℃ in the frequency range of less than 1MHz is at least more than 2. In order to further reduce the driving voltage, it is necessary to further increase the dielectric anisotropy at 25℃in the frequency range of less than 1MHz, preferably 5 or more, more preferably 10 or more.
As described above, the larger the refractive index anisotropy (Δn) at visible light (for example, wavelength 589 nm), the larger the dielectric constant anisotropy (Δε) in the high-frequency region (the range from microwave to terahertz wave (about 10 THz) becomes. The liquid crystal composition containing the compound represented by the general formula (1) of the present application preferably has a refractive index anisotropy (Δn) of 0.25 or more at 25 ℃. Particularly when the material is used for high-frequency applications, Δn is preferably 0.35 or more, and more preferably 0.45 or more.
In order to perform phase difference control in the high frequency region, the dielectric anisotropy in the high frequency region is preferably 0.5 or more. In order to perform phase control more appropriately, it is necessary to increase dielectric anisotropy in a high-frequency region thereof. In order to perform sufficient phase control, the dielectric constant anisotropy is preferably 1.0 or more, and more preferably 1.2 or more.
Furthermore, the composition of the present invention can be used in an element for electromagnetic wave control in the frequency range of 1GHz to 10 THz. Examples of applications include millimeter-wave band variable phase shifters, laser radar (Light Detection and Ranging; liDAR) elements, and antennas using metamaterial technology.
Articles containing the composition can also be used for applications other than electromagnetic wave control. By reversibly changing the orientation direction of the liquid crystal molecules, the refractive index anisotropy can be controlled in addition to the dielectric constant anisotropy. Examples of applications of the control of these characteristics include a liquid crystal lens, a birefringent lens for stereoscopic image display, and the like.
Examples (example)
The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention also includes a mixture of at least two of the compositions of the examples. The characteristics of the composition were measured by the method described below.
The measuring method comprises the following steps: the characteristics were measured by the following method. Many of these methods are those described in the JEITA standard (JEITA ED-2521B) which is examined and established by the society of the electronic information technology industry (Japan Electronics and Information Technology Industries Association, hereinafter referred to as JEITA), or those modified. In a Twisted Nematic (TN) cell used for measurement, a thin film transistor (Thin Film Transistor, TFT) was not mounted.
Upper limit temperature of nematic phase (NI; °c):
the sample was placed on a hot plate of a melting point measuring apparatus including a polarization microscope, and heated at a rate of 1 ℃/min. The temperature at which a portion of the sample changed from nematic phase to isotropic liquid was measured.
Lower limit temperature of nematic phase (T C ；℃)：
The samples having nematic phase were placed in glass bottles and kept in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days, and then the liquid crystal phase was observed. For example, when the sample maintains a nematic phase at-20deg.C and changes to a crystalline or smectic phase at-30deg.C, T will be C Recorded as < -20 ℃.
Viscosity (bulk viscosity; eta; measured at 20 ℃ C.; mPa.s):
for measurement, an E-type rotary viscometer manufactured by Tokyo counter Co., ltd was used.
Refractive index anisotropy (Δn < 0.30; measured at 25 ℃):
the measurement was performed using an Abbe refractometer having a polarizing plate attached to an eyepiece using light having a wavelength of 589nm. After rubbing the surface of the main prism in one direction, the sample was dropped onto the main prism. Refractive index n ∥ The measurement is performed when the direction of polarized light is parallel to the rubbing direction. Refractive index n ⊥ The measurement was performed when the direction of polarization was perpendicular to the rubbing direction. The value of the refractive index anisotropy is according to Δn=n ∥ -n ⊥ Is calculated by the equation (d).
Refractive index anisotropy (Δn+.0.30 case; measured at 25 ℃):
samples were placed into an element comprising two glass substrates and oriented antiparallel (anti-parallel). The retardation in the thickness direction (Rth) of the element was measured using a retardation film-optical material inspection apparatus (trade name: RETS-100 manufactured by Katsuka electronic Co., ltd.) and the refractive index anisotropy (. DELTA.n) was calculated from the interval (d: cell gap) between the retardation value (Rth) and the glass substrate by the following formula. The wavelength of the light used was 589nm.
Rth＝Δn·d
Dielectric constant anisotropy (. DELTA.. Epsilon.; measured at 25 ℃ C.):
samples were placed in a TN cell having a gap (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (10V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon.) of the liquid crystal molecules in the long axis direction was measured after 2 seconds ∥ ). A sine wave (0.5V, 1 kHz) was applied to the element, and the dielectric constant (. Epsilon.) of the liquid crystal molecules in the short axis direction was measured after 2 seconds ⊥ ). The value of the dielectric anisotropy is based on Δε=ε ∥ -ε ⊥ Is calculated by the equation (d).
Dielectric anisotropy at 28GHz (measured at room temperature):
regarding dielectric anisotropy at 28GHz (Deltaε@28GHz), a variable-length waveguide with a window material attached thereto was filled with liquid crystal by the method disclosed in Applied Optics, vol.44, no.7, p1150 (2005), and the liquid crystal was held in a static magnetic field of 0.3T for 3 minutes. The waveguide was supplied with 28GHz microwave, and the amplitude ratio of the reflected wave to the incident wave was measured. The direction of the static magnetic field and the tube length of the short-circuiting device were changed to measure them, and refractive indices (n: ne, no) and loss parameters (α: αe, αo) were determined.
The calculated refractive index, loss parameter and the following relational expression are used for calculating the complex dielectric constant (ε', ε ").
ε'＝n 2 -κ 2
ε”＝2nκ
α＝2ωc/κ
Here, c is the light velocity under vacuum, ω is the angular velocity, and κ is the extinction coefficient. From ne, ε 'is calculated' ∥ From no, ε 'is calculated' ⊥ The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) is based on ε' ∥ -ε' ⊥ To calculate.
Dielectric loss tangent at 28GHz (tan. Delta.; measured at room temperature):
The dielectric loss tangent (tan. Delta. @28 GHz) at 28GHz is calculated using the complex dielectric constant (. Epsilon. '. Epsilon.') and from ε '/ε'. Since tan δ also exhibits anisotropy, a large value is described.
The compounds in the examples are represented by notations based on the definition of table 2. The numbers in brackets after the notations correspond to the numbers of the compounds. The symbol of (-) refers to other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is a weight percentage (wt%) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.
Table 2 usage marks
R-(A 1 )-Z | -
Comparative example 1 liquid Crystal composition C1
NI＝128.3℃；Δn＝0.44；Δε＝12.3
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition C1 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.04
tanδ@28GHz＝0.014
Comparative example 2 liquid Crystal composition C2
NI＝121.5℃；Δn＝0.43；Δε＝9.7
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition C2 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.06
tanδ@28GHz＝0.014
Comparative example 3 liquid Crystal composition C3
NI＝147.3℃；Δn＝0.46；Δε＝15.5
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition C3 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.08
tanδ@28GHz＝0.014
Comparative example 4 liquid Crystal composition C4
NI＝178.6℃；Δn＝0.47；Δε＝9.0
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition C4 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.08
tanδ@28GHz＝0.014
EXAMPLE 1 liquid Crystal composition M1
NI＝182.6℃；Δn＝0.49；Δε＝8.4
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M1 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.14
tanδ@28GHz＝0.013
EXAMPLE 2 liquid Crystal composition M2
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NI＝186.5℃；Δn＝0.50；Δε＝10.9
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M2 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.17
tanδ@28GHz＝0.013
EXAMPLE 3 liquid Crystal composition M3
NI＝172.4℃；Δn＝0.49；Δε＝10.7
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M3 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.12
tanδ@28GHz＝0.013
EXAMPLE 4 liquid Crystal composition M4
NI＝170.7℃；Δn＝0.49；Δε＝13.4
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M4 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.14
tanδ@28GHz＝0.012
EXAMPLE 5 liquid Crystal composition M5
NI＝184.0℃；Δn＝0.51；Δε＝10.5
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M5 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.19
tanδ@28GHz＝0.012
EXAMPLE 6 liquid Crystal composition M6
NI＝202.4℃；Δn＝0.51；Δε＝10.9
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M6 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.19
tanδ@28GHz＝0.012
EXAMPLE 7 liquid Crystal composition M7
NI＝173.6℃；Δn＝0.50；Δε＝13.1
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M7 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.18
tanδ@28GHz＝0.013
EXAMPLE 8 liquid Crystal composition M8
NI＝166.1℃；Δn＝0.52；Δε＝20.5
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M8 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.34
tanδ@28GHz＝0.011
EXAMPLE 9 liquid Crystal composition M9
NI＝91.5℃；Δn＝0.45；Δε＝15.3
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M9 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.24
tanδ@28GHz＝0.008
EXAMPLE 10 liquid Crystal composition M10
NI＝159.2℃；Δn＝0.49；Δε＝17.4
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M10 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.20
tanδ@28GHz＝0.011
EXAMPLE 11 liquid Crystal composition M11
NI＝110.2℃；Δn＝0.47；Δε＝20.5
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M11 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.22
tanδ@28GHz＝0.011
EXAMPLE 12 liquid Crystal composition M12
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NI＝112.6℃；Δn＝0.48；Δε＝22.3
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M12 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.21
tanδ@28GHz＝0.010
EXAMPLE 13 liquid Crystal composition M13
NI＝115.0℃；Δn＝0.48；Δε＝19.0
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M13 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.25
tanδ@28GHz＝0.010
EXAMPLE 14 liquid Crystal composition M14
NI＝137.4℃；Δn＝0.49；Δε＝18.8
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M14 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.22
tanδ@28GHz＝0.011
EXAMPLE 15 liquid Crystal composition M15
NI＝135.0℃；Δn＝0.49；Δε＝19.4
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M15 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.21
tanδ@28GHz＝0.010
EXAMPLE 16 liquid Crystal composition M16
NI＝111.2℃；Δn＝0.46；Δε＝17.0
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M16 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.29
tanδ@28GHz＝0.009
EXAMPLE 17 liquid Crystal composition M17
NI＝146.8℃；Δn＝0.50；Δε＝18.9
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M17 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.24
tanδ@28GHz＝0.011
EXAMPLE 18 liquid Crystal composition M18
NI＝119.3℃；Δn＝0.48；Δε＝20.4
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M18 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.28
tanδ@28GHz＝0.009
EXAMPLE 19 liquid Crystal composition M19
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NI＝123.0℃；Δn＝0.48；Δε＝18.7
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M19 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.30
tanδ@28GHz＝0.009
EXAMPLE 20 liquid Crystal composition M20
NI＝115.4℃；Δn＝0.46；Δε＝18.8
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M20 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.30
tanδ@28GHz＝0.010
EXAMPLE 21 liquid Crystal composition M21
NI＝131.5℃；Δn＝0.50；Δε＝21.0
The dielectric anisotropy (. DELTA.. Epsilon. @28 GHz) at 28GHz of the liquid crystal composition M21 and the dielectric loss tangent (tan. Delta. @28 GHz) were as follows.
Δε@28GHz＝1.29
tanδ@28GHz＝0.008
The composition obtained by changing the compound represented by the formula (3-3) in comparative example 4 to the compound represented by the formula (1-5) was example 1. Here, the refractive index anisotropy (Δn) of the composition of comparative example 4 was 0.47, and Δn of the composition of example 1 was 0.49. Accordingly, it was confirmed that compound (1) had an effect of increasing Δn.
The compositions of comparative examples 1 to 4 had a Δε@28GHz of 1.04 to 1.08 and tan δ@28GHz of 0.014. On the other hand, the compositions of examples 1 to 21 had Δε@28GHz of 1.12 to 1.34, and further, tan δ@28GHz of 0.008 to 0.013.
The values of tan δ @28GHz of examples 1 to 21 are smaller than those of comparative examples 1 to 4, respectively.
The compositions of examples 1 to 21 each contain the compound (1). The more such a compound is contained as a structural component of the composition, the greater the dielectric constant anisotropy at high frequencies becomes. On the other hand, the value of tan δ@28GHz becomes smaller.
The liquid crystal composition using the compound (1) can relatively increase Δε@28GHz while maintaining the value of tan δ@28GHz small by increasing Δn at 589nm while maintaining the basic performance as a liquid crystal composition.
Regarding the characteristics required for the liquid crystal composition, it is required that the dielectric constant anisotropy (Δε) that can be large in the frequency region used for phase control is large and the dielectric loss tangent (tan δ) that is proportional to the absorption energy of the electromagnetic wave signal of the liquid crystal composition is small. From the results of the examples and comparative examples, it was demonstrated that: the composition of the present invention has a large dielectric anisotropy (Δε@28 GHz) and a small dielectric loss tangent (tan δ@28 GHz). In general, when tan δ is small, the absorption energy of electromagnetic waves becomes low. Therefore, the liquid crystal composition using the compound represented by the formula (1) can reduce the absorption energy of the electromagnetic wave signal, and the loss of the electromagnetic wave signal can be set smaller. From the above, the following can be concluded: the liquid crystal composition of the present invention can more efficiently transmit electromagnetic wave signals.
[ Industrial applicability ]
The liquid crystal composition of the present invention satisfies at least one of the characteristics of high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, large refractive index anisotropy in a frequency region in which electromagnetic wave signal control is performed, large dielectric constant anisotropy, low dielectric loss tangent, large dielectric constant anisotropy at low frequency for reducing driving voltage, and the like, or has an appropriate balance between at least two of the characteristics. The elements containing the composition can be used for the control of electromagnetic wave signals having a frequency in the range of 1GHz to 10 THz.
Claims (18)
1. A liquid crystal composition comprising at least one compound selected from the group of compounds represented by formula (1);
in the formula (1), the components are as follows,
R 1 is hydrogen, halogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen;
ring A 1 Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, 2,6, 7-trioxabicyclo [ 2.2.2.2]Octane-1, 4-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 11 Z is as follows 12 Is a single bond, -ch=ch-, -cf=cf-, -c≡c-, or-c≡c-;
L 11 、L 12 、L 13 、L 14 、L 15 、L 16 、L 17 l and L 18 Is hydrogen, halogen, alkyl of 1 to 3 carbon atoms or cycloalkyl of 3 to 5 carbon atoms;
Y 11 hydrogen, halogen or alkyl of 1 to 3 carbon atoms;
Y 12 hydrogen or halogen;
L 14 、L 15 、L 16 、L 17 、L 18 y and Y 11 At least one of which is an alkyl group having 1 to 3 carbon atoms;
a and c are 0 or 1, b is 0, 1 or 2, the sum of a, b and c is 1 or more and 3 or less, a is 0, b is 1, c is 0, Z 11 Is a single bond, L 11 、L 12 、L 13 、L 17 、L 18 Y and Y 12 When hydrogen is Y 11 And not methyl.
2. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of compounds represented by formula (2) and formula (3);
in the formula (2), the amino acid sequence of the compound,
R 2 is hydrogen, halogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-, in which groups at least one hydrogen may be substituted by halogen;
ring A 2 Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, 2,6, 7-trioxabicyclo [ 2.2.2.2]Octane-1, 4-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 21 Z is as follows 22 Is a single bond, -C.ident.C-or-C.ident.C-;
L 21 、L 22 、L 23 l and L 24 Is hydrogen, halogen, alkyl of 1 to 3 carbon atoms or cycloalkyl of 3 to 5 carbon atoms;
X 2 is-C.ident.C-CF 3 or-C.ident.C-C.ident.N;
Y 21 y and Y 22 Hydrogen, halogen or alkyl of 1 to 3 carbon atoms;
d is 0 or 1, e is 0, 1, 2 or 3, and the sum of d and e is 1 or more and 3 or less;
in the formula (3), the amino acid sequence of the compound,
R 31 is hydrogen or C1-12 alkyl, at least one of which is-CH 2 -may be substituted by-O-or-S-, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
R 32 is R 31 Or-n=c=s;
ring A 3 Is pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl or pyridine-2, 5-diyl, at least one hydrogen in these rings being optionally substituted by halogen or alkyl having 1 to 3 carbon atoms;
Z 31 z is as follows 32 Is a single bond, -C.ident.C-or-C.ident.C-;
L 31 、L 32 、L 33 、L 34 、L 35 、L 36 、L 37 、L 38 l and L 39 Hydrogen or halogen;
f is 0 or 1, g is 0, 1 or 2, and the sum of f and g is 0 or more and 2 or less.
3. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of compounds represented by the formulas (1-1) to (1-6) as the compound represented by the formula (1);
in the formulae (1-1) to (1-6),
R 1 ' is an alkyl group of 1 to 12 carbon atoms, whichOf alkyl groups, at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
L 11 '、L 12 '、L 13 '、L 14 '、L 15 '、L 16 '、L 17 ' and L 18 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 11 ' is hydrogen, fluorine, chlorine, methyl or ethyl;
Y 12 ' is hydrogen, fluorine or chlorine;
L 14 '、L 15 '、L 16 '、L 17 '、L 18 ' and Y 11 At least one of' is methyl or ethyl;
wherein in formula (1-1), L is 11 '、L 12 '、L 13 '、L 17 '、L 18 ' and Y 12 When' is hydrogen, Y 11 ' not methyl.
4. The liquid crystal composition according to claim 1 or 3, wherein the proportion of the compound represented by formula (1) is in the range of 5 to 80% by weight based on the weight of the liquid crystal composition.
5. The liquid crystal composition according to claim 2, comprising at least one compound selected from the group of compounds represented by the formulas (2-1) to (2-8) as the compound represented by the formula (2);
in the formulae (2-1) to (2-8),
R 2 ' is an alkyl group of 1 to 12 carbon atoms, at least one of which is- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-;
L 21 '、L 22 '、L 23 ' and L 24 ' is hydrogen, fluorine, chlorine, methyl, ethyl or cyclopropyl;
Y 21 ' and Y 22 ' is hydrogen, fluorine, chlorine, methylA radical or an ethyl radical.
6. The liquid crystal composition according to claim 2 or 5, wherein the proportion of the compound represented by formula (2) is in the range of 5 to 50% by weight based on the weight of the liquid crystal composition.
7. The liquid crystal composition according to claim 2, comprising at least one compound selected from the group of compounds represented by the formulas (3-1) to (3-6) as the compound represented by the formula (3);
In the formulae (3-1) to (3-6),
R 31 ' is an alkyl group of 1 to 12 carbon atoms, of which at least one-CH 2 -optionally substituted by-O-at least one- (CH) 2 ) 2 -may be substituted by-ch=ch-or-c≡c-; r is R 32 ' is R 31 ' or-n=c=s; l (L) 32 '、L 34 '、L 35 '、L 36 '、L 37 '、L 38 ' and L 39 ' is hydrogen, fluorine or chlorine;
in the formula (3-6), in L 35 '、L 36 '、L 38 ' and L 39 When' is hydrogen, R 32 ' is-n=c=s.
8. The liquid crystal composition according to claim 2 or 7, wherein the proportion of the compound represented by formula (3) is in the range of 5 to 50% by weight based on the weight of the liquid crystal composition.
9. The liquid crystal composition according to claim 1, wherein the refractive index anisotropy at 25 ℃ at a wavelength of 589nm is 0.35 or more.
10. The liquid crystal composition according to claim 1, wherein the dielectric anisotropy of the dielectric constant at 25 ℃ in the frequency range of less than 1MHz is 5 or more.
11. The liquid crystal composition according to claim 1, wherein the dielectric constant anisotropy of 25 ℃ at least one frequency of 1GHz to 10THz is in the range of 0.50 to 3.0.
12. The liquid crystal composition according to claim 1, comprising an optically active compound.
13. The liquid crystal composition according to claim 1, comprising a polymerizable compound.
14. The liquid crystal composition according to claim 1, which contains at least one of an antioxidant, an ultraviolet absorber, an antistatic agent, and a dichroic dye.
15. A liquid crystal cell comprising the liquid crystal composition according to claim 1, wherein the liquid crystal cell is used for switching such that the switching of the dielectric constant can be controlled reversibly by changing the orientation direction of liquid crystal molecules reversibly.
16. A liquid crystal cell comprising the liquid crystal composition according to claim 1 and used for electromagnetic wave control in a frequency range of 1GHz to 10 THz.
17. A liquid crystal lens comprising the liquid crystal composition according to claim 1.
18. A birefringent lens for stereoscopic image display comprising the liquid crystal composition according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-023427 | 2022-02-18 | ||
| JP2023000542A JP2023121129A (en) | 2022-02-18 | 2023-01-05 | Liquid crystal composition and liquid crystal device |
| JP2023-000542 | 2023-01-05 |
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| Publication Number | Publication Date |
|---|---|
| CN116622384A true CN116622384A (en) | 2023-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310053372.XA Pending CN116622384A (en) | 2022-02-18 | 2023-02-03 | Liquid crystal composition, liquid crystal element liquid crystal lens, and birefringent lens for stereoscopic image display |
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| Country | Link |
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| CN (1) | CN116622384A (en) |
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