Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
  • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
  • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/06—Non-steroidal liquid crystal compounds
  • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
  • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
  • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
  • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering

Definitions

• the present invention relates to a liquid crystal composition and liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices, and antennas that use the same.
• Liquid crystals are widely used in displays, but as a new application, liquid crystal antennas that transmit and receive radio waves between a mobile object such as a car and a communication satellite are attracting attention.
• satellite communication uses parabolic antennas, but when used in a mobile object such as a car, the parabolic antenna must be pointed toward the satellite at any time, which requires a large movable part.
• liquid crystal antennas can change the direction of radio waves by moving the liquid crystal inside the panel, so there is no need to move the antenna itself and the shape of the antenna can be made flat.
• low-orbit satellite constellations using a large number of low-orbit satellites are being studied.
• Liquid crystal antennas which can easily change the direction of radio waves, are useful for tracking low-orbit satellites that appear to be constantly moving from the ground.
• automatic driving of automobiles and the like requires downloading a large amount of data of high-precision 3D map information.
• an antenna using liquid crystal is incorporated into an automobile, it becomes possible to download a large amount of data from a communication satellite without any mechanical moving parts.
• the frequency band used in satellite communication is about 13 GHz, which is significantly different from the frequencies used for liquid crystal displays up to now. Therefore, the required physical properties of the liquid crystal are also significantly different, and the ⁇ n required for the liquid crystal for the antenna is, for example, about 0.4, and the operating temperature range is, for example, from -20 to 120°C.
• Infrared laser image recognition and distance measuring devices using liquid crystals are also attracting attention as sensors for automatic driving of moving objects such as automobiles.
• the ⁇ n required for liquid crystals for this purpose is, for example, 0.3 to 0.6, and the operating temperature range is, for example, 10 to 100°C.
• many liquid crystal compounds constituting a liquid crystal composition exhibiting a high ⁇ n of 0.2 or more have low compatibility, and therefore it is also important to select a liquid crystal compound having high compatibility.
• Patent Document 1 can be mentioned as a technique for liquid crystal for antennas.
• Non-Patent Document 1 proposes the use of liquid crystal materials as components of high frequency devices.
• Liquid crystal compositions with large ⁇ n tend to have high Tni because they use many compounds with extended ⁇ -conjugation, and when such liquid crystal compositions are dissolved, they need to be heated to a high temperature, which may cause the liquid crystal composition to deteriorate due to heat. There is also a concern about storage stability, and the liquid crystal composition is likely to solidify even at room temperature.
• An object of the present invention is to provide a liquid crystal composition having a large ⁇ n but not an excessively high Tni , i.e., an excellent balance between ⁇ n and Tni , and having good storage stability at room temperature, and to provide a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna each using the same.
• the white dot represents a bond to R iii1 .
• the black dot represents a bond to -C ⁇ C-.
• S iii1 represents any one of a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms; one or more hydrogen atoms in the alkyl or alkoxy group may each independently be substituted with a halogen atom; When there are multiple S iii1 , they may be the same or different.
• R o1 , R o2 , R o3 , R o4 and R o5 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms;
• One or more -CH 2 - in the alkyl group may each independently be replaced by -O-;
• One or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom.
• a o1 , A o2 , A o3 , A o4 and A o5 each independently represent the following general formulae (A o1/2/3/4/5 -1) to (A o1/2/3/4/5 -5)
• a black dot represents a bond to a -C ⁇ C- or benzene ring structure.
• S o1/2/3/4/5 each represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; one or more hydrogen atoms in the alkyl or alkoxy group may each independently be substituted with a halogen atom; When there are a plurality of S o1/2/3/4/5 , they may be the same or different.
• liquid crystal composition according to item 1 comprising one or more compounds selected from the group consisting of compounds represented by the following formula:
• Compounds represented by the general formulas (i) and (ii) include the following structural formulas (i-5), (i-6), (ii-5), (ii-6) and (ii-7):
• liquid crystal composition according to item 1 or 2 comprising one or more compounds selected from the group consisting of compounds represented by the following formula:
• Item 4 The liquid crystal composition according to any one of items 1 to 3, having a ⁇ n of 0.40 or more at 25° C. and 589 nm and/or a liquid crystal phase upper limit temperature (T ni ) of 170° C. or less.
• Item 5 A liquid crystal display device using the liquid crystal composition according to any one of items 1 to 4.
• Item 6 The liquid crystal display element according to item 5, which is driven by an active matrix method or a passive matrix method.
• Item 7 A liquid crystal display element that reversibly switches the dielectric constant by reversibly changing the alignment direction of the liquid crystal molecules of the liquid crystal composition according to any one of items 1 to 4.
• Item 8 A sensor using the liquid crystal composition according to any one of items 1 to 4.
• Item 9 A liquid crystal lens using the liquid crystal composition according to any one of items 1 to 4.
• Item 10 An optical communication device using the liquid crystal composition according to any one of items 1 to 4.
• Item 11 An antenna using the liquid crystal composition according to any one of items 1 to 4.
• Item 12 The antenna according to item 11, a first substrate having a plurality of slots; a second substrate facing the first substrate and having a power supply unit provided thereon; a first dielectric layer provided between the first substrate and the second substrate; A plurality of patch electrodes arranged corresponding to the plurality of slots; a third substrate on which the patch electrode is provided; a liquid crystal layer provided between the first substrate and the third substrate; Item 5.
• a liquid crystal composition containing one or more compounds selected from the group consisting of compounds represented by general formulas (i) and (ii) having three benzene ring structures, and -C ⁇ C- as a linking group between the ring structures, and an isothiocyanate group (-NCS), and one or more compounds represented by general formula (iii) having -C ⁇ C- as a linking group between the ring structures, and an isothiocyanate group (-NCS), the contents of the compounds represented by general formulas (i) and (ii) and the compound represented by general formula (iii) being predetermined, a liquid crystal composition having an excellent balance between ⁇ n and Tni and storage stability at room temperature can be provided, and the liquid crystal composition is useful for liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices, and antennas.
• the liquid crystal composition according to the present invention contains one or more compounds selected from the group consisting of compounds represented by the following general formulas (i) and (ii) having three benzene ring structures and a -C ⁇ C- group and an isothiocyanate group (-NCS) as a linking group between the ring structures, in an amount of 25% by mass or more relative to 100% by mass of the liquid crystal composition:
• R i1 and R ii1 each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• the alkyl group having 1 to 20 carbon atoms may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain alkyl group.
• the alkyl group having 1 to 20 carbon atoms preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• One or more -CH 2 - in the alkyl group may each independently be replaced by -O-.
• one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
• R i1 and R ii1 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one —CH 2 — in the alkyl group with —O—.
• the alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group.
• the alkoxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• the alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group.
• the alkenyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R i1 and R ii1 can represent an alkenyloxy group having 2 to 19 carbon atoms in which one —CH 2 — in the alkyl group is replaced with —O— and one or more —CH 2 —CH 2 — are replaced with —CH ⁇ CH—.
• the alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group.
• the alkenyloxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R i1 and R ii1 can represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with halogen atoms.
• the halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group.
• the halogenated alkyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• R i1 and R ii1 can represent a halogenated alkoxy group having 1 to 19 carbon atoms in which one -CH 2 - in the alkyl group is replaced with -O- and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms.
• the halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group.
• the halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• Specific examples of the alkyl group having 1 to 20 carbon atoms in R i1 and R ii1 include groups represented by the formulae (R i1/ii1 -1) to (R i1/ii1 -31).
• R i1/ii1 -1) to (R i1/ii1 -31) the black dots represent bonds to the benzene ring structure.
• R i1 and R ii1 are preferably linear alkyl groups having 2 to 6 carbon atoms.
• R i1 and R ii1 are preferably linear alkenyl groups having 2 to 6 carbon atoms.
• Examples of compounds represented by general formula (i) include compounds represented by the following structural formulas (i-1) to (i-6), and from the standpoint of solubility and low viscosity, compounds represented by structural formulas (i-5) and (i-6) are preferred.
• the compounds represented by general formula (i) or structural formulas (i-1) to (i-6) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the lower limit of the total content of the compounds represented by general formula (i) or structural formulas (i-1) to (i-6) in 100% by mass of the liquid crystal composition is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more, more preferably 30% by mass or more, and more preferably 35% by mass or more.
• the upper limit of the total content of the compounds represented by general formula (ii) or structural formulas (ii-1) to (ii-7) in 100% by mass of the liquid crystal composition is preferably 50% by mass or less, preferably 45% by mass or less, preferably 40% by mass or less, preferably 35% by mass or less, preferably 30% by mass or less, preferably 25% by mass or less, preferably 20% by mass or less, and preferably 15% by mass or less.
• the total content of the compounds (including subordinate concepts) represented by general formulas (i) and (ii) in 100% by mass of the liquid crystal composition is 25% by mass or more, preferably 25 to 50% by mass, and more preferably 30 to 45% by mass. If the content is less than 25% by mass, it may not be possible to ensure a large ⁇ n value for the liquid crystal composition.
• R i1 and Y i1 have the same meanings as R i1 and Y i1 in the general formula (i).
• a compound represented by general formula (s-2) can be obtained by reacting a compound represented by general formula (s-1) with 1-bromo-4-iodobenzene.
• the reaction method includes, for example, Suzuki coupling reaction using a palladium catalyst and a base.
• palladium catalysts include [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride, palladium(II) acetate, dichlorobis[di-tert-butyl(p-dimethylaminophenyl)phosphino]palladium(II), dichlorobis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium(0), and the like.
• the base include potassium carbonate, sodium carbonate, potassium phosphate, and the like.
• the reaction method includes, for example, Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base.
• a ligand such as triphenylphosphine or 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl may be added.
• a specific example of the copper catalyst is copper(I) iodide.
• a specific example of the base is triethylamine.
• the compound represented by general formula (s-4) can be reacted with an NCS agent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, and 1,1′-thiocarbonyl-di-2(1H)pyridone to obtain the target compound represented by general formula (s-5).
• an NCS agent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, and 1,1′-thiocarbonyl-di-2(1H)pyridone
• the reaction method includes, for example, Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base. Specific examples of the palladium catalyst, copper catalyst and base include those mentioned above.
• the compound represented by general formula (s-9) can be reacted with an NCS agent such as thiophosgene, disulfuric acid, 1,1-thiocarbonyldiimidazole, and 1,1′-thiocarbonyl-di-2(1H)pyridone to obtain the target compound represented by general formula (s-10).
• the liquid crystal composition according to the present invention contains one or more compounds represented by general formula (iii) having -C ⁇ C- as a linking group between ring structures and an isothiocyanate group (-NCS) in an amount of 20% by mass or more based on 100% by mass of the liquid crystal composition.
• -NCS isothiocyanate group
• R iii1 represents an alkyl group having 1 to 20 carbon atoms.
• the alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group.
• the alkyl group preferably has 2 to 10, preferably 2 to 6 carbon atoms.
• One or more -CH 2 - in the alkyl group may each independently be substituted with -O-.
• one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R iii1 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one --CH 2 -- in the alkyl group with --O--.
• the alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group.
• the alkoxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• the alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group.
• the alkenyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R iii1 can represent an alkenyloxy group having 2 to 19 carbon atoms in which one —CH 2 — in the alkyl group is replaced with —O— and one or more —CH 2 —CH 2 — are replaced with —CH ⁇ CH—.
• the alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group.
• the alkenyloxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R iii1 can represent a halogenated alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms in the alkyl group have been substituted with halogen atoms.
• the halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group.
• the halogenated alkyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• R iii1 can represent a halogenated alkoxy group having 1 to 19 carbon atoms, in which one -CH 2 - in the alkyl group is replaced with -O-, and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms.
• the halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group.
• the halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• Specific examples of the alkyl group having 1 to 20 carbon atoms for R iii1 include groups represented by the formulae (R iii1 -1) to (R iii1 -30).
• R iii1 is preferably a linear alkyl group having 1 to 8 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms.
• a iii1 represents a group selected from the group consisting of groups represented by the following formulae (A iii1 -1) to (A iii1 -5).
• a white dot represents a bond to R iii1
• a black dot represents a bond to --C ⁇ C--.
• S iii1 represents any one of a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group having 1 to 6 carbon atoms may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain alkyl group.
• the alkoxy group having 1 to 6 carbon atoms is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group.
• One or more hydrogen atoms in the alkyl group or alkoxy group may each independently be substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms in S iii1 include groups represented by formulas (S iii1 -1) to (S iii1 -16).
• the black dots represent bonds to the benzene ring structure.
• S iii1 -1) to (S iii1 -16) the black dots represent bonds to the benzene ring structure.
• S iii1 there are a plurality of S iii1 , they may be the same or different.
• general formula (A iii1 -2) preferably represents any one of the following formulae (A iii1 -2-1) to (A iii1 -2-4).
• a white dot represents a bond to R iii1
• a black dot represents a bond to -C ⁇ C-.
• general formula (A iii1 -3) preferably represents any one of the following formulae (A iii1 -3-1) to (A iii1 -3-4).
• a white dot represents a bond to R iii1
• a black dot represents a bond to -C ⁇ C-.
• general formula (A iii1 -4) preferably represents any one of the following formulae (A iii1 -4-1) to (A iii1 -4-4).
• a white dot represents a bond to R iii1
• a black dot represents a bond to -C ⁇ C-.
• general formula (A iii1 -5) preferably represents any one of the following formulae (A iii1 -5-1) to (A iii1 -5-4).
• a white dot represents a bond to R iii1
• a black dot represents a bond to -C ⁇ C-.
• Y iii1 represents a hydrogen atom or a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
• Y iii1 is preferably a fluorine atom.
• the compound represented by general formula (iii) is preferably a compound represented by the following general formula (iii-1) from the viewpoint of low viscosity.
• R iii1 has the same meaning as R iii1 in formula (iii) above.
• Specific examples of the compound represented by general formula (iii-1) include compounds represented by the following structural formulas (iii-1.1) to (iii-1.7), and the like. From the viewpoint of ⁇ n, the compounds represented by structural formulas (iii-1.5) and (iii-1.6) are preferred, and from the viewpoints of solubility and low viscosity, the compounds represented by structural formulas (iii-1.1) and (iii-i-8) are preferred.
• the compounds represented by general formula (iii), general formula (iii-1) or structural formulas (iii-1.1) to (iii-1.8) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the lower limit of the total content of the compounds represented by general formula (iii), general formula (iii-1) or structural formulas (iii-1.1) to (iii-1.8) in 100% by mass of the liquid crystal composition is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more.
• the upper limit of the total content of the compounds represented by general formula (iii), general formula (iii-1) or structural formulas (iii-1.1) to (iii-1.8) in 100% by mass of the liquid crystal composition is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less.
• the total content of the compounds represented by general formula (iii) (including subordinate concepts) in 100% by mass of the liquid crystal composition is 20% by mass or more, preferably 20 to 55% by mass, more preferably 25 to 55% by mass, and even more preferably 35 to 50% by mass. If it is less than 20 mass %, the content of other compounds increases, and T ni may become too high.
• the compound represented by general formula (iii) (including its sub-concepts) can be synthesized using known synthesis methods.
• the liquid crystal composition according to the present invention may contain one or more compounds selected from the group consisting of compounds represented by the following general formulas (o-1) to (o-5) in terms of ⁇ n and/or ⁇ r :
• R o1 , R o2 , R o3 , R o4 and R o5 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• the alkyl group may be a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group.
• the alkyl group preferably has 2 to 10, preferably 2 to 6 carbon atoms.
• One or more -CH 2 - in the alkyl group may each independently be substituted with -O-.
• one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the oxygen atoms are not directly bonded to each other.
• R o1 , R o2 , R o3 , R o4 and R o5 can represent an alkoxy group having 1 to 19 carbon atoms by replacing one —CH 2 — in the alkyl group with —O—.
• the alkoxy group is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group.
• the alkoxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R o1 , R o2 , R o3 , R o4 and R o5 can each represent an alkenyl group having 2 to 20 carbon atoms by replacing one or more -CH 2 -CH 2 - in the alkyl group with -CH ⁇ CH-.
• the alkenyl group is a linear, branched or cyclic alkenyl group, and is preferably a linear alkenyl group.
• the alkenyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R o1 , R o2 , R o3 , R o4 and R o5 can represent an alkenyloxy group having 2 to 19 carbon atoms in which one -CH 2 - in the alkyl group is replaced with -O- and one or more -CH 2 -CH 2 - are replaced with -CH ⁇ CH-.
• the alkenyloxy group is a linear, branched or cyclic alkenyloxy group, and is preferably a linear alkenyloxy group.
• the alkenyloxy group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
• R o1 , R o2 , R o3 , R o4 and R o5 can each represent a halogenated alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms in the alkyl group have been substituted with halogen atoms.
• the halogenated alkyl group may be linear, branched or cyclic, and is preferably a linear halogenated alkyl group.
• the halogenated alkyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• R o1 , R o2 , R o3 , R o4 and R o5 can each represent a halogenated alkoxy group having 1 to 19 carbon atoms in which one -CH 2 - in the alkyl group is replaced with -O- and one or more hydrogen atoms in the alkyl group are replaced with halogen atoms.
• the halogenated alkoxy group may be a linear, branched or cyclic halogenated alkoxy group, and is preferably a linear halogenated alkoxy group.
• the halogenated alkoxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
• R o1 , R o2 , R o3 , R o4 and R o5 include groups represented by the formulas (R o1/2/3/4/5 -1) to (R o1/2/3/4/5 -31).
• R o1 , R o2 , R o3 , R o4 and R o5 are preferably a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 2 to 6 carbon atoms.
• a o1 , A o2 , A o3 , A o4 and A o5 each independently represent a group selected from the group consisting of groups represented by the following general formulas (A o1/2/3/4/5 -1) to (A o1/2/3/4/5 -5).
• S o1/2/3/4/5 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group having 1 to 6 carbon atoms may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain alkyl group.
• the alkoxy group having 1 to 6 carbon atoms is a linear, branched or cyclic alkoxy group, and is preferably a linear alkoxy group.
• One or more hydrogen atoms in the alkyl group or alkoxy group may each independently be substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Specific examples of the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms (including substituted groups) in S o1/2/3/4/5 include groups represented by the formulas (S o1/2/3/4/5 -1) to (S o1/2/3/4/5 -16).
• the general formula (A o1/2/3/4/5 -2) preferably represents any one of the following formulae (A o1/2/3/4/5 -2-1) to (A o1/2/3/4/5 -2-4).
• the general formula (A o1/2/3/4/5 -3) preferably represents any one of the following formulae (A o1/2/3/4/5 -3-1) to (A o1/2/3/4/5 -3-4).
• the general formula (A o1/2/3/4/5 -4) preferably represents any one of the following formulae (A o1/2/3/4/5 -4-1) to (A o1/2/3/4/5 -4-4).
• the general formula (A o1/2/3/4/5 -5) preferably represents any one of the following formulae (A o1/2/3/4/5 -5-1) to (A o1/2/3/4/5 -5-4).
• white dots represent bonds to a cyclohexane ring structure
• -CH CH- or -C ⁇ C-
• black dots represent bonds to a -C ⁇ C- or benzene ring structure.
• Y o1 , Y o2 , Y o3 , Y o4 and Y o5 each independently represent a hydrogen atom or a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
• Y o1 , Y o2 , Y o3 , Y o4 and Y o5 are preferably fluorine atoms.
• the compound represented by general formula (o-1) is preferably a compound represented by the following general formula (o-1-1):
• R o1 has the same meaning as R o1 in formula (o-1) above.
• Specific examples of the compound represented by general formula (o-1-1) include compounds represented by the following structural formulas (o-1-1.1) to (o-1-1.7).
• the compound represented by general formula (o-2) is preferably a compound represented by the following general formula (o-2-1).
• R o2 has the same meaning as R o2 in general formula (o-2) above.
• Specific examples of the compound represented by general formula (o-2-1) include compounds represented by the following structural formulas (o-2-1.1) to (o-2-1.7).
• the compound represented by general formula (o-3) is preferably a compound represented by the following general formula (o-3-1).
• R o3 has the same meaning as R o3 in general formula (o-3) above.
• Specific examples of the compound represented by general formula (o-3-1) include compounds represented by the following structural formulas (o-3-1.1) to (o-3-1.7).
• the compound represented by general formula (o-4) is preferably a compound represented by the following general formula (o-4-1).
• R o4 has the same meaning as R o4 in general formula (o-4) above.
• Specific examples of the compound represented by general formula (o-4-1) include compounds represented by the following structural formulas (o-4-1.1) to (o-4-1.7).
• the compound represented by general formula (o-5) is preferably a compound represented by the following general formula (o-5-1):
• R o5 has the same meaning as R o5 in general formula (o-5) above.
• Specific examples of the compound represented by general formula (o-5-1) include compounds represented by the following structural formulas (o-5-1.1) to (o-5-1.7).
• the compounds represented by general formula (o-1), general formula (o-1-1) or structural formulas (o-1-1.1) to (o-1-1.7) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the total content of the compounds represented by general formula (o-1), general formula (o-1-1) or structural formulas (o-1-1.1) to (o-1-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and even more preferably 10 to 50% by mass.
• the compounds represented by general formula (o-2), general formula (o-2-1) or structural formulas (o-2-1.1) to (o-2-1.7) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the total content of the compounds represented by general formula (o-2), general formula (o-2-1) or structural formulas (o-2-1.1) to (o-2-1.7) in 100% by mass of the liquid crystal composition is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass.
• the total content of the compounds represented by general formula (o-3), general formula (o-3-1) or structural formulas (o-3-1.1) to (o-3-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 3 to 7% by mass.
• the compounds represented by general formula (o-4), general formula (o-4-1) or structural formulas (o-4-1.1) to (o-4-1.7) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the total content of the compounds represented by general formula (o-4), general formula (o-4-1) or structural formulas (o-4-1.1) to (o-4-1.7) in 100% by mass of the liquid crystal composition is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 3 to 7% by mass.
• the compounds represented by general formula (o-5), general formula (o-5-1) or structural formulas (o-5-1.1) to (o-5-1.7) used in the liquid crystal composition are one or more types, preferably 1 to 10 types, preferably 1 to 5 types, and preferably 1 to 3 types.
• the total content of the compounds represented by general formula (o-5), general formula (o-5-1) or structural formulas (o-5-1.1) to (o-5-1.7) in 100% by mass of the liquid crystal composition is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 25% by mass.
• the compounds represented by general formulas (o-1) to (o-5) can be synthesized using known synthesis methods.
• the liquid crystal composition according to the present invention can be produced, for example, by mixing a compound selected from the group consisting of the compounds represented by the above-mentioned general formula (i) and the compounds represented by the general formula (ii), the compound represented by the general formula (iii), and, if necessary, the above-mentioned other compounds and additives.
• Additives include stabilizers, dye compounds, polymerizable compounds, azotolane compounds, isothiocyanate compounds (NCS compounds), etc.
• the stabilizer examples include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, ⁇ -naphthylamines, ⁇ -naphthols, nitroso compounds, hindered phenols, and hindered amines.
• the hindered phenols include hindered phenol-based antioxidants represented by the following structural formulas (XX-1) to (XX-3).
• Hindered amines include hindered amine light stabilizers represented by the following structural formulas (YY-1) to (YY-2).
• the type of stabilizer used in the liquid crystal composition is one or more, preferably 1 to 10 types, preferably 1 to 8 types, preferably 1 to 6 types, preferably 1 to 4 types, preferably 1 to 2 types.
• the total content of the stabilizer in 100% by mass of the liquid crystal composition is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.50% by mass, and even more preferably 0.03 to 0.35% by mass.
• the liquid crystal phase upper limit temperature (T ni ) is the temperature at which the liquid crystal composition undergoes phase transition from a nematic phase to an isotropic phase.
• T ni is measured by preparing a preparation in which the liquid crystal composition is sandwiched between a slide glass and a cover glass, and observing the preparation under a polarizing microscope while heating the preparation on a hot stage. It can also be measured by differential scanning calorimetry (DSC). The unit used is "°C".
• Tni the higher the Tni, the more the nematic phase can be maintained even at high temperatures, and the wider the operating temperature range can be, but since the liquid crystal is heated and melted during production, if the temperature is too high, it is not preferable because the liquid crystal is thermally deteriorated and high-temperature melting equipment is required. Also, the higher the Tni , the poorer the storage stability at low temperatures tends to be, so it is difficult to achieve both high Tni and storage stability.
• the upper limit temperature (T ni ) of the liquid crystal phase of the liquid crystal composition according to the present invention can be appropriately set depending on whether the liquid crystal display element is used indoors, in a car, or outdoors where the external temperature can be controlled, but from the viewpoint of the driving temperature range, it is preferably 170° C. or lower, more preferably 110 to 170° C., and even more preferably 115 to 165° C.
• the liquid crystal phase lower limit temperature (T ⁇ n ) of the liquid crystal composition according to the present invention is preferably 10°C or lower, more preferably -70 to 0°C, and even more preferably -40 to -5°C, from the viewpoint of driving temperature.
• ⁇ n (refractive index anisotropy) correlates with ⁇ n in the near-infrared region used in the optical sensor described below.
• ⁇ n at 25° C. and 589 nm is determined from the difference ( ne ⁇ no ) between the extraordinary refractive index ( ne ) and the ordinary refractive index ( no ) of the liquid crystal composition using an Abbe refractometer.
• ⁇ n can be obtained from a phase difference measuring device.
• a liquid crystal composition is injected into a glass cell having a cell gap (d) of about 3.0 ⁇ m and a polyimide alignment film that has been subjected to anti-parallel rubbing treatment, and the in-plane Re is measured with a retardation film/optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The measurement is performed under conditions of a temperature of 25° C. and 589 nm, and has no unit. From the viewpoint of the phase modulation power of light of the wavelength, ⁇ n of the liquid crystal composition according to the present invention at 25° C. and 589 nm is preferably 0.40 or more, more preferably 0.40 to 0.55, more preferably 0.41 to 0.50, and even more preferably 0.43 to 0.48.
• the rotational viscosity ( ⁇ 1 ) is the viscosity coefficient related to the rotation of the liquid crystal molecules.
• ⁇ 1 can be measured by filling the liquid crystal composition into a glass cell having a cell gap of about 10 ⁇ m, applying a voltage of 50 V, and using LCM-2 (manufactured by Toyo Corporation).
• LCM-2 manufactured by Toyo Corporation.
• a horizontally aligned cell is used, whereas in the case of a liquid crystal composition having a negative dielectric anisotropy, a vertically aligned cell is used.
• the measurement is carried out at a temperature of 25° C., and the unit is mPa ⁇ s.
• the rotational viscosity ( ⁇ 1 ) of the liquid crystal composition according to the present invention at 25° C. is preferably from 150 to 1200 mPa ⁇ s, more preferably from 200 to 900 mPa ⁇ s, and even more preferably from 250 to 700 mPa ⁇ s, from the viewpoint of response speed.
• the dielectric anisotropy ⁇ r and the average value tan ⁇ iso of the dielectric tangent at 10 GHz were measured as representative characteristics in the high frequency range.
• ⁇ r is the dielectric constant
• tan ⁇ is the dielectric tangent
• the subscript " ⁇ ” indicates the component parallel to the alignment direction of the liquid crystal
• ⁇ indicates the component perpendicular to the alignment direction of the liquid crystal.
• ⁇ r and tan ⁇ iso can be measured by the following method.
• a liquid crystal composition is introduced into a capillary tube made of polytetrafluoroethylene (PTFE).
• the capillary used here has an inner radius of 0.80 mm and an outer radius of 0.835 mm, with an effective length of 4.0 cm.
• the capillary tube containing the liquid crystal composition is introduced into the center of a cavity resonator (manufactured by EM Lab Co., Ltd.) having a resonance frequency of 10 GHz.
• the cavity has an outer diameter of 30 mm and a width of 26 mm.
• a signal is then input, and the result of the output signal is recorded using a network analyzer (manufactured by Keysight Technologies, Inc.).
• the dielectric constant ( ⁇ r ) and loss angle ( ⁇ ) at 10 GHz are determined using the difference between the resonance frequency of a PTFE capillary tube containing no liquid crystal composition and the resonance frequency of a PTFE capillary tube containing a liquid crystal composition.
• the tangent of the obtained ⁇ is the dielectric tangent (tan ⁇ ).
• the resonance frequency and the like using a PTFE capillary tube filled with a liquid crystal composition are determined as values of characteristic components perpendicular to and parallel to the alignment direction of the liquid crystal molecules by controlling the alignment of the liquid crystal molecules.
• the magnetic field of a permanent magnet or electromagnet is used to align the liquid crystal molecules in the vertical direction (perpendicular to the effective length direction) or in the parallel direction (parallel to the effective length direction) of the PTFE capillary tube.
• the magnetic field has, for example, a pole-to-pole distance of 45 mm and a magnetic field strength of 0.23 Tesla near the center.
• the PTFE capillary tube containing the liquid crystal composition is rotated parallel or perpendicular to the magnetic field to obtain the desired characteristic components. The measurements were carried out at a temperature of 25° C., and both ⁇ r and tan ⁇ iso have no unit.
• the ⁇ r at 25° C. of the liquid crystal composition according to the present invention is preferably larger, and from the viewpoint of phase modulation power in the GHz band, it is preferably 0.90 or more, more preferably 0.90 to 1.50, more preferably 0.95 to 1.40, and even more preferably 1.00 to 1.35.
• the tan ⁇ iso at 25° C.
• the liquid crystal composition according to the present invention is preferably smaller, and from the viewpoint of loss in the GHz band, it is preferably 0.025 or less, more preferably 0.001 to 0.025, more preferably 0.003 to 0.020, more preferably 0.005 to 0.017, more preferably 0.007 to 0.015, more preferably 0.008 to 0.013, and more preferably 0.009 to 0.012.
• liquid crystal display elements Liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas
• a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna using the liquid crystal composition according to the present invention will be described below.
• the liquid crystal display element according to the present invention is characterized by using the above-mentioned liquid crystal composition, and is preferably driven by an active matrix system or a passive matrix system.
• the liquid crystal display element according to the present invention is preferably a liquid crystal display element in which the dielectric constant is reversibly switched by reversibly changing the alignment direction of the liquid crystal molecules of the above-mentioned liquid crystal composition.
• the sensor according to the present invention is characterized by using the above-mentioned liquid crystal composition, and examples of its embodiments include a distance measuring sensor that uses electromagnetic waves, visible light or infrared light, an infrared sensor that uses a change in temperature, a temperature sensor that uses a change in the wavelength of reflected light due to a change in the pitch of a cholesteric liquid crystal, a pressure sensor that uses a change in the wavelength of reflected light, an ultraviolet sensor that uses a change in the wavelength of reflected light due to a change in composition, an electrical sensor that uses a temperature change due to a voltage or current, a radiation sensor that uses a temperature change accompanying the track of a radiation particle, an ultrasonic sensor that uses a change in the arrangement of liquid crystal molecules due to mechanical vibration of ultrasonic waves, and an electromagnetic field sensor that uses a change in the wavelength of reflected light due to a change in temperature or a change in the arrangement of liquid crystal molecules due to an electric field.
• a distance measuring sensor that uses electromagnetic waves,
• the distance measurement sensor is preferably for use in LiDAR (Light Detection and Ranging) that uses a light source.
• LiDAR is preferably used for artificial satellites, aircraft, unmanned aerial vehicles (drones), automobiles, railways, and ships.
• the light source is preferably an LED or a laser, preferably a laser.
• the light used in LiDAR is preferably infrared light, and its wavelength is preferably 800 to 2000 nm. In particular, an infrared laser with a wavelength of 905 nm or 1550 nm is preferred.
• the liquid crystal composition according to the present invention exhibits a high ⁇ n value, and therefore has a large phase modulation power in the visible light, infrared light and electromagnetic wave regions, and can provide a sensor with excellent detection sensitivity.
• the liquid crystal lens according to the present invention is characterized by using the above-mentioned liquid crystal composition, and for example, in one embodiment thereof, has a first transparent electrode layer, a second transparent electrode layer, a liquid crystal layer containing the above-mentioned liquid crystal composition provided between the first transparent electrode layer and the second transparent electrode layer, an insulating layer provided between the second transparent electrode layer and the liquid crystal layer, and a high-resistance layer provided between the insulating layer and the liquid crystal layer.
• the liquid crystal lens according to the present invention is used, for example, as a 2D/3D switching lens, a lens for adjusting the focus of a camera, and the like.
• the optical communication device is characterized by using the above-mentioned liquid crystal composition.
• one of the embodiments thereof is a liquid crystal on silicon (LCOS) structure having a liquid crystal layer, in which liquid crystals constituting each of a plurality of pixels are two-dimensionally arranged on a reflective layer (electrode).
• LCOS liquid crystal on silicon
• the optical communication device according to the present invention is used, for example, as a spatial phase modulator.
• the antenna according to the present invention is characterized by using the above-mentioned liquid crystal composition. More specifically, the antenna of the present invention comprises a first substrate having a plurality of slots, a second substrate facing the first substrate and having a power supply section, a first dielectric layer provided between the first substrate and the second substrate, a plurality of patch electrodes arranged corresponding to the plurality of slots, a third substrate having the patch electrodes provided thereon, and a liquid crystal layer provided between the first substrate and the third substrate, wherein the liquid crystal layer contains the above-mentioned liquid crystal composition.
• the liquid crystal composition according to the present invention it is possible to provide an antenna that is highly reliable against external stimuli such as heat.
• the antenna according to the invention preferably operates in the Ka or K or Ku band frequencies used for satellite communications.
• the antenna according to the present invention preferably has a configuration in which a radial line slot array and a patch antenna array are combined.
• the structure of the antenna according to the present invention can be applied by taking into consideration the matters described in, for example, International Publication No. 2021/157189.
• n in the table is a natural number. Also, the alkyl group represented by n is a linear alkyl group.
• n in the table is a natural number.
• the alkylene group represented by n is a linear alkylene group.
• Examples 1 to 14 and Comparative Examples 1 and 2 Liquid crystal compositions were prepared using LC-A to B and LC-01 to 08, hindered phenol antioxidants (XX-1) to (XX-3), and hindered amine light stabilizers (YY-1) to (YY-2), and the physical properties were measured and a storage stability test was performed. The results are shown in Tables 4 and 5. Note that in Comparative Example 1, the high frequency characteristics ( ⁇ r and tan ⁇ iso ) were not measured because the crystallization occurred at room temperature.
• ⁇ Storage test> 0.5 g of the liquid crystal composition was weighed into a 1 mL sample bottle (manufactured by Maruemu Co., Ltd.), and degassed for 10 minutes at 150 to 250 Pa. The bottle was then purged with dry nitrogen and the attached lid was placed on. The bottle was stored in a temperature-controlled thermostatic chamber (SH-241, manufactured by Espec Corp.) at 25°C for two weeks, and the occurrence of crystallization of the liquid crystal composition was visually confirmed every week.
• SH-241 temperature-controlled thermostatic chamber
• a liquid crystal composition containing a predetermined amount of one or more compounds selected from the group consisting of the compounds represented by the general formulas (i) and (ii) and one or more compounds represented by the general formula (iii) has an excellent balance of ⁇ n and T ni and good storage stability at room temperature, and also exhibits good values of ⁇ r and tan ⁇ iso .
• the liquid crystal composition of the present invention can be used in liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas.

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