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WO2024134973A1 - Composé, composition de cristaux liquides, élément d'affichage à cristaux liquides, capteur, lentille à cristaux liquides, dispositif de communication optique et antenne l'utilisant chacun - Google Patents

Composé, composition de cristaux liquides, élément d'affichage à cristaux liquides, capteur, lentille à cristaux liquides, dispositif de communication optique et antenne l'utilisant chacun Download PDF

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Publication number
WO2024134973A1
WO2024134973A1 PCT/JP2023/029660 JP2023029660W WO2024134973A1 WO 2024134973 A1 WO2024134973 A1 WO 2024134973A1 JP 2023029660 W JP2023029660 W JP 2023029660W WO 2024134973 A1 WO2024134973 A1 WO 2024134973A1
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Prior art keywords
group
liquid crystal
formula
general formula
alkyl group
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PCT/JP2023/029660
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English (en)
Japanese (ja)
Inventor
正直 林
貴哉 池内
大樹 野呂
美花 高崎
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2023569680A priority Critical patent/JP7464204B1/ja
Publication of WO2024134973A1 publication Critical patent/WO2024134973A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q13/00—Waveguide horns or mouths; Slot antennas; Leaky-waveguide antennas; Equivalent structures causing radiation along the transmission path of a guided wave
    • H01Q13/20—Non-resonant leaky-waveguide or transmission-line antennas; Equivalent structures causing radiation along the transmission path of a guided wave
    • H01Q13/22—Longitudinal slot in boundary wall of waveguide or transmission line
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q21/00—Antenna arrays or systems
    • H01Q21/06—Arrays of individually energised antenna units similarly polarised and spaced apart
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q3/00—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system
    • H01Q3/26—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture
    • H01Q3/30—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture varying the relative phase between the radiating elements of an array
    • H01Q3/34—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture varying the relative phase between the radiating elements of an array by electrical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q3/00—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system
    • H01Q3/44—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the electric or magnetic characteristics of reflecting, refracting, or diffracting devices associated with the radiating element

Definitions

  • the present invention relates to a compound and a liquid crystal composition, liquid crystal display element, sensor, liquid crystal lens, optical communication device, and antenna that use the compound.
  • 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.
  • An object of the present invention is to provide a compound capable of providing a liquid crystal composition having large ⁇ n and large ⁇ r and having good storage stability at low temperature or room temperature, and a liquid crystal composition, a liquid crystal display element, a sensor, a liquid crystal lens, an optical communication device, and an antenna using the same.
  • X i1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a thioisocyano group, an isothiocyanate group, an isocyanate group, or an alkyl group having 1 to 20 carbon atoms; one or more -CH 2 - in the alkyl group may each independently be substituted by -O-, -S-, -CO- and/or -CS-; one or more -CH 2 -CH 2 - in the alkyl group may each independently be substituted by -CO-O-, -O-CO-, -CO-S-, -S-CO-, -CO-NH-
  • a i1 and A i2 each independently represent a hydrocarbon ring having 3 to 16 carbon atoms or a heterocycle having 3 to 16 carbon atoms;
  • One or more hydrogen atoms in A i1 and A i2 may each independently be substituted by a substituent S i1 ;
  • the substituent S i1 represents any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, and an alky
  • L i1 and L i2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms;
  • One or more -CH 2 - in the alkyl group may each independently be substituted by -O-, -S-, -CO- and/or -CS-; one or more -CH 2 -CH 2 - in the alkyl group may each independently be
  • R i1 , L i1 , L i2 , A i1 , A i2 and X i1 each have the same meaning as R i1 , L i1 , L i2 , A i1 , A i2 and X i1 in the above general formula (i), respectively. .) 2.
  • Item 3 The compound according to item 1 or 2, wherein X i1 represents a fluorine atom, a cyano group, an isothiocyanate group (-NCS), a linear alkyl group having 1 to 6 carbon atoms, or a linear alkoxy group having 1 to 6 carbon atoms.
  • X i1 represents a fluorine atom, a cyano group, an isothiocyanate group (-NCS), a linear alkyl group having 1 to 6 carbon atoms, or a linear alkoxy group having 1 to 6 carbon atoms.
  • Item 4 A liquid crystal composition containing one or more compounds according to any one of items 1 to 3.
  • Item 8 An optical communication device using the liquid crystal composition described in item 4.
  • Item 10 The antenna according to item 9, a first substrate having a plurality of slots; a second substrate facing the first substrate and provided with a power supply unit; 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 having large ⁇ n and large ⁇ r and having good storage stability at low temperature or room temperature can be obtained, and the liquid crystal composition is useful for liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas.
  • the compound according to the present invention is a compound represented by the following general formula (i) having a specific side chain structure including an indene structure and an isothiocyanate group (-NCS) group.
  • the liquid crystal composition according to the present invention also contains one or more compounds represented by general formula (i) having a specific side chain structure including an indene structure and an isothiocyanate group (-NCS) group.
  • general formula (i) having a specific side chain structure including an indene structure and an isothiocyanate group (-NCS) group.
  • the dashed line indicates the position of a double bond.
  • Specific examples of the indene structure include groups represented by the following general formulae (A indene -1) and (A indene -2).
  • R i1 represents 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 by -O-, -S-, -CO- and/or -CS-.
  • 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.
  • the oxygen atoms are not directly bonded to each other. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • R i1 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 i1 can represent an alkylsulfanyl group (alkylthio group) having 1 to 19 carbon atoms by replacing one --CH 2 -- in the alkyl group with --S--.
  • the alkylsulfanyl group is a linear, branched or cyclic alkylsulfanyl group, and is preferably a linear alkylsulfanyl group.
  • the alkylsulfanyl group preferably has 1 to 10, more preferably 1 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 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 i1 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 i1 include groups represented by formulae (R i1 -1) to (R i1 -39).
  • R i1 is preferably a linear alkyl group having 1 to 6 carbon atoms, a linear alkoxyalkyl group having 1 to 6 carbon atoms, or a linear alkenyl group having 2 to 6 carbon atoms.
  • X i1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a thioisocyano group, an isothiocyanate group, an isocyanate group, or an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain 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 by -O-, -S-, -CO- and/or -CS-.
  • 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.
  • the oxygen atoms are not directly bonded to each other. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • X i1 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.
  • X i1 can represent an alkylsulfanyl group (alkylthio group) having 1 to 19 carbon atoms by substituting one --CH 2 -- in the alkyl group with --S--.
  • the alkylsulfanyl group is a linear, branched or cyclic alkylsulfanyl group, and is preferably a linear alkylsulfanyl group.
  • the alkylsulfanyl group preferably has 1 to 10 carbon atoms, more preferably 1 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.
  • X i1 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.
  • X i1 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 X i1 include groups represented by formulae (X i1 -1) to (X i1 -39).
  • the black dot represents a bond to A i1 or A i2 .
  • X i1 represents a fluorine atom, a cyano group, an isothiocyanate group (-NCS), a linear alkyl group having 1 to 6 carbon atoms, or a linear alkoxy group having 1 to 6 carbon atoms.
  • a i1 and A i2 each independently represent a hydrocarbon ring having 3 to 16 carbon atoms or a heterocycle having 3 to 16 carbon atoms. More specifically, the hydrocarbon ring having 3 to 16 carbon atoms or the heterocycle having 3 to 16 carbon atoms is the following group (a), group (b), group (c), and group (d): (a) a 1,4-cyclohexylene group (in which one —CH 2 — or two or more non-adjacent —CH 2 — groups may be replaced by —O— or —S—).
  • One or more hydrogen atoms in A i1 and A i2 may each independently be substituted with a substituent S i1 .
  • the substituent S i1 represents any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, and an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain alkyl group.
  • the alkyl group preferably has 2 to 10, preferably 3 to 6, carbon atoms.
  • One or more -CH 2 - in the alkyl group may each independently be substituted with -O-, -S- and/or -CO-.
  • 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. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • the substituent S i1 is preferably a linear alkyl group having 1 to 10 carbon atoms, a chlorine atom, or a fluorine atom.
  • At least one of A i1 and A i2 is preferably substituted with at least one substituent S i1 .
  • a i2 is preferably substituted with at least one substituent S i1 .
  • substituent S i1 When there are a plurality of substituents S i1 , they may be the same or different.
  • substitution position of the substituent S i1 in A i1 is preferably any one of the following formulae (A i1 -SP-1) to (A i1 -SP-4).
  • a white dot represents a bond to Z i1
  • a black dot represents a bond to Z i2 or X i1 .
  • the substitution position of the substituent S i1 in A i2 is preferably any one of the following formulae (A i2 -SP-1) to (A i2 -SP-4).
  • a white dot represents a bond to Z i2
  • a black dot represents a bond to Z i2 or X i1 .
  • a i1 preferably represents any one of the following formulae (A i1 -1) to (A i1 -13).
  • a white dot represents a bond to Z i1
  • a black dot represents a bond to Z i2 or X i1 .
  • a i2 preferably represents any one of the following formulas (A i2 -1) to (A i2 -10).
  • a white dot represents a bond to Z i2
  • a black dot represents a bond to Z i2 or X i1 .
  • L i1 and L i2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, 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 substituted by -O-, -S-, -CO- and/or -CS-.
  • one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • the alkyl group is substituted with a specific group, the oxygen atoms are not directly bonded to each other.
  • L i1 and L i2 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.
  • L i1 and L i2 can represent an alkylsulfanyl group (alkylthio group) having 1 to 19 carbon atoms by replacing one --CH 2 -- in the alkyl group with --S--.
  • the alkylsulfanyl group is a linear, branched or cyclic alkylsulfanyl group, and is preferably a linear alkylsulfanyl group.
  • the alkylsulfanyl 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.
  • L i1 and L i2 can represent an alkynyl group having 2 to 20 carbon atoms by replacing one or more -CH 2 -CH 2 - in the alkyl group with -C ⁇ C-.
  • the alkynyl group may be a straight-chain, branched or cyclic alkynyl group, and is preferably a straight-chain alkynyl group.
  • the alkynyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
  • L i1 and L i2 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.
  • L i1 and L i2 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.
  • L i1 and L i2 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.
  • alkyl group having 1 to 20 carbon atoms (including substituted ones) in L i1 and L i2 include groups represented by the formulae (L i1/2 -1) to (L i1/2 -36).
  • the black dots represent bonds to the indene structure.
  • at least one of L i1 and L i2 is preferably a hydrogen atom, a fluorine atom, or a linear alkyl group having 1 to 6 carbon atoms, and it is more preferable that L i1 and L i2 are a hydrogen atom or a fluorine atom.
  • Z i1 and Z i2 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
  • the alkylene group is a linear, branched or cyclic alkylene group, and is preferably a linear alkylene group.
  • the alkylene group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
  • One or more -CH 2 - in the alkylene group may each independently be substituted with -O-, -CF 2 - and/or -CO-.
  • the alkylene group having 2 to 20 carbon atoms include groups represented by the formulae (Z i1/2 -1) to (Z i1/2 -24).
  • the white dots represent an indene structure, a bond to A i1 or A i2
  • the black dots represent a bond to A i1 or A i2 .
  • Z i1 and Z i2 each independently represent a single bond, —CH 2 —CH 2 —, —CO—O—, —N ⁇ N—, —N ⁇ CH—, —CH ⁇ CH— or —C ⁇ C—.
  • at least one of Z i1 and Z i2 is -C ⁇ C-.
  • n i1 represents an integer of 0 to 3, preferably an integer of 1 or 2.
  • a i2 or Z i2 may be the same or different.
  • the compound represented by general formula (i) is preferably a compound represented by the following general formulas (i-1) to (i-11).
  • R i1 , L i1 , L i2 , A i1 , A i2 and X i1 have the same meanings as R i1 , L i1 , L i2 , A i1 , A i2 and X i1 in the general formula (i), respectively, and the preferred groups are also the same.
  • the compound represented by general formula (i-1) is preferably a compound represented by the following general formulas (i-1-1) to (i-1-19).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-1-1) include compounds represented by the following structural formulas (i-1-1.1) to (i-1-1.10).
  • Specific examples of compounds represented by general formula (i-1-2) include compounds represented by the following structural formulas (i-1-2.1) to (i-1-2.5).
  • Specific examples of compounds represented by general formula (i-1-3) include compounds represented by the following structural formulas (i-1-3.1) to (i-1-3.6).
  • Specific examples of compounds represented by general formula (i-1-4) include compounds represented by the following structural formulas (i-1-4.1) to (i-1-4.6).
  • Specific examples of compounds represented by general formula (i-1-5) include compounds represented by the following structural formulas (i-1-5.1) to (i-1-5.5).
  • Specific examples of compounds represented by general formula (i-1-6) include compounds represented by the following structural formulas (i-1-6.1) to (i-1-6.6).
  • Specific examples of compounds represented by general formula (i-1-7) include compounds represented by the following structural formulas (i-1-7.1) to (i-1-7.4).
  • Specific examples of compounds represented by general formula (i-1-8) include compounds represented by the following structural formulas (i-1-8.1) to (i-1-8.5).
  • Specific examples of compounds represented by general formula (i-1-9) include compounds represented by the following structural formulas (i-1-9.1) to (i-1-9.4).
  • Specific examples of compounds represented by general formula (i-1-10) include compounds represented by the following structural formulas (i-1-10.1) to (i-1-10.2).
  • Specific examples of compounds represented by general formula (i-1-11) include compounds represented by the following structural formulas (i-1-11.1) to (i-1-11.6).
  • Specific examples of compounds represented by general formula (i-1-12) include compounds represented by the following structural formulas (i-1-12.1) to (i-1-12.6).
  • Specific examples of compounds represented by general formula (i-1-13) include compounds represented by the following structural formulas (i-1-13.1) to (i-1-13.4).
  • Specific examples of compounds represented by general formula (i-1-14) include compounds represented by the following structural formulas (i-1-14.1) to (i-1-14.4).
  • the compound represented by general formula (i-2) is preferably a compound represented by the following general formulas (i-2-1) to (i-2-7).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-2-1) include compounds represented by the following structural formulas (i-2-1.1) to (i-2-1.6).
  • Specific examples of compounds represented by general formula (i-2-2) include compounds represented by the following structural formulas (i-2-2.1) to (i-2-2.4).
  • Specific examples of compounds represented by general formula (i-2-3) include compounds represented by the following structural formulas (i-2-3.1) to (i-2-3.4).
  • Specific examples of compounds represented by general formula (i-2-4) include compounds represented by the following structural formulas (i-2-4.1) to (i-2-4.6).
  • Specific examples of compounds represented by general formula (i-2-5) include compounds represented by the following structural formulas (i-2-5.1) to (i-2-5.5).
  • Specific examples of compounds represented by general formula (i-2-6) include compounds represented by the following structural formulas (i-2-6.1) to (i-2-6.4).
  • Specific examples of compounds represented by general formula (i-2-7) include compounds represented by the following structural formulas (i-2-7.1) to (i-2-7.4).
  • the compound represented by general formula (i-3) is preferably a compound represented by the following general formulas (i-3-1) to (i-3-10).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-3-1) include the compounds represented by the following structural formulas (i-3-1.1) to (i-3-1.6).
  • Specific examples of compounds represented by general formula (i-3-2) include compounds represented by the following structural formulas (i-3-2.1) to (i-3-2.6).
  • Specific examples of compounds represented by general formula (i-3-3) include compounds represented by the following structural formulas (i-3-3.1) to (i-3-3.6).
  • Specific examples of compounds represented by general formula (i-3-4) include compounds represented by the following structural formulas (i-3-4.1) to (i-3-4.4).
  • Specific examples of compounds represented by general formula (i-3-5) include compounds represented by the following structural formulas (i-3-5.1) to (i-3-5.4).
  • Specific examples of compounds represented by general formula (i-3-6) include compounds represented by the following structural formulas (i-3-6.1) to (i-3-6.6).
  • the compound represented by general formula (i-4) is preferably a compound represented by the following general formulas (i-4-1) to (i-4-6).
  • Specific examples of the compound represented by general formula (i-4-1) include the compounds represented by the following structural formulas (i-4-1.1) to (i-4-1.4).
  • Specific examples of compounds represented by general formula (i-4-2) include compounds represented by the following structural formulas (i-4-2.1) to (i-4-2.4).
  • Specific examples of compounds represented by general formula (i-4-3) include compounds represented by the following structural formulas (i-4-3.1) to (i-4-3.4).
  • Specific examples of compounds represented by general formula (i-4-4) include compounds represented by the following structural formulas (i-4-4.1) to (i-4-4.4).
  • the compound represented by general formula (i-5) is preferably a compound represented by the following general formulas (i-5-1) to (i-5-4).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of compounds represented by general formula (i-5-1) include compounds represented by the following structural formulas (i-5-1.1) to (i-5-1.4).
  • Specific examples of compounds represented by general formula (i-5-2) include compounds represented by the following structural formulas (i-5-2.1) to (i-5-2.4).
  • Specific examples of compounds represented by general formula (i-5-3) include compounds represented by the following structural formulas (i-5-3.1) to (i-5-3.4).
  • Specific examples of compounds represented by general formula (i-5-4) include compounds represented by the following structural formulas (i-5-4.1) to (i-5-4.4).
  • the compound represented by general formula (i-6) is preferably a compound represented by the following general formulas (i-6-1) to (i-6-4).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-6-1) include the compounds represented by the following structural formulas (i-6-1.1) to (i-6-1.4).
  • Specific examples of compounds represented by general formula (i-6-2) include compounds represented by the following structural formulas (i-6-2.1) to (i-6-2.4).
  • Specific examples of compounds represented by general formula (i-6-3) include compounds represented by the following structural formulas (i-6-3.1) to (i-6-3.4).
  • Specific examples of compounds represented by general formula (i-6-4) include compounds represented by the following structural formulas (i-6-4.1) to (i-6-4.4).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-7-1) include the compounds represented by the following structural formulas (i-7-1.1) to (i-7-1.4).
  • Specific examples of compounds represented by general formula (i-7-2) include compounds represented by the following structural formulas (i-7-2.1) to (i-7-2.4).
  • Specific examples of compounds represented by general formula (i-7-3) include compounds represented by the following structural formulas (i-7-3.1) to (i-7-3.4).
  • Specific examples of compounds represented by general formula (i-7-4) include compounds represented by the following structural formulas (i-7-4.1) to (i-7-4.4).
  • the compound represented by general formula (i-8) is preferably a compound represented by the following general formulas (i-8-1) to (i-8-2).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of compounds represented by general formula (i-8-1) include compounds represented by the following structural formulas (i-8-1.1) to (i-8-1.2).
  • Specific examples of compounds represented by general formula (i-8-2) include compounds represented by the following structural formulas (i-8-2.1) to (i-8-2.2).
  • the compound represented by general formula (i-9) is preferably a compound represented by the following general formulas (i-9-1) to (i-9-4).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in the above general formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-9-1) include the compounds represented by the following structural formulas (i-9-1.1) to (i-9-1.4).
  • Specific examples of compounds represented by general formula (i-9-2) include compounds represented by the following structural formulas (i-9-2.1) to (i-9-2.4).
  • Specific examples of compounds represented by general formula (i-9-3) include compounds represented by the following structural formulas (i-9-3.1) to (i-9-3.4).
  • Specific examples of compounds represented by general formula (i-9-4) include compounds represented by the following structural formulas (i-9-4.1) to (i-9-4.4).
  • the compound represented by general formula (i-10) is preferably a compound represented by the following general formulas (i-10-1) to (i-10-2).
  • R i1 , X i1 and S i1 have the same meanings as R i1 , X i1 and S i1 in formula (i), respectively, and the preferred groups are also the same.
  • Specific examples of the compound represented by general formula (i-10-1) include the compounds represented by the following structural formulas (i-10-1.1) to (i-10-1.2).
  • Specific examples of compounds represented by general formula (i-10-2) include compounds represented by the following structural formulas (i-10-2.1) to (i-10-2.2).
  • the compound represented by general formula (i-11) is preferably a compound represented by the following general formulas (i-11-1) to (i-11-2).
  • Specific examples of the compound represented by general formula (i-11-1) include the compounds represented by the following structural formulas (i-11-1.1) to (i-11-1.2).
  • Specific examples of compounds represented by general formula (i-11-2) include compounds represented by the following structural formulas (i-11-2.1) to (i-11-2.2).
  • the total content of the compounds represented by 2) in 100% by mass of the liquid crystal composition is preferably 0.1 to 95% by mass, and more preferably 0.5 to 95% by mass, from the viewpoints of solubility, ⁇ n and/or ⁇ r . It is preferably up to 90% by mass, more preferably 1 to 85% by mass, more preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 15% by mass. It is preferred.
  • the compound represented by formula (i) (including its sub-concepts) can be synthesized by known synthesis methods, some of which are exemplified below.
  • the indene derivative (A-1), which is a synthetic intermediate for the compound according to the present invention, can be obtained, for example, by the production method shown below.
  • R i1 , L i1 and L i2 have the same meanings as R i1 , L i1 and L i2 in the general formula (i) above.
  • the indene derivative (A-2), which is a synthetic intermediate for the compound according to the present invention, can be obtained, for example, by the production method shown below.
  • R i1 , L i1 and L i2 have the same meanings as R i1 , L i1 and L i2 in the general formula (i) above.
  • the compound represented by the general formula (i) can be produced, for example, as follows. (Production Method 1) Production of a compound represented by the following general formula (s-6):
  • R i1 , A i2 , L i1 , L i2 , S i1 and X i1 have the same meanings as R i1 , A i2 , L i1 , L i2 , S i1 and X i1 in the general formula (i) above.
  • the compound represented by the general formula (s-1) is reacted with magnesium, and then treated with triisopropyl borate and then with hydrochloric acid to obtain a boric acid derivative, which is a compound represented by the general formula (s-2).
  • the compound represented by the general formula (s-2) is reacted with the compound represented by the general formula (s-3) to obtain the compound represented by the general formula (s-4).
  • 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.
  • 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.
  • 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.
  • R i1 , A i2 , L i1 , L i2 , S i1 and X i1 have the same meanings as R i1 , A i2 , L i1 , L i2 , S i1 and X i1 in the general formula (i) above.
  • the compound represented by the general formula (s-7) can be reacted with trimethylsilylacetylene, and then reacted with potassium carbonate in an alcohol solvent to obtain the compound represented by the general formula (s-8).
  • Reactions with trimethylsilylacetylene include the Sonogashira coupling reaction using a palladium catalyst, a copper catalyst and a base.
  • 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 and the base include those mentioned above.
  • the target compound represented by general formula (s-12) can be obtained by reacting the compound represented by general formula (s-10) with the compound represented by general formula (s-11).
  • the reaction method includes, for example, Suzuki coupling reaction using a palladium catalyst and a base. (Production Method 3) Production of a compound represented by the following general formula (s-17):
  • R i1 , A i2 , L i1 , L i2 , S i1 and X i1 have the same meanings as R i1 , A i2 , L i1 , L i2 , S i1 and X i1 in the general formula (i) above.
  • a compound represented by general formula (s-13) is reacted with a compound represented by general formula (s-14) to obtain a compound represented by general formula (s-15).
  • 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 and the base include those mentioned above.
  • the target compound represented by general formula (s-17) can be obtained by reacting the compound represented by general formula (s-15) with the compound represented by general formula (s-16).
  • 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 and the base include those mentioned above. (Production Method 4) Production of a compound represented by the following general formula (s-21):
  • R i1 , L i1 , L i2 and X i1 have the same meanings as R i1 , L i1 , L i2 and X i1 in the general formula (i) above.
  • a compound represented by general formula (s-18) is reacted with magnesium, and then treated with triisopropyl borate and then with hydrochloric acid to obtain a boric acid derivative, which is a compound represented by general formula (s-19).
  • the compound represented by general formula (s-19) is reacted with the compound represented by general formula (s-20) to obtain the target compound represented by general formula (s-21).
  • the reaction method includes, for example, Suzuki coupling reaction using a palladium catalyst and a base. Specific examples of the palladium catalyst and the base include those mentioned above. (Production Method 5) Production of a compound represented by the following general formula (s-24):
  • R i1 , L i1 , L i2 , S i1 and X i1 have the same meanings as R i1 , L i1 , L i2 , S i1 and X i1 in the general formula (i) above.
  • the target compound represented by general formula (s-24) can be obtained by reacting a compound represented by general formula (s-22) with a compound represented by general formula (s-23).
  • 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 and the base include those mentioned above. (Production Method 6) Production of a compound represented by the following formula (s-30):
  • R i1 , A i2 , L i1 , L i2 and S i1 have the same meanings as R i1 , A i2 , L i1 , L i2 and S i1 in the general formula (i) above.
  • a compound represented by general formula (s-27) can be obtained by reacting a compound represented by general formula (s-25) with a compound represented by general formula (s-26).
  • the reaction method includes, for example, Suzuki coupling reaction using a palladium catalyst and a base. Specific examples of the palladium catalyst and the base include those mentioned above.
  • R i1 , A i1 , A i2 , L i1 and L i2 have the same meanings as R i1 , A i1 , A i2 , L i1 and L i2 in the general formula (i) above.
  • a compound represented by general formula (s-31) is reacted with a compound represented by general formula (s-32) to obtain a compound represented by general formula (s-33).
  • 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 nitro group of the compound represented by general formula (s-33) is converted to an amino group using iron or the like, and the resulting compound is reacted with thiophosgene to obtain the target compound represented by general formula (s-34).
  • Reaction conditions other than those described in each step may be those described in, for example, Jikken Kagaku Koza (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Beilstein-Institut fur Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.
  • purification may be carried out in each step as necessary. Purification methods include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation. Specific examples of the purification agent include silica gel, alumina, and activated carbon.
  • the characteristic values of the compound represented by general formula (i) (including sub-concepts) can be measured as follows. First, a compound represented by general formula (i) (including subordinate concepts) is added to a mother liquid crystal to prepare liquid crystal compositions containing 0 mass %, 5 mass %, and 10 mass % of the compound represented by general formula (i) (including subordinate concepts) per 100 mass % of the liquid crystal composition, and ⁇ n (refractive index anisotropy) and ⁇ r of each liquid crystal composition are measured.
  • ⁇ n reffractive index anisotropy
  • ⁇ r of 100% by mass of the compound represented by general formula (i) (including subordinate concepts), that is, the compound represented by general formula (i) (including subordinate concepts) are determined from extrapolated values .
  • ⁇ 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 was carried out at a temperature of 25° C. and at 589 nm, and the measurement was unitless. The ⁇ n at 25° C.
  • the compound (including subordinate concepts) represented by general formula (i) according to the present invention is preferably 0.30 or more, more preferably 0.35 to 0.60, more preferably 0.37 to 0.55, and even more preferably 0.40 to 0.55, from the viewpoint of the phase modulation power of light of the wavelength.
  • the dielectric anisotropy ⁇ r at 10 GHz was measured as a representative characteristic in the high frequency range.
  • ⁇ r ( ⁇ r ⁇ ⁇ r ⁇ ).
  • ⁇ r is a dielectric constant
  • the subscript " ⁇ ” indicates a component parallel to the alignment direction of the liquid crystal
  • “ ⁇ ” indicates a component perpendicular to the alignment direction of the liquid crystal.
  • ⁇ r can be measured by the following method.
  • a liquid crystal composition is introduced into a capillary tube made of polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • 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 ) at 10 GHz is 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 resonance frequency and the like using a PTFE capillary tube filled with a liquid crystal composition are determined as values of characteristic components perpendicular 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) or in the parallel direction (parallel to the effective length) 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 made at a temperature of 25° C., and ⁇ r has no unit.
  • the ⁇ r at 25° C. of the compound (including subordinate concepts) represented by general formula (i) according to the present invention is preferably larger, and from the viewpoint of phase modulation power in the GHz band, it is preferably 0.33 or more, preferably 0.33 to 0.65, preferably 0.34 to 0.60, preferably 0.34 to 0.55, preferably 0.35 to 0.50, preferably 0.35 to 0.45, and preferably 0.35 to 0.40.
  • liquid crystal composition (Liquid Crystal Composition)
  • the liquid crystal composition according to the present invention can be produced, for example, by mixing the compound represented by the above general formula (i) (including sub-concepts) and, if necessary, other liquid crystal compounds and additives.
  • Additives include stabilizers, dye compounds, polymerizable compounds, azotolane 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 composition preferably contains, as other liquid crystal compounds, one or more compounds represented by the following general formula (ii) from the viewpoints of solubility, ⁇ n and/or ⁇ r.
  • R ii1 represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group may be a straight-chain, branched or cyclic alkyl group, and is preferably a straight-chain 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 by -O-, -S-, -NH-, -CO- and/or -CS-.
  • 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. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • 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.
  • R ii1 can represent an alkylsulfanyl group (alkylthio group) having 1 to 19 carbon atoms by replacing one —CH 2 — in the alkyl group with —S—.
  • the alkylsulfanyl group is a linear, branched or cyclic alkylsulfanyl group, and is preferably a linear alkylsulfanyl group.
  • the alkylsulfanyl group preferably has 1 to 10 carbon atoms, more preferably 1 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 ii1 can represent an alkynyl group having 2 to 20 carbon atoms by replacing one or more -CH 2 -CH 2 - in the alkyl group with -C ⁇ C-.
  • the alkynyl group may be a linear, branched or cyclic alkynyl group, and is preferably a linear alkynyl group.
  • the alkynyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
  • an alkynyl group represented by the following formula (R ii1 -A) is preferred.
  • R ii1A represents an alkyl group having 1 to 18 carbon atoms.
  • the alkyl group having 1 to 18 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 18 carbon atoms preferably has 1 to 8 carbon atoms.
  • One or more -CH 2 - in the alkyl group may each independently be substituted by -O-, -S-, -NH-, -CO- and/or -CS-.
  • 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. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • 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 ii1 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 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 for R ii1 include groups represented by formulae (R ii1 -1) to (R ii1 -56).
  • the black dot represents a bond to A ii1 .
  • the ring structure to which R ii1 is bonded is a phenyl group (aromatic)
  • a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 4 to 5 carbon atoms are preferred
  • the ring structure to which R ii1 is bonded is a saturated ring structure such as cyclohexane, pyran, and dioxane
  • a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms are preferred.
  • R ii1 preferably has a total of 5 or less carbon atoms and, if present, oxygen atoms, and is preferably linear.
  • R ii1 is preferably a linear or branched alkyl group having 2 to 8 carbon atoms, a linear alkoxy group having 2 to 8 carbon atoms, a linear halogenated alkoxy group having 1 to 8 carbon atoms, a linear alkynyl group having 2 to 8 carbon atoms, or a linear alkylsulfanyl group having 1 to 6 carbon atoms.
  • One or more hydrogen atoms in A ii1 and A ii2 may each independently be substituted with a substituent S ii1 .
  • the substituent S ii1 represents any one of a halogen atom, a pentafluorosulfanyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, and an alkyl group having 1 to 20 carbon atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • 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 substituted by -O-, -S-, -NH-, -CO- and/or -CS-.
  • 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. From the viewpoint of the stability of the compound, it is preferable that sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • the substituent S 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 substituent S ii1 can represent an alkylsulfanyl group (alkylthio group) having 1 to 19 carbon atoms by replacing one --CH 2 -- in the alkyl group with --S--.
  • the alkylsulfanyl group is a linear, branched or cyclic alkylsulfanyl group, and is preferably a linear alkylsulfanyl group.
  • the alkylsulfanyl group preferably has 2 to 10 carbon atoms, 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.
  • the substituent S ii1 can represent an alkynyl group having 2 to 20 carbon atoms by replacing one or more -CH 2 -CH 2 - in the alkyl group with -C ⁇ C-.
  • the alkynyl group may be a linear, branched or cyclic alkynyl group, and is preferably a linear alkynyl group.
  • the alkynyl group preferably has 2 to 10, more preferably 2 to 6, carbon atoms.
  • the substituent S ii1 can represent an alkenyloxy group having 2 to 19 carbon atoms by replacing one —CH 2 — in the alkyl group with —O— and one or more —CH 2 —CH 2 — groups 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.
  • the substituent S 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.
  • the substituent S 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 (including substituted ones) in the substituent S ii1 include groups represented by the formulae (S ii1R -1) to (S ii1R -36).
  • the black dot represents a bond to A ii1 or A ii2 .
  • the substituent S ii1 is preferably a linear alkyl group having 1 to 6 carbon atoms, a fluorine atom or a chlorine atom.
  • at least one of A ii1 or A ii2 is preferably substituted with at least one substituent S ii1 , preferably with a halogen atom, and more preferably with a fluorine atom.
  • substituents S ii1 may be the same or different.
  • substitution position of the substituent S ii1 in A ii1 is preferably any one of the following formulae (A ii1 -SP-1) to (A ii1 -SP-12).
  • a white dot represents a bond to R ii1 or Z ii1
  • a black dot represents a bond to Z ii1 .
  • the substitution position of the substituent S ii1 in A ii2 is preferably any one of the following formulae (A ii2 -SP-1) to (A ii2 -SP-8).
  • a ii1 preferably represents any one of the following formulae (A ii1 -1) to (A ii1 -34).
  • a white dot represents a bond to R ii1 or Z ii1
  • a black dot represents a bond to Z ii1 .
  • a ii2 preferably represents any one of the following formulas (A ii2 -1) to (A ii2 -10).
  • white dots represent bonds to Z ii1
  • black dots represent bonds to an isothiocyanate group (--NCS).
  • Z ii1 represents a single bond or an alkylene group having 1 to 20 carbon atoms.
  • One or more -CH 2 - in the alkylene group may each independently be substituted with -O-, -CF 2 - and/or -CO-.
  • the alkylene group having 1 to 20 carbon atoms is substituted with a specific group, the oxygen atoms are not directly bonded to each other.
  • sulfur atoms and/or oxygen atoms are not directly bonded to each other.
  • alkylene group having 1 to 20 carbon atoms include groups represented by the formulae (Z ii1 -1) to (Z ii1 -24).
  • a white dot represents a bond to A ii1
  • a black dot represents a bond to A ii1 or A ii2 .
  • n ii1 represents an integer of 1 to 4, preferably 1 or 2.
  • Z ii1 preferably represents a single bond or -C ⁇ C- from the viewpoint of ⁇ n and/or ⁇ r .
  • Z ii1 preferably represents a single bond or -C ⁇ C- from the viewpoint of ⁇ n and/or ⁇ r .
  • a ii1 and Z ii1 when a plurality of A ii1 and Z ii1 are present, they may be the same or different.
  • the compound represented by general formula (ii) is preferably a compound represented by the following general formulas (ii-1) to (ii-4).
  • R ii1 , A ii1 and A ii2 have the same meanings as R ii1 , A ii1 and A ii2 in the above general formula (ii), respectively.
  • a ii1-2 are each independently defined as A ii1 in formula (ii) above.
  • the compound represented by general formula (ii-1) is preferably a compound represented by the following general formula (ii-1-1):
  • R ii1 and S ii1 each independently have the same meaning as R ii1 and S ii1 in formula (ii) above.
  • Specific examples of the compound represented by general formula (ii-1-1) include compounds represented by the following structural formulas (ii-1-1.1) to (ii-1-1.8).
  • the compound represented by general formula (ii-2) is preferably a compound represented by the following general formulas (ii-2-1) to (ii-2-4).
  • R ii1 and S ii1 each independently represent the same meaning as R ii1 and S ii1 in the above general formula (ii), respectively.
  • Specific examples of compounds represented by general formula (ii-2-1) include compounds represented by the following structural formulas (ii-2-1.1) to (ii-2-1.2).
  • Specific examples of compounds represented by general formula (ii-2-2) include compounds represented by the following structural formulas (ii-2-2.1) to (ii-2-2.3).
  • Specific examples of compounds represented by general formula (ii-2-3) include compounds represented by the following structural formulas (ii-2-3.1) to (ii-2-3.3).
  • Specific examples of compounds represented by general formula (ii-2-4) include compounds represented by the following structural formulas (ii-2-4.1) to (ii-2-4.3).
  • the compound represented by general formula (ii-3) is preferably a compound represented by the following general formula (ii-3-1):
  • R ii1 and S ii1 each independently have the same meaning as R ii1 and S ii1 in formula (ii) above.
  • Specific examples of the compound represented by general formula (ii-3-1) include compounds represented by the following structural formulas (ii-3-1.1) to (ii-3-1.4).
  • the compound represented by general formula (ii-4) is preferably a compound represented by the following general formula (ii-4-1):
  • R ii1 and S ii1 each independently have the same meaning as R ii1 and S ii1 in formula (ii) above.
  • the number of types of compounds represented by general formula (ii) used in the liquid crystal composition is one or more, preferably 1 to 15, preferably 1 to 10, and preferably 1 to 5.
  • the total content of the compounds represented by general formula (ii) in 100% by mass of the liquid crystal composition is preferably 75 to 95% by mass, more preferably 80 to 95% by mass, and even more preferably 85 to 95% by mass or more.
  • the compounds represented by general formula (ii-1), general formula (ii-1-1) or structural formulas (ii-1-1.1) to (ii-1-1.8) 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 total content of the compounds represented by general formula (ii-1), general formula (ii-1-1) or structural formulas (ii-1-1.1) to (ii-1-1.8) in 100% by mass of the liquid crystal composition is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 10 to 40% by mass.
  • the compounds represented by general formula (ii-2), general formulas (ii-2-1) to (ii-2-4), structural formulas (ii-2-1.1) to (ii-2-1.2), structural formulas (ii-2-2.1) to (ii-2-2.3), structural formulas (ii-2-3.1) to (ii-2-3.3), or structural formulas (ii-2-4.1) to (ii-2-4.3) are used in the liquid crystal composition in one or more types, preferably 1 to 15 types, preferably 1 to 10 types, and preferably 1 to 7 types.
  • the total content of the compounds represented by general formula (ii-2), general formulas (ii-2-1) to (ii-2-4), structural formulas (ii-2-1.1) to (ii-2-1.2), structural formulas (ii-2-2.1) to (ii-2-2.3), structural formulas (ii-2-3.1) to (ii-2-3.3), or structural formulas (ii-2-4.1) to (ii-2-4.3) in 100% by mass of the liquid crystal composition is preferably 1 to 80% by mass, more preferably 3 to 75% by mass, more preferably 5 to 70% by mass, more preferably 5 to 25% by mass, and more preferably 5 to 15% by mass.
  • the compounds represented by general formula (ii-3), general formula (ii-3-1) or structural formulas (ii-3-1.1) to (ii-3-1.4) 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 (ii-3), general formula (ii-3-1) or structural formulas (ii-3-1.1) to (ii-3-1.4) in 100% by mass of the liquid crystal composition is preferably 1 to 80% by mass, more preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 1 to 10% by mass.
  • the compounds represented by general formula (ii-4), general formula (ii-4-1) or structural formulas (ii-4-1.1) to (ii-3-1.4) 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 (ii-4), general formula (ii-4-1) or structural formulas (ii-3-1.1) to (ii-3-1.4) in 100% by mass of the liquid crystal composition is preferably 1 to 25% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 15% by mass.
  • the compound represented by general formula (ii) (including its sub-concepts) can be synthesized using known synthesis methods.
  • 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, and from the viewpoint of the driving temperature range, it is preferably 100° C. or higher, more preferably 110 to 170° C., and even more preferably 115 to 165° C.
  • the liquid crystal phase lower limit temperature is the temperature at which the liquid crystal composition undergoes phase transition from another phase (glass phase, smectic phase, crystalline phase) to the nematic phase.
  • T ⁇ n is measured by filling a glass capillary with the liquid crystal composition, immersing it in a refrigerant at ⁇ 70° C. to cause the liquid crystal composition to undergo phase transition to another phase, and observing while increasing the temperature. It can also be measured by differential scanning calorimetry (DSC). The unit used is "°C".
  • the lower T ⁇ n is, the more the nematic phase can be maintained even at low temperatures, and therefore the wider the operating temperature range can be.
  • 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 using a retardation film/optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The measurement was performed at 25° C. and 589 nm, and has no unit. In order to increase ⁇ n, there is a method of using a compound with extended ⁇ -conjugation, but since the rotational viscosity ( ⁇ 1 ) also increases at the same time, it is difficult to use it frequently from the viewpoint of response speed. The ⁇ n at 25° C.
  • liquid crystal composition according to the present invention 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, from the viewpoint of the phase modulation power of light of the wavelength.
  • 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 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 measurement was 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 change in temperature 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 of the optical communication device is a liquid crystal on silicon (LCOS) having a configuration in which 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 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.
  • reaction liquid was extracted with toluene, and the organic layer was washed with saline, and then column chromatography (silica gel, toluene) and solvent distillation were performed.
  • 16.5 g of 4-bromo-2-fluoroaniline, 0.65 g of copper (I) iodide, 2.0 g of tetrakis (triphenylphosphine) palladium, 50 mL of triethylamine, and 150 mL of N,N-dimethylformamide were added to the reaction mixture.
  • the reaction vessel was heated to 85°C and stirred for an additional 3 hours.
  • a base liquid crystal (LC-1) was prepared, which exhibited the following physical properties. All values were actually measured.
  • T ni nematic phase-isotropic liquid phase transition temperature: 74.0°C ⁇ (dielectric anisotropy at 25 ° C. and 1 kHz): 5.11 ⁇ n (refractive index anisotropy at 25° C. and 589 nm): 0.141 ⁇ 1 (rotational viscosity coefficient at 25° C.): 107 mPa ⁇ s
  • LC-01 to LC-02 shown in Table 4 were prepared using the compound represented by general formula (i).
  • the compounds are described using the following abbreviations, and compounds which can take either cis or trans form are represented as trans forms unless otherwise specified. ⁇ Ring structure>
  • n in the table is a natural number.
  • n in the table is a natural number.
  • Liquid crystal compositions shown in Tables 5 to 7 were prepared using LC-01 to 02, hindered phenol antioxidants (XX-1) to (XX-3), and hindered amine light stabilizers (YY-1) to (YY-2), and the physical properties of the compositions were measured and a storage stability test was performed. The results are shown in Tables 5 to 7.
  • ⁇ 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. The bottle was then stored in a temperature-controlled thermostatic chamber (manufactured by Espec Corp., SH-241) at 25°C for two weeks, and the occurrence of crystallization of the liquid crystal composition was visually confirmed every week.
  • the liquid crystal compositions using the compound represented by general formula (i) had high T ni , large ⁇ n, large ⁇ r , small tan ⁇ iso , and good storage stability at room temperature. Furthermore, from Examples 20 to 31, it was confirmed that even when a hindered phenol-based antioxidant or a hindered amine-based light stabilizer was used in combination, T ni was high, ⁇ n was large, ⁇ r was large, tan ⁇ iso was small, and storage stability at room temperature was good.
  • the compounds of the present invention can be used in liquid crystal compositions, liquid crystal display elements, sensors, liquid crystal lenses, optical communication devices and antennas.

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Abstract

La présente invention aborde le problème de la fourniture : d'un composé qui permet l'obtention d'une composition à cristaux liquides qui a une grande valeur Δn, une grande valeur Δεr, et de bonnes propriétés de stockage à température ambiante ou basses températures; et une composition à cristaux liquides, un élément d'affichage à cristaux liquides, un capteur, une lentille à cristaux liquides, un dispositif de communication optique et une antenne, chacun utilisant ce composé.　La présente invention concerne en particulier : un composé qui est représenté par la formule générale (i) et comprend une structure d'indène spécifique et une structure de chaîne latérale spécifique comprenant un groupe isothiocyanate (-NCS) ; et une composition à cristaux liquides, un élément d'affichage à cristaux liquides, un capteur, une lentille à cristaux liquides, un dispositif de communication optique et une antenne, chacun utilisant ce composé.
PCT/JP2023/029660 2022-12-20 2023-08-17 Composé, composition de cristaux liquides, élément d'affichage à cristaux liquides, capteur, lentille à cristaux liquides, dispositif de communication optique et antenne l'utilisant chacun Ceased WO2024134973A1 (fr)

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