WO2020063295A1 - 适用于高频电磁波调制的液晶介质及其组件 - Google Patents

适用于高频电磁波调制的液晶介质及其组件 Download PDF

Info

Publication number
WO2020063295A1
WO2020063295A1 PCT/CN2019/104657 CN2019104657W WO2020063295A1 WO 2020063295 A1 WO2020063295 A1 WO 2020063295A1 CN 2019104657 W CN2019104657 W CN 2019104657W WO 2020063295 A1 WO2020063295 A1 WO 2020063295A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal medium
general formula
group
dielectric
Prior art date
Application number
PCT/CN2019/104657
Other languages
English (en)
French (fr)
Inventor
丁文全
周振婷
王盼盼
Original Assignee
江苏和成显示科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江苏和成显示科技有限公司 filed Critical 江苏和成显示科技有限公司
Priority to EP19864205.0A priority Critical patent/EP3858949A4/en
Priority to US17/272,416 priority patent/US11345854B2/en
Publication of WO2020063295A1 publication Critical patent/WO2020063295A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
    • C09K19/3458—Uncondensed pyrimidines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • 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
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P1/00—Auxiliary devices
    • H01P1/18—Phase-shifters
    • 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
    • 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
    • H01Q3/36—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 with variable phase-shifters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—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
    • C09K2019/181—Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—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
    • C09K2019/183—Ph-Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—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
    • C09K2019/188—Ph-C≡C-Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C09K2019/3063—Cy-Ph-C≡C-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/11—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the High Frequency technical field

Definitions

  • the invention relates to the field of liquid crystal materials, in particular to a liquid crystal medium and components capable of modulating high-frequency electromagnetic waves, and is particularly suitable for electromagnetic wave modulation in a microwave or millimeter wave region, and can be specifically applied to a liquid crystal phase shifter.
  • An antenna is a converter that converts a guided wave propagating on a transmission line into an electromagnetic wave that can propagate in an unbounded medium (usually free space), or vice versa, so as to be transmitted in a radio device Or parts that receive electromagnetic waves.
  • Engineering systems such as radio communications, broadcasting, television, radar, navigation, electronic countermeasures, remote sensing, and radio astronomy all use electromagnetic waves to transmit information, and they all need to rely on antennas to work.
  • the antenna has a special structural form, which can respond to a certain wavelength of electromagnetic waves in space and form an induced current to be transmitted to the receiver.
  • the antenna is an indispensable part of the wireless communication field, and its basic function is to transmit and receive radio waves. When transmitting, the high-frequency current is converted into electromagnetic waves; when it is received, the electric noisy waves are converted into high-frequency currents.
  • a smart antenna refers to an antenna array with spatial information (such as the direction of propagation) that can determine the signal, and an intelligent algorithm for tracking and locating the signal source, and can perform spatial filtering based on this information.
  • the base station smart antenna is an array antenna composed of multiple antenna units. By adjusting the weighted amplitude and phase of each unit signal, the array's pattern is changed to suppress interference and improve the signal-to-noise ratio.
  • the beam is directed at the user, so that the beam moves with the user.
  • the real meaning of smart antenna beam tracking is to form a high-gain narrow beam in the direction of the best path and track the change of the best path, making full use of the effective transmission power of the signal to reduce electromagnetic interference on it.
  • the phase shifter is the core component of phased array radar and satellite communication. It can change the phase difference ⁇ between adjacent antennas, so that the antenna does not need to rotate when the antenna beam is electrically scanned in space.
  • the basic requirements are: high phase shift accuracy, small size and light weight, sufficient frequency band, power capacity and phase shift, small insertion loss, and stable performance.
  • phase shifter is often called a phase shifter. It is a component often used in the microwave field. Its main function is to change the phase of transmitting electromagnetic waves.
  • phase change that is, the degree of phase shift
  • phase shift degree is the phase shift constant
  • l is the length of the transmission line
  • ⁇ g is the waveguide wavelength
  • ⁇ is the operating wavelength
  • ⁇ r is the dielectric constant
  • ⁇ c is the cutoff wavelength
  • phase shifter People are sometimes not satisfied with a fixed phase shift, and in many cases often require that the phase of the electromagnetic wave pass through the phase shifter can be adjusted within a certain range. This is the main application value of the phase shifter.
  • the requirement for the phase shifter is that the phase shift generated by the electromagnetic wave passing through the phase shifter can be adjusted, but at the same time, it does not want to bring other additional effects on the transmitted electromagnetic wave.
  • the formula shows that the phase shift degree The change depends on the change of the electrical length l / ⁇ g , and the change of the electrical length l / ⁇ g depends on two ways: changing the geometric length l of the transmission line; or changing the waveguide wavelength ⁇ g .
  • the change in the waveguide wavelength ⁇ g depends on the change in the dielectric constant ⁇ r or the cutoff wavelength ⁇ c .
  • the phase shifter adjusts the phase of the transmitted electromagnetic wave by adjusting the effect of the equivalent dielectric constant on wave propagation and changing the cut-off wavelength of the wave.
  • the phase shifter has the following key parameters:
  • the thickness of the liquid crystal used in the liquid crystal display is only a few microns, and the thickness of the liquid crystal in the phase shifter reaches several tens of microns. As the thickness of the liquid crystal layer increases, the effect of the calibration film on the liquid crystal becomes weaker, which makes the response time slower.
  • One of the methods to reduce the insertion loss is to increase the thickness of the liquid crystal layer. The relationship between the response time and the insertion loss restricts the insertion loss of the phase shifters currently prepared. Therefore, the insertion is reduced under the premise of improving the response time. Attrition is an urgent issue.
  • the maximum phase shift range and manufacturing tolerance sensitivity are indicators of the phase shift characteristics of the unit given at a specific frequency.
  • the phase emitted by the unit will also change, so the frequency range within which the unit's phase shift does not exceed a given value is defined as the unit bandwidth.
  • the ideal phase shift characteristic curve with broadband characteristics is: at different frequencies in the operating frequency range, the phase shift characteristic curves are parallel to each other; when the frequency changes, the phase change is only a constant.
  • the phase shifter can be divided into a ferrite phase shifter, a PIN diode phase shifter, a MEMS (microelectromechanical system) phase shifter, a gallium arsenide MMIC (monolithic microwave integrated circuit) shifter Phasers, ferroelectric phase shifters, and recently appeared liquid crystal phase shifters.
  • Liquid crystal media has been used in electro-optical displays for a long time to display information.
  • liquid crystal media have been used in microwave technology components or components.
  • the industrial application value of liquid crystal media in high-frequency technology is its dielectric. Performance can be controlled with variable voltages, especially for the gigahertz range.
  • the application of an electric field to the liquid crystal causes the dielectric constant parallel to the long axis of the liquid crystal molecules to be different from the dielectric constant perpendicular to the long axis of the molecules, and then the dielectric anisotropy is exhibited.
  • the above properties enable the liquid crystal medium to be used in a phase shifter to construct a tunable antenna without any moving parts.
  • a phase shifter that uses the dielectric anisotropy of a liquid crystal medium to achieve phase shifting is a liquid crystal phase shifter, which has a wide phase temperature for the liquid crystal medium, a response speed, a dielectric difference at high frequencies, and a high frequency.
  • the dielectric loss and driving voltage have extremely high requirements.
  • liquid crystal media or liquid crystal compositions suitable for high frequency electronic wave modulation There are currently some liquid crystal media or liquid crystal compositions suitable for high frequency electronic wave modulation, but these liquid crystal media generally have the following problems:
  • phase shift degree (tunability) at high frequency is not high
  • phase width is not enough, and crystallization will occur at low or normal temperature, which limits the operating range of the phase shifter.
  • the object of the present invention is to provide a low-temperature stability, large dielectric anisotropy, wide phase width, appropriate rotational viscosity, appropriate optical anisotropy, and appropriate high-frequency dielectric.
  • a liquid crystal medium having a low electric constant, a low dielectric loss, and a low loss tangent angle.
  • the liquid crystal medium is suitable for high-frequency electromagnetic wave modulation, and is particularly suitable for electromagnetic wave modulation in the microwave or millimeter wave region. It can be applied to smart antennas LCD Phaser.
  • the present invention provides a liquid crystal medium having a bright point higher than 110 ° C, a low-temperature storage temperature lower than -20 ° C, and an optical anisotropy greater than 0.35.
  • the liquid crystal medium includes:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 each independently represent a chain alkyl group containing 1 to 12 carbon atoms,
  • X 1 to X 5 each independently represent -H, -F, or -OCF 3 , and at least two of X 1 , X 2, and X 3 represent -F.
  • R 1 and R 2 are each independently selected from the group consisting of -C 2 H 5 , -C 3 H 7 , -C 4 H 9, and -C 5 H 11 .
  • the lower limit of the content of the compound of general formula I is 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%; relative
  • the upper limit of the content of the compound of the general formula I is 78%, 75%, 72%, 70%, 68%, or 65%.
  • the lower limit of the total content of the compound of the general formula II and / or III is 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30%; relative to the total weight of the liquid crystal composition of the present invention, the upper limit of the total content of the compound of the general formula II and / or III is 68%, 65%, 62%, 60%, 58% or 55%.
  • the compound of Formula II is selected from the group consisting of:
  • R 31 and R 41 each independently represent a chain alkyl group containing 2 to 6 carbon atoms
  • the compound of Formula III is selected from the group consisting of:
  • R 51 and R 61 each independently represent a chain alkyl group having 2 to 6 carbon atoms
  • R 71 represents a chain alkyl group containing 1 to 5 carbon atoms
  • the liquid crystal medium with a clear point higher than 110 ° C and a low-temperature storage temperature lower than -20 ° C can meet the outdoor use requirements of products such as phase shifters, and the optical anisotropy is greater than 0.35, which is beneficial to improve the high-frequency tunability of the liquid crystal medium Sex.
  • the components of the general formula I, general formula II and / or general formula III are beneficial for the liquid crystal medium to form large optical anisotropy, wide phase width, low high-frequency dielectric loss, and high Material quality.
  • the liquid crystal medium comprises 30 to 70% of one or more compounds selected from the general formula I, and 25 to 65% of one or more of the total weight of the liquid crystal medium.
  • the liquid crystal medium comprises: 30-70% of one or more compounds selected from the general formula I, and 1-40% or more of the total weight of the liquid crystal medium.
  • the liquid crystal medium comprises one or more compounds selected from the group consisting of 30 to 70% of the total weight of the liquid crystal medium, and one or more 5 to 35% of the total weight of the liquid crystal medium.
  • the liquid crystal medium may further include one or more selected from the general formula Compound of IV:
  • R 8 represents a chain alkyl group, a chain alkoxy group, a chain alkenyl group or a chain alkenyl group containing 4 to 12 carbon atoms;
  • R 9 represents -CN or -SCN
  • Z 1 represents a single bond, -CF 2 O-, -OCF 2- , -CO-O-, -O-CO-, or -CH 2 CH 2- ;
  • n 1 or 2.
  • the compound of Formula IV is selected from the group consisting of:
  • R 81 represents a linear alkyl group or a chain alkoxy group containing 4 to 10 carbon atoms
  • L 1 , L 2 , L 3 and L 4 each independently represent -H or -F.
  • the liquid crystal medium comprises 30 to 70% of one or more compounds selected from Formula I, and 20 to 65% of one or more of the total weight of the liquid crystal medium.
  • the lower limit of the total content of the compound of the general formula IV is 2%, 3%, 4%, 5%, 6%, 7%, 8 %, 9%, or 10%; relative to the total weight of the liquid crystal composition of the present invention, the upper limit of the total content of the compound of the general formula IV is 20%, 19%, 18%, 17%, 16%, or 15% .
  • the liquid crystal medium may further include one or more compounds selected from the general formula V:
  • R 10 and R 11 each independently represent a chain alkyl group, a chain alkoxy group, a chain alkenyl group, or a chain alkenyl group containing 1 to 12 carbon atoms;
  • Z 2 represents a single bond, -CF 2 O-, -OCF 2- , -CO-O-, -O-CO-, or -CH 2 CH 2- ;
  • n 0 or 1.
  • the compound of Formula V is selected from the group consisting of:
  • the liquid crystal medium comprises 30 to 70% of one or more compounds selected from Formula I, and 20 to 65% of one or more of the total weight of the liquid crystal medium.
  • the liquid crystal medium comprises 30 to 70% of one or more compounds selected from Formula I, and 20 to 65% of one or more of the total weight of the liquid crystal medium.
  • the liquid crystal medium comprises 30 to 65% of one or more compounds selected from Formula I, and 25 to 60% of one or more of the total weight of the liquid crystal medium.
  • the liquid crystal medium comprises 30-60% of one or more compounds selected from Formula I, and 25-60% of one or more of the total weight of the liquid crystal medium.
  • the lower limit of the content of the compound of the general formula V is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; relative to the present invention
  • the total weight of the liquid crystal composition, the upper limit of the content of the compound of the general formula V is 19%, 18%, 17%, 16% or 15%.
  • the compound of formula II of the present invention is preferably a compound of formula II-2.
  • the compound of general formula III of the present invention is preferably a compound of general formula III-3, general formula III-2.
  • the compound of general formula IV of the present invention is preferably a compound of general formula IV-1, general formula IV-3 or general formula IV-5.
  • the compound of general formula V of the present invention is preferably a compound of general formula V-1 or general formula V-3.
  • the liquid crystal medium of the present invention may further contain one or more additional additives, such as an antioxidant, a chiral dopant, or a UV stabilizer.
  • additional additives such as an antioxidant, a chiral dopant, or a UV stabilizer.
  • the total mass concentration of these additional ingredients is 10 ppm to 10%, preferably 100 ppm to 6%, based on the total mixture.
  • the respective mass percentage concentrations of the individual compounds used are preferably from 0.1% to 3%.
  • additives such as an antioxidant and a light stabilizer used in the liquid crystal medium of the present invention are preferably from the following.
  • the present invention also provides a component for high-frequency technology, which includes the above-mentioned liquid crystal medium.
  • the components for high-frequency technology are particularly suitable for operation in the microwave or millimeter wave range.
  • the liquid crystal medium of the invention has good low-temperature stability, large dielectric anisotropy, wide phase width, appropriate rotational viscosity, appropriate optical anisotropy, appropriate high-frequency dielectric constant, and low Dielectric loss and low loss tangent angle show strong tuning ability of high-frequency electromagnetic waves, especially suitable for electromagnetic wave modulation in the microwave or millimeter wave region, and have a good application prospect in liquid crystal phase shifters.
  • nPTPm the structural formula
  • n in the code represents the number of C atoms of the left alkyl group, for example, n is "3", which means that the alkyl group is -C 3 H 7 ;
  • P represents 1,4-phenylene
  • T represents ethynyl
  • m the number of C atoms of the right alkyl group.
  • m is "4", which means that the alkyl group is -C 4 H 9 .
  • Optical anisotropy was measured using an Abbe refractometer under a sodium light (589 nm) light source at 25 ° C;
  • ⁇ ⁇ ⁇ - ⁇ ⁇ , where ⁇ ⁇ is the dielectric constant parallel to the molecular axis, ⁇ ⁇ is the dielectric constant perpendicular to the molecular axis, test conditions: 25 ° C, 1KHz, test box is VA type, box thickness 6 ⁇ m.
  • Liquid crystal is introduced into a capillary of polytetrafluoroethylene (PTFE) or quartz glass.
  • the capillary has an inner radius of 180 ⁇ m and an outer radius of 350 ⁇ m, and the effective length is 2 cm.
  • the filled capillary was introduced into the center of a cylindrical cavity having a resonance frequency of 19 GHz.
  • the cavity has a length of 11.5 mm and a radius of 6 mm.
  • the input signal (source) is then applied and the results of the output signal are recorded using a commercially available network analyzer (“vector network analyzer"). For other frequencies, adjust the cavity size accordingly.
  • a liquid crystal medium having a composition and properties shown in Table 2 below was prepared.
  • a liquid crystal medium having a composition and properties shown in Table 3 below was prepared.
  • the above liquid crystal medium is additionally doped with 0.7% of the total mass of the liquid crystal medium.
  • a liquid crystal medium having a composition and properties shown in Table 4 below was prepared.
  • the above liquid crystal medium is additionally doped with 0.5% of the total mass of the liquid crystal medium. And 0.4% of the total mass of the liquid crystal medium
  • a liquid crystal medium having a composition and properties shown in Table 5 below was prepared.
  • the above liquid crystal medium is additionally doped with 1% of the total mass of the liquid crystal medium. And 0.8% of the total mass of the liquid crystal medium
  • the liquid crystal medium of the present invention has a lower dielectric loss and a loss tangent angle while maintaining substantially equivalent low-temperature stability and high-frequency dielectric constant. It also has larger optical anisotropy and better tuning ability for high-frequency electromagnetic waves.
  • the liquid crystal medium of the present invention has good low-temperature stability, large dielectric anisotropy, wide phase width, appropriate rotational viscosity, appropriate optical anisotropy, and appropriate high-frequency dielectric constant. , Low dielectric loss, and low loss tangent angle, showing strong high-frequency electromagnetic wave tuning ability.
  • the liquid crystal medium according to the present invention can be applied to the field of liquid crystal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

本发明公开了适用于高频电磁波调制的液晶介质，所述液晶介质的清亮点高于110℃，低温存储温度低于-20℃，光学各向异性大于0.35，所述液晶介质包含：占液晶介质总重量的30-80％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的20-70％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物。本发明还公开包含所述液晶介质的用于高频技术的组件。本发明的液晶介质具有良好的低温稳定性、较大的介电各向异性、较宽的相宽、适当的旋转粘度、适当的光学各向异性、适当的高频介电常数、较低的介电损耗、以及较低的损耗正切角，表现出较强的高频电磁波调谐能力，特别适用于微波或者毫米波区域的电磁波调制，在液晶移相器中具有较好的应用前景。

Description

适用于高频电磁波调制的液晶介质及其组件 技术领域
本发明涉及液晶材料领域，具体涉及可对高频电磁波进行调制的液晶介质及其组件，特别适用于微波或者毫米波区域的电磁波调制，具体可应用至液晶移相器。
背景技术
天线(antenna)是一种变换器，它可将传输线上传播的导行波变换成可以在无界媒介(通常是自由空间)中传播的电磁波，或者进行相反的变换，从而作为在无线电设备中发射或接收电磁波的部件。无线电通信、广播、电视、雷达、导航、电子对抗、遥感、射电天文等工程系统，凡是利用电磁波来传递信息的，都需要依靠天线进行工作。
天线具有一种特殊的结构形式，这种结构可以响应空间中某种特定波长的电磁波，并形成感应电流传递给接收器。天线作为无线通信领域不可缺少的一部分，其基本功能是发射和接收无线电波。发射时，将高频电流转换为电磁波；接收时，将电滋波转换为高频电流。
智能天线指的是带有可以判定信号的空间信息(比如传播方向)和跟踪、定位信号源的智能算法，并且可以根据此信息，进行空域滤波的天线阵列。基站智能天线是一种由多个天线单元组成的阵列天线，通过调节各单元信号的加权幅度和相位，改变阵列的方向图，从而抑制干扰，提高信噪比，其可以自动测出用户方向，将波束指向用户，实现波束跟随用户移动。智能天线波束跟踪的真正含义是在最佳路径方向形成高增益窄波束，并跟踪最佳路径的变化，充分利用信号的有效的发送功率以减小电磁对其的干扰。
移相器是相控阵雷达、卫星通信的核心部件，可改变相邻天线的相位差ΔΦ，可以使天线波束在空间进行电扫描时天线不需要转动。对其的基本要求主要有：移相精度要高，体积小重量轻，频带、功率容量和移相度要足够，插入损耗小，性能稳定等。
大多数相控阵系统是由铁氧体或者二极管移相器来进行控制的。移相器通常又可以称作相移器，是在微波领域经常使用的一种元器件，其主要作用就是用来改变传输电磁波的相位。
电磁波在通过一段长度为l的传输线时，在输出端其相位会产生相应的改变。这种相位改变，也就是移相度的表达式可以写为：
Figure PCTCN2019104657-appb-000001
其中，
Figure PCTCN2019104657-appb-000002
Figure PCTCN2019104657-appb-000003
为移相度，β为相移常数，l为传输线长度，λ g为波导波长，λ为工作波长，ε r为介电常数，并且λ c为截止波长。
人们有时候不满足于固定的相位移，很多情况下往往要求电磁波通过移相器时相位能够在一定范围内可调，这就是移相器的主要应用价值。对移相器的要求就是在电磁波通过移相器时其产生的相位移可以调节，但同时又不希望对传输的电磁波带来其它附加的影响。
根据上述
Figure PCTCN2019104657-appb-000004
公式可知，移相度
Figure PCTCN2019104657-appb-000005
的变化主要取决于电长度l/λ g的改变，而电长度l/λ g的改变依靠两个途径来实现：改变传输线的几何长度l；或者改变波导波长λ g。波导波长λ g的改变依赖于介电常数ε r的变化，或是截止波长λ c的变化。移相器正是通过调节等效介电常数对波传播的影响改变波的截止波长来实现对传输电磁波的相位的调节。
移相器有如下关键参数：
(1)移相度
由于移相度和介电各向异性之间成正比例关系，要获得高的移相度，必须利用介电各向异性大的液晶。由于混晶可以达到高介电各向异性，所以制备得到高介电各向异性的液晶材料是制备液晶移相器的关键。
(2)插入损耗
液晶显示器中用的液晶的厚度仅有几微米，而在移相器中液晶厚度达到了几十微米，随着液晶层厚度的增加，校准膜对液晶的作用变弱，使得响应时间变慢，而降低插入损耗的方法之一就是增加液晶层的厚度，响应时间和插入损耗之间相互制约的关系致使目前制备的移相器的插入损耗一般比较高，因而在提高响应时间的前提下降低插入损耗是急待解决的问题。
(3)单元带宽
最大移相范围和制造容差敏感度是在特定频率处给出的单元移相特性指标。事实上，当工作频率改变时，单元发出的相位也会发生改变，于是将单元移相量的变化不超过给定值的频率范围定义为单元带宽。具有宽带特性的理想的移相特性曲线是：在工作频率范围内的不同频率上，相移特性曲线相互平行；当频率改变时，相位的变化只为一个常数。
根据移相器使用的材料，可以将移相器分为铁氧体移相器、PIN二极管移相器、MEMS(微机电系统)移相器、砷化镓MMIC(单片微波集成电路)移相器、铁电移相器、以及最近出现的液晶移相器等。
液晶介质长久以来一直用于电光学显示器中以显示信息，然而近年来，液晶介质已被用于微波技术用的元件或组件中，液晶介质在高频技术中的工业应用价值在于其的介电性能可以通过可变的电压而控制，特别是对于千兆赫范围而言。对液晶施加电场，会使得平 行于液晶分子长轴的介电常数与垂直于分子长轴方向的介电常数各不相同，这时就表现出了介电各向异性。上述性能使得液晶介质能够应用于移相器中从而构造不含任何活动部件的可调谐天线。
利用液晶介质的介电各向异性的变化来实现移相目的的移相器即为液晶移相器，其对于液晶介质的相温宽、响应速度、高频下的介电差、高频下的介电损耗、以及驱动电压都有极高的要求。
目前已有一些适用于高频电子波调制的液晶介质或者液晶组合物，但是这些液晶介质普遍具有如下的问题：
1、高频下移相度(可调谐度)不高；
2、高频下插入损耗过大；以及
3、相宽不够，低温或者常温会发生晶析，限制了移相器的操作范围。
因此，进一步改进现有液晶介质的高频调制性能，特别是微波或者毫米波范围内的使用性能等，已经成为液晶材料亟待开发的方向。
发明内容
发明目的：本发明的目的是提供一种具有良好的低温稳定性、较大的介电各向异性、较宽的相宽、适当的旋转粘度、适当的光学各向异性、适当的高频介电常数、较低的介电损耗、以及较低的损耗正切角的液晶介质，所述液晶介质适用于高频电磁波调制，特别适用于微波或者毫米波区域的电磁波调制，具体可应用于智能天线中的液晶移相器。
本发明的技术方案：
为了实现上述发明目的，本发明提供一种液晶介质，其清亮点高于110℃，低温存储温度低于-20℃，光学各向异性大于0.35，所述液晶介质包含：
占液晶介质总重量的30-80％的一种或更多种选自通式Ⅰ的化合物：
Figure PCTCN2019104657-appb-000006
占液晶介质总重量的20-70％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物
Figure PCTCN2019104657-appb-000007
其中，
R 1、R 2、R 3、R 4、R 5、R 6和R 7各自独立地表示含有1-12个碳原子的链状烷基、
Figure PCTCN2019104657-appb-000008
Figure PCTCN2019104657-appb-000009
所述链状烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，并且存在于这些基团中的一个或更多个-H可分别独立地被-F或-Cl取代；并且
X 1～X 5各自独立地表示-H、-F或-OCF 3，且X 1、X 2和X 3中至少两个表示-F。
在一些实施方案中，R 1和R 2各自独立地选自由-C 2H 5、-C 3H 7、-C 4H 9和-C 5H 11组成的组。
在优选的实施方案中，通式Ⅰ的化合物的含量的下限值为31％、32％、33％、34％、35％、36％、37％、38％、39％或40％；相对于本发明的液晶组合物的总重量，通式I的化合物的含量的上限值为78％、75％、72％、70％、68％或65％。
在优选的实施方案中，相对于本发明的液晶介质的总重量，通式Ⅱ和/或Ⅲ的化合物的总含量的下限值为21％、22％、23％、24％、25％、26％、27％、28％、29％或30％；相对于本发明的液晶组合物的总重量，通式Ⅱ和/或Ⅲ的化合物的总含量的上限值为68％、65％、62％、60％、58％或55％。
在一些实施方案中，通式Ⅱ的化合物选自如下化合物组成的组：
Figure PCTCN2019104657-appb-000010
其中，
R 31和R 41各自独立地表示含有2-6个碳原子的链状烷基、
Figure PCTCN2019104657-appb-000011
在一些实施方案中，通式Ⅲ的化合物选自如下化合物组成的组：
Figure PCTCN2019104657-appb-000012
其中，
R 51和R 61各自独立地表示含有2-6个碳原子的链状烷基、
Figure PCTCN2019104657-appb-000013
并且
R 71表示含有1-5个碳原子的链状烷基、
Figure PCTCN2019104657-appb-000014
本发明的清亮点高于110℃、低温存储温度低于-20℃的液晶介质可以满足移相器等产品的户外使用需求，并且光学各向异性大于0.35有利于提高液晶介质的高频可调谐性。在本发明的液晶介质中，通式I、通式Ⅱ和/或通式Ⅲ的组分有利于液晶介质形成大的光学各向异性、宽的相宽、低的高频介电损耗以及高的材料品质。
在一些实施方案中，液晶介质包含：占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的25-65％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物。
在一些实施方案中，液晶介质包含：占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的1-40％的一种或更多种选自通式Ⅱ的化合物，以及占液晶介质总重量的1-40％的一种或更多种选自通式Ⅲ的化合物。
在一些实施方案中，液晶介质包含：占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的5-35％的一种或更多种选自通式Ⅱ的化合物，以及占液晶介质总重量的5-35％的一种或更多种选自通式Ⅲ的化合物。
为了提高液晶介质的介电各向异性，改进液晶介质的相宽，并进一步改进液晶介质的高频介电损耗以及材料品质，液晶介质中还可以进一步包含一种或更多种选自通式Ⅳ的化合物：
Figure PCTCN2019104657-appb-000015
其中，
R 8表示含有4-12个碳原子的链状烷基、链状烷氧基、链状烯基或链状烯氧基；
R 9表示-CN或-SCN；
环
Figure PCTCN2019104657-appb-000016
和环
Figure PCTCN2019104657-appb-000017
各自独立地表示
Figure PCTCN2019104657-appb-000018
其中
Figure PCTCN2019104657-appb-000019
中的一个或更多个-CH 2-可被-O-替代，环中的一个或更多个单键可被双键替代，
Figure PCTCN2019104657-appb-000020
中的一个或更多个-H可被-CN、-F或-Cl取代，一个或更多个环中-CH＝可被-N＝替代；并且
Z 1表示单键、-CF 2O-、-OCF 2-、-CO-O-、-O-CO-或-CH 2CH 2-；
m表示1或2。
在一些实施方案中，通式Ⅳ的化合物选自如下化合物组成的组：
Figure PCTCN2019104657-appb-000021
其中，
R 81表示含有4-10个碳原子的链状烷基或链状烷氧基；
L 1、L 2、L 3和L 4各自独立地表示-H或-F。
在一些实施方案中，液晶介质包含占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的20-65％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物，以及占液晶介质总重量的1-25％的一种或更多种选自通式Ⅳ的化合物。
在优选的实施方案中，相对于本发明的液晶介质的总重量，通式Ⅳ的化合物的总含量 的下限值为2％、3％、4％、5％、6％、7％、8％、9％或10％；相对于本发明的液晶组合物的总重量，通式Ⅳ的化合物的总含量的上限值为20％、19％、18％、17％、16％或15％。
在一些实施方案中，液晶介质中还可以包含一种或更多种选自通式Ⅴ的化合物：
Figure PCTCN2019104657-appb-000022
其中，
R 10和R 11各自独立地表示含有1-12个碳原子的链状烷基、链状烷氧基、链状烯基或链状烯氧基；
Z 2表示单键、-CF 2O-、-OCF 2-、-CO-O-、-O-CO-或-CH 2CH 2-；并且
n表示0或1。
在一些实施方案中，通式Ⅴ的化合物选自如下化合物组成的组：
Figure PCTCN2019104657-appb-000023
在一些实施方案中，液晶介质包含占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的20-65％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物，占液晶介质总重量的1-25％的一种或更多种选自通式Ⅴ的化合物。
在一些实施方案中，液晶介质包含占液晶介质总重量的30-70％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的20-65％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物，占液晶介质总重量的1-25％的一种或更多种选自通式Ⅳ的化合物，以及占液晶介质总重量的1-25％的一种或更多种选自通式Ⅴ的化合物。
在一些实施方案中，液晶介质包含占液晶介质总重量的30-65％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的25-60％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物，占液晶介质总重量的5-20％的一种或更多种选自通式Ⅳ的化合物，以及占液晶介质总重量的1-20％的一种或更多种选自通式Ⅴ的化合物。
在一些实施方案中，液晶介质包含占液晶介质总重量的30-60％的一种或更多种选自通式Ⅰ的化合物，占液晶介质总重量的25-60％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的 化合物，占液晶介质总重量的5-20％的一种或更多种选自通式Ⅳ的化合物，以及占液晶介质总重量的1-20％的一种或更多种选自通式Ⅴ的化合物。
在优选的实施方案中，通式Ⅴ的化合物的含量的下限值为2％、3％、4％、5％、6％、7％、8％、9％或10％；相对于本发明的液晶组合物的总重量，通式Ⅴ的化合物的含量的上限值为19％、18％、17％、16％或15％。
在一些实施方案中，本发明的通式II的化合物优选自通式II-2的化合物。
在一些实施方案中，本发明的通式III的化合物优选自通式III-3、通式III-2的化合物。
在一些实施方案中，本发明的通式IV的化合物优选自通式IV-1、通式IV-3或通式Ⅳ-5的化合物。
在一些实施方案中，本发明的通式V的化合物优选自通式V-1或通式V-3的化合物。
本发明的液晶介质可以进一步含有另外的一种或更多种添加剂，如抗氧化剂、手性掺杂剂或UV稳定剂。基于总混合物而言，这些另外的成分的总质量百分浓度为10ppm-10％，优选100ppm-6％。所使用的单个化合物的各自的质量百分浓度优选为0.1％-3％。
另外，本发明的液晶介质所使用的抗氧化剂、光稳定剂等添加剂优选自以下物质。
Figure PCTCN2019104657-appb-000024
Figure PCTCN2019104657-appb-000025
Figure PCTCN2019104657-appb-000026
本发明还提供一种用于高频技术的组件，其包含上述液晶介质。所述用于高频技术的组件特别适合于微波或者毫米波范围内操作。
有益效果：
本发明的液晶介质具有良好的低温稳定性、较大的介电各向异性、较宽的相宽、适当的旋转粘度、适当的光学各向异性、适当的高频介电常数、较低的介电损耗、以及较低的损耗正切角，表现出较强的高频电磁波调谐能力，特别适用于微波或者毫米波区域的电磁波调制，在液晶移相器中具有较好的应用前景。
具体实施方式
以下将结合具体实施方案来说明本发明。需要说明的是，下面的实施例为本发明的示例，仅用来说明本发明，而不用来限制本发明。在不偏离本发明主旨或范围的情况下，可进行本发明构思内的其他组合和各种改良。
为便于表达，以下各实施例中，液晶介质的基团结构用表1所列的代码表示：
表1液晶化合物的基团结构代码
Figure PCTCN2019104657-appb-000027
Figure PCTCN2019104657-appb-000028
以如下结构式的化合物为例：
Figure PCTCN2019104657-appb-000029
该结构式如用表1所列代码表示，则可表达为：nPTPm，代码中的n表示左端烷基的C原子数，例如n为“3”，即表示该烷基为-C 3H 7；代码中的P代表1,4-亚苯基，T代表乙炔基，m表示右端烷基的C原子数，例如m为“4”，即表示该烷基为-C 4H 9。
以下对比例2、实施例1-2中测试项目的简写代号如下(对比例1的测试条件参见对比例1所属的对比文件)：
Cp               清亮点(向列-各向同性相转变温度，℃)
LTS              低温存储温度(℃)
Δn              光学各向异性(589nm，25℃)
ne               非寻常光折射率
no               寻常光折射率
Δε             介电各向异性(1KHz，25℃)
ε ∥             平行介电各向异性(1KHz，25℃)
ε ⊥             垂直介电各向异性(1KHz，25℃)
γ1              旋转粘度(mPa·s，25℃)
其中，
光学各向异性使用阿贝折光仪在钠光灯(589nm)光源下、在25℃测试得到；并且
Δε＝ε ∥-ε ⊥，其中，ε ∥为平行于分子轴的介电常数，ε ⊥为垂直于分子轴的介电常数，测试条件：25℃、1KHz、测试盒为VA型，盒厚6μm。
高频性能测试方法：
将液晶引入聚四氟乙烯(PTFE)或者石英玻璃的毛细管中，毛细管具有180μm的内半径和350μm的外半径，有效长度为2cm。将经填充的毛细管引入到共振频率为19GHz的圆柱形空腔的中央。该空腔具有11.5mm的长度和6mm的半径。然后施加输入信号(源)，并使用市售的网络分析器(“vector network analyzer”)记录输出信号的结果。对于其他频率，相应调整腔的尺寸。
借助于A.Penirschke、S.Müller、P.Scheele、C.Weil、M.Wittek、C.Hock和R.Jakoby：“Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz”，34 thEuropean Microwave Conference-Amsterdam，第545-548页中的方程10和11，按其中所述的，由在采用装有液晶的毛细管的测量与不采用装有液晶的毛细管的测量之间共振频率和Q因子的变化来测定介电常数和在相应目标频率下的介电损耗和损耗正切角。
对比例1(CN103842474B实施例1)
制备具有如下表2中所示的组成和性质的液晶介质。
表2液晶介质的配方及其物理性能
Figure PCTCN2019104657-appb-000030
对比例2
制备具有如下表3中所示的组成和性质的液晶介质。
表3液晶介质的配方及其物理性能
Figure PCTCN2019104657-appb-000031
Figure PCTCN2019104657-appb-000032
上述液晶介质中另外还掺入液晶介质总质量的0.7％的
Figure PCTCN2019104657-appb-000033
实施例1
制备具有如下表4中所示的组成和性质的液晶介质。
表4液晶介质的配方及其物理性能
Figure PCTCN2019104657-appb-000034
上述液晶介质中另外还掺入液晶介质总质量的0.5％的
Figure PCTCN2019104657-appb-000035
以及液晶介质总质量的0.4％的
Figure PCTCN2019104657-appb-000036
实施例2
制备具有如下表5中所示的组成和性质的液晶介质。
表5液晶介质的配方及其物理性能
Figure PCTCN2019104657-appb-000037
上述液晶介质中另外还掺入液晶介质总质量的1％的
Figure PCTCN2019104657-appb-000038
以及液晶介质总质量的0.8％的
Figure PCTCN2019104657-appb-000039
对比例2、实施例1-2的高频性能测试结果如下表6所示：
(注：对比例1的液晶介质在常温下就会发生晶析，因此无法测试如下高频性能)
表7高频性能测试结果
Figure PCTCN2019104657-appb-000040
Figure PCTCN2019104657-appb-000041
根据上述测试数据，可以得出如下结论：
从对比例1与实施例1、实施例2对比可知，本发明的液晶介质具有明显更好的低温稳定性，可满足移相器的户外使用需求；并且
从对比例2与实施例1、实施例2对比可知，本发明的液晶介质在维持基本相当的低温稳定性和高频介电常数的同时，具有更低的介电损耗和损耗正切角，此外还具有较大的光学各向异性，具有更好的高频电磁波调谐能力。
综合看来，本发明的液晶介质具有良好的低温稳定性、较大的介电各向异性、较宽的相宽、适当的旋转粘度、适当的光学各向异性、适当的高频介电常数、较低的介电损耗、以及较低的损耗正切角，表现出较强的高频电磁波调谐能力。
本发明还可以由其他多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员当可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明所附的权利要求的保护范围。
工业实用性
本发明所涉及的液晶介质可以应用于液晶领域。

Claims (10)

  1. 一种适用于高频电磁波调制的液晶介质，其特征在于，所述液晶介质的清亮点高于110℃，低温存储温度低于-20℃，光学各向异性大于0.35，所述液晶介质包含：
    占液晶介质总重量的30-80％的一种或更多种选自通式Ⅰ的化合物：
    Figure PCTCN2019104657-appb-100001
    占液晶介质总重量的20-70％的一种或更多种选自通式Ⅱ和/或通式Ⅲ的化合物：
    Figure PCTCN2019104657-appb-100002
    其中，
    R 1、R 2、R 3、R 4、R 5、R 6和R 7各自独立地表示含有1-12个碳原子的链状烷基、
    Figure PCTCN2019104657-appb-100003
    Figure PCTCN2019104657-appb-100004
    所述链状烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，并且存在于这些基团中的一个或更多个-H可以各自独立地被-F或-Cl取代；并且
    X 1～X 5各自独立地表示-H、-F或-OCF 3，且X 1、X 2和X 3中至少两个表示-F。
  2. 根据权利要求1所述的液晶介质，其特征在于，R 1和R 2各自独立地选自由-C 2H 5、-C 3H 7、-C 4H 9和-C 5H 11组成的组。
  3. 根据权利要求1所述的液晶介质，其特征在于，所述通式Ⅱ的化合物选自由如下化合物组成的组：
    Figure PCTCN2019104657-appb-100005
    Figure PCTCN2019104657-appb-100006
    以及
    Figure PCTCN2019104657-appb-100007
    其中，
    R 31和R 41各自独立地表示含有2-6个碳原子的链状烷基、
    Figure PCTCN2019104657-appb-100008
  4. 根据权利要求1所述的液晶介质，其特征在于，所述通式Ⅲ的化合物选自由如下化合物组成的组：
    Figure PCTCN2019104657-appb-100009
    Figure PCTCN2019104657-appb-100010
    以及
    Figure PCTCN2019104657-appb-100011
    其中，
    R 51和R 61各自独立地表示含有2-6个碳原子的链状烷基、
    Figure PCTCN2019104657-appb-100012
    并且
    R 71表示含有1-5个碳原子的链状烷基、
    Figure PCTCN2019104657-appb-100013
  5. 根据权利要求1所述的液晶介质，其特征在于，所述液晶介质还包含一种或更多种选自通式Ⅳ的化合物：
    Figure PCTCN2019104657-appb-100014
    其中，
    R 8表示含有4-12个碳原子的链状烷基、链状烷氧基、链状烯基或链状烯氧基；
    R 9表示-CN或-SCN；
    环
    Figure PCTCN2019104657-appb-100015
    和环
    Figure PCTCN2019104657-appb-100016
    各自独立地表示
    Figure PCTCN2019104657-appb-100017
    其中
    Figure PCTCN2019104657-appb-100018
    中的一个或更多个-CH 2-可被-O-替代，环中的一个或更多个单键可被双键替 代，
    Figure PCTCN2019104657-appb-100019
    中的一个或更多个-H可被-CN、-F或-Cl取代，一个或更多个-CH＝可被-N＝替代；并且
    Z 1表示单键、-CF 2O-、-OCF 2-、-CO-O-、-O-CO-或-CH 2CH 2-；
    m表示1或2。
  6. 根据权利要求5所述的液晶介质，其特征在于，所述通式Ⅳ的化合物选自由如下化合物组成的组：
    Figure PCTCN2019104657-appb-100020
    Figure PCTCN2019104657-appb-100021
    以及
    Figure PCTCN2019104657-appb-100022
    其中，
    R 81表示含有4-10个碳原子的链状烷基或链状烷氧基；并且
    L 1、L 2、L 3和L 4各自独立地表示-H或-F。
  7. 根据权利要求1所述的液晶介质，其特征在于，所述液晶介质中还可以包含一种或更多种选自通式Ⅴ的化合物：
    Figure PCTCN2019104657-appb-100023
    其中，
    R 10和R 11各自独立地表示含有1-12个碳原子的链状烷基、链状烷氧基、链状烯基或链状烯氧基；
    Z 2表示单键、-CF 2O-、-OCF 2-、-CO-O-、-O-CO-或-CH 2CH 2-；并且
    n表示0或1。
  8. 根据权利要求7所述的液晶介质，其特征在于，所述通式Ⅴ的化合物选自由如下化合物组成的组：
    Figure PCTCN2019104657-appb-100024
    Figure PCTCN2019104657-appb-100025
    以及
    Figure PCTCN2019104657-appb-100026
  9. 根据权利要求1-8中任一项所述的液晶介质，其特征在于，所述液晶介质还含有一种或更多种添加剂。
  10. 一种用于高频技术的组件，所述组件包含如权利要求1-9中任一项所述的液晶介质。
PCT/CN2019/104657 2018-09-29 2019-09-06 适用于高频电磁波调制的液晶介质及其组件 WO2020063295A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19864205.0A EP3858949A4 (en) 2018-09-29 2019-09-06 LIQUID CRYSTAL DIELECTRIC APPLICABLE TO HIGH FREQUENCY ELECTROMAGNETIC WAVES MODULATION, AND ASSOCIATED COMPONENT
US17/272,416 US11345854B2 (en) 2018-09-29 2019-09-06 Liquid crystal dielectric applicable to high-frequency electromagnetic wave modulation, and component thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811148106.0 2018-09-29
CN201811148106.0A CN110964540B (zh) 2018-09-29 2018-09-29 适用于高频电磁波调制的液晶介质及其组件

Publications (1)

Publication Number Publication Date
WO2020063295A1 true WO2020063295A1 (zh) 2020-04-02

Family

ID=69951154

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/104657 WO2020063295A1 (zh) 2018-09-29 2019-09-06 适用于高频电磁波调制的液晶介质及其组件

Country Status (5)

Country Link
US (1) US11345854B2 (zh)
EP (1) EP3858949A4 (zh)
CN (1) CN110964540B (zh)
TW (1) TWI723539B (zh)
WO (1) WO2020063295A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220119710A1 (en) * 2020-10-21 2022-04-21 Jnc Corporation Liquid crystal composition and element used for phase control of electromagnetic wave signal

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110964540B (zh) * 2018-09-29 2023-04-14 江苏和成显示科技有限公司 适用于高频电磁波调制的液晶介质及其组件

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102510891A (zh) * 2009-09-25 2012-06-20 默克专利股份有限公司 用于高频技术的组件和液晶介质
CN103320143A (zh) * 2013-06-05 2013-09-25 江苏和成显示科技股份有限公司 液晶组合物及其应用
WO2018077765A1 (en) * 2016-10-24 2018-05-03 Merck Patent Gmbh Liquid-crystalline medium

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2503456B2 (ja) * 1986-11-14 1996-06-05 カシオ計算機株式会社 液晶組成物
WO2002100979A1 (de) * 2001-06-13 2002-12-19 Merck Patent Gmbh Flüssigkristallines medium und flüssigkristallanzeige mit hoher verdrillung
DE102004029429B4 (de) * 2003-07-11 2019-04-04 Merck Patent Gmbh Bauelemente für die Hochfrequenztechnik
WO2011066905A1 (de) * 2009-12-03 2011-06-09 Merck Patent Gmbh Bauteile für die hochfrequenztechnik, flüssigkristalline medien und verbindungen
DE102012003867A1 (de) * 2011-03-24 2012-09-27 Merck Patent Gmbh Mesogene Verbindungen, flüssigkristalline Medien und Bauteile für die Hochfrequenztechnik
US9605204B2 (en) * 2011-12-21 2017-03-28 Merck Patent Gmbh Liquid crystal medium and high frequency components comprising same
CN102634347B (zh) * 2012-03-20 2014-04-16 江苏和成显示科技股份有限公司 具有大的光学各向异性的液晶组合物及液晶显示元件
CN104870611B (zh) * 2012-12-21 2017-04-26 默克专利股份有限公司 液晶介质、用于高频技术的组件和介晶化合物
JP6961485B2 (ja) * 2014-12-29 2021-11-05 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung 液晶媒体およびそれを含む高周波数素子
US10676670B2 (en) * 2014-12-30 2020-06-09 Merck Patent Gmbh Liquid-crystalline medium and high-frequency components comprising same
CN104650927A (zh) * 2015-02-09 2015-05-27 石家庄诚志永华显示材料有限公司 液晶组合物
WO2017162716A1 (en) * 2016-03-24 2017-09-28 Merck Patent Gmbh Liquid-crystalline medium
CN107434973B (zh) * 2016-05-27 2023-01-10 江苏和成显示科技有限公司 液晶化合物及其组合物和应用
CN110964540B (zh) * 2018-09-29 2023-04-14 江苏和成显示科技有限公司 适用于高频电磁波调制的液晶介质及其组件

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102510891A (zh) * 2009-09-25 2012-06-20 默克专利股份有限公司 用于高频技术的组件和液晶介质
CN103320143A (zh) * 2013-06-05 2013-09-25 江苏和成显示科技股份有限公司 液晶组合物及其应用
WO2018077765A1 (en) * 2016-10-24 2018-05-03 Merck Patent Gmbh Liquid-crystalline medium

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. PENIRSCHKES. MULLERP. SCHEELEC. WEILM. WITTEKC. HOCKR. JAKOBY: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz", 34TH EUROPEAN MICROWAVE CONFERENCE-AMSTERDAM, pages 545 - 548
See also references of EP3858949A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220119710A1 (en) * 2020-10-21 2022-04-21 Jnc Corporation Liquid crystal composition and element used for phase control of electromagnetic wave signal
US12060514B2 (en) * 2020-10-21 2024-08-13 Jnc Corporation Liquid crystal composition and element used for phase control of electromagnetic wave signal

Also Published As

Publication number Publication date
EP3858949A1 (en) 2021-08-04
TWI723539B (zh) 2021-04-01
US11345854B2 (en) 2022-05-31
CN110964540A (zh) 2020-04-07
TW202012602A (zh) 2020-04-01
EP3858949A4 (en) 2022-06-22
US20210317369A1 (en) 2021-10-14
CN110964540B (zh) 2023-04-14

Similar Documents

Publication Publication Date Title
KR101990164B1 (ko) 액정 매질 및 이를 포함하는 고주파 컴포넌트
JP6189323B2 (ja) 液晶媒体およびそれを含む高周波コンポーネント
CN108865180B (zh) 一种液晶组合物及包含其的高频组件
TWI567174B (zh) 液晶介質及含彼之高頻組件
CN109735348B (zh) 一种高介电各向异性的液晶组合物以及高频组件
WO2021208315A1 (zh) 一种具有极低介电损耗的液晶组合物及其高频组件
WO2020063295A1 (zh) 适用于高频电磁波调制的液晶介质及其组件
JP2022075534A (ja) 液晶組成物並びにこれを用いた液晶表示素子、センサ、液晶レンズ、光通信機器及びアンテナ
JP2022048990A (ja) 電磁波信号の位相制御用の素子に使用される液晶組成物
WO2022145248A1 (ja) 液晶材料の製造方法及び液晶材料の評価方法とその測定装置、並びに液晶材料
Liu et al. Synthesis and microwave dielectric properties of polyphenylene liquid crystal compounds with lateral substitution by methyl and fluorine
CN110964541B (zh) 适用于高频电磁波调制的液晶介质及其组件
CN108865179B (zh) 一种液晶组合物和包含其的高频组件
CN112824489B (zh) 液晶组合物、高频组件及微波天线阵列
CN103351881A (zh) 低介电频率依赖性液晶组合物及包含该组合物的pm显示器
TW202116981A (zh) 液晶組成物、液晶元件、感測器、液晶透鏡、光通信設備及天線
JP2019143115A (ja) 液晶組成物および液晶高周波アンテナ
CN112824494B (zh) 液晶组合物、高频组件及微波天线阵列
CN112824484B (zh) 液晶组合物、高频组件及微波天线阵列
CN114106849B (zh) 一种含有共轭烯化合物的液晶组合物及其应用
CN112824486B (zh) 液晶组合物、高频组件及微波天线阵列
CN112824485A (zh) 液晶组合物、高频组件及微波天线阵列
CN112824483A (zh) 液晶组合物、高频组件及微波天线阵列

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19864205

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2019864205

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2019864205

Country of ref document: EP

Effective date: 20210429