WO2013034227A1 - Liquid-crystalline medium and high-frequency components comprising same - Google Patents

Liquid-crystalline medium and high-frequency components comprising same Download PDF

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Publication number
WO2013034227A1
WO2013034227A1 PCT/EP2012/003363 EP2012003363W WO2013034227A1 WO 2013034227 A1 WO2013034227 A1 WO 2013034227A1 EP 2012003363 W EP2012003363 W EP 2012003363W WO 2013034227 A1 WO2013034227 A1 WO 2013034227A1
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compounds
liquid
formula
independently
another
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PCT/EP2012/003363
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French (fr)
Inventor
Atsutaka Manabe
Dagmar Klass
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Merck Patent Gmbh
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Priority to JP2014527516A priority Critical patent/JP6140160B2/en
Priority to KR1020147008703A priority patent/KR101990164B1/en
Priority to EP12746283.6A priority patent/EP2753676B1/en
Priority to CN201280042892.0A priority patent/CN103764792B/en
Priority to US14/342,034 priority patent/US20140217325A1/en
Publication of WO2013034227A1 publication Critical patent/WO2013034227A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
    • C07C15/54—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed containing a group with formula
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
    • 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
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed 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
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004—Cy-Cy
    • 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 present invention relates to liquid-crystalline media and to high- frequency components comprising same, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, in particular for microwave phased-array antennas.
  • Liquid-crystalline media have been used for some time in electro-optical displays (liquid crystal displays - LCDs) in order to display information.
  • liquid-crystalline media have also been proposed for use in components for microwave technology, such as, for example, in WO 201 1/009524 A8, DE 10 2004 029 429 A and in JP 2005-120208 (A).
  • phase shifter losses are determined primarily by the dielectric LC losses and the losses at the waveguide junctions.
  • DE 10 2004 029 429 A describes the use of liquid-crystalline media in microwave technology, inter alia in phase shifters.
  • DE 10 2004 029 429 A has already investigated liquid-crystalline media with respect to their properties in the corresponding frequency range.
  • Liquid-crystalline media comprising for example compounds of the formula below, are used as a host mixture for the investigation of compounds, which are suggested for the usage in components for microwave applications and are described in F. Golden, "Liquid Crystal Based Microwave Components with Fast Response Times: Materials, Technology, Power Handling
  • Fast switching performances are especially needed for mobile applications e.g. for receiving and sending communication, television or video to vehicles like ships, planes, trains and cars.
  • Other preferred applications are short-distance antennas of the wireless routers to the laptop PCs, tablet computers and mobile devices.
  • liquid-crystalline media having particular, hitherto rather unusual, uncommon properties, or combinations of properties, are required.
  • Novel liquid-crystalline media having improved properties are thus necessary.
  • fast switching liquid-crystalline media with low values for the rotational viscosity ( ⁇ ) are required, which also exhibit an acceptable tunability ( ⁇ ).
  • the dielectric anisotropy in the microwave region is defined as
  • the tuneability ( ⁇ ) is defined as ⁇ ( ⁇ ⁇ / ⁇ ⁇ . ⁇ ).
  • the material quality ( ⁇ ) is defined as ⁇ ( ⁇ / tan ⁇ ⁇ tjm ), where the maximum dielectric loss is tan ⁇ ⁇ ⁇ max. ⁇ tan ⁇ ⁇ r . x ; tan ⁇ ⁇ r j i ⁇ .
  • liquid- crystalline medium having a suitably high ⁇ , broad nematic phase ranges, a suitable high ⁇ and especially, low rotational rotation viscosity in connection with an acceptable tunability that do not have the
  • the invention further relates to a component for high-frequency technology comprising a liquid-crystalline medium as described above and below.
  • a component for high-frequency technology comprising a liquid-crystalline medium as described above and below.
  • both high-frequency technology and hyper-frequency technology denote applications having frequencies in the range from 1 MHz to 1 THz, preferably from 1 GHz to 500 GHz, more preferably
  • the invention further relates to the use of liquid-crystalline media as described above and below in a component for high-frequency technology.
  • the invention further relates to a microwave device, comprising a component as described above and below.
  • Said devices and components include, without limitation, phase shifters, varactors, wireless and radio wave antenna arrays, phased array antennas, reflectarray antenna, adaptable matching circuit, tunable filter and others.
  • liquid-crystalline media of this invention show the following advantageous properties:
  • the media are especially suitable for mass production and can be processed using industry standard equipment.
  • the compounds of the formula I are selected from the group of compounds of the formulae IA to IC,
  • the compounds of the formula IA are preferably selected from the group of compounds of formulae IA-1 to IA-6,
  • More preferred compounds of formulae IA-1 to IA-6 are selected from compounds of formulae IA-1 and/or IA-2 and/or IA-3, even more preferred are compounds of formula IA-2.
  • the compounds of the formula IB are preferably selected from compounds of formulae IB-1 to IB-3,
  • Most preferred compounds of formula IB are compounds of formula IB-1.
  • R 1 1 * has the meaning indicated above for R 11 in formula and preferably denote C n H 2 n+i ,
  • R 12 in formula I has the meaning indicated above for R 12 in formula I and preferably denote C n H 2n+1 , n denotes an integer in the range from 1 to 7 and preferably from 1 to 5,
  • L has, each and independently to one another in each occurrence one of the meanings of R 1 different from H, r denotes, each and independently to one another in
  • each occurrence 0, 1, 2, 3 or 4, and y and z independently of one another, denote 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • More preferred compounds of formulae IB-1a to IB-1e are compounds of formulae IB-1a and IB-1c.
  • Compounds of the formula IC are preferably selected from the group of the compounds of formulae IC-1 to IC-3, most preferably of formula IC-1
  • R 11 has the meaning indicated above in formula I and
  • the compounds of the formula IC are selected from the group of compounds of the formulae IC-4 to IC-12:
  • liquid-crystalline media comprise one or more compounds of formula II,
  • R 21 has the meaning indicated above for R 1 in formula I and preferably denotes C n H 2n+ i or O-CnH 2 n+i,
  • CH 2 CH-(CH 2 )z, more preferably C n H 2n +i, and
  • Compounds of the formula II are preferably selected from the group of compounds of formulae HA to IIE,
  • n denotes an integer in the range from 1 to 7 and
  • Especially preferred compounds of formulae IIA to HE are compounds of formulae IIC and IID, and wherein m denotes 2 and 4.
  • liquid-crystalline media comprise optionally one or more compounds of formula
  • R 11 in formula I has the meaning indicated above for R 11 in formula I and preferably denotes C n H 2n +i or 0-C n H 2n +i or
  • CH 2 CH-(CH 2 )z or (CH 2 ) Z -C ⁇ C- C n H 2n+ i and n denotes an integer in the range from 1 to 7 and
  • Z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2, and denote independently of one another, and in case A 32 and/or A 33 is/are present twice, also these independently of one another denote
  • L 31 and L 3 denote independently of one another H or F, X 31 denotes halogen, halogenated alkyl or alkoxy with 1 to 5
  • Z 31 to Z 33 denote independently of one another, and in case Z 31 and/or Z 32 is/are present twice, also these
  • Compounds of the formula III are preferably selected from the group of compounds of formulae IIIA to MID,
  • R 31 , A 31 to A 33 , Z 31 to Z 33 , L 31 and L 32 and X 31 have the meanings indicated above in formula III.
  • Preferred compounds of formula IIIA are selected from compounds of formulae IIIA-1 to IIIA-31 as indicated below:
  • Especially preferred compounds of formulae IIIA-1 to IIIA-31 are compounds of formulae IIIA-4, IIIA-6, IIIA-8 and IIIA-22.
  • Compounds of formula IIIB are preferably selected from the group of compounds of formulae IIIB-1 to IIIB-11 as indicated below:
  • R 31 and X 31 have the meanings indicated above in formula III.
  • Especially preferred compounds of formulae IIIB-1 to IIIB-11 are compounds of formulae IIIB-1 , IIIB-4 and IIIB-10, more preferably IIIB-10.
  • Preferred compounds of formula IMC are selected of formulae IIIC-1 to IIIC-9 as indicated below:
  • Preferred compounds of formula MID are selected of compounds of formulae IIID-1 and IIID-2:
  • the media in accordance with the present invention optionally comprise one or more compounds of the formula IV having three six-membered rings,
  • R 41 and R 42 independently of one another, denote unfluorinated a!kyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyi having 2 to 15, preferably 3 to 10, C atoms, preferably
  • Compounds of the formula IVA are preferably selected from the group of compounds of the formulae IVA-1 to IVA-7,
  • L 41 and L 42 each, independently of one another, denote H or F.
  • the media in accordance with the present invention optionally comprise one or more compounds of the formula V having four six-membered rings, wherein independently of one another, denote unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably
  • Z 51 to Z 53 independently of one another, denote -CH 2 CH 2 -, trans-
  • -CH CH- or a single bond, preferably one or more of them denotes a single bond, and particularly preferably all denote a single bond,
  • the compounds of the formula V are preferably selected from the group of compounds of the formulae VA to VC,
  • the preferred combinations of (R 51 and R 52 ) are, in particular, (C n H 2n +i and C m H 2m +i) and (C n H 2n -n and 0-C m H 2m+ i).
  • the compounds of the formula VA are preferably selected from the group of compounds of the formulae VA-1 to VA-6,
  • R 51 has the meaning indicated above in formula V and
  • R 52 has the meaning indicated above in formula V and
  • n and m independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • (R 51 and R 52 ) are, in particular, (C n H 2 n ⁇ i and
  • the compounds of formula VB are preferably selected from the group of compounds of the formulae VB-1 and VB-2,
  • R 51 has the meaning indicated above in formula Vand preferably denotes C n H 2 n+i, and n denotes an integer in the range from 1 to 7 and
  • the compounds of the formula VC are preferably selected from
  • R has the meaning indicated above and preferably
  • n and m independently of one another denote an in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
  • the preferred combinations of (R 51 and R° 2 ) here are, in particular, (C n H 2n+ i and C m H 2m+ i ) and (C n H 2n+ i and 0-C m H 2m+1 ), particularly preferably (C n H 2n+ i and 0-C m H 2m+1 ).
  • the compounds of formulae I to V can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • R 1 has the meaning indicated above for R 1 in formula and preferably denotes C n H 2n +i ,
  • R 12 * has the meaning indicated above for R 12 in formula
  • C n H 2 n+i denotes an integer in the range from 1 to 7 and preferably from 1 to 5, has, each and independently to one another in each occurrence one of the meanings of R 11 different from H, denotes, each and independently to one another in each occurrence 0, 1 : 2, 3 or 4.
  • R 11 * has the meaning indicated above for R 11 in formula I and preferably denotes C n H 2n +i,
  • R 12 * has the meaning indicated above for R 12 in formula I and preferably denotes C n H 2n +i, denotes an integer in the range from 1 to 7 and preferably from 1 to 5, has, each and independently to one another in each occurrence one of the meanings of R 11 different from H, r denotes, each and independently to one another in each occurrence 0, 1 , 2, 3 or 4.
  • the liquid-crystalline media according to the invention consist of a plurality of compounds, preferably 3 to 20, more preferably 3 to 15 and more preferably 3 to 10 compounds. These compounds are mixed in a
  • the liquid-crystalline media comprise one or more compounds of the formula I and one or more compounds of the formula II.
  • the liquid- crystalline media comprise one or more compounds of the formula I, one or more compounds of the formula II and one or more compounds of the formula III.
  • liquid-crystalline media comprise one or more compounds of the formula I, one or more
  • liquid-crystalline media comprise one or more compounds of the formula I, one or more
  • liquid-crystalline media which comprise one or more compounds of the formula I and one or more compounds of the formula II, and/or one or more compounds of the formula III, and/or one or more compounds of the formula IV and/or one or more compounds of the formula V.
  • the liquid-crystalline media in accordance with the present application preferably comprise 5 to 80 %, preferably 10 to 75 %, more preferably 15 to 65 % in total of the whole mixture of compounds of the formula I.
  • the liquid-crystalline media comprises one, two, three or more compounds of formula I.
  • liquid-crystalline media in accordance with the present application preferably comprise
  • totai 0 to 50 %, preferably 3 to 45 % and particularly preferably 5 to 40 % of compounds of the formula IV and/or V, but all together in a total amount ⁇ 100 %.
  • liquid-crystalline media comprising, 5 to 80 %, more preferably 10 to 75 %, even more preferably 15 to 65 % in total of the whole mixture of one or more compounds of formula I, preferably selected from compounds of formulae IA : IB and IC, more preferably selected from compounds of formulae IA-2, IB-1a, IB-1c and IC-I to IC-3, and
  • III preferably selected from compounds of formulae IIIA to HID, more preferably selected from compounds of formulae IIIA-4 and/or IIIA-6 and/or IIIB-4 and/or IIIB-10 and/or IIIC-4 and/or IIIC-7, and/or
  • IV preferably selected from compounds of formulae IVA-1 to IVA-7, more preferably selected from compounds of formula IVA-1 , and /or 1 to 40 %, preferably 3 to 35 % and particularly preferably 5 to 30 %, in total of the whole mixture of one or more compounds of the formula V, preferably selected from compounds of formulae VA to VC more preferably selected from compounds of formulae VA-3 and/or VB-1 , but in a total amount of the total mixture ⁇ 100 %.
  • liquid-crystalline media according to the present invention consist exclusively of the above-mentioned compounds.
  • compositions in connection with compositions means that the entity in question, i.e. the medium comprises the compound or compounds indicated, preferably in a total concentration of 3 % or more and more preferably 5 % or more. Additionally, “consist exclusively” means that the entity in question comprises preferably 99 % or more and more preferably 100.0 % of the compound or compounds indicated.
  • the liquid-crystalline media according to the present invention may contain further additives, like dyes, antioxidants, chiral dopants, UV stabilizers, in usual concentrations.
  • the total concentration of these further constituents is in the range of 50 ppm to 10 %, preferably 100 ppm to 6 %, based on the total mixture.
  • the concentrations of the individual compounds used each are preferably in the range of 0.1 % to 3 %.
  • the liquid-crystalline media in accordance with the present invention preferably have a clearing point of 80°C or more, more preferably 90°C or more, even more preferably 100°C or more, most preferably 120°C or more but having crystallisation points of - 20°C or lower, more preferably - 30°C or lower, even more preferably - 40°C or lower. Most preferably, all limits are independently combined with each other.
  • the liquid-crystalline media according to the invention preferably have nematic phases of in each case at least from -20°C to 80°C, preferably from -30°C to 100°C and more particularly preferably from -40°C to 120°C. Most preferably, all limits are independently combined with each other.
  • the expression have a nematic phase here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating from the nematic phase.
  • the ⁇ of the liquid-crystalline media in accordance with the invention are preferably 1 or more, more preferably 2 or more and more preferably 3 or more.
  • dielectrically positive describes compounds or components where ⁇ > 3.0
  • dielectrically neutral describes those where -1.5 ⁇ ⁇ ⁇ 3.0
  • dielectrically negative describes those where ⁇ ⁇ -1.5.
  • ⁇ is determined at a frequency of 1 kHz and at 20°C.
  • the dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10 %, the concentration is reduced to 5%.
  • the capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 ⁇ .
  • the voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.
  • ⁇ is defined as ( ⁇
  • the host mixture used for dielectrically positive compounds is mixture ZLI-4792 and that used for dielectrically neutral and dielectrically negative compounds is mixture ZLI-3086, both from Merck KGaA, Germany.
  • the absolute values of the dielectric constants of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 00 %.
  • the ⁇ of the liquid-crystalline media in accordance with the present invention is preferably in the range from 0.230 or more to 0.90 or less, more preferably in the range from 0.240 or more to 0.90 or less, even more preferably in the range from 0.250 or more to 0.85 or less. Most preferably, all limits are independently combined with each other.
  • liquid-crystalline media according to the invention are characterised by high dielectric anisotropy values in the microwave range at 19 GHz is, for example, 0.50 or more, preferably 0.60 or more, more preferably 0.70 or more. Most preferably, all limits are independently combined with each other.
  • the liquid-crystalline media are investigated with respect to their properties in the microwave frequency range as described in A. Penirschke, S.
  • the liquid crystal is introduced into a polytetrafluoroethylene (PTFE) or fused silica capillary.
  • the capillary has an internal radius of 180 ⁇ and an external radius of 350 ⁇ .
  • the effective length is 2.0 cm.
  • the filled capillary is introduced into the centre of the cavity with a resonance frequency of 30 GHz.
  • This cavity has a length of 6.6 mm, a width of 7.1 mm and a height of 3.6 mm.
  • the input signal (source) is then applied, and the result of the output signal is recorded using a commercial vector network analyser. For other frequencies (e.g. 19 GHz), the dimensions of the cavity can be adjusted accordingly.
  • the values for the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by alignment of the liquid crystal in a magnetic field.
  • the magnetic field of a permanent magnet is used.
  • the strength of the magnetic field is 0.35 tesla.
  • the alignment of the magnets is set correspondingly and then rotated correspondingly through 90°.
  • the rotational viscosity ( ⁇ ) of the preferred liquid-crystalline media are, preferably in combination with the above indicated ranges for the nematic phase, ⁇ to 600 mPa s, preferably ⁇ 400 mPa-s, more preferably
  • the tunability ( ⁇ ) of the liquid-crystalline media are preferably in
  • the material quality ( ⁇ ) of the preferred liquid-crystalline materials are ⁇ 8, preferably ⁇ 9, more preferably 10, but ⁇ 35, preferably ⁇ 30 and more preferably ⁇ 25. Most preferably, all limits are independently combined with each other.
  • the preferred ranges for T(N,I), ⁇ 1 ( ⁇ and ⁇ are combined with each other.
  • the liquid crystalline media according tc the present invention are very well suited for the preparation of microwave components, such as tunable phase shifters. These may be tuned by the application of magnetic and/or electric fields. Tuning by electric fields is generally preferred. These phase shifters are operable in the UHF-band (0.3-1 GHz), L-band (1-2GHz), S- band (2-4GHz), C-band (4-8GHz), X-band (8-12GHz), Ku-band (12- 18GHz), K-band (18-27GHz), Ka-band (27-40GHz), V-band (50-75GHz), W-band (75-110GHz) and up to 1THz.
  • Preferable frequencies for operation are C-band, X-band, Ku-band, K- band, Ka-band, V-band, W-band, and up to 1THz.
  • Particularly preferable frequencies for operation are Ku-band, K-band, Ka-band, V-band, W-band, and up to 1THz.
  • phase shifters typically loaded line phase shifters, "inverted microstrip lines” (short IMSL), Finline phase shifters, preferably Antipodal Finline phase shifters, slotline phase shifters, microstrip line phase shifters or coplanar waveguides (CPW) phase shifters are used.
  • IMSL inverted microstrip lines
  • Finline phase shifters preferably Antipodal Finline phase shifters, slotline phase shifters, microstrip line phase shifters or coplanar waveguides (CPW) phase shifters are used.
  • CPW coplanar waveguides
  • reconfigurable antenna arrays which are fully electrically reconfigurable and which allow to steer the main beam direction of the antennas, to blank out interferers and/or to achieve high directivity.
  • Another preferred embodiment is waveguide partially filled with the liquid crystals according to the present invention, as described in WO 2011/036243 A1 , which is encompassed herein by reference herewith.
  • inventive phase shifters are combined into array antennas, preferably into phased array antennas, reflectarray antennas, and arrays consisting of Vivaldi antennas.
  • tunable antenna arrays are satellite communication systems, for operation e.g. between satellites, from satellites to ground stations, from mobile ground stations via satellite to stationary ground stations or to other mobile ground stations, e.g. for receiving and sending communication, television or video to vehicles like ships, planes, trains and cars.
  • Other preferred applications are short-distance antennas of the wireless routers to the laptop PCs, tablet computers and mobile devices.
  • mesogenic group means a group with the ability to induce liquid crystal (LC) phase behaviour.
  • the compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds (e.g. liquid-crystalline host mixture), or when the mesogenic compounds or the mixtures thereof are polymerised.
  • liquid crystal is used hereinafter for both mesogenic and LC materials.
  • alkyl preferably encompasses straight chain and branched alkyl groups having 1 to 15 carbon atoms, in particular the straight chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 10 carbon atoms are generally preferred.
  • alkenyl preferably encompasses straight chain and branched alkenyl groups having 2 to 15 carbon atoms, in particular the straight-chain groups.
  • Particularly preferred alkenyl groups are C2- to C 7 -1 E-alkenyl, C - to C -3E-alkenyl, C 5 - to C 7 -4-alkenyl, C 6 - to C 7 -5-alkenyl and C 7 -6-alkenyl, in particular C2- to C 7 -1 E-alkenyl, C 4 - to C 7 -3E-alkenyl and C 5 - to C 7 -4- alkenyl.
  • alkenyl groups are vinyl, 1 E-pro- penyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-butenyl, 3E- pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.
  • fluoroalkyl preferably encompasses straight-chain groups having terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl,
  • oxaalkyi or "alkoxyalkyl” preferably encompasses straight-chain radicals of the formula C n H 2n +i-0-(CH 2 ) m , wherein n and m each, independently of one another, denote 1 to 10.
  • n is 1 and m is 1 to 6.
  • V -CH CH- Zl -O-CO-
  • n and m each denote integers and the three dots are placeholders for other abbreviations from this table.
  • a liquid-crystalline mixture M-1 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-2 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-3 having the composition and properties indicated in the following table is prepared.
  • a liquid-crystalline mixture M-4 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-5 having the composition and properties indicated in the following table is prepared.
  • a liquid-crystalline mixture M-6 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-7 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-8 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-9 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-10 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystaliine mixture M-11 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-12 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-13 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-14 having the composition and propertie indicated in the following table is prepared.
  • a liquid-crystalline mixture M-15 having the composition and properties indicated in the following table is prepared.
  • a liquid-crystalline mixture M-16 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-17 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-18 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-19 having the composition and properties indicated in the following table is prepared.
  • a liquid-crystalline mixture M-20 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-21 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-22 having the composition and properties as indicated in the following table is prepared.
  • a liquid-cp/stalline mixture M-23 having the composition and properties indicated in the following table is prepared.
  • a liquid-crystalline mixture M-24 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-25 having the composition and properties as indicated in the following table is prepared.
  • a liquid-crystalline mixture M-25 having the composition and properties as indicated in the following table is prepared.

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Abstract

The present invention relates to liquid-crystalline media and to high- frequency components comprising same, especially microwave components for high-frequency devices, such as devices for shifting the phase microwaves, in particular for microwave phased-array antennas.

Description

Liquid-crystalline medium and
high-frequency components comprising same
The present invention relates to liquid-crystalline media and to high- frequency components comprising same, especially microwave components for high-frequency devices, such as devices for shifting the phase of microwaves, in particular for microwave phased-array antennas.
Liquid-crystalline media have been used for some time in electro-optical displays (liquid crystal displays - LCDs) in order to display information.
Recently, however, liquid-crystalline media have also been proposed for use in components for microwave technology, such as, for example, in WO 201 1/009524 A8, DE 10 2004 029 429 A and in JP 2005-120208 (A).
As a typical microwave application, the concept of the inverted microstrip line as described by K.C. Gupta, R. Garg, I. Bahl and P. Bhartia: Microstrip Lines and Slotlines, 2nd ed., Artech House, Boston, 1996, is employed, for example, in D. Dolfi, M. Labeyrie, P. Joffre and J. P. Huignard: Liquid Crystal Microwave Phase Shifter. Electronics Letters, Vol. 29, No. 10, pp. 926-928, May 1993, N. Martin, N. Tentillier, P. Laurent, B. Splingart, F. Huert, PH. Gelin, C. Legrand: Electrically Microwave Tuneable
Components Using Liquid Crystals. 32nd European Microwave Conference, pp. 393-396, Milan 2002, or in Weil, C: Passiv steuerbare
Mikrowellenphasenschieber auf der Basis nichtlinearer Dielektrika
[Passively Controllable Microwave Phase Shifters based on Nonlinear Dielectrics], Darmstadter Dissertationen D17, 2002, C. Weil, G. Lussem, and R. Jakoby: Tuneable Invert-Microstrip Phase Shifter Device Using Nematic Liquid Crystals, IEEE MTT-S Int. Microw. Symp., Seattle, Washington, June 2002, pp. 367-370, together with the commercial liquid crystal K15 from Merck KGaA. C. Weil, G. Lussem, and R. Jakoby: Tuneable Invert-Microstrip Phase Shifter Device Using Nematic Liquid Crystals, IEEE MTT-S Int. Microw. Symp., Seattle, Washington, June 2002, pp. 367-370, achieve phase shifter qualities of 12 dB at 10 GHz with a control voltage of about 40 V therewith. The insertion losses of the LC, i.e. the losses caused only by the polarisation losses in the liquid crystal, are given as - -
approximately 1 to 2 dB at 10 GHz in Weil, C: Passiv steuerbare
Mikrowellenphasenschieber auf der Basis nichtlinearer Dielektrika
[Passively Controllable Microwave Phase Shifters based on Nonlinear Dielectrics], Darmstadter Dissertationen D17, 2002. In addition, it has been determined that the phase shifter losses are determined primarily by the dielectric LC losses and the losses at the waveguide junctions. T. Kuki, H. Fujikake, H. Kamoda and T. Nomoto: Microwave Variable Delay Line Using a Membrane Impregnated with Liquid Crystal. IEEE MTT-S Int.
Microwave Symp. Dig. 2002, pp. 363-366, June 2002, and T. Kuki, H. Fujikake, T. Nomoto: Microwave Variable Delay Line Using Dual- Frequency Switching-Mode Liquid Crystal. IEEE Trans. Microwave Theory Tech., Vol. 50, No. 11 , pp. 2604-2609, November 2002, also address the use of polymerised LC films and dual-frequency switching-mode liquid crystals in combination with planar phase shifter arrangements.
A. Penirschke, S. Muller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz", 34th European Microwave Conference - Amsterdam, pp. 545-548 describe, inter alia, the properties of the known single liquid crystal substance K15 (Merck KGaA, Germany) at a frequency of 9 GHz.
A. Gaebler, F. Goelden, S. Muller, A. Penirschke and R. Jakoby "Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formulation of the Vector Variational Approach", 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, describe the corresponding properties of the known liquid-crystalline mixture E7 (likewise Merck KGaA, Germany).
DE 10 2004 029 429 A describes the use of liquid-crystalline media in microwave technology, inter alia in phase shifters. DE 10 2004 029 429 A has already investigated liquid-crystalline media with respect to their properties in the corresponding frequency range.
Liquid-crystalline media comprising for example compounds of the formula below,
Figure imgf000004_0001
are used as a host mixture for the investigation of compounds, which are suggested for the usage in components for microwave applications and are described in F. Golden, "Liquid Crystal Based Microwave Components with Fast Response Times: Materials, Technology, Power Handling
Capability", Dissertation, Technische Universitat Darmstadt, 2009, (D17),
A. Lapanik, ..Single compounds and mixtures for microwave applications,
Dielectric, microwave studies on selected systems", Dissertation,
Technische Universitat Darmstadt, 2009, (D17),
„Nematic LC mixtures with high birefringence in microwave region",
A. Lapanik, F. Golden, S. Muller, A. Penirschke, R. Jakoby und W. Haase,
Freqt/e/iz 201 1 , 65, 15-19,
..Highly birefringent nematic mixtures at room temperature for microwave applications", A. Lapanik, F. Golden, S. Muller, R. Jakoby und W. Haase, Journal of Optical Engineering, published online, as well as in the laid- open documents DE 10 2010 045 370.6 und DE 10 2010 051 508.0.
However, these compositions are afflicted with serious disadvantages. Most of them result, besides other deficiencies, in slow switching
performances.
Fast switching performances are especially needed for mobile applications e.g. for receiving and sending communication, television or video to vehicles like ships, planes, trains and cars. Other preferred applications are short-distance antennas of the wireless routers to the laptop PCs, tablet computers and mobile devices.
For these applications, liquid-crystalline media having particular, hitherto rather unusual, uncommon properties, or combinations of properties, are required.
Novel liquid-crystalline media having improved properties are thus necessary. In particular, fast switching liquid-crystalline media with low values for the rotational viscosity (γι) are required, which also exhibit an acceptable tunability (τ).
In this context, the dielectric anisotropy in the microwave region is defined as
ΔεΓ≡ (ε Γ.ιι - εΓ,χ). The tuneability (τ) is defined as τ≡ (ΔεΓ / ε Γ.ιι). The material quality (η) is defined as η≡ (τ / tan δε tjm), where the maximum dielectric loss is tan δε ≡ max. { tan δε r.x ; tan δε rj i }.
!n addition, there is a demand for an improvement in the low-temperature behaviour of the components. Both an improvement in the operating properties and in the shelf life is necessary here. Therefore, there is a considerable demand for liquid-crystalline media having suitable properties for corresponding practical applications.
Surprisingly, it has now been found that it is possible to achieve liquid- crystalline medium having a suitably high Δε, broad nematic phase ranges, a suitable high Δη and especially, low rotational rotation viscosity in connection with an acceptable tunability that do not have the
disadvantages of the prior-art materials, or at least only do so to a considerably reduced extent.
These improved liquid-crystalline media in accordance with the present invention, comprise one or more compounds of the formula I,
Figure imgf000006_0001
wherein
R11 and R12are each independently -F, -CI, -CN, -NCS or a straight-chain or branched alkyl group with 1 to 15 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or -CN, it being also possible for one or more non-adjacent -CH2- groups to be replaced, in each occurrence independently from one another, by -0-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, - O-CO-O-, -S-CO-, -CO-S-, -CH=CH-, -CH=CF-, -CF=CF- or -C≡C- in such a manner that oxygen atoms are not linked directly to one another,
Figure imgf000006_0002
denote independently of one another other, in each occu
Figure imgf000006_0003
Z1 denotes a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-,
-CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -C4H9-, -CF=CF- or -C≡C-.
The invention further relates to a component for high-frequency technology comprising a liquid-crystalline medium as described above and below. In this context, both high-frequency technology and hyper-frequency technology denote applications having frequencies in the range from 1 MHz to 1 THz, preferably from 1 GHz to 500 GHz, more preferably
2 GHz to 300 GHz, comprising a component for high-frequency technology comprising a liquid-crystalline medium as described above and below, suitable for operation in the microwave range.
The invention further relates to the use of liquid-crystalline media as described above and below in a component for high-frequency technology.
The invention further relates to a microwave device, comprising a component as described above and below.
Said devices and components include, without limitation, phase shifters, varactors, wireless and radio wave antenna arrays, phased array antennas, reflectarray antenna, adaptable matching circuit, tunable filter and others.
In particular, the liquid-crystalline media of this invention show the following advantageous properties:
- they exhibit a high birefringence Δη, usually an. Δη 0.230 or more, and/or
- they exhibit a acceptable nematic phase ranges usually up to 80°C or more, and/or
- they exhibit high dielectric anisotropy values in the microwave range
(19 GHz), usually 0.50 or more, and/or
- they exhibit high values for the material quality (η) of 7 or more, and/or
- they exhibit low values for the rotational viscosity usually below
600 mPa s or less together with acceptable values for tunability of 0.15 or more.
The media are especially suitable for mass production and can be processed using industry standard equipment.
Furthermore, exhibit the liquid-crystalline media according to the present invention good storage stability and good low temperature stability. in a preferred embodiment, the compounds of the formula I are selected from the group of compounds of the formulae IA to IC,
Figure imgf000008_0001
have the meanings indicated above in formula I,
Figure imgf000008_0002
have the meanings indicated above in formula I,
The compounds of the formula IA are preferably selected from the group of compounds of formulae IA-1 to IA-6,
Figure imgf000008_0003
Figure imgf000009_0001
Figure imgf000009_0002
has the meaning indicated above in formula I and preferably denotes CnH2n+i or 0-CnH2n+i or CH2=CH- (CH2)z, and wherein denotes an integer in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2, and R 2 has the meaning indicated above in formula I and preferably denotes -F, -CI, -CN or -NCS, more preferably -CN.
More preferred compounds of formulae IA-1 to IA-6 are selected from compounds of formulae IA-1 and/or IA-2 and/or IA-3, even more preferred are compounds of formula IA-2.
The compounds of the formula IB are preferably selected from compounds of formulae IB-1 to IB-3,
Figure imgf000010_0001
has the meaning indicated above in formula I and preferably denotes CnH2n+i or 0-CnH2n+i or CH2=CH- (CH2)z or (CH2)z-C≡C- CnH2n+i, more preferably CnH2n+i, has the meaning indicated above in formula I and preferably denotes CmH2m+i or 0-CmH2m+1 or (CH2)Z- CH=CH2 or (CH2)Z-C≡C- CmH2m+1, more preferably CmH2fT1+i or 0-CmH2m+1, most preferably CmH2m+i and wherein m and n independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
Most preferred compounds of formula IB are compounds of formula IB-1.
Especially preferred compounds of formula IB-1 are indicated below:
Figure imgf000011_0001
wherein
R 1 1* has the meaning indicated above for R11 in formula and preferably denote CnH2n+i ,
has the meaning indicated above for R12 in formula I and preferably denote CnH2n+1, n denotes an integer in the range from 1 to 7 and preferably from 1 to 5,
L has, each and independently to one another in each occurrence one of the meanings of R 1 different from H, r denotes, each and independently to one another in
each occurrence 0, 1, 2, 3 or 4, and y and z independently of one another, denote 0, 1 , 2, 3 or 4, preferably 0 or 2.
More preferred compounds of formulae IB-1a to IB-1e are compounds of formulae IB-1a and IB-1c.
Compounds of the formula IC are preferably selected from the group of the compounds of formulae IC-1 to IC-3, most preferably of formula IC-1
Figure imgf000012_0001
wherein
R11 has the meaning indicated above in formula I and
preferably denotes CnH2n+i or 0-CnH2n+i or CH2=CH- (CH2)z or (CH2)z-C≡C- CnH2n+i and R12 has the meaning indicated above in formula I and preferably denotes CmH2m+i or O-CmH2m+i or (CH2)Z- CH=CH2, (CH2)z-C≡C- CmH2m+ and wherein n and m independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
Preferred combinations of (R11 and R 2), in particular in formulae IC-1 and IC-3, are (CnH2n+i and CmH2m+1), (CnH2n+1 and 0-CmH2m+1), (CH2=CH- (CH2)z and CmH2m+i), (CH2=CH-(CH2)Z and 0-CmH2m+1), (CnH2n+1 and (CH2)z-CH=CH2), ((CnHn+1)-CH=CH-(CH2)z and 0-CmH2m+1) and ((CnH2n+i and (CH2)z-CH=CH-(CmH2m+1)).
In another preferred embodiment, the compounds of the formula IC are selected from the group of compounds of the formulae IC-4 to IC-12:
Figure imgf000013_0001
Figure imgf000014_0001
has the meaning indicated above in formula I and preferably denotes CnH2n+i or O-CnH2n+i or CH2=CH- (CH2)z or (CH2)Z-C≡C- CnH2n+1 and denotes an integer in the range from 1 to 7 and preferably from 1 to 5, and denotes 0, 1 , 2, 3 or 4, preferably 0 or 2, and denotes -F: -CI, -CN or -NCS, preferably -CN or -NCS. Especially preferred compounds of formulae !C-4 to IC- 13 are IC-4, IC-5, IC-6, IC-7, IC-9, IC-10 and IC-11.
In a preferred embodiment, the liquid-crystalline media comprise one or more compounds of formula II,
Figure imgf000015_0001
wherein
R21 has the meaning indicated above for R 1 in formula I and preferably denotes CnH2n+i or O-CnH2n+i,
CH2=CH-(CH2)z, more preferably CnH2n+i, and
R22 has the meaning indicated above for R11 in formula I and preferably denotes CmH2m+ or 0-CmH2rt1+1 or (CH2)Z-CH=CH2, more preferably CmH2m+1, and wherein n and m independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and denotes 0, 1, 2, 3 or 4, preferably 0 or 2.
Compounds of the formula II are preferably selected from the group of compounds of formulae HA to IIE,
Figure imgf000015_0002
Figure imgf000016_0001
m denotes an integer in the range from 1 to 7 and
preferably from 1 to 5.
Especially preferred compounds of formulae IIA to HE are compounds of formulae IIC and IID, and wherein m denotes 2 and 4.
In a preferred embodiment the liquid-crystalline media according to the present invention, comprise optionally one or more compounds of formula
Figure imgf000016_0002
has the meaning indicated above for R11 in formula I and preferably denotes CnH2n+i or 0-CnH2n+i or
CH2=CH-(CH2)z or (CH2)Z-C≡C- CnH2n+i and n denotes an integer in the range from 1 to 7 and
preferably from 1 to 5, and Z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2, and
Figure imgf000017_0001
denote independently of one another, and in case A32 and/or A33 is/are present twice, also these independently of one another denote
Figure imgf000017_0002
L31 and L3 denote independently of one another H or F, X31 denotes halogen, halogenated alkyl or alkoxy with 1 to 5
C-atoms or halogenated alkenyl or alkenyloxy with 2 or 3 C-atoms or -CN or -NCS, preferably -F, -CI, -OCF3, -CN or -NCS, more preferably -F, -CI, -OCF3 or -CN,
Z31 to Z33 denote independently of one another, and in case Z31 and/or Z32 is/are present twice, also these
independently of one another denote -CH2CH2-, -CF2CF2-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH2O-, -CF2O- or a single bond, preferably -CH2CH2-, -CH=CH-, -CF20- or a single bond, more preferably -CF20- or a single bond, and p and q are independently of one another 0, 1 , 2 and 3,
preferably 0, 1 and 2 and wherein p + q > 1. 12 003363
- 17 -
Compounds of the formula III are preferably selected from the group of compounds of formulae IIIA to MID,
Figure imgf000018_0001
wherein R31, A31 to A33, Z31 to Z33, L31 and L32 and X31 have the meanings indicated above in formula III.
Preferred compounds of formula IIIA are selected from compounds of formulae IIIA-1 to IIIA-31 as indicated below:
R31— V y-i ' IMA-1
Figure imgf000019_0001
35
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
wherein R31 and X31 have the meanings indicated above in formula III.
Especially preferred compounds of formulae IIIA-1 to IIIA-31 are compounds of formulae IIIA-4, IIIA-6, IIIA-8 and IIIA-22.
Compounds of formula IIIB are preferably selected from the group of compounds of formulae IIIB-1 to IIIB-11 as indicated below:
Figure imgf000023_0002
Figure imgf000024_0001
wherein R31 and X31 have the meanings indicated above in formula III.
Especially preferred compounds of formulae IIIB-1 to IIIB-11 are compounds of formulae IIIB-1 , IIIB-4 and IIIB-10, more preferably IIIB-10.
Preferred compounds of formula IMC are selected of formulae IIIC-1 to IIIC-9 as indicated below:
Figure imgf000025_0001
F F F
F F
Figure imgf000025_0002
Figure imgf000026_0001
wherein R3 and X31 have the meanings indicated above in formula III.
Especially preferred are compounds of formulae IIIC-1 , IIIC-4 and IIIC-7.
Preferred compounds of formula MID are selected of compounds of formulae IIID-1 and IIID-2:
Figure imgf000026_0002
wherein R and X have the meanings indicated above in formula III.
The media in accordance with the present invention optionally comprise one or more compounds of the formula IV having three six-membered rings,
iV
Figure imgf000026_0003
wherein
R41 and R42, independently of one another, denote unfluorinated a!kyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyi having 2 to 15, preferably 3 to 10, C atoms, preferably
unfluorinated alkyl or alkenyl,
,42
Z4 and independently of one another, denote -CH2CH2-, trans- CH=CH or a single bond, preferably one or more of them denotes a single bond, and particularly preferably all denote a single bond, and
Figure imgf000027_0001
independently of one another, denote
Figure imgf000027_0002
Figure imgf000028_0001
Compounds of the formula IVA are preferably selected from the group of compounds of the formulae IVA-1 to IVA-7,
Figure imgf000028_0002
where in each case the compounds of the formula IVA-1 are excluded from the compounds of the formulae IVA-2 and IVA-3, the compounds of the formula IVA-2 are excluded from the compounds of the formula IVA-3 and the compounds of the formula iVA-6 are excluded from the
compounds of the formula IVA-7, and wherein the parameters R41 and R42 have the respective meanings indicated above for formula VI and
L41 and L42 each, independently of one another, denote H or F.
The preferred combinations of (R4 and R42) here are (CnH2n+i and
CmH2m+1), (CnH2n+i and 0-CmH2m+i), (CH2=CH-(CH2)Z and CmH2m+1), (CH2=CH-(CH2)z and 0-CmH2m+1), (CnH2n+1 and (CH2)Z-CH=CH2),
and O-CmH2m+i) and ((CnH2n+i and (CH2)Z-
Figure imgf000029_0001
rein denotes an integer in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
Especially preferred compounds of formulae IVA-1 to IVA-7
compounds of the formula IVA-1.
The media in accordance with the present invention optionally comprise one or more compounds of the formula V having four six-membered rings,
Figure imgf000029_0002
wherein independently of one another, denote unfluorinated alkyl or alkoxy having 1 to 15, preferably 3 to 10, C atoms or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, preferably 3 to 10, C atoms, preferably
unfluorinated alkyl or alkenyl,
Z51 to Z53 independently of one another, denote -CH2CH2-, trans-
-CH=CH- or a single bond, preferably one or more of them denotes a single bond, and particularly preferably all denote a single bond,
Figure imgf000030_0001
independently of one another, denote
Figure imgf000030_0002
The compounds of the formula V are preferably selected from the group of compounds of the formulae VA to VC,
VA
Figure imgf000030_0003
Figure imgf000031_0001
wherein the parameters have the respective meanings indicated above in formula V and preferably one of
Figure imgf000031_0002
to denotes
Figure imgf000031_0003
and
R5 has the meaning indicated above in formula V and preferably denotes CnH2n+i or CH2=CH-(CH2)z, and
R52 has the meaning indicated above in formula V and preferably denotes CmH2m+i or 0-CmH2m+i or (CH2)Z- CH=CH2, and wherein n and m independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and z. denotes 0, 1 , 2, 3 or 4, preferably 0 or 2. The preferred combinations of (R51 and R52) are, in particular, (CnH2n+i and CmH2m+i) and (CnH2n-n and 0-CmH2m+i).
The compounds of the formula VA are preferably selected from the group of compounds of the formulae VA-1 to VA-6,
Figure imgf000032_0001
wherein
R 51 has the meaning indicated above in formula V and
preferably denotes CnH2n+i or CH2=CH-(CH2)z,
R 52 has the meaning indicated above in formula V and
preferably denotes CmH2m+i or 0-CmH2m+1 or (CH2)Z- CH=CH2, n and m independently of one another, denote an integer in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The preferred combination of (R51 and R52) are, in particular, (CnH2n÷i and
Figure imgf000033_0001
The compounds of formula VB are preferably selected from the group of compounds of the formulae VB-1 and VB-2,
Figure imgf000033_0002
wherein the parameters have the meanings given above in formula V and preferably
R51 has the meaning indicated above in formula Vand preferably denotes CnH2n+i, and n denotes an integer in the range from 1 to 7 and
preferably from 1 to 5.
The compounds of the formula VC are preferably selected from
compounds of the formulae VC-1 ,
Figure imgf000033_0003
wherein has the meaning indicated above and preferably denotes CnH2n+i or CH2=CH-(CH2)z, 52
R has the meaning indicated above and preferably
denotes CmH2m+1 or O-CmH2m+, or (CH2)z-CH=CH2> n and m independently of one another, denote an in the range from 1 to 7 and preferably from 1 to 5, and z denotes 0, 1 , 2, 3 or 4, preferably 0 or 2.
The preferred combinations of (R51 and R°2) here are, in particular, (CnH2n+i and CmH2m+i ) and (CnH2n+i and 0-CmH2m+1), particularly preferably (CnH2n+i and 0-CmH2m+1).
Other mesogenic compounds, which are not explicitly mentioned above, can optionally and advantageously also be used in the media in accordance with the present invention. Such compounds are known to the person skilled in the art.
The compounds of formulae I to V can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
A preferred method of preparation of compounds of formula IB-1 c is shown in the following synthesis scheme.
Figure imgf000035_0001
H- R12 Sonogashira coupling
Figure imgf000035_0002
wherein has the meaning indicated above for R1 in formula and preferably denotes CnH2n+i ,
R 12* has the meaning indicated above for R12 in formula
and preferably denotes CnH2n+i , denotes an integer in the range from 1 to 7 and preferably from 1 to 5, has, each and independently to one another in each occurrence one of the meanings of R11 different from H, denotes, each and independently to one another in each occurrence 0, 1 : 2, 3 or 4.
A preferred method of preparation of compounds of formula IB-le is shown in the following synthesis scheme.
Figure imgf000036_0001
H— Ξ
coupling
Figure imgf000036_0002
Me3Si— --
1. Li-Silazane
2. 9-BBN
PdCI2, Base
Figure imgf000036_0003
1. Li-Silazane
2. 9-BBN
3. CyHex)3P)2PdCl2, Base
Figure imgf000036_0004
Sonogashira coupling
Figure imgf000036_0005
wherein
R 11* has the meaning indicated above for R11 in formula I and preferably denotes CnH2n+i,
R 12* has the meaning indicated above for R12 in formula I and preferably denotes CnH2n+i, denotes an integer in the range from 1 to 7 and preferably from 1 to 5, has, each and independently to one another in each occurrence one of the meanings of R11 different from H, r denotes, each and independently to one another in each occurrence 0, 1 , 2, 3 or 4.
The liquid-crystalline media according to the invention consist of a plurality of compounds, preferably 3 to 20, more preferably 3 to 15 and more preferably 3 to 10 compounds. These compounds are mixed in a
conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the dissolution process. It is, however, also possible to prepare the media in other conventional ways, for example using so-called pre-mixes, which can be, for example, homologous or eutectic mixtures of compounds, or using so-called "multibottle" systems, the constituents of which are themselves ready-to-use mixtures. in a preferred embodiment of the present invention, the liquid-crystalline media comprise one or more compounds of the formula I and one or more compounds of the formula II.
In a more preferred embodiment of the present invention, the liquid- crystalline media comprise one or more compounds of the formula I, one or more compounds of the formula II and one or more compounds of the formula III.
In an even more preferred embodiment, the liquid-crystalline media comprise one or more compounds of the formula I, one or more
compounds of the formula II, one or more compounds of the formula Ml and one or more compounds of the formula IV.
In an especially preferred embodiment, the liquid-crystalline media comprise one or more compounds of the formula I, one or more
compounds of the formula II, one or more compounds of the formula III, one or more compounds of the formula IV and one or more compounds of the formula V. In particular, preference are given to the liquid-crystalline media, which comprise one or more compounds of the formula I and one or more compounds of the formula II, and/or one or more compounds of the formula III, and/or one or more compounds of the formula IV and/or one or more compounds of the formula V.
The liquid-crystalline media in accordance with the present application preferably comprise 5 to 80 %, preferably 10 to 75 %, more preferably 15 to 65 % in total of the whole mixture of compounds of the formula I.
In a preferred embodiment, the liquid-crystalline media comprises one, two, three or more compounds of formula I.
The liquid-crystalline media in accordance with the present application preferably comprise
- in total 1 to 20 %, preferably 3 to 15 % and particularly preferably 5 to 10 % of compounds of the formula I A, and/or
- in total 5 to 60 %, preferably 7 to 50 % and particularly preferably 10 to 40 % of compounds of the formula IB, and/or
- in total 3 to 50 %, preferably 4 to 45 % and particularly preferably 5 to 35 % of compounds of the formula IC, and/or
- in total 0 to 80 %, preferably 12 to 70 %, particularly preferably 15 to 60 % of compounds of the formula II, and/or
- in total 0 to 30 %, preferably 1 to 25 % and particularly preferably 5 to 20 % of compounds of the formula III, and/or
- in totai 0 to 50 %, preferably 3 to 45 % and particularly preferably 5 to 40 % of compounds of the formula IV and/or V, but all together in a total amount < 100 %.
Further preferred are liquid-crystalline media comprising, 5 to 80 %, more preferably 10 to 75 %, even more preferably 15 to 65 % in total of the whole mixture of one or more compounds of formula I, preferably selected from compounds of formulae IA: IB and IC, more preferably selected from compounds of formulae IA-2, IB-1a, IB-1c and IC-I to IC-3, and
10 to 80 %, preferably 2 to 70 %, particularly preferably 15 to 60 %, in total of the whole mixture of one or more compounds of formula II, preferably selected from compounds of formulae IIA to HE, more preferably selected from compounds of formulae IIC and/or I ID, and/or optionally 0 to 50 %, more preferably 0 to 45 %, even more
preferably 0 to 40 % in total of the whole mixture compounds of the formulae III to V. but in a total amount of the total mixture < 100 %.
Especially preferred concentrations of compounds of formulae III to V are:
1 to 30 %, preferably 3 to 25 % and particularly preferably 5 to 20 %, in total of the whole mixture of one or more compounds of the formula
III, preferably selected from compounds of formulae IIIA to HID, more preferably selected from compounds of formulae IIIA-4 and/or IIIA-6 and/or IIIB-4 and/or IIIB-10 and/or IIIC-4 and/or IIIC-7, and/or
1 to 40 %, preferably 3 to 35 % and particularly preferably 5 to 30 %, in total of the whole mixture of one or more compounds of the formula
IV, preferably selected from compounds of formulae IVA-1 to IVA-7, more preferably selected from compounds of formula IVA-1 , and /or 1 to 40 %, preferably 3 to 35 % and particularly preferably 5 to 30 %, in total of the whole mixture of one or more compounds of the formula V, preferably selected from compounds of formulae VA to VC more preferably selected from compounds of formulae VA-3 and/or VB-1 , but in a total amount of the total mixture < 100 %.
In particular, the liquid-crystalline media according to the present invention consist exclusively of the above-mentioned compounds.
In this application, "comprise" in connection with compositions means that the entity in question, i.e. the medium comprises the compound or compounds indicated, preferably in a total concentration of 3 % or more and more preferably 5 % or more. Additionally, "consist exclusively" means that the entity in question comprises preferably 99 % or more and more preferably 100.0 % of the compound or compounds indicated.
The liquid-crystalline media according to the present invention may contain further additives, like dyes, antioxidants, chiral dopants, UV stabilizers, in usual concentrations. The total concentration of these further constituents is in the range of 50 ppm to 10 %, preferably 100 ppm to 6 %, based on the total mixture. The concentrations of the individual compounds used each are preferably in the range of 0.1 % to 3 %.
The liquid-crystalline media in accordance with the present invention preferably have a clearing point of 80°C or more, more preferably 90°C or more, even more preferably 100°C or more, most preferably 120°C or more but having crystallisation points of - 20°C or lower, more preferably - 30°C or lower, even more preferably - 40°C or lower. Most preferably, all limits are independently combined with each other.
Most preferably, the liquid-crystalline media according to the invention preferably have nematic phases of in each case at least from -20°C to 80°C, preferably from -30°C to 100°C and more particularly preferably from -40°C to 120°C. Most preferably, all limits are independently combined with each other. The expression have a nematic phase here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that no clearing occurs on heating from the nematic phase.
The Δε of the liquid-crystalline media in accordance with the invention, at 1 kHz and 20°C, are preferably 1 or more, more preferably 2 or more and more preferably 3 or more.
In the present application, the expression dielectrically positive describes compounds or components where Δε > 3.0, dielectrically neutral describes those where -1.5 < Δε < 3.0 and dielectrically negative describes those where Δε < -1.5. Δε is determined at a frequency of 1 kHz and at 20°C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10 %, the concentration is reduced to 5%. The capacitances of the test mixtures are determined both in a cell having homeotropic alignment and in a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 μιη. The voltage applied is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, but it is always selected to be below the capacitive threshold of the respective test mixture.
Δε is defined as (ε| | - εχ), while ε3νΘ. is (ε| | + 2 ε±) / 3.
The host mixture used for dielectrically positive compounds is mixture ZLI-4792 and that used for dielectrically neutral and dielectrically negative compounds is mixture ZLI-3086, both from Merck KGaA, Germany. The absolute values of the dielectric constants of the compounds are determined from the change in the respective values of the host mixture on addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 00 %.
The Δη of the liquid-crystalline media in accordance with the present invention, at 589 nm (NaD) and 20°C, is preferably in the range from 0.230 or more to 0.90 or less, more preferably in the range from 0.240 or more to 0.90 or less, even more preferably in the range from 0.250 or more to 0.85 or less. Most preferably, all limits are independently combined with each other.
Furthermore, the liquid-crystalline media according to the invention are characterised by high dielectric anisotropy values in the microwave range at 19 GHz is, for example, 0.50 or more, preferably 0.60 or more, more preferably 0.70 or more. Most preferably, all limits are independently combined with each other.
The liquid-crystalline media are investigated with respect to their properties in the microwave frequency range as described in A. Penirschke, S.
Muller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35 GHz", 34th European Microwave Conference - Amsterdam, pp. 545-548.
Compare in this respect also A. Gaebler, F. Golden, S. Muller, A. Penirschke and R. Jakoby "Direct Simulation of Material Permittivites
12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, and
DE 10 2004 029 429 A, wherein a measurement method is likewise described in detail.
The liquid crystal is introduced into a polytetrafluoroethylene (PTFE) or fused silica capillary. The capillary has an internal radius of 180 μιη and an external radius of 350 μΐτι. The effective length is 2.0 cm. The filled capillary is introduced into the centre of the cavity with a resonance frequency of 30 GHz. This cavity has a length of 6.6 mm, a width of 7.1 mm and a height of 3.6 mm. The input signal (source) is then applied, and the result of the output signal is recorded using a commercial vector network analyser. For other frequencies (e.g. 19 GHz), the dimensions of the cavity can be adjusted accordingly.
The change in the resonance frequency and the Q factor between the measurement with the capillary filled with the liquid crystal and the measurement without the capillary filled with the liquid crystal is used to deter- mine the dielectric constant and the loss angle at the corresponding target frequency by means of equations 10 and 11 in A. Penirschke, S. MCiller, P. Scheele, C. Weil, M. Wittek, C. Hock and R. Jakoby: "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz", 34th European Microwave Conference - Amsterdam, pp. 545-548, as described therein.
The values for the components of the properties perpendicular and parallel to the director of the liquid crystal are obtained by alignment of the liquid crystal in a magnetic field. To this end, the magnetic field of a permanent magnet is used. The strength of the magnetic field is 0.35 tesla. The alignment of the magnets is set correspondingly and then rotated correspondingly through 90°.
The rotational viscosity (γι) of the preferred liquid-crystalline media are, preferably in combination with the above indicated ranges for the nematic phase,≤ to 600 mPa s, preferably < 400 mPa-s, more preferably
< 300 mPa-s but 50 mPa s, preferably >100 mPa-s and more preferably
> 150 mPa s. Most preferably, all limits are independently combined with each other.
The tunability (τ) of the liquid-crystalline media are preferably in
combination with the above indicated ranges for the rotational viscosity
> 0.15, preferably > 0.17, more preferably > 0.18, but 0.35, preferably
< 0.30 and more preferably≤ 0.25. Most preferably, all limits are
independently combined with each other.
The material quality (η) of the preferred liquid-crystalline materials are≥8, preferably≥ 9, more preferably 10, but≤ 35, preferably < 30 and more preferably≤ 25. Most preferably, all limits are independently combined with each other.
Preferably the preferred ranges for T(N,I), γ1 ( τ and η are combined with each other. The liquid crystalline media according tc the present invention are very well suited for the preparation of microwave components, such as tunable phase shifters. These may be tuned by the application of magnetic and/or electric fields. Tuning by electric fields is generally preferred. These phase shifters are operable in the UHF-band (0.3-1 GHz), L-band (1-2GHz), S- band (2-4GHz), C-band (4-8GHz), X-band (8-12GHz), Ku-band (12- 18GHz), K-band (18-27GHz), Ka-band (27-40GHz), V-band (50-75GHz), W-band (75-110GHz) and up to 1THz.
Preferable frequencies for operation are C-band, X-band, Ku-band, K- band, Ka-band, V-band, W-band, and up to 1THz. Particularly preferable frequencies for operation are Ku-band, K-band, Ka-band, V-band, W-band, and up to 1THz.
The construction of the phase shifters according to the present application is known to the expert. Typically loaded line phase shifters, "inverted microstrip lines" (short IMSL), Finline phase shifters, preferably Antipodal Finline phase shifters, slotline phase shifters, microstrip line phase shifters or coplanar waveguides (CPW) phase shifters are used. These
components allow the realization of reconfigurable antenna arrays, which are fully electrically reconfigurable and which allow to steer the main beam direction of the antennas, to blank out interferers and/or to achieve high directivity. Another preferred embodiment is waveguide partially filled with the liquid crystals according to the present invention, as described in WO 2011/036243 A1 , which is encompassed herein by reference herewith.
In a preferred embodiment the inventive phase shifters are combined into array antennas, preferably into phased array antennas, reflectarray antennas, and arrays consisting of Vivaldi antennas.
Especially preferred applications for the tunable antenna arrays according to the present application are satellite communication systems, for operation e.g. between satellites, from satellites to ground stations, from mobile ground stations via satellite to stationary ground stations or to other mobile ground stations, e.g. for receiving and sending communication, television or video to vehicles like ships, planes, trains and cars. Other preferred applications are short-distance antennas of the wireless routers to the laptop PCs, tablet computers and mobile devices.
For an overview of terms and definitions in connection with liquid crystals and mesogens see Pure Appl. Chem. 73(5), 888 (2001) and C.
Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368.
In the present application, the term "compounds" is taken to mean both one compound and a plurality of compounds, unless expressly stated otherwise.
The term "mesogenic group" means a group with the ability to induce liquid crystal (LC) phase behaviour. The compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds (e.g. liquid-crystalline host mixture), or when the mesogenic compounds or the mixtures thereof are polymerised. For the sake of simplicity, the term "liquid crystal" is used hereinafter for both mesogenic and LC materials.
The parameter ranges indicated in this application all include the limit values, unless expressly stated otherwise.
Throughout this application, the following conditions and definitions apply, unless expressly stated otherwise. All concentrations are quoted in per cent by weight and relate to the respective mixture as a whole; all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees. All physical properties are determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and are quoted for a temperature of 20°C, unless expressly stated otherwise. The optical aniso- tropy (Δη) is determined at a wavelength of 589.3 nm. The dielectric aniso- tropy (Δε) is determined at a frequency of 1 kHz or if explicitly stated at a frequency 19 GHz. The term "alkyl" preferably encompasses straight chain and branched alkyl groups having 1 to 15 carbon atoms, in particular the straight chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2 to 10 carbon atoms are generally preferred.
The term "alkenyl" preferably encompasses straight chain and branched alkenyl groups having 2 to 15 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C2- to C7-1 E-alkenyl, C - to C -3E-alkenyl, C5- to C7-4-alkenyl, C6- to C7-5-alkenyl and C7-6-alkenyl, in particular C2- to C7-1 E-alkenyl, C4- to C7-3E-alkenyl and C5- to C7-4- alkenyl. Examples of further preferred alkenyl groups are vinyl, 1 E-pro- penyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-butenyl, 3E- pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.
The term "fluoroalkyl" preferably encompasses straight-chain groups having terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl,
4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.
The term "oxaalkyi" or "alkoxyalkyl" preferably encompasses straight-chain radicals of the formula CnH2n+i-0-(CH2)m, wherein n and m each, independently of one another, denote 1 to 10. Preferably, n is 1 and m is 1 to 6.
All temperatures, such as, for example, the melting point T(C,N) or T(C,S), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of the liquid crystals, are quoted in degrees Celsius. All temperature differences are quoted in differential degrees.
In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations also referred to as acronyms. In these acronyms, the chemical formulae are abbreviated as follows using Tables A to C below. All groups CnH2n+1, CmH2m+i and C|H21+1 or CnH2n-1, CmH2m-1 and C|H2 denote straight-chain alkyl or alkenyl, preferably 1-E-alkenyl, respectively, in each case having n, m or I C atoms. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows ihe linking groups. Table C gives the meanings of the codes for the left- hand or right-hand end groups. Table D shows illustrative structures of compounds with their respective abbreviations.
Table A: Ring elements
Figure imgf000047_0001
Figure imgf000048_0001
Table B: Linking groups
E -CH2CH2- Z -CO-O-
V -CH=CH- Zl -O-CO-
X -CF=CH- O -CH2-O- XI -CH=CF- 01 -O-CH2-
Figure imgf000049_0001
T -C≡C- Ql -O-CF2-
W -CF2CF2-
Table C: End groups
Left-hand side Right- ■hand side
Use alone
-n- CnH2n+1" -n — CnH2n+1
-nO- CnH2n+1"0- -nO -0-CnH2n+1
-V- CH2=CH- -V -CH=CH2
-nV-
-Vn-
-nVm-
Figure imgf000049_0002
mH
-N- N≡C- -N -C≡N
-S- S=C=N- -S -N=C=S
-F- F- -F -F
-CL- Cl- -CL -CI
-M- CFH2- -M -CFH2
-D- CF2H- -D -CF2H
-T- CF3- -T -CF3
- O- CFH20 - -OM -OCFH2
Figure imgf000049_0003
-OXF- CF2=CH-O- -OXF -0-CH=CF2
-A- H-C≡C- -A -C≡C-H
-nA- CnH2n+1-C≡C- -An -C≡C-CnH2n+i
-NA- ≡C-C≡C- -AN -C≡C-C≡N
Use together with others
.A...- -C≡C- ■ a a — ^^-=^^—
.V...- CH=CH- -...V... -CH=CH
.Z...- -CO-O- -..,Z... -CO-O-
.Zl...- -O-CO- -...Zl... -O-CO-
.K...- -CO- -...K... -CO-
.W...- -CF=CF -...W... -CF=CF- wherein n and m each denote integers and the three dots are placeholders for other abbreviations from this table.
The following table shows illustrative structures together with their respec- tive abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds, which are preferably used.
Table D: Illustrative structures
Figure imgf000050_0001
CP-n-m H 2n*V --0--C„H,
CP-n-Om
CnH^ - - V-(CH2)— CH=CH-C,H
PP-n-mVI
Figure imgf000051_0001
PTP-n-(0)m
Figure imgf000051_0002
CCP-n-m
Figure imgf000051_0003
CCP-V-n
Figure imgf000051_0004
CCP-Vn-m
Figure imgf000051_0005
CCP-n-m
Figure imgf000051_0006
CGP-n-m
Figure imgf000051_0007
CPTP-n-(0)m
Figure imgf000052_0001
PGP-n-m
Figure imgf000052_0002
PGP-n-mV
Figure imgf000052_0003
PGP-n-mVI
Figure imgf000052_0004
PPTUI-n-(0)m
Figure imgf000052_0005
CCCP-n-m
Figure imgf000052_0006
CGPC-n-m
Figure imgf000052_0007
CPPP-n-m
Figure imgf000053_0001
CPGP-n-m
Figure imgf000053_0002
CCZPC-n-m
Figure imgf000053_0003
CP-n-N
Figure imgf000053_0004
CU-n-N
Figure imgf000053_0005
PGIP-n-N
Figure imgf000053_0006
PZG-n-N
Figure imgf000053_0007
CPU-n-F
Figure imgf000054_0001
CCG-V-F
Figure imgf000054_0002
CCG-Vn-F
Figure imgf000054_0003
CCU-n-F
Figure imgf000054_0004
CPZU-n-N
Figure imgf000054_0005
PGIGI-n-F
Figure imgf000054_0006
PGIGI-n-CL
Figure imgf000055_0001
Figure imgf000055_0002
Figure imgf000055_0003
CPGU-n-F
Figure imgf000055_0004
CPGU-n-OT
Figure imgf000055_0005
PPGU-n-F
Figure imgf000055_0006
PUQU-n-F
Figure imgf000055_0007
PGUQU-n-F
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000056_0003
Figure imgf000056_0004
25
30
35 Examples
The following examples illustrate the present invention without limiting it in any way.
However, it is clear to the person skilled in the art from the physical properties what properties can be achieved and in what ranges they can be modified. In particular, the combination of the various properties that can preferably be achieved is thus well defined for the person skilled in the art.
Example 1
A liquid-crystalline mixture M-1 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 103 °C
1 PPTUI-3-2 10.0 Δε(20 , 1 kHz) = 2.7
2 PPTUI-3-4 15.0 γι (20°C) = 336 mPa · s
3 PPTUI-4-4 25.0 tan δε Γι1 (20°C, 19 GHz) = 0.0130
4 GGP-5-CL 20.0 tan δε τ,Μ (20°C, 19 GHz) = 0.0043
5 PTP-3-5 15.0 x (20°C, 19 GHz) = 0.229
6 PTP-4-5 15.0 η (20°C, 19 GHz) = 18.0
∑ 100.0
Example 2
A liquid-crystalline mixture M-2 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 128 °C
1 PZG-4-N 5.0 An(20°C,589.3 nm) = 0.289
2 PPTUI-3-2 20.0 Δε(20°α 1 kHz) = 5.2
3 PPTUI-3-4 33.0 γι (20°C) = 317 mPa · s
4 PTP-3-5 5.0 tan 6£ r>± (20°C, 19 GHz) = 0.0155
5 PTP-4-5 5.0 tan δε Γ, | | (20°C, 19 GHz) = 0.0048
6 CC-3-V 10.0 -c (20°C, 19 GHz) = 0.218
7 GGP-3-CL 5.0 η (20°C, 19 GHz) = 14.0
8 GGP-5-CL 10.0
9 CPGP-5-2 3.5
10 CPGP-5-3 3.5
∑ 100.0
Example 3
A liquid-crystalline mixture M-3 having the composition and properties indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 91 °C
1 PZG-4-N 6.0 Δε(20Χ, 1 kHz) = 3.6
2 PPTUI-3-2 10.0 γι (20°C) = 231 mPa · s
3 PPTUI-3-4 16.0 tan 5e r,x (20°C, 19 GHz) = 0.0138
4 PPTUI-4-4 30.0 tan δε Γ, | | (20°C, 19 GHz) = 0.0049
5 PTP-3-5 16.0 T (20°C, 19 GHZ) = 0.211
6 PTP-4-5 16.0 η (20°C, 19 GHz) = 15.3
7 CC-3-V 6.0
∑ 100.0
Example 4
A liquid-crystalline mixture M-4 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 98 °C
1 PPTUI-3-2 10.0 An(20°C,589.3 nm) = 0.265
2 PPTUI-3-4 15.0 Δε(20°α 1 kHz) = 2.1
3 PPTUI-4-4 30.0 Yi (20°C) = 220 mPa · s
4 PTP-3-5 14.0 tan 6£ r,i (20°C, 19 GHz) = 0.0104
5 PTP-4-5 14.0 tan δε Γ, π (20°C, 19 GHz) = 0.0037
6 PGUQU-3-F 2.0 τ (20Χ, 19 GHz) = 0.209
7 PGUQU-5-F 3.0 η (20°C, 19 GHz) = 20.1
8 CC-3-V 12.0
∑ 100.0 Example 5
A liquid-crystalline mixture M-5 having the composition and properties indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 102 °C
1 PPTUI-3-2 20.0 An(20°C,589.3 nm) = 0.257
2 PPTUI-3-4 30.0 Δε(20°α 1 kHz) = 3.5
3 PTP-3-5 10.0 71 (20°O = 172 mPa · s
4 PTP-4-5 10.0 tan 5f r,± (20°C, 19 GHz) = 0.0110
5 PGUQU-3-F 3.0 tan δε Γ,| | (20°C, 19 GHz) = 0.0036
6 PGUQU-5-F 7.0 -c (20°C, 19 GHz) = 0.208
7 CC-3-V 20.0 η (20°C, 19 GHz) = 19.0
∑ 100.0
Example 6
A liquid-crystalline mixture M-6 having the composition and properties as indicated in the following table is prepared.
Figure imgf000060_0001
Example 7
A liquid-crystalline mixture M-7 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 86 °C
1 PZG-4-N 7.0 An(20°C,589.3 nm) = 0.245
2 PPTUI-3-2 10.0 Δε(20°α 1 kHz) = 3.8
3 PPTUI-3-4 15.0 71 (20°C) = 163 mPa · s
4 PPTUI-4-4 25.0 tan δε Γι± (20°C, 19 GHz) = 0.0146
5 PTP-3-5 13.0 tan δε Γ, | | (20°C, 19 GHz) = 0.0050
6 PTP-4-5 13.0 T (20°C, 19 GHz) = 0.195
7 CC-3-V 17.0 η (20°C, 19 GHz) = 13.3
∑ 100.0
Example 8
A liquid-crystalline mixture M-8 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 90 °C
1 PZG-4-N 10.0 Δη(20Χ,589.3 nm) = 0.245
2 PPTUI-3-2 20.0 Δε(20 , 1 kHz) = 5.5
3 PPTUI-3-4 30.0 Y1 (20°C) = 154 mPa · s
4 PTP-3-5 10.0 tan 5£ rJL (20°C, 19 GHz) = 0.0165
5 PTP-4-5 10.0 tan 5e r, | | (20°C, 19 GHz) = 0.0058
6 CC-3-V 20.0 τ (20°C, 19 GHz) = 0.193
∑ 100.0 η (20°C, 19 GHz) = 1 .6 Example 9
A liquid-crystalline mixture M-9 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 88 °C
1 PZG-5-N 10.0 Δη(20Χ, 589.3 nm) = 0.2386
2 PPTUI-3-2 10.0 Δε(20Χ, 1 kHz) = 5.2
3 PPTUI-3-4 15.0 γι (20°C) = 156 mPa s
4 PPTUI-4-4 25.0 tan δε Γ ΐ (20°C, 19 GHz) = 0.0160
5 PTP-3-5 10.0 tan δε r, M (20°C, 19 GHz) = 0.0054
6 PTP-4-5 10.0 T (20°C, 19 GHz) = 0.187
7 CC-3-V 20.0 η (20°C, 19 GHz) = 1 1.7
∑ 100.0
Example 10
A liquid-crystalline mixture M-10 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 67 °C
1 PZG-4-N 10.0 An(20°C,589.3 nm) = 0.232
2 PPTUI-3-2 20.0 Δε(20 , 1 kHz) = 5.0
3 PPTUI-3-4 30.0 γι (20°C) = 147 mPa · s
4 PTP-3-5 10.0 tan δε Γ,χ (20°C, 19 GHz) = 0.0160
5 PTP-4-5 10.0 tan δε r, 1 1 (20°C, 19 GHz) = 0.0064
6 PCH-32 20.0 τ (20°C, 19 GHz) = 0.181
∑ 100.0 η (20°C, 19 GHz) = 1.3 Example 11
A liquid-crystaliine mixture M-11 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 106 °C
1 PPTUI-3-2 20.0 Δη(20 ,589.3 nm) = 0.267
2 PPTUI-3-4 30.0 Δε(20 , 1 kHz) = 4.0
3 PTP-3-5 11.0 Yi (20°C) = 196 mPa - s
4 PTP-4-5 11.0
5 PGUQU-3-F 3.0
6 PGUQU-5-F 7.0
7 PPGU-3-F 2.0
8 CC-3-V 16.0
∑ 100.0
Example 12
A liquid-crystalline mixture M-12 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 105 °C
1 PPTUI-3-2 20.0 An(20°C, 589.3 nm) = 0.267
2 PPTUI-3-4 30.0 Δε(20 , 1 kHz) = 3.9
3 PTP-3-5 11.0 γι (20°C) = 193 mPa - s
4 PTP-4-5 11.0
5 PGUQU-3-F 3.0
6 PGUQU-5-F 7.0
7 PGIP-3-N 2.0
8 CC-3-V 16.0
∑ 100.0 Example 13
A liquid-crystalline mixture M-13 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 107 X
1 PPTUI-3-2 20.0 Δη(20Χ,589.3 nm) = 0.266
2 PPTUI-3-4 28.0 Δε(20 , 1 kHz) = 4.3
3 PTP-3-5 11.0 γι (20°C) = 141 mPa · s
4 PTP-4-5 11.0
5 PGUQU-4-F 3.0
6 PGUQU-5-F 7.0
7 PPGU-3-F 2.0
8 PGIP-3-N 2.0
9 CC-3-V 16.0
∑ 100.0
Example 14
A liquid-crystalline mixture M-14 having the composition and propertie indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 93 °C
1 PP-1-2V1 9.0 An(20°C,589.3 nm) = 0.266
2 PPTUI-4-4 18.0 Δε(20Χ, 1 kHz) = 3.0
3 PTP-2-01 9.0 71 (20°C) = 187 mPa · s
4 PTP-3-01 9.0
5 PTP-2-A1 4.5
6 PTP-3-A1 4.5
7 PGP-2-2V 18.0
8 PGP-3-2V 9.0
9 PGUQU-5-F 9.0
10 CC-3-V 10.0
∑ 100.0
Example 15
A liquid-crystalline mixture M-15 having the composition and properties indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 101 °C
1 PP-1-2V1 10.0 An(20°C,589.3 nm) = 0.297
2 PPTUI-4-4 20.0 Δε(20°α 1 kHz) = 3.5
3 PTP-2-01 10.0 γι (20°C) = 273 mPa · s
4 PTP-3-01 10.0
5 PTP-2-A1 5.0
6 PTP-3-A1 5.0
7 PGP-2-2V 20.0
8 PGP-3-2V 10.0
9 PGUQU-5-F 10.0
∑ 100.0
Example 16
A liquid-crystalline mixture M-16 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 105 °C
1 CC-3-V 20.0 An(20°C,589.3 nm) = 0.246
2 PPTUI-3-2 20.0 Δε(20°α 1 kHz) = 5.0
3 PTP-2-01 10.0 γι (20°C) = 105 mPa - s
4 PTP-3-O1 10.0
5 PGP-2-2V 24.0
6 PGUQU-3-F 3.0
7 PGUQU-4-F 3.0
8 PGUQU-5-F 5.0
9 PPGUQU-4-F 5.0
∑ 100.0
Example 17
A liquid-crystalline mixture M-17 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 104 °C
1 PPTUI-3-2 20.0 An(20°C,589.3 nm) = 0.269
2 PPTUI-3-4 28.0 Δε(20 , 1 kHz) = 3.7
3 PTP-3-5 13.0 γι (20°C) = 316 mPa · s
4 PTP-4-5 13.0
5 PGUQU-5-F 8.0
6 PPGU-3-F 2.0
7 PGIP-3-N 2.0
8 CC-3-V 14.0
∑ 100.0
Example 18
A liquid-crystalline mixture M-18 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 102 °C
1 PPTUI-3-2 20.0 Δη(20Χ,589.3 nm) = 0.277
2 PPTUI-3-4 30.0
3 PTP-3-5 15.0
4 PTP-4-5 15.0
5 PGUQU-5-F 8.0
6 PPGU-3-F 2.0
7 CC-3-V 10.0
∑ 100.0 Example 19
A liquid-crystalline mixture M-19 having the composition and properties indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 106 °C
1 PZG-4-N 8.0 An(20°C,589.3 nm) = 0.261
2 PPTUI-3-2 20.0 Δε(20°α 1 kHz) = 4.8
3 PPTUI-3-4 40.0 γι (20°C) = 174 mPa · s
4 PP-1-2V1 12.0
5 CC-3-V 20.0
∑ 100.0
Example 20
A liquid-crystalline mixture M-20 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 94 °C
1 PZG-4-N 10.0 An(20°C,589.3 nm) = 0.253
2 PPTUI-3-2 20.0 Δε(20°α 1 kHz) = 5.6
3 PPTUI-3-4 30.0 Yi (20°C) = 195 mPa - s
4 PGP-2-2V 10.0
5 PGP-2-3 10.0
6 PCH-32 20.0
∑ 100.0 Example 21
A liquid-crystalline mixture M-21 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone
No. Abbreviation / mass-% T(N, I) = 129 °C
1 PPTUI-3-2 20.0 An(20°C,589.3 nm) = 0.270
2 PPTUI-3-4 30.0 Δε(20°α 1 kHz) = 3.7
3 PGP-2-2V 10.0 γι (20°C) = 220 mPa · s
4 PGP-2-3 10.0
5 PGUQU-3-F 3.0
6 PGUQU-5-F 7.0
7 CC-3-V 20.0
∑ 100.0
Example 22
A liquid-crystalline mixture M-22 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 116
1 PPTUI-3-2 20.0 An(20°C,589.3 nm) = 0.267
2 PPTUI-3-4 38.0
3 PP-1-2V1 12.0
4 PGUQU-3-F 3.0
5 PGUQU-5-F 7.0
6 CC-3-V 20.0
∑ 100.0 Example 23
A liquid-cp/stalline mixture M-23 having the composition and properties indicated in the following table is prepared.
Figure imgf000071_0001
Example 24
A liquid-crystalline mixture M-24 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 80 °C
1 PZG-4-N 10.0 An(20°C,589.3 nm) = 0.243
2 PPTUI-3-2 20.0 Δε(20°α 1 kHz) = 5.3
3 PPTUI-3-4 30.0 y^ (20X) = 168 mPa · s
4 PGP-2-2V 5.0
5 PGP-2-3 - 5.0
6 PTP-3-5 5.0
7 PTP-4-5 5.0
8 PCH-32 20.0
∑ 100.0 Example 25
A liquid-crystalline mixture M-25 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) - 67 °C
1 PZG-4-N 8.50 An(20°C,589.3 nm) = 0.1516
2 CC-3-V 50.00 Δε(20Χ, 1 kHz) = 3.7
3 PPTUI-3-2 19.00 Vo (20°C) = 1.87 V
4 PTP-4-5 5.50 γι (20°C) = 51 mPa · s
5 PP-1-2V1 6.00 k! (20°C) = 11.6 pN
6 PGP-2-2V 11.00 k3 (20°C) = 12.3 pN
∑ 100.0 tan δε (20°C, 19 GHz) = 0.0140
tan δε Γ,| | (20°C, 19 GHz) = 0.0054
T (20°C, 19 GHZ) = 0.136
η (20°C, 19 GHz) = 9.6
Comparative Example 1
A liquid-crystalline mixture M-25 having the composition and properties as indicated in the following table is prepared.
Composition Physical Properties
Compound Cone.
No. Abbreviation / mass-% T(N, I) = 173 °C
1 PPTUI-3-2 20.0 Δη(20 ,589.3 nm) = 0.335
2 PPTUI-3-4 36.0 Δε(20°α 1 kHz) = 4.6
3 GGP-3-CL 10.0 γι (20°C) = 746 mPa · s
4 GGP-5-CL 20.0 tan δε Γ,χ (20°C, 19 GHz) = 0.0143
5 CPGP-5-2 7.0 tan δε Γ, | | (20°C, 19 GHz) = 0.0038
6 CPGP-5-3 7.0 T (20°C, 19 GHz) = 0.252
∑ 100.0 η (20°C, 19 GHz) = 17.6
In comparison to the Examples 1 to 23, this mixture exhibits clearly a
higher value for τ.

Claims

Patent Claims
1. Liquid-crystalline medium for components, characterized in that it comprises at least one compound of the formula I,
Figure imgf000074_0001
wherein and R12 are each independently F, CI, CN, NCS or a straight- chain or branched alkyl group with 1 to 15 C atoms which may be unsubstituted, mono- or polysubstituted by halogen or CN, it being also possible for one or more non-adjacent CH2 groups to be replaced, in each occurrence independently from one another, by -0-, -S-, -NH-, -N(CH3)-, -CO-, -COO-, -OCO-, -O-CO-O-, -S-CO-, -CO-S-, -CH=CH-, -CH=CF-,-CF=CF- or -C≡C- in such a manner that oxygen atoms are not linked directly to one another,
Figure imgf000074_0002
denote independently of one another, in each occurrence,
Figure imgf000074_0003
denotes a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -C4H9-, -CF=CF- or -C≡C-.
2. Liquid-crystalline medium according to Claim 1. characterized in that it comprises one or more compounds of formuia II
Figure imgf000075_0001
wherein
R21 has the meaning indicated for R1 in Claim 1 , and
R22 has the meaning indicated for R12 in Claim 1.
Liquid-crystalline medium according to Claim 1 or 2, characterized that it comprises one or more compounds of formula III
Figure imgf000075_0002
denote independently of one another, and in case A32 and/or A33 is/are present twice, also these independently of one another denote
Figure imgf000075_0003
Figure imgf000076_0001
wherein denote independently of one another H or F, denotes halogen, halogenated alkyl or alkoxy with 1 to 3 C-atoms or halogenated alkenyl or alkenyloxy with 2 or 3 C-atoms or CN or NCS, denote independently of one another, and in case Z and/or Z32 is/are present twice, also these independently of one another denote -CH2CH2-,
-CF2CF2-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH20-, -CF20- or a single bond, and p and q denote independently of one another 0, 1 , 2 or 3, and wherein p + q > 1.
Liquid-crystalline medium according to one or more of Claims 1 to 3, characterized in that it optionally comprises one or more compounds selected of formulae IV and V
Figure imgf000076_0002
wherein
R41 to R52 independently of one another, denote unfluorinated alkyl or alkoxy having 1 to 15 or unfluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 15, and Z independently of one another, denote -CH2CH2-, trans- -CH=CH- or a single bond,
Figure imgf000077_0001
independently of one another, denote
Figure imgf000077_0002
independently of one another, denote
Figure imgf000077_0003
Figure imgf000078_0001
5. Liquid-crystalline medium according to one or more of Claims 1 to 4, characterized in that it comprises one, two or more compounds of the subformulae IA to IC
Figure imgf000078_0002
wherein
R1 and R12 have the meanings indicated in Claim 1 , and
Figure imgf000078_0003
have the meanings indicated in Claim 1.
6. Liquid-crystalline medium according to one or more of Claims 1 to 5, characterized in that the proportion of compounds of the formula I in the mixture as a whole is in the range from 5 to 80 % by weight. Liquid-crystalline medium according to one or more of Claims 1 to 6, characterized in that the proportion of compounds of the formula IA in the mixture as a whole is in the range from 1 to 20 % by weight.
Liquid-crystalline medium according to one or more of Claims 1 to 7, characterized in that the proportion of compounds of the formula IB in the mixture as a whole is in the range from 5 to 60 % by weight.
9. Liquid-crystalline medium according to one or more of Claims 1 to 8, characterized in that the proportion of compounds of the formula IC in the mixture as a whole is in the range from 3 to 50 % by weight.
10. Liquid-crystalline medium according to one or more of Claims 1 to 9, characterized in that the proportion of compounds of the formula II in the mixture as a whole is in the range from 10 to 80 % by weight.
11. Liquid-crystalline medium according to one or more of Claims 1 to 10, characterized in that the proportion of compounds of the formula III in the mixture as a whole is in the range from 1 to 30 % by weight.
12. Liquid-crystalline medium according to one or more of Claims 1 to 11 , characterized in that the proportion of compounds of the formula IV and V in the mixture as a whole is in the range from 1 to 40 % by weight.
13. Process for the preparation of a liquid-crystalline medium according to one or more of Claims 1 to 12, characterized in that at least one compound of the formula I is mixed with at least one further liquid- crystalline compound, and additives are optionally added. Compound of formula IB-1c
Figure imgf000080_0001
wherein
R 11* has the meaning indicated above for R11 in Claim 1 ,
R 12* has the meaning indicated above for R12 in Claim 1 , has, each and independently to one another in each occurrence one of the meanings of R1 r different from H, and denotes, each and independently to one another in each occurrence 0, 1 , 2, 3 or 4.
Compound of formula IB-1e
Figure imgf000080_0002
wherein
R i r has the meaning indicated above for R 1 in Cla
R 12* has the meaning indicated above for R12 in Claim 1 , has, each and independently to one another in each occurrence one of the meanings of R11* different from H, and r denotes, each and independently to one another in each occurrence 0, 1 , 2, 3 or 4.
16. Component for high-frequency technology, characterized in that it comprises a liquid-crystalline medium according to one or more of Claims 1 to 12.
17. Component according to Claim 16, characterized in that it is suitable for operation in the microwave range.
18. Component according to Claim 16 or 17, characterized in that it is a phase shifter.
19. Use of a liquid-crystal medium according to one or more of claims 1 to 12 in a component for high-frequency technology.
20. Microwave device, characterized in that it comprises one or more components according to one or more of Claims 16 to 18.
PCT/EP2012/003363 2011-09-05 2012-08-07 Liquid-crystalline medium and high-frequency components comprising same WO2013034227A1 (en)

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