US20170088776A1 - Liquid crystal medium and electrooptical display containing same - Google Patents

Liquid crystal medium and electrooptical display containing same Download PDF

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US20170088776A1
US20170088776A1 US15/375,689 US201615375689A US2017088776A1 US 20170088776 A1 US20170088776 A1 US 20170088776A1 US 201615375689 A US201615375689 A US 201615375689A US 2017088776 A1 US2017088776 A1 US 2017088776A1
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condition
liquid
formula
applies
compounds
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US15/375,689
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Melanie Klasen-Memmer
Izumi Saito
Herbert Plach
Kazuaki Tarumi
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Merck Patent GmbH
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Merck Patent GmbH
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Priority to US15/375,689 priority Critical patent/US20170088776A1/en
Assigned to MERCK PATENT GMBH reassignment MERCK PATENT GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TARUMI, KAZUAKI, KLASEN-MEMMER, MELANIE, PLACH, HERBERT, SAITO, IZUMI
Publication of US20170088776A1 publication Critical patent/US20170088776A1/en
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    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
    • C09K19/3003Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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    • C09K19/06Non-steroidal liquid crystal compounds
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    • C09K19/34Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
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    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/34Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/345Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing two nitrogen atoms
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    • C09K19/42Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/139Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
    • G02F1/1393Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent the birefringence of the liquid crystal being electrically controlled, e.g. ECB-, DAP-, HAN-, PI-LC cells
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    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
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    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098Unsaturated non-aromatic rings, e.g. cyclohexene rings
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    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
    • C09K19/3003Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004Cy-Cy
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    • C09K19/00Liquid crystal materials
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    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
    • C09K19/3003Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3009Cy-Ph
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    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
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    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
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    • C09K19/3001Cyclohexane rings
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    • C09K19/34Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13712Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy
    • G02F2001/13712

Definitions

  • the present invention relates to liquid-crystal media and to the use thereof in liquid-crystal displays, and to these liquid-crystal displays, particularly liquid-crystal displays which use the ECB (electrically controlled birefringence) effect with dielectrically negative liquid crystals in a homeotropic starting alignment.
  • the liquid-crystal media according to the invention are distinguished by a particularly low response time in the displays according to the invention at the same time as a high voltage holding ratio.
  • VAN vertical aligned nematic displays in the MVA (multi-domain vertical alignment, for example: Yoshide, H. et al., Paper 3.1: “MVA LCD for Notebook or Mobile PCs . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6 to 9 and Liu, C. T. et al., Paper 15.1: “A 46-inch TFT-LCD HDTV Technology . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp.
  • ECB displays like ASV displays, use liquid-crystalline media of negative dielectric anisotropy ( ⁇ ), whereas TN and to date all conventional IPS displays use liquid-crystalline media of positive dielectric anisotropy.
  • liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electric voltage.
  • liquid-crystal media which are generally predominantly composed of liquid-crystal compounds, all of which have the same sign of the dielectric anisotropy and have the greatest possible value of the dielectric anisotropy. In general, at most relatively small proportions of neutral compounds and if possible no compounds having the opposite sign of the dielectric anisotropy to the medium are employed. In the case of liquid-crystal media of negative dielectric anisotropy for ECB displays, predominantly compounds of negative dielectric anisotropy are thus employed.
  • the liquid-crystal media employed generally consist predominantly and usually even essentially of liquid-crystal compounds of negative dielectric anisotropy.
  • liquid-crystal media of the prior art having correspondingly low addressing voltages have relatively low electrical resistances or a low voltage holding ratio and result in undesirably high power consumptions in the displays.
  • the addressing voltage of the displays of the prior art is often too great, in particular for displays which are not connected directly or not continuously to the power supply network, such as, for example, displays for mobile applications.
  • phase range must be sufficiently broad for the intended application.
  • the response times of the liquid-crystal media in the displays must be improved, i.e. reduced. This is particularly important for displays for television or multimedia applications.
  • optimise the rotational viscosity of the liquid-crystal media ( ⁇ 1 ) i.e. to achieve media having the lowest possible rotational viscosity.
  • the results achieved here are inadequate for many applications and therefore make it appear desirable to find further optimisation approaches.
  • the short response time of the displays is preferably achieved by using liquid-crystal media according to the invention which have a low value of 0.25 ms or less for the peak times (t max ) calculated by the method explained below.
  • the quotient of the peak time and the square of the birefringence of the liquid-crystal mixture (t max / ⁇ n 2 ) of the liquid-crystal media according to the invention is preferably 22 ms or less.
  • This quotient (t max / ⁇ n 2 ) which takes into account the effect of the optimum layer thickness of the liquid-crystal displays, is proportional to the response time of the liquid-crystal mixtures in the corresponding displays.
  • the peak time (t max ) is the time which passes before current flowing through the cell after application of a short, high voltage pulse to a cell filled with liquid crystal passes through a maximum in its time curve (l(t)). It is determined as follows in accordance with the present invention. Firstly, the time curve of the current (l(t)) or the current density (L(t)/S) is calculated in accordance with the following equations (1) and (2), where equation (1) describes the current as a function of the tilt angle of the liquid-crystal director and equation (2) describes the correlation between the tilt angle and the time that has passed after application of the voltage.
  • the position of the maximum t max of the function l(t) or l( ⁇ b (t)) can be determined in various ways.
  • the function l(t) can be calculated numerically and the value and position of the maximum selected numerically or determined graphically.
  • numerical methods are preferred, and particular preference is given to the use of corresponding mathematics software Mathematica (for example: version 3) from Wolfram Research, Inc., into which an implicit representation of l(t) is entered, and the maximum of l(t) is determined numerically via derivation of the function after time (dl/dt).
  • the liquid-crystal media according to the invention have a value of the peak time (t max ) of 0.25 ms or less, particularly preferably of 0.20 ms or less, still more preferably of 0.16 ms or less, very particularly preferably of 0.13 ms or less and especially preferably of 0.12 ms or less.
  • the value t max of the liquid-crystal media according to the invention is preferably 0.18 ms or less, particularly preferably 0.16 ms or less, still more preferably 0.14 ms or less, very particularly preferably 0.12 ms or less and especially preferably 0.10 ms or less.
  • the value t max of the liquid-crystal media according to the invention is preferably 0.19 ms or less, particularly preferably 0.17 ms or less, still more preferably 0.15 ms or less, very particularly preferably 0.13 ms or less and especially preferably 0.12 ms or less.
  • the value t max of the liquid-crystal media according to the invention is preferably 0.20 ms or less, particularly preferably 0.18 ms or less, still more preferably 0.16 ms or less, very particularly preferably 0.14 ms or less and especially preferably 0.13 ms or less.
  • the value t max of the liquid-crystal media according to the invention is preferably 0.21 ms or less, particularly preferably 0.20 ms or less, still more preferably 0.18 ms or less, very particularly preferably 0.16 ms or less and especially preferably 0.15 ms or less.
  • the value t max of the liquid-crystal media according to the invention is preferably 0.25 ms or less, particularly preferably 0.22 ms or less, still more preferably 0.20 ms or less, very particularly preferably 0.19 ms or less and especially preferably 0.18 ms or less.
  • a further parameter for characterisation of the corresponding liquid-crystal media is the quotient of the calculated peak time (t max ) and the square of the birefringence ( ⁇ n), i.e.: t max / ⁇ n 2 .
  • the liquid-crystal media according to the invention preferably have a value of t max / ⁇ n 2 of 22 ms or less, particularly preferably of 20 ms or less, still more preferably of 18 ms or less, very particularly preferably of 16 ms or less and especially of 15 ms or less.
  • the value t max / ⁇ n 2 of the liquid-crystal media according to the invention is preferably 18 ms or less, particularly preferably 16 ms or less, still more preferably 14 ms or less, very particularly preferably 12 ms or less and especially preferably 10 ms or less.
  • the value t/ ⁇ n 2 of the liquid-crystal media according to the invention is preferably 19 ms or less, particularly preferably 17 ms or less, still more preferably 15 ms or less, very particularly preferably 13 ms or less and especially preferably 12 ms or less.
  • the value t/ ⁇ n 2 of the liquid-crystal media according to the invention is preferably 22 ms or less, particularly preferably 20 ms or less, still more preferably 18 ms or less, very particularly preferably 16 ms or less and especially preferably 14 ms or less.
  • the value t/ ⁇ n 2 of the liquid-crystal media according to the invention is preferably 24 ms or less, particularly preferably 22 ms or less, still more preferably 20 ms or less, very particularly preferably 17 ms or less and especially preferably 14 ms or less.
  • the value t/ ⁇ n 2 of the liquid-crystal media according to the invention is preferably 26 ms or less, particularly preferably 23 ms or less, still more preferably 21 ms or less, very particularly preferably 19 ms or less and especially preferably 16 ms or less.
  • the present invention likewise relates to liquid-crystal displays which contain or use the liquid-crystal media according to the invention.
  • These displays can be addressed directly, by means of a time multiplex method or by means of an active matrix, for example by TFTs (thin film transistors), varistors or diodes. Preference is given to displays with active matrix addressing.
  • the present invention relates to the corresponding process for reducing the response time of the displays.
  • liquid-crystal media preferably comprise
  • the medium comprises one or more compounds of the formula I, selected from the group of the compounds of the formulae I-1 to I-5
  • the medium comprises one or more compounds of the formula I-3, selected from the group of the compounds of the formulae I-3a to I-3d, preferably of the formulae I-3b and/or I-3d,
  • the medium particularly preferably comprises one or more compound(s) of the formula II-1, selected from the group
  • the medium comprises one or more compounds of the formula II-3, especially preferably one or more compound(s) in which R 21 denotes vinyl or 1-propenyl and R 22 denotes alkyl, preferably n-alkyl, particularly preferably R 21 denotes vinyl and R 22 denotes methyl.
  • the medium comprises one or more compounds of the formula II-5, especially preferably one or more compound(s) in which R 21 denotes alkyl, vinyl or 1-propenyl and R 22 denotes alkyl, preferably n-alkyl.
  • compositions with their constituents which can be components and compounds, and to the components with their constituents, the compounds.
  • Component A preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to I-5 and very particularly preferably selected from the group of the compounds of the formulae I-1a to I-5d.
  • Component B preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds of the formula II, preferably selected from the group of the compounds of the formulae II-1 to II-6, particularly preferably selected from the group of the compounds of the formulae II-1 to II-4 and very particularly preferably selected from the group of the compounds of the formulae II-1a to II-4d.
  • component C of the liquid-crystal media in accordance with the present invention are selected from the known chiral dopants.
  • Component C preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds selected from the group of the compounds of the following formulae III to V
  • the compounds of the formulae Ill to V are preferably selected from the group of the compounds of the formulae III-1 to III-3, IV-1 and IV-2 or V-1 and V-2,
  • liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
  • component A preferably of compounds of the formula I, and
  • component B preferably of compounds of the formula II, and
  • component C preferably of compounds selected from the group of the formulae III to V.
  • liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
  • the liquid-crystal mixture according to the invention comprises in total 1% or more to 40% or less, preferably 3% or more to 30% or less, particularly preferably 5% or more to 25% or less and very particularly preferably 10% or more to 20% or less, of compounds selected from the group of the formulae III, IV and V.
  • the individual compounds are employed in the mixtures in concentrations of in each case 1% or more to 30% or less, preferably 2% or more to 30% or less and particularly preferably 4% or more to 16% or less.
  • liquid-crystal media especially preferably in each case comprise in total
  • liquid-crystal media comprise:
  • liquid-crystal media which comprise
  • the liquid-crystal media according to the invention preferably have a nematic phase of in each case at least from ⁇ 20° C. or less to 70° C. or more, particularly preferably from ⁇ 30° C. or less to 80° C. or more, very particularly preferably from ⁇ 40° C. or less to 85° C. or more and most preferably from ⁇ 40° C. or less to 90° C. or more.
  • the term “have a nematic phase” here means firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly that clearing still does not occur on heating from the nematic phase.
  • the investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and testing is carried out by storage in test cells having a layer thickness corresponding to the electro-optical application, for at least 100 hours. If the storage stability at a temperature of ⁇ 20° C. in a corresponding test cell is 1000 h or more, the medium is referred to as stable at this temperature. At temperatures of ⁇ 30° C. and ⁇ 40° C., the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured by conventional methods in capillaries.
  • liquid-crystal media according to the invention are characterised by optical anisotropy values in the moderate to low range.
  • the birefringence values are preferably in the range from 0.065 or more to 0.130, particularly preferably in the range from 0.070 to 0.100 and very particularly preferably in the range from 0.075 to 0.090.
  • birefringence values are preferably in the range from 0.060 or more to 0.120, particularly preferably in the range from 0.070 to 0.090 and very particularly preferably in the range from 0.075 to 0.085.
  • the liquid-crystal media according to the invention have negative dielectric anisotropy and have relatively high values of the dielectric anisotropy (
  • dielectric anisotropy
  • the liquid-crystal media according to the invention have relatively small values for the threshold voltage (V 0 ) in the range from 1.7 V or more to 2.5 V or less, preferably from 1.8 V or more to 2.4 V or less, particularly preferably from 1.9 V or more to 2.3 V or less and very particularly preferably from 1.95 V or more to 2.1 V or less.
  • V 0 threshold voltage
  • the liquid-crystal media according to the invention preferably have relatively low values of the average dielectric anisotropy ( ⁇ av. ⁇ ( ⁇ ⁇ +2 ⁇ ⁇ )/3), which are preferably in the range from 5.0 or more to 7.0 or less, preferably from 5.5 or more to 6.5 or less, still more preferably from 5.7 or more to 6.4 or less, particularly preferably from 5.8 or more to 6.2 or less and very particularly preferably from 5.9 or more to 6.1 or less.
  • the average dielectric anisotropy ⁇ av. ⁇ ( ⁇ ⁇ +2 ⁇ ⁇ )/3
  • liquid-crystal media according to the invention have high values for the voltage holding ratio in liquid-crystal cells.
  • these are greater than or equal to 95%, preferably greater than or equal to 97%, particularly preferably greater than or equal to 98% and very particularly preferably greater than or equal to 99%, and after 5 minutes in the oven at 100° C. in the cells, greater than or equal to 90%, preferably greater than or equal to 93%, particularly preferably greater than or equal to 96% and very particularly preferably greater than or equal to 98%.
  • liquid-crystal media having a low addressing voltage or threshold voltage have a lower voltage holding ratio than those having a relatively large addressing voltage or threshold voltage, and vice versa.
  • means less than or equal to, preferably less than, and “ ⁇ ” means greater than or equal to, preferably greater than.
  • dielectrically positive compounds denotes compounds having a ⁇ of >1.5
  • dielectrically neutral compounds denotes those where ⁇ 1.5 ⁇ 1.5
  • dielectrically negative compounds denotes those where ⁇ is ⁇ 1.5.
  • the dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture at 1 kHz in at least one test cell having a thickness of 20 ⁇ m with a homeotropic surface alignment and in at least one test cell having a thickness of 20 ⁇ m with a homogeneous surface alignment.
  • the measurement voltage is typically from 0.5 V to 1.0 V, but it is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
  • the host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792 and the host mixture used for dielectrically negative compounds is ZLI-2857, both from Merck KGaA, Germany.
  • the change in the dielectric constants of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed gives the values for the respective compounds to be investigated.
  • the compound to be investigated is dissolved in the host mixture in an amount of 10%. If the solubility of the substance is too low to do this, the concentration is halved in steps until the investigation can be carried out at the desired temperature.
  • threshold voltage relates to the capacitive threshold (V 0 ), also known as the Freedericksz threshold, unless explicitly stated otherwise.
  • V 0 capacitive threshold
  • V 10 optical threshold for 10% relative contrast
  • the electro-optical properties for example the threshold voltage (V 0 ) (capacitive measurement) and the optical threshold (V 10 ), are, like the switching behaviour, determined in test cells produced at Merck KGaA.
  • the measurement cells have substrates comprising soda-lime glass and are constructed in an ECB or VA configuration with polyimide alignment layers (SE-1211 with **26 diluent (mixing ratio 1:1), both from Nissan Chemicals, Japan), which are rubbed perpendicular to one another.
  • the area of the transparent, virtually square electrodes comprising ITO is 1 cm 2 .
  • the layer thickness of the test cells used is selected corresponding to the birefringence of the liquid-crystal mixture investigated in such a way that the optical retardation is (0.33 ⁇ 0.01) ⁇ m.
  • the polarisers one of which is located in front of the cell and one of which is located behind the cell, form, with their absorption axes, an angle of 90° to one another and are with these axes parallel to the rubbing direction on their respective adjacent substrate.
  • the layer thickness is usually about 4.0 ⁇ m.
  • the cells are filled by means of capillarity under atmospheric pressure and are investigated in the unsealed state.
  • the liquid-crystal mixtures used are, unless stated otherwise, not mixed with a chiral dopant, but they are also particularly suitable for applications in which such doping is necessary.
  • the electro-optical properties and the response times of the test cells are determined in a DMS 301 measuring instrument from Autronic-Melchers, Düsseldorf, Germany, at a temperature of 20° C.
  • the addressing wave form used is a rectangular wave having a frequency of 60 Hz.
  • the voltage is quoted as V rms (root mean square).
  • the voltage is increased from 0 V to twice the value of the optical threshold (2V 10 ) and back.
  • the response times indicated apply to the total time which passes from the change in the voltage until 90% of the respective total change in the light intensity has been reached, i.e. ⁇ on ⁇ t(0%>90%) and ⁇ off ⁇ t(100%->10%), i.e. also encompass the respective delay times.
  • the voltage holding ratio is determined in test cells produced at Merck KGaA.
  • the measurement cells have substrates comprising soda-lime glass and are constructed with polyimide alignment layers (AL-3046 from Japan Synthetic Rubber, Japan) having a layer thickness of 50 nm, which are rubbed perpendicular to one another.
  • the layer thickness is a uniform 6.0 ⁇ m.
  • the area of the transparent electrodes comprising ITO is 1 cm 2 .
  • the rotational viscosity is determined by the rotating permanent magnet method and the flow viscosity in a modified Ubbelohde viscometer.
  • the rotational viscosity values determined at 20° C. are 161 mPa ⁇ s, 133 mPa ⁇ s and 186 mPa ⁇ s respectively, and the flow viscosity values ( ⁇ ) are 21 mm 2 s ⁇ ⁇ 1 , 14 mm 2 s ⁇ ⁇ 1 and 27 mm 2 s ⁇ ⁇ 1 respectively.
  • the voltage holding ratio is determined at 20° C. and after 5 minutes in the oven at 100° C.
  • the voltage used has a frequency of 60 Hz.
  • the liquid-crystal media according to the invention may also, if required, comprise further additives, such as, for example, stabilisers, pleochroic dyes and chiral dopants (as component C), in the conventional amounts.
  • the amount of these additives employed is in total 0% or more to 10% or less, based on the amount of the mixture as a whole, preferably 0.1% or more to 6% or less.
  • the concentration of the individual compounds employed is preferably 0.1% or more to 3% or less. The concentration of these and similar additives is not taken into account in the quoting of the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
  • compositions consist of a plurality of compounds, preferably 3 or more to 30 or less, particularly preferably 6 or more to 20 or less and very particularly preferably 10 or more to 16 or less, compounds, which are mixed in a conventional manner.
  • the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent of the mixture. This is advantageously carried out at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completeness of the dissolution process is particularly easy to observe.
  • the melting point T (C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius.
  • n and m are each integers, and the three dots “ . . . ” are place-holders for other abbreviations from this table.
  • the media according to the invention comprise one or more compounds selected from the group of the compounds of Table E.
  • the liquid-crystal media are investigated with respect to their applicational properties.
  • their respective electro-optical characteristic lines, response times and their voltage holding ratio in test cells are determined.
  • the indicated values for the above-mentioned properties are generally average values of the measurements of two test cells in each case.
  • the deviations between the results of the individual cells were generally a maximum of 4 to 5%.
  • the mixture M-2 is a mixture which consists of equal parts of M1 and M-3.
  • the compositions of the mixtures are shown in the following table, the investigation results in the table after next.
  • the response time of the liquid-crystal displays decreases significantly from Example 1-1 via Example 1-2 to Example 1-3 in parallel with the predicted response time t max or t max / ⁇ n 2 , in accordance with the teaching of the present invention.
  • the mixture M-5 is a mixture which consists of equal parts of M-4 and M-6.
  • the compositions of the mixtures are shown in the following table, the investigation results in the table after next.
  • the response time of the liquid-crystal displays additionally decreases significantly from Example 2-1 via Example 2-2 to Example 2-3 in parallel to the change in the composition of the mixtures, in accordance with the preferred teaching of the present invention.
  • liquid-crystal mixtures of Examples 1 and 2 are particularly distinguished by good response times, this applies in particular to mixtures M-2, M-3, M-5 and M-6.
  • the liquid-crystal mixtures of Examples 1 and 2, particularly the four mixtures just mentioned, can advantageously be used in ECB displays of all known designs, such as, for example: MVA, PVA and ASV, and also in IPS and PA LCD displays.

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Abstract

The present invention relates to nematic liquid-crystal media of negative dielectric anisotropy which have a peak time (tmax.) of 0.25 ms or less, which is determined as described in the disclosure, and which preferably have a value of the quotient of the peak time and the square of the birefringence (tmax/Δn2) of 22 ms or less, and to the use of these liquid-crystal media in liquid-crystal displays, and to these liquid-crystal displays.

Description

  • The present invention relates to liquid-crystal media and to the use thereof in liquid-crystal displays, and to these liquid-crystal displays, particularly liquid-crystal displays which use the ECB (electrically controlled birefringence) effect with dielectrically negative liquid crystals in a homeotropic starting alignment. The liquid-crystal media according to the invention are distinguished by a particularly low response time in the displays according to the invention at the same time as a high voltage holding ratio.
  • Displays which use the ECB effect have become established as so-called VAN (vertically aligned nematic) displays in the MVA (multi-domain vertical alignment, for example: Yoshide, H. et al., Paper 3.1: “MVA LCD for Notebook or Mobile PCs . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6 to 9 and Liu, C. T. et al., Paper 15.1: “A 46-inch TFT-LCD HDTV Technology . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 750 to 753) and PVA (patterned vertical alignment, for example: Kim, Sang Soo, Paper 15.4: “Super PVA Sets New State-of-the-Art for LCD-TV”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 760 to 763) designs besides ASV (advanced super view, for example: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Paper 15.2: “Development of High Quality LCDTV”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757) displays and IPS (in plane switching) displays (for example: Yeo, S. D., Paper 15.3: “A LC Display for the TV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 & 759), besides the long-known displays, as one of the three more recent types of liquid-crystal display that are currently the most important besides TN (twisted nematic) displays, in particular for television applications. In general form, the technologies are compared, for example, in Souk, Jun, SID Seminar 2004, Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6/1 to M-6/26 and Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7/1 to M-7/32. Although the response times of modern ECB displays have already been significantly improved by addressing methods with overdrive, for example: Kim, Hyeon Kyeong et al., paper 9.1: “A 57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 106 to 109, the achievement of video-compatible response times, in particular for the switching of grey shades, is still a problem which has not yet been solved to a satisfactory extent.
  • ECB displays, like ASV displays, use liquid-crystalline media of negative dielectric anisotropy (Δ∈), whereas TN and to date all conventional IPS displays use liquid-crystalline media of positive dielectric anisotropy.
  • In liquid-crystal displays of this type, the liquid crystals are used as dielectrics, whose optical properties change reversibly on application of an electric voltage.
  • Since in displays in general, i.e. also in displays in accordance with these mentioned effects, the operating voltage should be as low as possible, use is made of liquid-crystal media which are generally predominantly composed of liquid-crystal compounds, all of which have the same sign of the dielectric anisotropy and have the greatest possible value of the dielectric anisotropy. In general, at most relatively small proportions of neutral compounds and if possible no compounds having the opposite sign of the dielectric anisotropy to the medium are employed. In the case of liquid-crystal media of negative dielectric anisotropy for ECB displays, predominantly compounds of negative dielectric anisotropy are thus employed. The liquid-crystal media employed generally consist predominantly and usually even essentially of liquid-crystal compounds of negative dielectric anisotropy.
  • In the media used in accordance with the present application, at most significant amounts of dielectrically neutral liquid-crystal compounds and generally only very small amounts or even no dielectrically positive compounds are typically employed, since in general the liquid-crystal displays are intended to have the lowest possible addressing voltages.
  • The liquid-crystal media of the prior art having correspondingly low addressing voltages have relatively low electrical resistances or a low voltage holding ratio and result in undesirably high power consumptions in the displays.
  • In addition, the addressing voltage of the displays of the prior art is often too great, in particular for displays which are not connected directly or not continuously to the power supply network, such as, for example, displays for mobile applications.
  • In addition, the phase range must be sufficiently broad for the intended application.
  • In particular, the response times of the liquid-crystal media in the displays must be improved, i.e. reduced. This is particularly important for displays for television or multimedia applications. In order to improve the response times, it has repeatedly been proposed in the past to optimise the rotational viscosity of the liquid-crystal media (γ1), i.e. to achieve media having the lowest possible rotational viscosity. However, the results achieved here are inadequate for many applications and therefore make it appear desirable to find further optimisation approaches.
  • There is therefore a great demand for liquid-crystal media which do not have the disadvantages of the media from the prior art, or at least do so to a significantly reduced extent.
  • Surprisingly, it has been found that it has been possible to achieve liquid-crystal displays which have a short response time in ECB displays and at the same time have a sufficiently broad nematic phase, favourable birefringence (Δn) and a high voltage holding ratio.
  • In accordance with the present invention, the short response time of the displays is preferably achieved by using liquid-crystal media according to the invention which have a low value of 0.25 ms or less for the peak times (tmax) calculated by the method explained below.
  • The quotient of the peak time and the square of the birefringence of the liquid-crystal mixture (tmax/Δn2) of the liquid-crystal media according to the invention is preferably 22 ms or less. This quotient (tmax/Δn2), which takes into account the effect of the optimum layer thickness of the liquid-crystal displays, is proportional to the response time of the liquid-crystal mixtures in the corresponding displays.
  • For the purposes of the present invention, the peak time (tmax) is the time which passes before current flowing through the cell after application of a short, high voltage pulse to a cell filled with liquid crystal passes through a maximum in its time curve (l(t)). It is determined as follows in accordance with the present invention. Firstly, the time curve of the current (l(t)) or the current density (L(t)/S) is calculated in accordance with the following equations (1) and (2), where equation (1) describes the current as a function of the tilt angle of the liquid-crystal director and equation (2) describes the correlation between the tilt angle and the time that has passed after application of the voltage.
  • Equation ( 1 ) I ( θ b ) = S ( 2 α 1 sin 2 θ b cos 2 θ b - γ 2 cos 2 θ b + γ 3 ) ( ɛ 0 Δɛ sin 2 θ b ) 2 E b 3 ( α 1 γ 1 + γ 2 2 ) sin 2 2 θ b - γ 1 2 - γ 2 2 + 2 γ 1 γ 3 Equation ( 2 ) t ( θ b ) = β 2 2 ɛ 0 Δɛ E b 2 β 3 { - ln ( tan θ b tan θ 0 ) + - β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 + β 1 β 4 tan 2 θ 0 + β 7 + β 1 ) + β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 - β 1 β 4 tan 2 θ 0 + β 7 - β 1 ) } + β 6 2 ɛ 0 Δɛ E b 2 β 1 ln [ ( α 1 cos 2 θ b + γ 2 + β 1 ) ( α 1 cos 2 θ 0 + γ 2 - β 1 ) ( α 1 cos 2 θ b + γ 2 - β 1 ) ( α 1 cos 2 θ 0 + γ 2 + β 1 ) ]
  • where:
    • S=electrode area (this is not necessary for determination of the maximum of l(t)),
    • Eb=U/I (U=90 V and I=22 μm assumed for the calculations for the present invention),
    • θ0=bulk tilt angle at time t=0
    • θb=bulk tilt angle
    • α1 to α5=Leslie viscosity coefficients,
    • β11 22 2+2α1γ3,
    • β21 22 2−2γ1γ3,
    • β32−γ3,
    • β423,
    • β52 21γ3,
    • β61γ12 2,
    • β713
    • γ1=−□α2; (rotational viscosity),
    • γ23−α2 and
    • γ3345.
  • For the Leslie viscosity coefficients, the following assumptions are used for the present invention:
  • α1=−10 mPas and
    α3=0 mPas.
  • In addition, for α3=0 in accordance with Parodi:

  • α45=−α2+2η2

  • i.e.

  • α451+2η2.
  • The following is additionally assumed here:

  • η2≈ρ*ν
  • where:
    ρ=density (about 1 g/cm3) and
    ν=flow viscosity.
  • For better legibility, the two equations (1) and (2) are shown again in FIG. 1.
  • The position of the maximum tmax of the function l(t) or l(θb(t)) can be determined in various ways. Thus, for example, the function l(t) can be calculated numerically and the value and position of the maximum selected numerically or determined graphically. For the purposes of the present invention, numerical methods are preferred, and particular preference is given to the use of corresponding mathematics software Mathematica (for example: version 3) from Wolfram Research, Inc., into which an implicit representation of l(t) is entered, and the maximum of l(t) is determined numerically via derivation of the function after time (dl/dt).
  • The liquid-crystal media according to the invention have a value of the peak time (tmax) of 0.25 ms or less, particularly preferably of 0.20 ms or less, still more preferably of 0.16 ms or less, very particularly preferably of 0.13 ms or less and especially preferably of 0.12 ms or less.
  • For a Δn of 0.080±0.010, the value tmax of the liquid-crystal media according to the invention is preferably 0.18 ms or less, particularly preferably 0.16 ms or less, still more preferably 0.14 ms or less, very particularly preferably 0.12 ms or less and especially preferably 0.10 ms or less.
  • For a Δn of 0.100±0.010, the value tmax of the liquid-crystal media according to the invention is preferably 0.19 ms or less, particularly preferably 0.17 ms or less, still more preferably 0.15 ms or less, very particularly preferably 0.13 ms or less and especially preferably 0.12 ms or less.
  • For a Δn of 0.120±0.010, the value tmax of the liquid-crystal media according to the invention is preferably 0.20 ms or less, particularly preferably 0.18 ms or less, still more preferably 0.16 ms or less, very particularly preferably 0.14 ms or less and especially preferably 0.13 ms or less.
  • For a Δn of 0.150±0.020, the value tmax of the liquid-crystal media according to the invention is preferably 0.21 ms or less, particularly preferably 0.20 ms or less, still more preferably 0.18 ms or less, very particularly preferably 0.16 ms or less and especially preferably 0.15 ms or less. For a Δn of 0.200±0.030 the value tmax of the liquid-crystal media according to the invention is preferably 0.25 ms or less, particularly preferably 0.22 ms or less, still more preferably 0.20 ms or less, very particularly preferably 0.19 ms or less and especially preferably 0.18 ms or less.
  • Since different values of the optical retardation (d·Δn) are in some cases required for the particular applications of the liquid-crystal media in the various display types or designs and the response time in the case of most electro-optical effects is inversely proportional to the square of the layer thickness of the liquid-crystal cells (d), a further parameter for characterisation of the corresponding liquid-crystal media is the quotient of the calculated peak time (tmax) and the square of the birefringence (Δn), i.e.: tmax/Δn2.
  • The liquid-crystal media according to the invention preferably have a value of tmax/Δn2 of 22 ms or less, particularly preferably of 20 ms or less, still more preferably of 18 ms or less, very particularly preferably of 16 ms or less and especially of 15 ms or less.
  • For an average dielectric constant (∈av.) of 4.0±0.5, the value tmax/Δn2 of the liquid-crystal media according to the invention is preferably 18 ms or less, particularly preferably 16 ms or less, still more preferably 14 ms or less, very particularly preferably 12 ms or less and especially preferably 10 ms or less.
  • For an ∈av. of 5.0±0.5, the value t/Δn2 of the liquid-crystal media according to the invention is preferably 19 ms or less, particularly preferably 17 ms or less, still more preferably 15 ms or less, very particularly preferably 13 ms or less and especially preferably 12 ms or less.
  • For an ∈av. of 6.0±0.5, the value t/Δn2 of the liquid-crystal media according to the invention is preferably 22 ms or less, particularly preferably 20 ms or less, still more preferably 18 ms or less, very particularly preferably 16 ms or less and especially preferably 14 ms or less.
  • For an ∈av. of 7.0±0.5, the value t/Δn2 of the liquid-crystal media according to the invention is preferably 24 ms or less, particularly preferably 22 ms or less, still more preferably 20 ms or less, very particularly preferably 17 ms or less and especially preferably 14 ms or less.
  • For an ∈av. of 8.0±0.5, the value t/Δn2 of the liquid-crystal media according to the invention is preferably 26 ms or less, particularly preferably 23 ms or less, still more preferably 21 ms or less, very particularly preferably 19 ms or less and especially preferably 16 ms or less.
  • The present invention likewise relates to liquid-crystal displays which contain or use the liquid-crystal media according to the invention. These displays can be addressed directly, by means of a time multiplex method or by means of an active matrix, for example by TFTs (thin film transistors), varistors or diodes. Preference is given to displays with active matrix addressing.
  • In addition, the present invention relates to the corresponding process for reducing the response time of the displays.
  • The liquid-crystal media according to the invention preferably comprise
    • a) a dielectrically negative, liquid-crystalline component (component A), which preferably comprises one or more dielectrically negative compound(s) of the formula
  • Figure US20170088776A1-20170330-C00001
      • in which at least one of
  • Figure US20170088776A1-20170330-C00002
  • denotes
  • Figure US20170088776A1-20170330-C00003
      • and the others, if present, in each case, independently of one another, have the same meaning or denote
  • Figure US20170088776A1-20170330-C00004
        • preferably, independently of one another,
  • Figure US20170088776A1-20170330-C00005
        • particularly preferably
  • Figure US20170088776A1-20170330-C00006
        •  denotes
  • Figure US20170088776A1-20170330-C00007
        •  and/or, if present,
  • Figure US20170088776A1-20170330-C00008
        • denote
  • Figure US20170088776A1-20170330-C00009
      • R11 and R12, independently of one another, denote alkyl having 1 to 7 C atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5 C atoms, alkoxy having 1 to 7 C atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 1 to 5 C atoms, or alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7 C atoms, preferably having 2 to 4 C atoms, preferably alkenyl, where one or more H atoms in all groups may be replaced by halogen atoms, preferably F atoms,
      • L11 and L12, independently of one another, denote C—F or N, preferably at least one of L11 and L12 denotes C—F, particularly preferably L11 and L12 both denote C—F,
      • Z11 and Z12, in each case independently of one another, denote —CH2—CH2—, —C≡C—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —CH2—CF2—, —CF2—CH2—, —CF2—CF2—, —CO—O—, —O—CO—, —OCH2—, —CH2O—, —OCF2, —CF2O— or a single bond, preferably —CH2—CH2—, —CH═CH—, —CH2—CF2—, —CF2—CH2—, —CF2—CF2—, —OCH2—, —CH2O—, —OCF2, —CF2O— or a single bond, particularly preferably one of Z11 and Z12 denotes —CH2—CH2— or a single bond and the other denotes a single bond, particularly preferably both denote a single bond, and
      • n denotes 0, 1 or 2, preferably 0 or 1, and
    • b) a dielectrically neutral, liquid-crystalline component (component B), which preferably comprises one or more dielectrically neutral compound(s) of the formula II
  • Figure US20170088776A1-20170330-C00010
      • in which
      • R21 and R22, in each case independently of one another, have one of the meanings given for R11 and R12 and preferably denote alkyl having 1 to 7 C atoms, preferably n-alkyl and particularly preferably n-alkyl having 1 to 5 C atoms, alkoxy having 1 to 7 C atoms, preferably n-alkoxy and particularly preferably n-alkoxy having 2 to 5 C atoms, or alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7 C atoms, preferably having 2 to 4 C atoms, preferably alkenyloxy,
      • Z21 to Z23, in each case independently of one another, have one of the meanings given for Z11 and Z12 and preferably denote —CH2—CH2—, —CH═CH—, —C≡C—, —COO— or a single bond, preferably —CH2—CH2— or a single bond and particularly preferably a single bond,
  • Figure US20170088776A1-20170330-C00011
        • in each case independently of one another, denote
  • Figure US20170088776A1-20170330-C00012
        • preferably
  • Figure US20170088776A1-20170330-C00013
        •  denote
  • Figure US20170088776A1-20170330-C00014
        • and, if present,
  • Figure US20170088776A1-20170330-C00015
        •  denotes
  • Figure US20170088776A1-20170330-C00016
      • p and q, in each case independently of one another, denote 0 or 1, preferably (p+q) denotes 0 or 1, particularly preferably q denotes 0 and especially preferably p and q both denote 0,
      • and optionally
    • c) a chiral component (component C) which comprises one or more chiral compounds.
  • In a preferred embodiment, the medium comprises one or more compounds of the formula I, selected from the group of the compounds of the formulae I-1 to I-5
  • Figure US20170088776A1-20170330-C00017
      • in which the parameters have the respective meaning indicated above for the formula land preferably
      • R11 denotes alkyl or alkenyl and
      • R12 denotes alkyl, alkenyl, alkoxy or alkenyloxy.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula I-1, selected from the group of the compounds of the formulae I-1a to I-1d, preferably of the formulae I-1b and/or I-1d, particularly preferably of the formula I-1d,
  • Figure US20170088776A1-20170330-C00018
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 7 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula I-2, selected from the group of the compounds of the formulae I-2a to I-2d, preferably of the formulae I-2a and/or I-2b, particularly preferably of the formula I-2b,
  • Figure US20170088776A1-20170330-C00019
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 7 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
  • In a further preferred embodiment, the medium comprises one or more compounds of the formula I-3, selected from the group of the compounds of the formulae I-3a to I-3d, preferably of the formulae I-3b and/or I-3d,
  • Figure US20170088776A1-20170330-C00020
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 7 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula I-4, selected from the group of the compounds of the formulae I-4a to I-4d, preferably of the formulae I-4a and/or I-4c, particularly preferably of the formula I-4a,
  • Figure US20170088776A1-20170330-C00021
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 7 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula I-5, selected from the group of the compounds of the formulae I-5a to I-5d, preferably of the formulae I-5a and/or I-5c, particularly preferably of the formula I-5a,
  • Figure US20170088776A1-20170330-C00022
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 7 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula II from the group of the compounds of the formulae II-1 to II-8, preferably selected from the group of the compounds of the formulae II-1 to II-6, preferably from the group II-1 to II-4 and particularly preferably from the group II-2 and II-3,
  • Figure US20170088776A1-20170330-C00023
      • in which the parameters have the respective meaning indicated above for the formula II, and
      • Y1 denotes H or F, and
      • preferably
      • R21 denotes alkyl or alkenyl and
      • R22 denotes alkyl, alkenyl or alkoxy, preferably alkyl or alkenyl, particularly preferably alkenyl.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula II-1, selected from the group of the compounds of the formulae II-1a to II-1e, preferably of the formulae II-1a and/or II-1c and/or II-1d, particularly preferably of the formulae II-1c and/or II-1d and very particularly preferably of the formula II-1c and of the formula II-1d,
  • Figure US20170088776A1-20170330-C00024
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 5 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl and alkenyl′, independently of one another, denote alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula II-2, selected from the group of the compounds of the formulae II-2a to II-2d, preferably of the formulae II-2a and/or II-2b, particularly preferably of the formula II-2b,
  • Figure US20170088776A1-20170330-C00025
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 5 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula II-3, selected from the group of the compounds of the formulae II-3a to II-3d, preferably of the formulae II-3a and/or II-3d, particularly preferably of the formula II-3d,
  • Figure US20170088776A1-20170330-C00026
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 5 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
      • In a further preferred embodiment, the medium comprises one or more compounds of the formula II-4 selected from the group of the compounds of the formulae II-4a to II-4d, preferably of the formulae II-4a and/or II-4d, particularly preferably of the formula II-4d,
  • Figure US20170088776A1-20170330-C00027
      • in which
      • alkyl and alkyl′, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms
      • alkoxy denotes alkoxy having 1 to 5 C atoms, preferably having 2 to 4 C atoms, and
      • alkenyl denotes alkenyl having 2 to 7 C atoms, preferably having 2 to 5 C atoms.
  • The medium particularly preferably comprises one or more compound(s) of the formula II-1, selected from the group
      • of the formulae II-1c, especially preferably
      • of the formula II-1 in which R21 denotes vinyl or 1-propenyl and R22 denotes alkyl, preferably n-alkyl, particularly preferably R21 denotes vinyl and R22 denotes propyl, and
      • of the formula II-1d, especially preferably
      • of the formula II-1 in which R21 and R22, independently of one another, denote vinyl or 1-propenyl, preferably R21 denotes vinyl and particularly preferably R21 and R22 denote vinyl.
  • In a preferred embodiment, the medium comprises one or more compounds of the formula II-3, especially preferably one or more compound(s) in which R21 denotes vinyl or 1-propenyl and R22 denotes alkyl, preferably n-alkyl, particularly preferably R21 denotes vinyl and R22 denotes methyl.
  • In a preferred embodiment, the medium comprises one or more compounds of the formula II-5, especially preferably one or more compound(s) in which R21 denotes alkyl, vinyl or 1-propenyl and R22 denotes alkyl, preferably n-alkyl.
  • For the present invention, in connection with the detailing of the constituents of the compositions:
      • comprise: means that the concentration of the constituents in question in the composition is preferably 10% or more, particularly preferably 20% or more,
      • consist predominantly of: means that the concentration of the constituents in question in the composition is preferably 50% or more, particularly preferably 55% or more and very particularly preferably 60% or more,
      • consist essentially completely of: means that the concentration of the constituents in question in the composition is preferably 80% or more, particularly preferably 90% or more and very particularly preferably 95% or more, and
      • consist virtually completely of: means that the concentration of the constituents in question in the composition is preferably 98% or more, particularly preferably 99% or more and very particularly preferably 100.0%.
  • This applies both to the media as compositions with their constituents, which can be components and compounds, and to the components with their constituents, the compounds.
  • Component A preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to I-5 and very particularly preferably selected from the group of the compounds of the formulae I-1a to I-5d.
  • Component B preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds of the formula II, preferably selected from the group of the compounds of the formulae II-1 to II-6, particularly preferably selected from the group of the compounds of the formulae II-1 to II-4 and very particularly preferably selected from the group of the compounds of the formulae II-1a to II-4d.
  • The chiral compound or the chiral compounds which can be used in component C of the liquid-crystal media in accordance with the present invention are selected from the known chiral dopants. Component C preferably consists predominantly, particularly preferably essentially completely and very particularly preferably virtually completely, of one or more compounds selected from the group of the compounds of the following formulae III to V
  • Figure US20170088776A1-20170330-C00028
      • in which
      • R31 to R43
      • and R5, in each case independently of one another, have the meaning given above for R21 under the formula II, and alternatively denote H, CN, F, Cl CF3, OCF3, CF2H or OCF2H, and at least one of R31 and R32 denotes a chiral group,
      • Z31 to Z53
      • and Z5, in each case independently of one another, denote —CH2CH2—, —CH═CH—, —COO—, —O—CO— or a single bond, preferably Z31, Z32, Z41, Z44 and Z45 denote a single bond, Z33, Z42 and Z43 denote —COO— or a single bond, Z42 preferably denotes —COO—, and Z43 and Z5 denote —O—CO—,
  • Figure US20170088776A1-20170330-C00029
        • in each case independently of one another, denote
  • Figure US20170088776A1-20170330-C00030
      • s, t, u, v, and w, in each case independently of one another, denote 0 or 1, preferably s and t both denote 0 and u and v both denote 1.
  • The compounds of the formulae Ill to V are preferably selected from the group of the compounds of the formulae III-1 to III-3, IV-1 and IV-2 or V-1 and V-2,
  • Figure US20170088776A1-20170330-C00031
      • in which the parameters in each case have the meaning given above under the formulae III to V and preferably
      • R31 to R5 denote alkyl, alkenyl or alkoxy, H, CN, F, CI, CF3, OCF3, CF2H or OCF2H, and at least one of R31 and R32 denotes a chiral group, preferably isooctyloxy,
      • Z31 denotes a single bond,
      • Z33 in the formula III-2 denotes a single bond and in the formula III-3 denotes —COO—, Z42 denotes —COO—,
      • Z43 denotes —O—CO—,
      • m denotes an integer from 1 to 8, preferably 6, and
      • l denotes an integer from 0 to 8, preferably 1, which is different from m.
      • The compounds are especially preferably selected from the group of the compounds of the following formulae III-1a, III-1b, III-2a to III-2c and III-3a, IV-1a and IV-2a or V-1a and V-2a
  • Figure US20170088776A1-20170330-C00032
  • In a preferred embodiment, the liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
  • 30% or more to 85% or less, preferably 40% or more to 80% or less, preferably 50% or more to 70% or less and particularly preferably 60% or more to 70% or less and very particularly preferably 65% or more to 69% or less, of component A, preferably of compounds of the formula I, and
  • 15% or more to 70% or less, preferably 20% or more to 60% or less, particularly preferably 30% or more to 50% or less and very particularly preferably 35% or more to 45% or less, of component B, preferably of compounds of the formula II, and
  • 0% or more to 15% or less, preferably 0% or more to 10% or less, particularly preferably 0.1% or more to 6% or less and very particularly preferably 1% or more to 5% or less, of component C, preferably of compounds selected from the group of the formulae III to V.
  • In a further preferred embodiment, the liquid-crystal media according to the invention comprise in total, based on the mixture as a whole,
  • 25% or more to 45% or less, preferably 30% or more to 40% or less, particularly preferably 32% or more to 39% or less and very particularly preferably 33% or more to 37% or less, of compounds of the formula I-1,
  • 15% or more to 45% or less, preferably 18% or more to 32% or less, particularly preferably 20% or more to 30% or less and very particularly preferably 21% or more to 25% or less, of compounds of the formula I-2,
  • 0% or more to 30% or less, preferably 5% or more to 25% or less, particularly preferably 10% or more to 20% or less and very particularly preferably 13% or more to 18% or less, of compounds of the formula I-3,
  • 0% or more to 20% or less, preferably 0% or more to 15% or less, particularly preferably 0% or more to 10% or less and very particularly preferably 0% or more to 5% or less, of compounds selected from the group of the formulae I-4 and 1-5, preferably of the formula I-4,
  • 15% or more to 45% or less, preferably 20% or more to 40% or less, particularly preferably 25% or more to 37% or less and very particularly preferably 30% or more to 35% or less, of compounds selected from the group of the formulae II-1 and II-5, preferably of the formula II-5,
  • 0% or more to 20% or less, preferably 0% or more to 15% or less, particularly preferably 0% or more to 10% or less and very particularly preferably 0% or more to 5% or less, of compounds selected from the group of the formulae II-2 and II-4, preferably of the formula II-4, and
  • 0% or more to 20% or less, preferably 0% or more to 15% or less, particularly preferably 1% or more to 12% or less and very particularly preferably 3% or more to 8% or less of compounds selected from the group of the formulae II-3 and II-6, preferably of the formula II-6.
  • In a preferred embodiment, the liquid-crystal mixture according to the invention comprises in total 1% or more to 40% or less, preferably 3% or more to 30% or less, particularly preferably 5% or more to 25% or less and very particularly preferably 10% or more to 20% or less, of compounds selected from the group of the formulae III, IV and V.
  • Here, as throughout the present disclosure and the claims, the term “compounds”, also written as “compound(s)”, denotes both one and a plurality of compounds, unless explicitly stated otherwise.
  • The individual compounds are employed in the mixtures in concentrations of in each case 1% or more to 30% or less, preferably 2% or more to 30% or less and particularly preferably 4% or more to 16% or less.
  • In a preferred embodiment, the liquid-crystal media especially preferably in each case comprise in total
  • 29% to 38% of compounds of the formula I-1,
  • 14% to 28% of compounds of the formula I-2,
  • 3% to 17% of compounds of the formula I-3,
  • 0% to 5% of compounds of the formula I-4,
  • 0% to 5% of compounds of the formula I-5,
  • 28% to 42% of compounds of the formula II-1 and II-4,
  • 0% to 5% of compounds of the formula II-2 and II-5 and
  • 0% to 5% of compounds of the formula II-3 and II-6.
  • The liquid-crystal media in this embodiment very particularly preferably comprise in each case in total
  • 31% to 36% of compounds of the formula I-1,
  • 17% to 23% of compounds of the formula I-2,
  • 5% to 15% of compounds of the formula I-3,
  • 0% to 3% of compounds of the formula I-4,
  • 0% to 3% of compounds of the formula I-5,
  • 30% to 37% of compounds of the formula II-1 and II-4,
  • 0% to 2% of compounds of the formula II-2 and II-5 and
  • 0% to 3% of compounds of the formula II-3 and II-6.
  • In a particularly preferred embodiment, which may be identical and preferably is identical with the preferred embodiments described above for the preferred concentration ranges, the liquid-crystal media comprise:
      • one or more compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to 1-5, preferably of the formulae I-1 and/or 1-2 and/or 1-3, preferably where R11 denotes n-alkyl or alkenyl, preferably alkenyl, particularly preferably vinyl, and R12 alkyl or alkoxy, preferably alkoxy, preferably
      • one or more compounds of the formula I-1 in which R11 preferably denotes n-propyl or n-pentyl and R22 preferably denotes ethoxy and/or
      • one or more compounds of the formula I-2 in which R11 preferably denotes ethyl or n-butyl, preferably n-butyl, and R22 preferably denotes ethoxy and/or
      • one or more compounds of the formula II, preferably selected from the group of the compounds of the formulae II-1 to II-6, preferably of the formulae II-1 and/or II-3 and/or 1-5 and/or II-6, preferably where R21 denotes n-alkyl or alkenyl, preferably alkenyl, particularly preferably vinyl, and R22 denotes alkyl or alkoxy, preferably alkoxy, particularly preferably methyl or propyl, preferably
      • one or more compounds of the formula II-1 in which R21 preferably denotes alkenyl, particularly preferably vinyl or 1-propenyl, very particularly preferably vinyl, and R22 preferably denotes alkyl, preferably n-alkyl and very particularly preferably propyl and/or
      • one or more compounds of the formula II-1 in which R21 and R22 preferably denote alkenyl, particularly preferably vinyl or 1-propenyl, very particularly preferably R21 denotes vinyl and especially preferably R21 and R22 both denote vinyl and/or
      • one or more compounds of the formula II-3 in which R21 preferably denotes alkenyl, preferably vinyl, and R22 preferably denotes alkyl, preferably methyl, and/or
      • one or more compounds of the formula II-5 and/or
      • one or more compounds of the formula II-6 and/or
      • one or more compounds selected from the group of the compounds of the formula III and/or
      • one or more compounds selected from the group of the compounds of the formula IV.
  • Particular preference is given here to liquid-crystal media which comprise
      • one or more compounds of the formula I, preferably selected from the group of the compounds of the formulae I-1 to I-5, preferably where R11 denotes n-alkyl and R12 denotes alkoxy, and in particular in each case per compound in concentrations of 6% or more to 20% or less per compound and/or
      • one or more compounds of the formula II-1, in particular in each case per compound in concentrations of 2% or more, preferably 4% or more, to 11% or less per compound, and/or
      • one or more compounds of the formulae II-3, II-2 and II-4, in particular in each case per compound in concentrations of 2% or more, preferably 4% or more, to 11% or less per compound, and/or
      • one or more compounds of the formulae III to V, in particular in each case per compound in concentrations of 0.1% or more, preferably 0.4% or more, to 8% or less per compound.
  • The liquid-crystal media according to the invention preferably have a nematic phase of in each case at least from −20° C. or less to 70° C. or more, particularly preferably from −30° C. or less to 80° C. or more, very particularly preferably from −40° C. or less to 85° C. or more and most preferably from −40° C. or less to 90° C. or more.
  • The term “have a nematic phase” here means firstly that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and secondly that clearing still does not occur on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and testing is carried out by storage in test cells having a layer thickness corresponding to the electro-optical application, for at least 100 hours. If the storage stability at a temperature of −20° C. in a corresponding test cell is 1000 h or more, the medium is referred to as stable at this temperature. At temperatures of −30° C. and −40° C., the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured by conventional methods in capillaries.
  • Furthermore, the liquid-crystal media according to the invention are characterised by optical anisotropy values in the moderate to low range. The birefringence values are preferably in the range from 0.065 or more to 0.130, particularly preferably in the range from 0.070 to 0.100 and very particularly preferably in the range from 0.075 to 0.090.
  • In an overlapping particularly preferred embodiment of the present invention, birefringence values are preferably in the range from 0.060 or more to 0.120, particularly preferably in the range from 0.070 to 0.090 and very particularly preferably in the range from 0.075 to 0.085.
  • The liquid-crystal media according to the invention have negative dielectric anisotropy and have relatively high values of the dielectric anisotropy (|Δ∈|), which are preferably in the range from 2.7 or more to 5.3 or less, preferably up to 4.5 or less, preferably from 2.9 or more to 4.5 or less, particularly preferably from 3.0 or more to 4.0 or less and very particularly preferably from 3.5 or more to 3.9 or less.
  • The liquid-crystal media according to the invention have relatively small values for the threshold voltage (V0) in the range from 1.7 V or more to 2.5 V or less, preferably from 1.8 V or more to 2.4 V or less, particularly preferably from 1.9 V or more to 2.3 V or less and very particularly preferably from 1.95 V or more to 2.1 V or less.
  • The liquid-crystal media according to the invention preferably have relatively low values of the average dielectric anisotropy (∈av.≡(∈+2∈)/3), which are preferably in the range from 5.0 or more to 7.0 or less, preferably from 5.5 or more to 6.5 or less, still more preferably from 5.7 or more to 6.4 or less, particularly preferably from 5.8 or more to 6.2 or less and very particularly preferably from 5.9 or more to 6.1 or less.
  • In addition, the liquid-crystal media according to the invention have high values for the voltage holding ratio in liquid-crystal cells.
  • In freshly filled cells at 20° C. in the cells, these are greater than or equal to 95%, preferably greater than or equal to 97%, particularly preferably greater than or equal to 98% and very particularly preferably greater than or equal to 99%, and after 5 minutes in the oven at 100° C. in the cells, greater than or equal to 90%, preferably greater than or equal to 93%, particularly preferably greater than or equal to 96% and very particularly preferably greater than or equal to 98%.
  • In general, liquid-crystal media having a low addressing voltage or threshold voltage have a lower voltage holding ratio than those having a relatively large addressing voltage or threshold voltage, and vice versa.
  • These preferred values for the individual physical properties are preferably also maintained in each case combined with one another by the media according to the invention.
  • For the present invention, “≦” means less than or equal to, preferably less than, and “≧” means greater than or equal to, preferably greater than.
  • For the present invention,
  • Figure US20170088776A1-20170330-C00033
  • denote trans-1,4-cyclohexylene.
  • For the present invention, the term “dielectrically positive compounds” denotes compounds having a Δ∈ of >1.5, the term “dielectrically neutral compounds” denotes those where −1.5≦Δ∈≦1.5, and the term “dielectrically negative compounds” denotes those where Δ∈ is <−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture at 1 kHz in at least one test cell having a thickness of 20 μm with a homeotropic surface alignment and in at least one test cell having a thickness of 20 μm with a homogeneous surface alignment. The measurement voltage is typically from 0.5 V to 1.0 V, but it is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
  • The host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792 and the host mixture used for dielectrically negative compounds is ZLI-2857, both from Merck KGaA, Germany. The change in the dielectric constants of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed gives the values for the respective compounds to be investigated. The compound to be investigated is dissolved in the host mixture in an amount of 10%. If the solubility of the substance is too low to do this, the concentration is halved in steps until the investigation can be carried out at the desired temperature.
  • All temperature values indicated for the present invention are indicated in ° C. and all temperature differences correspondingly in differential degrees, unless explicitly stated otherwise.
  • For the present invention, the term “threshold voltage” relates to the capacitive threshold (V0), also known as the Freedericksz threshold, unless explicitly stated otherwise. In the examples, as generally customary, the optical threshold for 10% relative contrast (V10) is also determined and indicated.
  • The electro-optical properties, for example the threshold voltage (V0) (capacitive measurement) and the optical threshold (V10), are, like the switching behaviour, determined in test cells produced at Merck KGaA. The measurement cells have substrates comprising soda-lime glass and are constructed in an ECB or VA configuration with polyimide alignment layers (SE-1211 with **26 diluent (mixing ratio 1:1), both from Nissan Chemicals, Japan), which are rubbed perpendicular to one another. The area of the transparent, virtually square electrodes comprising ITO is 1 cm2. The layer thickness of the test cells used is selected corresponding to the birefringence of the liquid-crystal mixture investigated in such a way that the optical retardation is (0.33±0.01) μm. The polarisers, one of which is located in front of the cell and one of which is located behind the cell, form, with their absorption axes, an angle of 90° to one another and are with these axes parallel to the rubbing direction on their respective adjacent substrate. The layer thickness is usually about 4.0 μm. The cells are filled by means of capillarity under atmospheric pressure and are investigated in the unsealed state. The liquid-crystal mixtures used are, unless stated otherwise, not mixed with a chiral dopant, but they are also particularly suitable for applications in which such doping is necessary. The electro-optical properties and the response times of the test cells are determined in a DMS 301 measuring instrument from Autronic-Melchers, Karlsruhe, Germany, at a temperature of 20° C. The addressing wave form used is a rectangular wave having a frequency of 60 Hz. The voltage is quoted as Vrms (root mean square). During measurement of the response times, the voltage is increased from 0 V to twice the value of the optical threshold (2V10) and back. The response times indicated apply to the total time which passes from the change in the voltage until 90% of the respective total change in the light intensity has been reached, i.e. τon≡t(0%>90%) and τoff≡t(100%->10%), i.e. also encompass the respective delay times. Since the individual response times are dependent on the addressing voltage, the sum of the two individual response times (Σ=τonoff) or the average response time (τav.=(τonoff)/2) are also indicated in order to improve comparability of the results.
  • The voltage holding ratio is determined in test cells produced at Merck KGaA. The measurement cells have substrates comprising soda-lime glass and are constructed with polyimide alignment layers (AL-3046 from Japan Synthetic Rubber, Japan) having a layer thickness of 50 nm, which are rubbed perpendicular to one another. The layer thickness is a uniform 6.0 μm. The area of the transparent electrodes comprising ITO is 1 cm2.
  • For the purposes of the present invention, all concentrations are, unless explicitly stated otherwise, indicated in percent by weight and relate to the corresponding mixture or mixture component. All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. Δn is determined at 589 nm and Δ∈ at 1 kHz.
  • The rotational viscosity is determined by the rotating permanent magnet method and the flow viscosity in a modified Ubbelohde viscometer. For liquid-crystal mixtures ZLI-2293, ZLI-4792 and MLC-6608, all products from Merck KGaA, Darmstadt, Germany, the rotational viscosity values determined at 20° C. are 161 mPa·s, 133 mPa·s and 186 mPa·s respectively, and the flow viscosity values (ν) are 21 mm2−1, 14 mm2−1 and 27 mm2−1 respectively.
  • The voltage holding ratio is determined at 20° C. and after 5 minutes in the oven at 100° C. The voltage used has a frequency of 60 Hz.
  • The liquid-crystal media according to the invention may also, if required, comprise further additives, such as, for example, stabilisers, pleochroic dyes and chiral dopants (as component C), in the conventional amounts. The amount of these additives employed is in total 0% or more to 10% or less, based on the amount of the mixture as a whole, preferably 0.1% or more to 6% or less. The concentration of the individual compounds employed is preferably 0.1% or more to 3% or less. The concentration of these and similar additives is not taken into account in the quoting of the concentrations and concentration ranges of the liquid-crystal compounds in the liquid-crystal media.
  • The compositions consist of a plurality of compounds, preferably 3 or more to 30 or less, particularly preferably 6 or more to 20 or less and very particularly preferably 10 or more to 16 or less, compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent of the mixture. This is advantageously carried out at elevated temperature. If the selected temperature is above the clearing point of the principal constituent, the completeness of the dissolution process is particularly easy to observe. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example using premixes or from a so-called “multibottle system”.
  • The following examples serve to illustrate the invention without restricting it. In the examples, the melting point T (C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I) of a liquid-crystal substance are indicated in degrees Celsius.
  • For the present invention and in the following examples, the structures of the liquid-crystal compounds are indicated by means of acronyms, with the transformation into chemical formulae taking place in accordance with Tables A to C below. All radicals CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n, CmH2m and ClH2l are straight-chain alkyl radicals or alkylene radicals, each having n, m and l C atoms respectively. The ring elements of the nuclei of the compound are coded in Table A, the bridging units are listed in Table B, and the meanings of the symbols for the left-hand or right-hand end groups of the molecules are listed in Table C. Illustrative molecular structures and their abbreviations are listed in Table D.
  • TABLE A
    Ring elements
    C
    Figure US20170088776A1-20170330-C00034
    D
    Figure US20170088776A1-20170330-C00035
    DI
    Figure US20170088776A1-20170330-C00036
    A
    Figure US20170088776A1-20170330-C00037
    AI
    Figure US20170088776A1-20170330-C00038
    P
    Figure US20170088776A1-20170330-C00039
    G
    Figure US20170088776A1-20170330-C00040
    GI
    Figure US20170088776A1-20170330-C00041
    U
    Figure US20170088776A1-20170330-C00042
    UI
    Figure US20170088776A1-20170330-C00043
    Y
    Figure US20170088776A1-20170330-C00044
    Np
    Figure US20170088776A1-20170330-C00045
    tH
    Figure US20170088776A1-20170330-C00046
    dH
    Figure US20170088776A1-20170330-C00047
  • TABLE B
    Bridging units
    E —CH2CH2 Z —CO—O—
    V —CH═CH— ZI —O—CO—
    X —CF═CH— O —CH2—O—
    XI —CH═CF— OI —O—CH2
    B —CF═CF— Q —CF2—O—
    T —C≡C— QI —O—CF2
    W —CF2CF2 T —C≡C—
  • TABLE C
    End groups
    On the left standing alone On the right standing alone
    -n- CnH2n+1 -n —CnH2n+1
    -nO- CnH2n+1O— —nO —O CnH2n+1
    -V- CH2═CH— —V —CH═CH2
    -nV- CnH2n+1—CH═CH— -nV —CnH2n—CH═CH2
    -Vn- CH2═CH—CnH2n -Vn —CH═CH—CnH2n+1
    -nVm- CnH2n+1—CH═CH—CmH2m -nVm —CnH2n—CH═CH—CmH2m+1
    -N- N≡C— -N —C≡N
    -S- S═C═N— -S —N═C═S
    -F- F— -F —F
    -CL- Cl— -CL —Cl
    -M- CFH2 -M —CFH2
    -D- CF2H— -D —CF2H
    -T- CF3 -T —CF3
    -MO- CFH2O— -OM —OCFH2
    -DO- CF2HO— -OD —OCF2H
    -TO- CF3O— -OT —OCF3
    -A- H—C≡C— -A —C≡C—H
    -nA- CnH2n+1—C≡C— -An —C≡C—CnH2n+1
    -NA- NC—C≡C— -AN —C≡C—CN
    On the left in combination On the right in combination
    -...A...- —C≡C— -...A... —C≡C—
    -...V...- CH═CH— -...V... —CH═CH—
    -...Z...- —CO—O— -...Z... —CO—O—
    -...ZI...- —O—CO— -...ZI... —O—CO—
    -...K...- —CO— -...K... —CO—
    -...W...- —CF═CF— -...W... —CF═CF—
  • in which n and m are each integers, and the three dots “ . . . ” are place-holders for other abbreviations from this table.
  • TABLE D
    Figure US20170088776A1-20170330-C00048
      CC-n-m
    Figure US20170088776A1-20170330-C00049
      CC-n-Om
    Figure US20170088776A1-20170330-C00050
      CC-n-V
    Figure US20170088776A1-20170330-C00051
      CC-n-Vm
    Figure US20170088776A1-20170330-C00052
      CC-n-mV
    Figure US20170088776A1-20170330-C00053
      CC-n-mVI
    Figure US20170088776A1-20170330-C00054
      CC-V-V
    Figure US20170088776A1-20170330-C00055
      CC-V-mV
    Figure US20170088776A1-20170330-C00056
      CC-V-Vm
    Figure US20170088776A1-20170330-C00057
      CC-Vn-mV
    Figure US20170088776A1-20170330-C00058
      CC-nV-mV
    Figure US20170088776A1-20170330-C00059
      CC-nV-Vm
    Figure US20170088776A1-20170330-C00060
      CP-n-m
    Figure US20170088776A1-20170330-C00061
      CP-nO-m
    Figure US20170088776A1-20170330-C00062
      CP-n-Om
    Figure US20170088776A1-20170330-C00063
      CCP-n-m
    Figure US20170088776A1-20170330-C00064
      CCP-nO-m
    Figure US20170088776A1-20170330-C00065
      CCP-n-Om
    Figure US20170088776A1-20170330-C00066
      CCP-n-V
    Figure US20170088776A1-20170330-C00067
      CCP-n-Vm
    Figure US20170088776A1-20170330-C00068
      CCP-n-mV
    Figure US20170088776A1-20170330-C00069
      CCP-n-mVI
    Figure US20170088776A1-20170330-C00070
      CCP-V-m
    Figure US20170088776A1-20170330-C00071
      CCP-nV-m
    Figure US20170088776A1-20170330-C00072
      CCP-Vn-m
    Figure US20170088776A1-20170330-C00073
      CCP-nVm-I
    Figure US20170088776A1-20170330-C00074
      CCY-n-m
    Figure US20170088776A1-20170330-C00075
      CCY-nO-m
    Figure US20170088776A1-20170330-C00076
      CCY-n-Om
    Figure US20170088776A1-20170330-C00077
      CCY-V-m
    Figure US20170088776A1-20170330-C00078
      CCY-nV-m
    Figure US20170088776A1-20170330-C00079
      CCY-nVm-I
    Figure US20170088776A1-20170330-C00080
      CPP-n-m
    Figure US20170088776A1-20170330-C00081
      CPP-nO-m
    Figure US20170088776A1-20170330-C00082
      CPP-n-Om
    Figure US20170088776A1-20170330-C00083
      CPP-V-m
    Figure US20170088776A1-20170330-C00084
      CCP-nV-m
    Figure US20170088776A1-20170330-C00085
      CPP-Vn-m
    Figure US20170088776A1-20170330-C00086
      CCP-nVm-I
    Figure US20170088776A1-20170330-C00087
      CPY-n-m
    Figure US20170088776A1-20170330-C00088
      CPY-nO-m
    Figure US20170088776A1-20170330-C00089
      CPY-n-Om
    Figure US20170088776A1-20170330-C00090
      PYP-n-m
    Figure US20170088776A1-20170330-C00091
      PYP-nO-m
    Figure US20170088776A1-20170330-C00092
      PYP-n-Om
  • TABLE E
    Stabilisers which can be added, for example, to the mixtures according to
    the invention are indicated below.
    Figure US20170088776A1-20170330-C00093
    Figure US20170088776A1-20170330-C00094
    Figure US20170088776A1-20170330-C00095
    Figure US20170088776A1-20170330-C00096
    Figure US20170088776A1-20170330-C00097
    Figure US20170088776A1-20170330-C00098
    Figure US20170088776A1-20170330-C00099
    Figure US20170088776A1-20170330-C00100
    Figure US20170088776A1-20170330-C00101
    Figure US20170088776A1-20170330-C00102
    Figure US20170088776A1-20170330-C00103
    Figure US20170088776A1-20170330-C00104
    Figure US20170088776A1-20170330-C00105
    Figure US20170088776A1-20170330-C00106
    Figure US20170088776A1-20170330-C00107
  • In a preferred embodiment of the present invention, the media according to the invention comprise one or more compounds selected from the group of the compounds of Table E.
  • TABLE F
    Table F indicates chiral dopants which are preferably employed in the
    mixtures according to the invention.
    Figure US20170088776A1-20170330-C00108
      C 15
    Figure US20170088776A1-20170330-C00109
      CB 15
    Figure US20170088776A1-20170330-C00110
      R/S-811
    Figure US20170088776A1-20170330-C00111
      CM 44
    Figure US20170088776A1-20170330-C00112
      CN
    Figure US20170088776A1-20170330-C00113
      R/S-2011
    Figure US20170088776A1-20170330-C00114
      R/S-1011
    Figure US20170088776A1-20170330-C00115
      R/S-3011
    Figure US20170088776A1-20170330-C00116
      R/S-4011
  • EXAMPLES
  • The following examples are intended to explain the invention without limiting it. However, they illustrate the range of properties which can preferably be achieved, as well as the compounds preferably to be employed.
  • The liquid-crystal media are investigated with respect to their applicational properties. In particular, their respective electro-optical characteristic lines, response times and their voltage holding ratio in test cells are determined.
  • The indicated values for the above-mentioned properties are generally average values of the measurements of two test cells in each case. The deviations between the results of the individual cells were generally a maximum of 4 to 5%.
  • Example 1
  • Three liquid-crystal mixtures are achieved, all of which have virtually the same values of the clearing point, the birefringence, the dielectric anisotropy and even the rotational viscosity, but differ significantly in the value of the calculated peak times or the predicted response times (tmax or tmax/Δn2) respectively. The mixture M-2 is a mixture which consists of equal parts of M1 and M-3. The compositions of the mixtures are shown in the following table, the investigation results in the table after next.
  • TABLE 1a
    Example No.
    1-1 1-2 1-3
    Mixture No.
    M-1 M-2 M-3
    Composition
    Compound Concentration/%
    CY-3-O4 18.0 15.0 12.0
    CY-5-O2 6.0 12.0
    CY-5-O4 13.0 12.5 12.0
    CCY-3-O2 8.0 9.5 11.0
    CCY-4-O2 8.0 4.0
    CCY-5-O2 5.0 10.0
    CCY-2-1 8.0 4.0
    CCY-3-1 8.0 4.0
    CPY-2-O2 4.0 8.0
    PYP-2-3 5.0 2.5
    CC-3-V 8.0 16.0
    CC-3-V1 8.0 8.5 9.0
    CC-4-V 10.0 5.0
    CC-3-4 8.0 4.0
    CC-3-5 6.0 7.0 8.0
    CCP-V-1 1.0 2.0
    Σ 100.0 100.0 100.0
  • TABLE 1b
    Example No.
    1-1 1-2 1-3
    Mixture No.
    M-1 M-2 M-3
    Physical properties
    T (N.I)/° C. 70.4 70.0 70.0
    ne [589 nm, 20° C.] 1.5586 1.5588 1.5564
    no [589 nm, 20° C.] 1.4764 1.4767 1.4738
    Δn [589 nm, 20° C.] 0.0822 0.0821 0.0826
    ε|| [1 kHz, 20° C.] 3.4 3.5 3.6
    ε [1 kHz, 20° C.] 6.6 6.9 7.4
    Δε [1 kHz, 20° C.] −3.2 −3.4 −3.8
    εav.[1 kHz, 20° C.] 5.53 5.83 6.13
    ν [20° C.]/mm2 s−1 20 18.5 17
    ν [0° C.]/mm2 s−1 n.d. n.d. 55
    γ1 [20° C.]/mPa · s 113 113 113
    k1 [20° C.]/pN 12.7 13.2 12.6
    k3 [20° C.]/pN 12.9 13.7 14.6
    k3/k1 [20° C.] 1.02 1.04 1.16
    V0 [20° C.]/V 2.14 2.11 2.08
    V10 [20° C.]/V 2.54 2.57 2.48
    Calculated times
    tmax/ms 0.161 0.143 0.120
    tmax/Δn2/ms 23.9 21.1 17.7
    Experimental response times: τ(0 V => 2 × V10)
    τon [2x V10, 20° C.]/ms 10.1 8.3 7.0
    τoff [2x V10, 20° C.]/ms 10.6 10.0 10.8
    Σ [2x V10, 20° C.]/ms 20.7 18.3 17.8
    Note:
    n.d. not determined.
  • As can be seen from the results, the response time of the liquid-crystal displays decreases significantly from Example 1-1 via Example 1-2 to Example 1-3 in parallel with the predicted response time tmax or tmax/Δn2, in accordance with the teaching of the present invention.
  • Example 2
  • Three liquid-crystal mixtures are achieved, all of which have virtually the same values of the clearing point, the birefringence, the dielectric anisotropy, the rotational viscosity and even in the value of the calculated peak times or response times (tmax or tmax/Δn2), but differ significantly in their composition. The mixture M-5 is a mixture which consists of equal parts of M-4 and M-6. The compositions of the mixtures are shown in the following table, the investigation results in the table after next.
  • TABLE 2a
    Example No.
    2-1 2-2 2-3
    Mixture No.
    M-4 M-5 M-6
    Composition
    Compound Concentration/%
    CY-3-O2 16.0 8.0
    CY-3-O4 9.0 18.0
    CY-5-O2 14.0 7.0
    CY-5-O4 8.5 17.0
    CCY-3-O2 12.0 11.0 10.0
    CCY-5-O2 11.0 10.5 10.0
    CCY-2-1 9.0 4.5
    CCY-3-1 8.0 4.0
    CPY-2-O2 5.0 10.0
    CPY-3-O2 1.0 2.0
    CC-3-4 8.0 4.0
    CC-3-5 9.0 10.5 12.0
    CC-5-O1 3.0 6.0
    CC-5-V 7.5 15.0
    CP-5-3 7.0 3.5
    CP-3-O1 6.0 3.0
    Σ 100.0 100.0 100.0
  • TABLE 2b
    Example No.
    2-1 2-2 2-3
    Mixture No.
    M-4 M-5 M-6
    Physical properties
    T (N.I)/° C. 71.0 70.0 70.0
    ne [589 nm, 20° C.] 1.5587 1.5584 1.5567
    no [589 nm, 20° C.] 1.4765 1.4759 1.4746
    Δn [589 nm, 20° C.] 0.0822 0.0825 0.0821
    ε|| [1 kHz, 20° C.] 3.6 3.7 3.7
    ε [1 kHz, 20° C.] 7.4 7.5 7.6
    Δε [1 kHz, 20° C.] −3.8 −3.9 −3.9
    εav. [1 kHz, 20° C.] 6.13 6.23 6.3
    ν [20° C.]/mm2 s−1 21 21.5 22
    ν [0° C.]/mm2 s−1 67 n.d. n.d.
    ν [−20° C.]/mm2 s−1 416 n.d. n.d.
    ν [−30° C.]/mm2 s−1 1.380 n.d. n.d.
    γ1 [20° C.] mPa · s 133 130 127
    k1 [20° C.]/pN 13.0 13.3 13.4
    k3 [20° C.]/pN 15.1 14.0 13.1
    k3/k1 [20° C.] 1.15 1.05 0.98
    V0 [20° C.]/V 2.10 2.01 1.92
    V10 [20° C.]/V 2.53 2.44 2.40
    Calculated times
    tmax/ms 0.147 0.145 0.147
    tmax/Δn2/ms 21.8 21.3 21.8
    Experimental response times: τ(0 V => 2 × V10)
    τon [2x V10, 20° C.]/ms 10.0 7.6 7.3
    τoff [2x V10, 20° C.]/ms 11.7 12.0 11.4
    Σ [2x V10, 20° C.]/ms 21.7 19.6 18.7
    Note:
    n.d. not determined.
  • As can be seen from the results, all three mixtures of this example have good response times in accordance with their low value for tmax or tmax/Δn2, in accordance with the teaching of the present invention.
  • As can furthermore be seen from the results, the response time of the liquid-crystal displays additionally decreases significantly from Example 2-1 via Example 2-2 to Example 2-3 in parallel to the change in the composition of the mixtures, in accordance with the preferred teaching of the present invention.
  • The liquid-crystal mixtures of Examples 1 and 2 are particularly distinguished by good response times, this applies in particular to mixtures M-2, M-3, M-5 and M-6. The liquid-crystal mixtures of Examples 1 and 2, particularly the four mixtures just mentioned, can advantageously be used in ECB displays of all known designs, such as, for example: MVA, PVA and ASV, and also in IPS and PA LCD displays.

Claims (57)

1-11. (canceled)
12. Δn electro-optical display containing a liquid-crystal medium having negative dielectric anisotropy, and having a peak time (tmax) of 0.25 ms or less, which is determined with the aid of equations (1) and (2),
Equation ( 1 ) I ( θ b ) = S ( 2 α 1 sin 2 θ b cos 2 θ b - γ 2 cos 2 θ b + γ 3 ) ( ɛ 0 Δɛ sin 2 θ b ) 2 E b 3 ( α 1 γ 1 + γ 2 2 ) sin 2 2 θ b - γ 1 2 - γ 2 2 + 2 γ 1 γ 3 Equation ( 2 ) t ( θ b ) = β 2 2 ɛ 0 Δɛ E b 2 β 3 { - ln ( tan θ b tan θ 0 ) + - β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 + β 1 β 4 tan 2 θ 0 + β 7 + β 1 ) + β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 - β 1 β 4 tan 2 θ 0 + β 7 - β 1 ) } + β 6 2 ɛ 0 Δɛ E b 2 β 1 ln [ ( α 1 cos 2 θ b + γ 2 + β 1 ) ( α 1 cos 2 θ 0 + γ 2 - β 1 ) ( α 1 cos 2 θ b + γ 2 - β 1 ) ( α 1 cos 2 θ 0 + γ 2 + β 1 ) ]
where:
S=electrode area
Eb=U/l (U=90 V and l=22 μm are assumed),
θ0=bulk tilt angle at time t=0
θb=bulk tilt angle
α1 to α5=Leslie viscosity coefficients,
β11 22 2+2α1γ3,
β21 22 2−2γ1γ3,
β32−γ3,
β423,
β52 21γ3,
β61γ12 2,
β713
γ1=−□α2; (rotational viscosity),
γ23−α2 and
γ3345, wherein
for the Leslie viscosity coefficients, the following assumptions apply
α1=−10 mPas and
α3=0 mPas,
in addition, for α3=0 in accordance with Parodi:

α45=−α2+2η2

η2≈ρ*υ
where:
ρ=density of about 1 g/cm3 and
υ=flow viscosity,
wherein
the medium comprises 98% or more of components A and B, and
the medium comprises 60-70% of components A,
component A is a dielectrically negative, liquid-crystalline component, which consists of:
33% to 37%, based on the medium, of at least one compound of formula I-1
Figure US20170088776A1-20170330-C00117
and 3% to 17%, based on the medium, of at least one compound of formula I-3
Figure US20170088776A1-20170330-C00118
in which R11″ is C3-7-alkyl, R11′ is C1-7-alkyl, R12′ is alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkenyl or alkenyloxy having 2 to 7 C atoms, where in R11′ and R12′ one or more H atoms in all groups may be replaced by halogen atoms,
wherein in at least one compound of formula I-1 R12′ is C4-alkoxy,
and the remainder of component A is of one or more dielectrically negative compound(s) of formula I, which are not compounds of formula I-1 or I-3,
Figure US20170088776A1-20170330-C00119
in which at least one of
Figure US20170088776A1-20170330-C00120
denotes
Figure US20170088776A1-20170330-C00121
and the others, if present, in each case, independently of one another, have the same meaning or denote
Figure US20170088776A1-20170330-C00122
R11 and R12, independently of one another, denote alkyl having 1 to 7 C atoms,
L11 and L12, independently of one another, denote C—F or N,
Z11 and Z12, in each case independently of one another, denote —CH2—CH2—, —C≡C—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —CH2—CF2—, —CF2—CH2—, —CF2—CF2—, —CO—O—, —O—CO—, —OCH2—, —CH2O—, or a single bond, and
n denotes 0, 1 or 2,
and
component B is a dielectrically neutral, liquid-crystalline component, which consists of one or more dielectrically neutral compound(s) of formula II
Figure US20170088776A1-20170330-C00123
in which
R21 and R22, in each case independently of one another, are C1-7-alkyl, C1-7-alkoxy, or alkoxyalkyl, alkenyl or alkenyloxy having 2-7 cations in which one or more H atoms in all groups may be replaced by halogen atoms,
Z21 to Z23, in each case independently of one another, are —CH2—CH2—, —C≡C—, —CH═CH—, —COO— or a single bond,
and
Figure US20170088776A1-20170330-C00124
in each case independently of one another, denote
Figure US20170088776A1-20170330-C00125
and
p and q, in each case independently of one another, denote 0 or 1;
and wherein one or more of the following conditions apply:
condition 1: the liquid-crystal medium has a value of the quotient of peak time and square of birefringence (tmax/Δn2) of 22 ms or less;
condition 2: the liquid-crystal medium has an average of the dielectric constants in the range from 5.5 or more to 6.5 or less;
condition 3: the liquid-crystal medium has a dielectric anisotropy in the range from −3.0 or less to −4.0 or more;
condition 4: the liquid-crystal medium has a birefringence in the range from 0.070 to 0.110;
condition 5: the liquid crystalline medium comprises 30% to 37% of at least one compound of formula II that is of formula II-1 or II-4
Figure US20170088776A1-20170330-C00126
in which
R21 and R22, in each case independently of one another, denote alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkenyl or alkenyloxy having 2 to 7 C atoms, where one or more H atoms in all groups may be replaced by halogen atoms;
condition 6: R11′ is C1-3-alkyl;
condition 7: R11′ is C2-3-alkyl;
condition 8: R11 is C3-7-alkyl;
condition 9: I-3 is
Figure US20170088776A1-20170330-C00127
and n and m are 2;
condition 10: I-3 is
Figure US20170088776A1-20170330-C00128
and n is 3 and m is 2;
condition 11: the compounds of Formula I are compounds of one or more of Formulae I-2, I-4 or I-5
Figure US20170088776A1-20170330-C00129
condition 12: the medium comprises 99% to 100% of components A and B;
condition 13: the concentration of the compounds of formula I-3 is 10% or more;
condition 14: the concentration of the compounds of formula I-3 is 13% or more;
condition 15: the concentration of component A is 65-69%;
condition 16: one or more compounds of formula I are of formula I-2
Figure US20170088776A1-20170330-C00130
wherein R11 and R12, independently of one another, denote alkyl having 1 to 7 C atoms,
which compounds of formula I-2 have a concentration of 20-30%, based on the medium;
condition 17: Z21 and Z23 are each independently —CH2—CH2 or a single bond;
condition 18: Z21 and Z23 are single bonds;
condition 19: the one or more compounds of Formula II are of one or more of the following formulae
Figure US20170088776A1-20170330-C00131
in which Y1 is H or F, and R21 and R22 are defined as for the compounds of formula II;
condition 20: the concentration of the compounds of formula I-2 is 21% to 25%;
condition 21: the one or more compounds of Formula II contain or are a compound of the formula CC-3-V:
Figure US20170088776A1-20170330-C00132
condition 22: component A contains 34% to 37% of at least one compound of formula I-1;
condition 23: component A contains at least two compounds of formula I-1 in which R12 is C4-alkoxy;
condition 24: the liquid crystalline medium contains three or more compounds of formula I-1;
condition 25: the liquid crystalline medium contains four or more compounds of formula I-1;
condition 26: the compounds of formula I-3 contain at least one compound of I-3 in which R11′ is C3-5 alkyl;
condition 27: Z21 to Z23 are each a single bond.
13. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 1 applies.
14. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 2 applies.
15. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 3 applies.
16. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 4 applies.
17. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 5 applies.
18. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 6 applies.
19. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 7 applies.
20. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 8 applies.
21. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 9 applies.
22. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 10 applies.
23. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 11 applies.
24. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 12 applies.
25. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 13 applies.
26. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 14 applies.
27. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 15 applies.
28. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 16 applies.
29. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 17 applies.
30. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 18 applies.
31. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 19 applies.
32. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 20 applies.
33. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 21 applies.
34. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 22 applies.
35. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 23 applies.
36. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 24 applies.
37. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 25 applies.
38. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 26 applies.
39. An electro-optical display containing a liquid-crystal medium according to claim 12 wherein condition 27 applies.
40. A method for optimizing of the response time of a liquid-crystal display, comprising using in said display a liquid-crystal medium having negative dielectric anisotropy, and having a peak time (tmax) of 0.25 ms or less, which is determined with the aid of equations (1) and (2),
Equation ( 1 ) I ( θ b ) = S ( 2 α 1 sin 2 θ b cos 2 θ b - γ 2 cos 2 θ b + γ 3 ) ( ɛ 0 Δɛ sin 2 θ b ) 2 E b 3 ( α 1 γ 1 + γ 2 2 ) sin 2 2 θ b - γ 1 2 - γ 2 2 + 2 γ 1 γ 3 Equation ( 2 ) t ( θ b ) = β 2 2 ɛ 0 Δɛ E b 2 β 3 { - ln ( tan θ b tan θ 0 ) + - β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 + β 1 β 4 tan 2 θ 0 + β 7 + β 1 ) + β 5 + γ 2 β 1 2 β 4 β 1 ln ( β 4 tan 2 θ b + β 7 - β 1 β 4 tan 2 θ 0 + β 7 - β 1 ) } + β 6 2 ɛ 0 Δɛ E b 2 β 1 ln [ ( α 1 cos 2 θ b + γ 2 + β 1 ) ( α 1 cos 2 θ 0 + γ 2 - β 1 ) ( α 1 cos 2 θ b + γ 2 - β 1 ) ( α 1 cos 2 θ 0 + γ 2 + β 1 ) ]
where:
S=electrode area
Eb=U/l (U=90 V and l=22 μm are assumed),
θ0=bulk tilt angle at time t=0
θb=bulk tilt angle
α1 to α5=Leslie viscosity coefficients,
β11 22 2+2α1γ3,
β21 22 2−2γ1γ3,
β32−γ3,
β423,
β52 21γ3,
β61γ12 2,
β713
γ1=−□α2; (rotational viscosity),
γ23−α2 and
γ3345, wherein
for the Leslie viscosity coefficients, the following assumptions apply
α1=−10 mPas and
α3=0 mPas,
in addition, for α3=0 in accordance with Parodi:

α45=−α2+2η2

η2≈ρ*υ
where:
ρ=density of about 1 g/cm3 and
υ=flow viscosity,
wherein
the medium comprises 98% or more of components A and B, and the medium comprises 60-70% of components A,
component A is a dielectrically negative, liquid-crystalline component, which consists of:
33% to 37%, based on the medium, of at least one compound of formula I-1
Figure US20170088776A1-20170330-C00133
and 3% to 17%, based on the medium, of at least one compound of formula I-3
Figure US20170088776A1-20170330-C00134
in which R11″ is C3-7-alkyl, R11′ is C1-7-alkyl, R12′ is alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkenyl or alkenyloxy having 2 to 7 C atoms, where in R11′ and R12′ one or more H atoms in all groups may be replaced by halogen atoms,
wherein in at least one compound of formula I-1 R12′ is C4-alkoxy,
and the remainder of component A is of one or more dielectrically negative compound(s) of formula I, which are not compounds of formula I-1 or I-3,
Figure US20170088776A1-20170330-C00135
in which at least one of
Figure US20170088776A1-20170330-C00136
denotes
Figure US20170088776A1-20170330-C00137
and the others, if present, in each case, independently of one another, have the same meaning or denote
Figure US20170088776A1-20170330-C00138
R11 and R12, independently of one another, denote alkyl having 1 to 7 C atoms,
L11 and L12, independently of one another, denote C—F or N,
Z11 and Z12, in each case independently of one another, denote —CH2—CH2—, —C≡C—, —CH═CH—, —CF═CF—, —CF═CH—, —CH═CF—, —CH2—CF2—, —CF2—CH2—, —CF2—CF2—, —CO—O—, —O—CO—, —OCH2—, —CH2O—, or a single bond, and
n denotes 0, 1 or 2,
and
component B is a dielectrically neutral, liquid-crystalline component, which consists of one or more dielectrically neutral compound(s) of formula II
Figure US20170088776A1-20170330-C00139
in which
R21 and R22, in each case independently of one another, are C1-7-alkyl, C1-7-alkoxy, or alkoxyalkyl, alkenyl or alkenyloxy having 2-7 cations in which one or more H atoms in all groups may be replaced by halogen atoms,
Z21 to Z23, in each case independently of one another, are —CH2—CH2—, —C≡C—, —CH═CH—, —COO— or a single bond,
and
Figure US20170088776A1-20170330-C00140
in each case independently of one another, denote
Figure US20170088776A1-20170330-C00141
and
p and q, in each case independently of one another, denote 0 or 1;
and wherein one or more of the following conditions apply:
condition 1: the liquid-crystal medium has a value of the quotient of peak time and square of birefringence (tmax/Δn2) of 22 ms or less;
condition 2: the liquid-crystal medium has an average of the dielectric constants in the range from 5.5 or more to 6.5 or less;
condition 3: the liquid-crystal medium has a dielectric anisotropy in the range from −3.0 or less to −4.0 or more;
condition 4: the liquid-crystal medium has a birefringence in the range from 0.070 to 0.110;
condition 5: the liquid crystalline medium comprises 30% to 37% of at least one compound of formula II that is of formula II-1 or II-4
Figure US20170088776A1-20170330-C00142
in which
R21 and R22, in each case independently of one another, denote alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkenyl or alkenyloxy having 2 to 7 C atoms, where one or more H atoms in all groups may be replaced by halogen atoms;
condition 6: R11′ is C1-3-alkyl;
condition 7: R11′ is C2-3-alkyl;
condition 8: R11 is C3-7-alkyl;
condition 9: I-3 is
Figure US20170088776A1-20170330-C00143
and n and m are 2;
condition 10: I-3 is
Figure US20170088776A1-20170330-C00144
and n is 3 and m is 2;
condition 11: the compounds of Formula I are compounds of one or more of Formulae I-2, I-4 or 1-5
Figure US20170088776A1-20170330-C00145
condition 12: the medium comprises 99% to 100% of components A and B;
condition 13: the concentration of the compounds of formula I-3 is 10% or more;
condition 14: the concentration of the compounds of formula I-3 is 13% or more;
condition 15: the concentration of component A is 65-69%;
condition 16: one or more compounds of formula I are of formula I-2
Figure US20170088776A1-20170330-C00146
wherein R11 and R12, independently of one another, denote alkyl having 1 to 7 C atoms,
which compounds of formula I-2 have a concentration of 20-30%, based on the medium;
condition 17: Z21 and Z23 are each independently —CH2—CH2 or a single bond;
condition 18: Z21 and Z23 are single bonds;
condition 19: the one or more compounds of Formula II are of one or more of the following formulae
Figure US20170088776A1-20170330-C00147
in which Y1 is H or F, and R21 and R22 are defined as for the compounds of formula II;
condition 20: the concentration of the compounds of formula I-2 is 21% to 25%;
condition 21: the one or more compounds of Formula II contain or are a compound of the formula CC-3-V:
Figure US20170088776A1-20170330-C00148
condition 22: component A contains 34% to 37% of at least one compound of formula I-1;
condition 23: component A contains at least two compounds of formula I-1 in which R12 is C4-alkoxy;
condition 24: the liquid crystalline medium contains three or more compounds of formula I-1;
condition 25: the liquid crystalline medium contains four or more compounds of formula I-1;
condition 26: the compounds of formula I-3 contain at least one compound of I-3 in which R11′ is C3-5 alkyl;
condition 27: Z21 to Z23 are each a single bond.
41. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 1 applies.
42. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 2 applies.
43. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 3 applies.
44. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 4 applies.
45. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 5 applies.
46. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 6 applies.
47. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 7 applies.
48. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 8 applies.
49. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 9 applies.
50. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 10 applies.
51. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 11 applies.
52. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 12 applies.
53. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 13 applies.
54. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 14 applies.
55. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 15 applies.
56. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 16 applies.
57. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 17 applies.
58. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 18 applies.
59. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 19 applies.
60. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 20 applies.
61. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 21 applies.
62. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 22 applies.
63. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 23 applies.
64. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 24 applies.
65. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 25 applies.
66. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 26 applies.
67. A method for optimizing of the response time of a liquid-crystal display according to claim 40 wherein condition 27 applies.
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