EP3408350A1 - Milieu à cristaux liquides - Google Patents

Milieu à cristaux liquides

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Publication number
EP3408350A1
EP3408350A1 EP16820168.9A EP16820168A EP3408350A1 EP 3408350 A1 EP3408350 A1 EP 3408350A1 EP 16820168 A EP16820168 A EP 16820168A EP 3408350 A1 EP3408350 A1 EP 3408350A1
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EP
European Patent Office
Prior art keywords
compounds
atoms
alkyl
independently
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP16820168.9A
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German (de)
English (en)
Inventor
Michael Wittek
Dagmar Klass
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Publication of EP3408350A1 publication Critical patent/EP3408350A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/321—Compounds containing a bicyclo [2,2,2] octane ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/301—Cy-Cy-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C09K2019/3037—Cy-Cy-C2H4-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3028—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon single bonds
    • C09K2019/304—Cy-C2H4-Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used

Definitions

  • the present invention relates to a liquid-crystalline medium containing bicyclooctane derivatives, the use thereof for electro-optical purposes, in particular for liquid-crystal light valves for use in
  • Liquid crystals are mainly used as dielectrics in display devices, since the optical properties of such substances can be influenced by an applied voltage. electro-optical
  • TN cells with twisted nematic structure or STN cells ("super-twisted nematic").
  • STN cells super-twisted nematic
  • Modern TN and STN displays are based on an active matrix of individually addressable liquid crystal light valves (the pixels) with integrated red, green and blue color filters for additive generation of the color images.
  • Adaptive front lighting system produce a adapted to the particular situation and the environmental conditions headlights and are able to react, for example, the light and weather conditions, the vehicle movement or the presence of other road users to the environment and constant optimally illuminate and not disturb other road users.
  • AFS Adaptive front lighting system
  • Light modulator in the form of a liquid crystal (LCD) display panel consisting of a grid of translucent elements, analogous to the pixels of a liquid crystal display, an electrically switchable, complete or partial shading of the cone of light generated with the aim of dazzle the driver of oncoming vehicles not or less.
  • LCD liquid crystal
  • Such spatial light modulators are referred to as liquid crystal light valves as already mentioned. Because of the similar functioning as with projectors one speaks also of
  • Vehicle lights of the projector type preferably delivers a digital camera.
  • a liquid crystal light valve according to the present invention may comprise a single area for modulating the light or a grid (matrix) of a plurality of identical or different sub-areas
  • a grid of liquid crystal light valves is or may be considered as a special case of a monochrome matrix liquid crystal display as a part of a liquid crystal display.
  • An illumination device in the sense of the invention is in particular an AFS or part of an AFS.
  • a lighting device according to the invention is used in particular for illuminating an area in front of a vehicle or motor vehicle.
  • Motor vehicle in the sense of the invention is in particular a land vehicle which can be used individually in road traffic. Motor vehicles within the meaning of the invention are in particular not on land vehicles
  • Liquid crystal light valve is a TN cell as optical
  • Used modulation element which represents picture elements corresponding to the desired brightness profile of the vehicle lighting, for example, a driving voltage to the TN liquid crystal for modulating (control) the transmittance of a picture element is created. Because of the polarizers required there, only about half of the light from the light source can be used. A likewise based on a TN cell alternative, which makes it possible to harness more than half of the light of the light source of the illumination device is disclosed in DE 10 2013 113 807 A1. Therein, the light by means of a polarizing beam splitter into two partial beams with each other
  • Such lighting devices are characterized by comparatively high operating temperatures of typically 60-80 ° C, which makes special demands on the liquid crystal media used: the clearing points must be higher than 120 ° C, preferably higher than 140 ° C and because of the strong light exposure, these media have a particularly high light stability. This may u.U. For example, be favored by using materials with the least possible birefringence.
  • the liquid crystal materials must also have good chemical and thermal stability and good electrical field stability. Furthermore, the liquid crystal materials should have low viscosity and give relatively short response times, lowest possible operating voltages and high contrast in the cells.
  • Cells a nematic or cholesteric mesophase, preferably from -40 ° C to 150 ° C. Since liquid crystals are usually used as mixtures of several components, it is important that the
  • materials for cells of twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.
  • materials for cells of twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.
  • MFK displays matrix liquid crystal displays with integrated non-linear elements for switching individual pixels (MFK displays)
  • media with high positive dielectric anisotropy, broad nematic phases, relatively low birefringence, very high resistivity, good light and temperature stability and less Steam pressure desired are known and the design principle can also be used for the lighting device according to the invention.
  • pixels may be used for active elements (i.e., transistors).
  • active elements i.e., transistors.
  • MOS Metal Oxide Semiconductor
  • diodes on silicon wafer as substrate.
  • TFT Thin-film transistors
  • the TN effect is usually used as the electro-optic effect.
  • TFTs made of compound semiconductors, such as e.g. CdSe or TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on worldwide with great intensity.
  • the TFT matrix is applied on the inside of one glass plate of the display, while the other glass plate on the inside carries the transparent counter electrode. Compared to the size of the
  • the TFT is very small and does not disturb the picture practically.
  • the TFT displays and corresponding light valves for
  • Illuminators usually operate as TN cells with crossed polarizers in transmission and are backlit.
  • MFK displays here includes any matrix display with integrated nonlinear elements, i.
  • Liquid crystal mixtures [TOGASHI, S., SEKOGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H.,
  • Liquid crystal mixtures with very high resistivity at the same time large working temperature range and high light stability.
  • Vehicles are desired media that allow the following advantages in the cells: extended nematic phase range (especially at high temperatures)
  • liquid-crystal media of the laid-open specification DE 102 23 061 A1 and DE 10 2008 062858 A1 have a low ⁇ , but the clearing points are around 80 ° C. in a range which is too low for the application according to the invention.
  • the invention has for its object to provide media, especially for the above-mentioned liquid crystal light valves for lighting devices for motor vehicles, which do not have the disadvantages mentioned above or only to a lesser extent, and preferably at the same time very high clearing points and low birefringence.
  • the invention thus relates to a liquid-crystalline medium based on a mixture of polar compounds, characterized
  • R 01 is an alkyl or alkoxy radical having 1 to 15 C atoms, where in these radicals one or more H atoms may be replaced by F, Cl, or CN and also one or more CH 2 groups each independently
  • O- or -O-CO- can be replaced so that O atoms are not directly linked to one another, an alkyl or alkoxy radical having 1 to 15 C atoms, wherein in these radicals one or more H atoms by Cl or CN can be replaced and one or more Ch groups each independently by A_.
  • Y is F, Cl, CF3, or alkyl or alkoxy having 1 to 6 C atoms, in which one or more H atoms may be replaced by F, r is 0 or 1, and s is 0, 1, 2, 3 or 4.
  • WO 98/13326 The compounds described therein contain unsaturated alkoxy or ester linkaged unsaturated alkenyl side chains linked to a cyclohexane ring and are therefore unsuitable for use in the present invention.
  • the compounds of the formula BO have hitherto not been described in the prior art and, in addition to excellent thermal and UV stability, exhibit broad nematic phases, very good solubility and outstanding properties
  • the invention thus also relates to compounds of the formula BO and to processes for their preparation.
  • all atoms also include their isotopes.
  • one or more hydrogen atoms (H) may be replaced by deuterium (D), which is particularly preferred in some embodiments; a high degree of deuteration allows or facilitates the analytical detection of compounds, especially in the case of low concentrations.
  • R 01 and / or R 02 is an alkyl radical or an alkoxy radical, this may be straight-chain or branched. Preferably, it is straight-chain, has 2, 3, 4, 5, 6 or 7 carbon atoms and thus preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl , Octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
  • 2-, 3- or 4-oxypentyl 2-, 3-, 4- or 5-oxyhexyl, 2-, 3-, 4-, 5- or 6- oxyheptyl, 2-, 3-, 4-, 5- , 6-, or 7-Oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8 - or 9-oxadexyl.
  • R 02 is an alkyl radical in which a CH 2 group is replaced by
  • -CH CH- is replaced, it may be straight-chain or branched.
  • It is preferably straight-chain and has 2 to 10 C atoms. It therefore means especially vinyl, prop-1, or prop-2-enyl, but-1, 2 or but-
  • R 01 and / or R 02 is an alkyl radical in which one CH 2 group has been replaced by -O- and one by -CO-, these are preferably adjacent. Thus, they include an acyloxy group -CO-O- or an oxycarbonyl group -O-CO-. Preferably, these are straight-chain and have 2 to 6 carbon atoms.
  • R 02 is an alkyl radical in which a CH 2 group is replaced by
  • -CH CH- and an adjacent CH2 group is replaced by CO or CO-O or O-CO, this may be straight-chain or branched. It is preferably straight-chain and has 4 to 12 C atoms. It therefore particularly denotes acryloyloxymethyl, 2-acryloyl-oxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxyhexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyl-oxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2 Methacryloyl oxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacrylooxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl,
  • R 01 and / or R 02 is an alkyl or alkenyl radical which is monosubstituted by CN or CF 3, this radical is preferred
  • R 01 is an alkyl or alkenyl radical which is at least monosubstituted by F and / or Cl, this radical is preferably
  • the substituent is preferably F.
  • the resulting radicals also include perfluorinated radicals.
  • the fluoro or chloro substituent may be in any position, but preferably in the ⁇ position. If R 02 is an alkyl or alkenyl radical which is at least monosubstituted by Cl, this radical is preferably straight-chain.
  • the substituent is preferably Cl. at
  • the chlorine substituent may be in any position, but preferably in the ⁇ position.
  • Liquid-crystalline base materials are important, but especially as chiral dopants, if they are optically active. smectic
  • Branched groups of this type usually contain no more than one chain branch.
  • R 01 and / or R 02 represents an alkyl radical in which two or more
  • CH 2 groups are replaced by -O- and / or -CO-O-, it may be straight-chain or branched. Preferably, it is branched and has 3 to 12 carbon atoms. It therefore particularly denotes bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-biscarboxypentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, Bis (methoxy-carbonyl) -methyl, 2,2-bis (methoxycarbonyl) -ethyl, 3,3-bis (methoxycarbonyl) -propyl, 4,4-bis (methoxycarbonyl) -butyl
  • the compounds of the formula BO are preferably selected from the subformulae BO-1 and BO-2
  • BO-2 wherein the parameters have the meaning given above and preferably YF, Z 1 is a single bond and s is 0, 1 or 2.
  • the media according to the invention contain
  • R and R 2 are an alkyl or alkoxy radical having 1 to 15 C atoms, wherein in these radicals one or more H atoms may be replaced by F and also one or more Chb groups each independently
  • L 2 and L 22 independently of one another are H or F, preferably
  • X 1 and X 2 F, Cl, CN, halogenated alkyl radical, halogenated
  • trans-CF CF-, -CH2O- or a single bond, preferred
  • L 1 to L 4 are each independently H or F, mean.
  • X 1 is particularly preferably F, Cl, CF 3, OCF 3, or OCHF 2.
  • the compounds of the formula I are selected from the compounds of the formulas 1-1 a to 1-1 d
  • R 1 is n-alkyl having 1 to 7 carbon atoms.
  • the medium contains at least one
  • the media according to the invention comprise one or more compounds selected from the group of the compounds of the formulas IA and IB,
  • L 13 and L 14 are independently H or F and the other parameters have the meaning given under formula I and preferably
  • L 11 to L 14 are each independently H or F, mean.
  • X 1 is particularly preferably F, Cl, CF 3, OCF 3 or OCHF 2.
  • the compounds of the formula IA are preferably selected from the following sub-formulas IA-1 to IA-7, particularly preferably from the compounds of the formula IA-1.
  • the compounds of the formula IA are particularly preferably selected from the compounds of the formulas IA-1a to IA-1d
  • R 1 has the meaning indicated above and X 1 is preferably F or OCF 3. Very particular preference is given to the compounds of the formula IA-1d.
  • Particularly preferred compounds of the formula IB are selected from
  • the compounds of the formula II are preferably selected from the compounds of the sub-formulas 11-1 to 11-14.
  • R 2 n-alkyl having up to 7 C atoms, X 2 F, Cl, halogenated alkyl or halogenated alkoxy having up to 6 C atoms, and at least one of L 21 and L 22 is F.
  • X 2 is more preferably F, Cl, CF 3, OCF 3, or OCHF 2.
  • the medium according to the invention particularly preferably contains one or more compounds selected from the compounds of the formula 11-1, II-5, II-9 and 11-12, very particularly preferably selected from the group consisting of
  • R 2 has the meaning given above and preferably n-alkyl having 1 to 7 carbon atoms.
  • the medium contains one or more compounds selected from the group of the compounds of formulas II-1b, II-5a, II-5b and II-9a.
  • the medium contains one or more compounds of general formula III wherein
  • R 3 has the meaning given above under formula II for R 2 ,
  • trans- CH CH-
  • trans- -CF CF-
  • the compounds of the formula III are preferably selected from the group of the compounds of the formulas III-1 to III-9:
  • the medium contains one or more
  • the medium contains one or more
  • R 3 preferably denotes n-alkyl having 1 to 7 carbon atoms.
  • the medium according to the invention preferably contains one or more compounds of the formula IV
  • R 41 is alkyl and R 42 is alkyl or alkoxy or R 4 is alkenyl and R 42 is alkyl, mean,
  • Z 41 and Z 42 are independently of each other -CH 2 CH 2 -,
  • trans- -CH CH-
  • trans- -CF CF-
  • -CH2O- -CF2O-
  • -C ⁇ C- or a single bond preferably one or more of them signifies a single bond and p is 0, 1 or 2, preferably 0 or 1.
  • the compounds of the formula IV are preferably selected from the group of the compounds IV-1 to IV-13
  • R 41 and R 42 independently of one another n-alkyl having 1 to 7 carbon atoms and
  • H or F means, preferably F.
  • the medium according to the invention particularly preferably contains one or more compounds selected from the group of compounds IV-5, IV-8 and IV-11.
  • R 51 and R 52 independently of one another have the meanings given above under formula II for R 2 , preferably R 5 is alkyl and R 52 is alkyl or alkenyl,
  • r is 0, 1 or 2, preferably 1 or 2, particularly preferably 1.
  • the medium contains one or more compounds selected from the group of the compounds of the formulas V-1 and V-2
  • R 51 and R 52 have the respective meanings given above under formula V and are preferably alkyl
  • Another object of the invention are electro-optical components, in particular light valves, based on the TN or STN effect, with two plane-parallel support plates which form a cell with a border, integrated non-linear elements for switching individual pixels on the carrier plates and one in the Cell nematic liquid crystal mixture having positive dielectric anisotropy and high resistivity containing the media of the invention and the use of these media for electro-optic
  • Another object of the invention is its use in
  • Liquid crystal displays in particular TN, STN or MFK displays.
  • Another object of the invention are lighting devices for motor vehicles and electro-optical displays that contain these components.
  • liquid-crystal mixtures according to the invention enable a significant expansion of the available parameter space.
  • the electro-optical components according to the invention preferably operate in the first
  • the UV stability of the mixtures according to the invention is also considerably better, i. they show a much smaller decrease in HR under UV exposure.
  • liquid-crystal mixtures according to the invention make it possible, while maintaining the nematic phase, to -20 ° C. and preferably to -30 ° C., particularly preferably to -40 ° C., clearing points above 120 ° C.,
  • the mixtures are characterized by low operating voltages.
  • the TN thresholds are below 2.0 V, preferably below 1, 5 V, more preferably ⁇ 1, 3 V.
  • the liquid-crystal mixtures according to the invention have an optical anisotropy ( ⁇ ) in the range from 0.050 to 0.110, preferably from 0.060 to 0.100, particularly preferably from 0.080 to 0.090.
  • the rotational viscosity ⁇ of the mixtures according to the invention at 20 ° C is preferably ⁇ 350 mPa-s, more preferably ⁇ 300 mPa-s.
  • the nematic phase range is preferably at least 140 K,
  • At least 180 K in particular at least 180 K. This range preferably extends at least from -40 ° to + 140 °.
  • the medium contains one or more compounds of the formula BO in a total concentration in the range from 5 to 35%, preferably from 10 to 30%, particularly preferably from 15% to 25%.
  • the medium contains one or more compounds of the formula I in a total concentration in the range from 20 to 70%, preferably from 25 to 60%, particularly preferably from 30% to 50%.
  • the total concentration of compounds of formula II in the medium is 10% to 40%, preferably 15% to 35% and particularly preferably 20% to 30%.
  • the medium contains one or more compounds of formula 11-1 b.
  • the total concentration of the compounds of the formulas IV-1, IV-2, IV-3, IV-4, IV-5 and IV-6 in the medium is 3 to 20, preferably 5 to 18, particularly preferably 8 to 16%.
  • the medium contains at least one compound of formula IV-5.
  • the total concentration of compounds of the formulas IV-7, IV-8, IV-9, IV-10, IV-11, IV-12 and IV-13 is 2% to 20%, preferably 4% to 16% and more preferably 6% to 13%.
  • the medium preferably contains at least one compound of the formula IV-8 or IV-11.
  • the proportion of the compounds having unsaturated side chains (R is alkenyl or alkynyl) in the medium is 0 to 10%, preferably 0 to 5%, particularly preferably 0 to 2%.
  • Compounds of the formulas BO and I contain one or more compounds of the formula II, in particular compounds of the formula 11-1 b. All these compounds are colorless, stable and well miscible with each other and with other liquid crystal materials.
  • the optimum ratio of the compounds of the formulas BO, I to V, IA and IB depends largely on the desired properties, on the choice of the components of the formulas BO, I to V, IA and IB and the choice of further optional components.
  • the total amount of compounds of the formulas BO, I to V, IA and IB in the mixtures according to the invention is not critical.
  • the mixtures may therefore contain one or more other components to optimize various properties.
  • the observed effect on the response times and the threshold voltage is generally greater the higher the total concentration of compounds of the formulas I, IA, IB, II and III.
  • the higher the proportion of compounds of the formulas BO, IA, IB, III and IV the higher the clearing point.
  • Electrode base plates and electrodes with surface treatment corresponds to the usual construction for such components.
  • the usual construction here broadly and includes all modifications and modifications of the components, in particular also matrix display elements based on poly-Si TFT or MIM.
  • liquid crystal valves to the usual on the basis of the twisted nematic cell is the choice of the liquid crystal parameters of the liquid crystal layer.
  • the preparation of the liquid crystal mixtures which can be used according to the invention is carried out in a conventional manner.
  • the desired amount of the components used in lesser amount is dissolved in the constituent of the main component, expediently at elevated temperature.
  • solutions of the components in an organic solvent e.g. in acetone, chloroform or methanol, and the solvent after
  • the dielectrics may also contain further additives known to the person skilled in the art and described in the literature. For example, 0-15% pleochroic dyes or chiral dopants may be added.
  • V10 denotes the voltage for 10% transmission (viewing direction perpendicular to the disk surface)
  • ton denotes the switch-on time and totr the switch-off time at an operating voltage corresponding to 2.0 times the value of V10.
  • ⁇ denotes the optical anisotropy and n 0 den
  • the electro-optical data are measured in a TN cell in the 1st minimum (i.e., at a d ⁇ ⁇ value of 0.5) at 20 ° C, unless expressly stated otherwise.
  • the optical data are at 20 ° C
  • liquid-crystalline mixtures which, in addition to the compounds of the formula BO, have at least one, two, three or four
  • Table D shows exemplary compounds that can be used as stabilizers in the media of the invention.
  • the liquid-crystalline media contain one or more compounds of Table D.
  • Tetrahydrofuran (THF) is added dropwise, while cooling with ice, with 128 ml of isopropylmagnesium chloride solution (2M in THF, 0.26 mol).
  • Sulfuric acid (25 mL, 95-97proz.) Is introduced at room temperature and treated dropwise with a melt of 1-pentyl-bicyclo [2.2.2] octan-4-ol and 1-fluoro-3- (4-propylcyclohexyl) benzene. After 1 h, another 10 ml of sulfuric acid are added and the mixture is stirred for 3 h at room temperature. The mixture is then heated for 30 min at 30 ° C and then poured directly on ice. The aqueous phase is extracted with ether, the combined organic phases are washed with water, dried over sodium sulfate and concentrated. The residue is filtered through silica gel with n-heptane.

Abstract

L'invention concerne un milieu à cristaux liquides qui contient un ou plusieurs composés de formule BO, dans laquelle les paramètres ont la signification indiquée dans la revendication 1 ; l'utilisation de ce milieu à cristaux liquides pour des applications électro-optiques, en particulier dans des valves optiques à cristaux liquides destinées à des dispositifs d'éclairage pour véhicules automobiles, ainsi que des valves optiques à cristaux liquides contenant ce milieu et des dispositifs d'éclairage pour véhicules automobiles comprenant ces valves optiques à cristaux liquides, de même que des composés de formule BO.
EP16820168.9A 2016-01-25 2016-12-30 Milieu à cristaux liquides Withdrawn EP3408350A1 (fr)

Applications Claiming Priority (2)

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DE102016000633 2016-01-25
PCT/EP2016/002188 WO2017129216A1 (fr) 2016-01-25 2016-12-30 Milieu à cristaux liquides

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CN (1) CN108603117A (fr)
DE (1) DE102016015630A1 (fr)
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DE102018003171A1 (de) * 2017-04-27 2018-10-31 Merck Patent Gmbh Flüssigkristallines Medium
CN109825310A (zh) * 2019-03-08 2019-05-31 江苏锦润光电有限公司 一种快速响应的液晶介质

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GB2065104B (en) * 1979-10-26 1983-11-30 Secr Defence Liquid crystal bicyclo-octane compounds
DE3022818C2 (de) 1980-06-19 1986-11-27 Merck Patent Gmbh, 6100 Darmstadt Flüssigkristall-Anzeigeelement
JPS61233635A (ja) * 1985-03-22 1986-10-17 メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング ビシクロオクタン誘導体
JPH01244934A (ja) 1988-03-28 1989-09-29 Nissan Motor Co Ltd 車両用前照灯装置
GB9620108D0 (en) 1996-09-26 1996-11-13 Secr Defence Liquid crystal alkenyl bicyclo[2 2 2]octanes and mixtures and devices containing such compounds
JP4432123B2 (ja) * 1997-01-22 2010-03-17 チッソ株式会社 液晶性化合物、およびこれを含む液晶組成物、およびこれを用いた液晶表示素子
DE19910004A1 (de) 1999-03-08 2000-09-21 Oezsoy Fazil Abblendvorrichtung für Kfz-Scheinwerfer
DE10223061A1 (de) 2002-05-24 2003-12-11 Merck Patent Gmbh Flüssigkristallines Medium
EP1887069B1 (fr) 2006-08-11 2010-11-10 Merck Patent GmbH Mésogènes réactifs bicyclooctyles
JP5422898B2 (ja) * 2007-03-08 2014-02-19 Ｊｎｃ株式会社 ハロゲン化アルキル基と結合した２，２，２−ビシクロオクタンを有する新規な化合物およびこれを用いた液晶組成物
EP2229427B1 (fr) * 2008-01-14 2012-07-18 Merck Patent GmbH Milieu cristallin liquide
DE102013113807A1 (de) 2013-12-11 2015-06-11 Hella Kgaa Hueck & Co. Beleuchtungseinrichtung für ein Kraftfahrzeug

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WO2017129216A1 (fr) 2017-08-03
TW201736580A (zh) 2017-10-16
KR20180102164A (ko) 2018-09-14
US20190031957A1 (en) 2019-01-31
CN108603117A (zh) 2018-09-28
DE102016015630A1 (de) 2017-07-27

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