WO2020152206A1 - Liquid-crystalline medium - Google Patents

Liquid-crystalline medium Download PDF

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Publication number
WO2020152206A1
WO2020152206A1 PCT/EP2020/051480 EP2020051480W WO2020152206A1 WO 2020152206 A1 WO2020152206 A1 WO 2020152206A1 EP 2020051480 W EP2020051480 W EP 2020051480W WO 2020152206 A1 WO2020152206 A1 WO 2020152206A1
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Prior art keywords
imidazolium
atoms
liquid
denotes
compounds
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PCT/EP2020/051480
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English (en)
French (fr)
Inventor
Jung-Min Lee
Hyun-Woo BAE
Dong-Mee Song
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Merck Patent Gmbh
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Priority to KR1020217026838A priority Critical patent/KR20210116635A/ko
Publication of WO2020152206A1 publication Critical patent/WO2020152206A1/en

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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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    • C09K19/60—Pleochroic dyes
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    • 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
    • C09K19/3048—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon double bonds
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    • 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
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    • 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
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
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    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
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    • C09K19/58—Dopants or charge transfer agents
    • C09K19/582—Electrically active dopants, e.g. charge transfer agents
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
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    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
    • C09K2019/181—Ph-C≡C-Ph
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    • 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)
    • C09K2019/3006—Cy-Cy-Cy
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    • 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)
    • C09K2019/3009—Cy-Ph
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    • 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
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    • 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
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    • 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)
    • C09K2019/3025—Cy-Ph-Ph-Ph
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    • 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)
    • C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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    • 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
    • C09K2019/3031—Cy-Cy-C2H4-Cy
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    • 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
    • C09K2019/3036—Cy-C2H4-Ph
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    • 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
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
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    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • C09K2019/3071—Cy-Cy-COO-Cy
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    • C09K19/3001—Cyclohexane rings
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    • C09K2019/3078—Cy-Cy-COO-Ph-Cy

Definitions

  • Liquid-crystalline medium The invention relates to a liquid-crystalline medium having negative dielectric anisotropy, a guest-host liquid crystal medium derived therefrom and the use of said medium in devices such as light shutters, switchable windows or switchable mirrors.
  • Liquid crystals are used in particular as dielectrics in display devices, since the optical properties of such substances can be influenced by an applied voltage.
  • Electro-optical devices based on liquid crystals are known to the person skilled in the art and can be based on various effects. Devices of this type are, for example, cells having dynamic scattering, DAP
  • the LC medium comprises one or more dichroic dyes in addition to the liquid crystal.
  • the transparency of the liquid crystal to light can be modulated if the dyes change their alignment together with the liquid crystal, i.e. the maximum contrast between the clear and dark states of an LC cell depends on the alignment of the dichroic dyes.
  • Dichroic dyes have the ability to align themselves with nematic liquid crystal molecules when mixed together. When an electric field is applied to such a guest-host mixture, the nematic liquid crystal host molecules reorient and align either with or perpendicular to the electric field in order to minimize the torque they experience from the electric field.
  • the dichroic dye (guest) molecules may not be directly affected by the external electric field but can align themselves with the liquid crystal host molecules.
  • the long axes of the liquid crystal and dye molecules line up relative to the substrates in a way which causes the dye molecules not to absorb most of the light that is directed through the guest-host liquid crystal mixture normal to the substrates, whether the light passing therethrough is polarized or not, whereby the liquid crystal cell remains in a relatively clear state in the absence of the electric field, and
  • the long axes of the liquid crystal and dye molecules line up relative to the substrates in a way which causes the dye molecules to absorb at least some light that is directed through the guest-host liquid crystal mixture normal to the substrates, so long as the last mentioned light is polarized along the long axes of the dye molecules, whereby the liquid crystal cell darkens in the presence of the electric field.
  • a guest-host vertical alignment LC display is described for example in JP 2001100253, and US 357,374.
  • devices of this type are known as switching elements for regulating the passage of light or energy (light shutter), for example from WO 2009/141295 and WO 2010/118422; an example of an application are switchable windows that can be darkened on demand by means of an electrical field.
  • switchable mirrors e.g. for rear view mirrors for automotive applications using guest-host liquid crystals are proposed in DE 3340670.
  • DSM dynamic scattering mode
  • the liquid crystal-dichroic dye mixture further contains small amounts of salt as for example cetyl trimethyl ammonium bromide, Conducting Salt 235,
  • the salt has to have sufficient solubility in the liquid crystal host and a high
  • the solubilty in an amount sufficient to show the desired effect often causes problems as salts by their highly polar nature usually have a low solubilty in the highly lipophilic liquid-crystal materials.
  • the added salt can cause reliability problems in the dye doped liquid crystal as it might trigger decomposition processes especially under heat or light stress. Upon cooling, crystallisation of the salt might occur.
  • the object of the present invention is to provide a dye-doped liquid crystal that can be switched to a scattering state, having high reliability and high stability towards high or low temperature and light.
  • the present invention provides a liquid-crystalline medium according to claim 1.
  • Advantageous embodiments of the invention are subject of the dependent claims and can also be taken from the description.
  • the liquid-crystalline media according to the invention comprise
  • a + denotes an organic cation
  • B- denotes an organic or inorganic anion, preferably an organic anion.
  • These media enable switching of an electrooptical device from a first transparent state with a first transmission value to a second transparent state with a lower transmission value than the first transmission value, and switching from said second transparent state to a third opaque state.
  • the mixtures according to the invention are distinguished by a high solubility of dichroic dyes and a high solubility of the ionic liquid therein.
  • the ionic liquid in the liquid crystal is highly electrochemically stable inside the device under applied voltage, especially under additional heat or light stress, in particular under UV load.
  • the opaque state is highly scattering and enables devices with no or very low transmission, suffiently low for applications e.g. in privacy windows.
  • the invention furthermore relates to an electro-optical device based on the guest host effect containing a liquid crystalline medium according to the invention, such as light shutter, switchable windows, switchable mirrors, automotive mirrors, sun roof, augmented or virtual reality devices such as glasses or goggles or the like.
  • the invention further relates to the use of the medium in said devices, where the medium can be switched from a first transparent state with low haze to a second transparent state with low haze and less transmission than the first transparent state at a first voltage, and where the medium can be switched to an opaque state with high haze at a second voltage higher than the first voltage.
  • Fig.1 shows the change of the total transmittance of a test cell with the applied voltage.
  • Fig.2 shows the change of the haze of a test cell with the applied voltage.
  • Halogen denotes F, Cl, Br or I.
  • an alkyl radical and/or an alkoxy radical is taken to mean straight- chain or branched alkyl.
  • It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetra- decyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.
  • alkenyl i.e.
  • an alkyl or alkenyl radical which is at least monosubstituted by halogen is preferably straight-chain, and halogen is preferably F or Cl.
  • halogen is preferably F.
  • the resultant radicals also include perfluorinated radicals.
  • the fluorine or chlorine substituent may be in any desired position, but is preferably in the w-position.
  • a mono- or polyfluorinated alkyl or alkoxy radical having 1, 2 or 3 C atoms or a mono- or polyfluorinated alkenyl radical having 2 or 3 C atoms is particularly preferably F, Cl, CF 3 , CHF 2 , OCF 3 , OCHF 2 , OCFHCF 3 , OCFHCHF 2 , OCFHCHF 2 , OCF 2 CH 3 , OCF 2 CHF 2 , OCF 2 CHF 2 , OCF 2 CHF 2 ,
  • Liquid-crystal hosts with negative dielectric anisotropy are widely used in displays for example of the vertical alignment (VA) mode (Song, J. (2014). Vertical alignment Liquid Crystal mode. In Handbook of Liquid Crystals (eds J. W. Goodby, C. Tschierske, P. Raynes, H. Gleeson, T. Kato and P. J. Collings).
  • VA vertical alignment
  • Suitable media are well described in the literature such as for example in US 20030071244 A1 or US 20100134751 A1.
  • a dichroic dye is taken to mean a compound having an elongated molecular structure which is dissolved in a host liquid crystal with the purpose of absorbing light, where the dye molecule ist aligned with the liquid crystal an can be oriented with the liquid crystal molecules upon application of an electric field.
  • the dichroic dyes used herein have an absorption maximum in the visible wavelength range.
  • Dychroic dyes are known to the skilled person and well described in the literature, e.g.
  • the absorption maximum of the dichroic dye or dyes used in the liquid crystalline media according to the present invention is not specifically limited, but it is preferred to have an absorption maximum in the yellow region (Y), magenta region (M), or cyan region (C).
  • the dichroic dye used in the liquid crystal medium of the present invention may be a single compound or a combination of a plurality of dyes. When several dyes are mixed it is preferred to use a mixture of the dichroic dyes having absorption maxima in the Y, M, and C regions, respectively.
  • Dichroic dyes are known to the person skilled in the art and are reviewed in for example Cowling, Stephen J., Liquid Crystal Dyes, in: Handbook of Liquid Crystals, Wiley- VCH Verlag GmbH & Co. KGaA (2014). Methods of displaying a full colour by mixing a yellow dye, a magenta dye and a cyan dye is specifically described in "Colour Chemistry” (by Sumio Tokita, Maruzen Company, Limited, 1982).
  • the yellow region is the range of 430 to 490 nm
  • the magenta region is the range of 500 to 580 nm
  • the cyan region is the range of 600 to 700 nm.
  • the chromophore used in the dichroic dye is not particularly limited, but it is preferred to use azo dyes, azulene dyes, anthraquinone dyes, benzoquinone dyes, napthoquinone dyes, benzothiazole dyes,
  • dithiobenzoquinone perylene dyes, merocyanine dyes, azomethine dyes, phthaloperylene dyes, indigo dyes, azulene dyes, dioxazine dyes, tetrazine dyes, polythiophene dyes, naphthimidazo-4,9-dione dyes and phenoxazine dyes.
  • Preferred dyes according to the present invention are azo dyes, perylene dyes, anthraquinone dyes, and benzothiazole dyes, particularly preferred azo dyes.
  • the azo dyes may contain any number of azo groups such as monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and pentakisazo dyes, and preferably monoazo dyes, bisazo dyes, and trisazo dyes.
  • Cyclic structures contained in the azo dyes are aryl groups and/or heteroaryl groups. Preferred aryl groups are derived, for example, from the parent structures benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluorene, indene, etc.
  • Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, furan, thiophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole,
  • aryl and heteroaryl groups may also be substituted by alkyl, cycloalkyl, alkoxy, thioalkyl, alkylamino, dialkylamino, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
  • azo dyes F355 ® , F357 ® and F593 ® from Nippon Kankoh Shikiso Kenkyusho Ltd., Okayama, Japan
  • the concentration of the dichroic dye or dyes in the medium is preferably 1% by weight or more, particularly preferably 1.5% by weight or more and very particularly 2% by weight or more.
  • Ionic liquids are salts with a melting point below 100° C. According to the invention, preference is given to using ionic liquids with low melting points, that are particularly preferably liquid at room temperature.
  • the liquid-crystal media according to the invention comprise one or more ionic liquids having a melting point in the range of from 10°C to 99°C, more preferably from 15°C to 95° C, particularly preferably from 20°C to 90°C to and in particular from 25°C to 80°C.
  • Ionic liquids are characterized by their special properties, such as a practically non-existent vapor pressure, a low viscosity and high
  • Ionic liquids are salts and thus comprise at least one cation and at least one anion.
  • the cation of the ionic liquid(s) is an organic cation.
  • Suitable counterions are organic and/or inorganic anions.
  • liquid-crystal media according to the invention are preferred in which the ionic liquid comprises an organic cation A + and an organic and / or inorganic, preferably organic anion B-.
  • Preferred cations A + are those from the groups imidazolium, pyridinium,
  • pyrrolidinium, phosphonium, ammonium, in particular pyrrolidinium, guanidinium and isuronium are especially preferred cations for ionic liquids.
  • Especially preferred cations for ionic liquids are selected from the group of imidazolium ions of formula A-1
  • R 1 , R 2 , R 3 , R 4 and R 5 identically or differently, denote H or straight chain or branched alkyl, alkenyl or arylalkyl, each having 1 to 20 C atoms, and in which one or more non-adjacent CH 2 groups are optionally replaced with -O- and one or more H atoms are optionally replaced with halogen or CN.
  • R 1 and R 3 preferably denote alkyl having 1 to 12 C atoms
  • R 2 preferably denotes H or alkyl having 1 to 3 C atoms, more preferably H or methyl, in particular H
  • R 4 and R 5 preferably denote H.
  • Very preferred examples are 1-methyl-imidazolium, 1-ethyl-imidazolium, 1- propyl-imidazolium, 1-lsopropyl-imidazolium, 1-butyl-imidazolium, 1-pentyl- imidazolium, 1-hexylimidazolium, 1-heptyl-imidazolium, 1-octyl- imidazolium, 1-nonyl-imidazolium, 1-decylimidazolium, 1-undecyl- imidazolium, 1-dodecyl-imidazolium, 1-tridecyl-imidazolium, 1-tetradecyl- imidazolium, 1-pentadecyl-imidazolium, 1-hexadecyl-imidazolium, 1- heptadecylimidazolium, 1-octadecyl-imidazolium, 1-nonadecy
  • Preferred anions are selected from the groups of halides, sulfates, sulfonates, amides, imides and methanes, borates, phosphates and antimonates, anions of fatty acids, trifluoroacetates and cobalt
  • Preferred anions are chloride, bromide, iodide, methylsulfate, ethylsulfate, propylsulfate, butylsulfate, hexylsulfate, octylsulfate,
  • trifluorophosphate tris(nonafluorobutyl) trifluorophosphate, bis(2,4,4- trimethylpentyl) phosphinate, hexafluoroantimonate, diethyl phosphate. All of the above-mentioned cations can be combined with all of the above- mentioned anions to give ionic liquids which can be used according to the invention.
  • Examples are 1-methyl-imidazolium tosylate, 1-methyl- imidazolium tetrafluoroborate, 1-methyl-imidazolium hexafluorophosphate, 1-methyl-imidazolium trifluoromethansulfonate, 1-methyl-3- octylimidazolium chloride, 3-methyl-1-octylimidazolium bromide, 3-methyl- 1-octylimidazolium chloride, 3-methyl-1-octylimidazolium octylsulfate, 3- methyl-1-octylimidazolium methylsulfate, 3-methyl-1-octylimidazolium tetrafluoroborate, 3-methyl-1-octylimidazolium hexafluorophosphate, 3- methyl-1-octylimidazolium hexafluoroantimonate, 3-methyl-1- octylimid
  • n-octylpyridinium chloride bistrifluoromethanesulfonate n-octylpyridinium chloride, n-octylpyridinium tris-(trifluoromethylsulfonyl)methan, n-octylpyridinium bis- (trifluoromethylsulfonyl)imide, 1-decyl-3-methylimidazolium chloride, 1- decyl-3-methylimidazolium bromide, 1-decyl-3-methylimidazolium tris- (pentafluoroethyl)trifluorophosphate, 1-decyl-3methylimidazolium
  • bis(trifluoromethylsulfonyl)imide (2-hydroxyethyl)trimethylammonium dimethylphosphate, tributylmethyphosphonium dimethylphosphate, lithium bis(trifluoromethylsulfonyl)imide, tetramethylammonium bis- (trifluoromethylsulfonyl)imide, tetramethylammonium bis- (trifluoromethyl)imide, tetramethylammonium tris- (pentafluoroethyl)trifluorophosphate, tetramethylammonium bis[oxalato- (2-)]-borate, tetraethylammonium bis-(trifluoromethyl)imide,
  • tetraethylammonium bis-(trifluoromethylsulfonyl)imide tetraethylammonium tris-(pentafluoroethyl)trifluorophosphate
  • tetraethylammonium bis[1,2- benzenediolato(2- ⁇ -O,O']-borate tetraethylammonium bis[ salicylato-(2-)]- borate
  • tetraethylammonium bis[2,2 '-biphenyldiolato(2-)-O,O']-borate tetraethylammonium bis[malonato-(2-)]-borate
  • tetrabutylammonium bromide tetrabutylammonium bis-(trifluoromethylsulfonyl)imide
  • n is an integer from 1 to 6, preferably 2, m is an integer from 1 to 10, preferably 1, R denotes alkyl having 1 to 6 C atoms, preferably 1 C atom.
  • the medium according to the invention comprises one or more ionic liquids comprising a cation of formula A-1 and an anion selected from the anoins of formulae B-1 to B-7 defined above.
  • the nematic host comprises one or more compounds selected from the group of the compounds of the formulae IIA, IIB and IIC,
  • R 2C each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is un- substituted, monosubstituted by CN or CF 3 or at least monosubstituted by halogen, where, in addition, one or more CH 2 groups in these radicals may be replaced by -O-, -S-, -C oC-, -CF 2 O-, -OCF 2 -, -OC-O- or -O-CO- in such a way that O atoms are not linked directly to one another, or a cycloalkyl ring having 3 to 6 C atoms, L 1-4 each, independently of one another, denote F, Cl, CF 3 or
  • CHF 2 , Z 2 and Z 2’ each, independently of one another, denote a single bond
  • Z 2 may have identical or different meanings.
  • Z 2 and Z 2' may have identical or different meanings.
  • R 2A , R 2B and R 2C each preferably denote alkyl having 1-6 C atoms, in particular CH 3 , C 2 H 5 , n-C 3 H 7 , n-C 4 H 9 , n-C 5 H 11 .
  • Z 2 and Z 2' in the formulae IIA and IIB preferably each, independently of one another, denote a single bond, furthermore a -C 2 H 4 - or -CH 2 O- bridge.
  • Z 2 denotes -C 2 H 4 - or -CH 2 O-
  • Z 2' is preferably a single bond or, if Z 2' denotes -C 2 H 4 - or -CH 2 O-, Z 2 is preferably a single bond.
  • (O)C v H 2v+1 preferably denotes OC v H 2v+1 , furthermore C v H 2v+1 .
  • (O)C v H 2v+1 preferably denotes C v H 2v+1 .
  • L 3 and L 4 preferably each denote F.
  • Preferred compounds of the formulae IIA, IIB and IIC are indicated below:
  • alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-7 C atoms
  • alkenyl denotes a straight chain alkenyl radical having 2 to 7 C atoms
  • (O) denotes -O- or a single bond.
  • Particularly preferred mixtures according to the invention comprise one or more compounds of the formulae IIA-2, IIA-8, IIA-14, IIA-26, IIA-28, IIA-33, IIA-39, IIA-45, IIA-46, IIA-47, IIB-2, IIB-11, IIB-16, IIB-17, IIB-18 and IIC-1.
  • the proportion of compounds of the formulae IIA and/or IIB in the mixture as a whole is preferably at least 20% by weight.
  • Particularly preferred media according to the invention comprise at least one compound of the formula IIC-1,
  • the medium according to the invention comprises one or more compounds of formula N,
  • R N denotes alkyl or alkenyl having up to 12 C atoms, wherein one or more non adjacent CH2 groups may be replaced by -O- and/or a cycloalkyl ring having 3 to 5 C atoms, and wherein one or more H atoms may be replaced by F, on each occurrence, identically or differently, denotes (a) a trans-1,4-cyclohexylene radical, in which one or more non-adjacent CH2 groups may be replaced by -O- and/or -S-, (b) a 1,4-phenylene radical, in which one or two CH groups may be replaced by N, (c) trans-1,4-cyclohexenylene, (d) a radical from the group consisting of 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetra- hydronaphthal
  • L N1 , L N2 , L N3 and L N4 each, independently of one another, denote H, Cl, or F, n is 1, 2 or 3.
  • Preferred compounds of formula N are selected from the group of compounds of the formulae N-1 and N-2:
  • R N denotes alkyl or alkenyl having up to 7 C atoms, identically or differently, denote
  • L N1 and L N2 independently of one another, denote H or F, and Z N denotes -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH2CH2-,
  • Particularly preferred compounds of formula N are selected from the group of compounds of formulae N-1 to N-8, very particularly preferred of formula N-1:
  • the liquid-crystalline medium comprises one or more stabilisers, preferably selected from the group consisting of compounds of the formulae ST-1 to ST-18.
  • R ST denotes H, an alkyl or alkoxy radical having 1 to 15 C atoms, where, in addition, one or more CH2 groups in these radicals may each be replaced, independently of one another, by
  • Z ST each, independently of one another, denote -CO-O-, -O-CO-,
  • n preferably denotes 3.
  • n preferably denotes 7.
  • Very particularly preferred mixtures according to the invention comprise one or more stabilizers from the group of the compounds of the formulae ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1 and ST-12:
  • the compounds of the formulae ST-1 to ST-18 are preferably each present in the liquid-crystal mixtures according to the invention in amounts of 0.005 – 0.5%, based on the mixture. If the mixtures according to the invention comprise two or more compounds from the group of the compounds of the formulae ST-1 to ST-17, the con- centration correspondingly increases to 0.01– 1% in the case of two compounds, based on the mixtures. However, the total proportion of the compounds of the formulae ST-1 to ST- 17, based on the mixture according to the invention, should not exceed 2%.
  • the medium according to the invention comprises one or more chiral dopants and thus shows a cholesteric phase.
  • these chiral dopants have an absolute value of the helical twisting power (short: HTP) in the range of from 1 mm -1 to 150 mm -1 , preferably in the range of from 10 mm -1 to 100 mm -1 .
  • HTP helical twisting power
  • the media comprise two or more chiral dopants, these may have opposite signs of their HTP-values. This condition is preferred for some specific
  • the chiral compounds present in the media according to the present invention may be used to compensate various temperature dependent properties of the resulting media in the devices.
  • the chiral dopants present in the media according to the instant application are mesogenic compounds and most preferably they exhibit a mesophase on their own.
  • the temperature dependence of the HTP of the individual compounds may be high or low.
  • the temperature dependence of the pitch of the medium can be compensated by mixing compounds having different temperature dependence of the HTP in corresponding ratios.
  • optically active component a large variety of chiral dopants, some of which are commercially available, is available to the person skilled in the art, such as, for example, cholesteryl nonanoate, R- and S-811, R- and S- 1011, R- and S-2011, R- and S-3011 R- and S-4011, B(OC)2C*H-C-3 or CB15 (all Merck KGaA, Darmstadt).
  • Particularly suitable dopants are compounds which contain one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups which form a mesogenic group with the chiral group.
  • Suitable chiral groups are, for example, chiral branched hydrocarbon radicals, chiral ethanediols, binaphthols or dioxolanes, furthermore mono- or polyvalent chiral groups selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acids, chiral substituted glycols, steroid derivatives, terpene derivatives, amino acids or sequences of a few, preferably 1-5, amino acids.
  • Preferred chiral groups are sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose and dextrose; sugar alcohols, such as, for example, sorbitol, mannitol, iditol, galactitol or anhydro derivatives thereof, in particular dianhydrohexitols, such as dianhydrosorbide (1,4:3,6- dianhydro-D-sorbide, isosorbide), dianhydromannitol (isosorbitol) or dianhydroiditol (isoiditol); sugar acids, such as, for example, gluconic acid, gulonic acid and ketogulonic acid; chiral substituted glycol radicals, such as, for example, mono- or oligoethylene or propylene glycols, in which one or more CH 2 groups are substituted by alkyl or alkoxy; amino acids, such as, for example, alanine, valine, pheny
  • Suitable chiral groups and mesogenic chiral compounds are described, for example, in DE 3425503, DE 3534777, DE 3534778, DE 3534779 and DE 3534780, DE 4342280, EP 01038941 and DE 19541820.
  • alkyl preferably alkyl, more preferably n-alkyl,
  • alkyl preferably alkyl, more preferably n-alkyl,
  • R a32 is different from R b32 ;
  • R z denotes H, CH 3 , F, Cl, or CN, preferably H or F
  • R 8 has one of the meanings of R a11 given above, preferably alkyl, more preferably n-alkyl having 1 to 15 C atoms, Z 8 denotes- C(O)O-, CH 2 O, CF 2 O or a single bond, preferably -C(O)O-,
  • a 11 is defined as A 12 below, or alternatively denotes
  • a 12 denotes
  • r 0, 1, 2, 3 or 4,
  • L and L 11 on each occurrence, independently of one another, denote alkyl, alkenyl or alkoxy having up to 12 C atoms, in which one or more H atoms are optionally replaced with halogen, halogen, SF 5 or CN,
  • a 21 denotes
  • a 22 has the meanings given for A 12
  • a 31 has the meanings given for A 11 , or
  • a 32 has the meanings given for A 12 , n2 on each occurrence, identically or differently, is 0, 1 or 2, and n3 is 1, 2 or 3.
  • dopants selected from the group consisting of the compounds of the following formulae:
  • n is, on each occurrence, identically or differently, an integer from 1 to 9 and
  • n is, on each occurrence, identically or differently, an integer from 2 to 9.
  • Particularly preferred compounds of formula A are compounds of formula A- III.
  • Further preferred dopants are derivatives of the isosorbide, isomannitol or isoiditol of the following formula A-IV:
  • dianhydrosorbitol preferably dianhydrosorbitol.
  • dopants are chiral ethanediols, such as, for example, diphenylethanediol (hydrobenzoin), in particular mesogenic hydrobenzoin derivatives of the following formula A-V:
  • 1,4-phenylene which may also be mono-, di- or trisubstituted by L, or 1,4- cyclohexylene
  • L is H, F, Cl, CN or optionally halogenated alkyl, alkoxy
  • X is CH 2 or -C(O)-
  • Z 0 is -COO-, -OCO-, -CH 2 CH 2 - or a single bond
  • R 0 is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyl- oxy having 1-12 carbon atoms.
  • Chiral compounds preferably used according to the present invention are selected from the group consisting of the formulae shown below. Examples of compounds of formula A-IV are:
  • the compounds of the formula A-V are described in GB-A-2,328,207.
  • Very particularly preferred dopants are chiral binaphthyl derivatives, as described in WO 02/94805, chiral binaphthol acetal derivatives, as described in WO 02/34739, chiral TADDOL derivatives, as described in WO 02/06265, and chiral dopants having at least one fluorinated bridging group and a terminal or central chiral group, as described in WO 02/06196 and WO 02/06195. Particular preference is given to chiral compounds of the formula A-VI
  • X 1 , X 2 , Y 1 and Y 2 are each, independently of one another, F, Cl, Br, I, CN,
  • SCN, SF5, straight-chain or branched alkyl having from 1 to 25 carbon atoms, which is unsubstituted or monosubstituted or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH 2 groups may each, independently of one another, be replaced by -O-, -S-, -NH-, NR 0 -, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH CH- or -C oC- in such a way that O and/or S atoms are not bonded directly to one another, a polymerizable group or cycloalkyl or aryl having up to 20 carbon atoms, which may optionally be monosubstituted or polysubstituted by halogen, preferably F, or by a polymerizable group, R 0 is H or
  • U 1 and U 2 are each, independently of one another, CH2, O, S, CO or CS, V 1 and V 2 are each, independently of one another, (CH2)n, in which from one to four non-adjacent CH 2 groups may each be replaced by O or S, and one of V 1 and V 2 and, in the case where
  • n 1, 2 or 3
  • Z 1 and Z 2 are each, independently of one another, -O-, -S-, -CO-, -COO-,
  • a 1 , A 2 and A 3 are each, independently of one another, 1,4-phenylene, in which one or two non-adjacent CH groups may each be replaced by N, 1,4-cyclohexylene, in which one or two non- adjacent CH 2 groups may each be replaced by O or S, 1,3- dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4- bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydro- naphthalene-2,
  • Particular preference is given to chiral binaphthyl derivatives of the formula A-VI-1
  • ring B, R 0 and Z 0 are as defined for the formulae A-IV and A-V, and b is 0, 1, or 2, in particular those selected from the following formulae A-VI-1a to A-VI-1c:
  • ring B, R 0 and Z 0 are as defined for the formula A-VI-1, and R 0 as defined for formula A-IV or H or alkyl having from 1 to 4
  • R 0 is as defined for the formula A-VI, and X is H, F, Cl, CN or R 0 , preferably F.
  • the concentration of the one or more chiral dopant(s), in the LC medium is preferably in the range from 0.001 % to 20 %, preferably from 0.05 % to 5 %, more preferably from 0.1 % to 2 %, and, most preferably from 0.5 % to 1.5 %.
  • concentration ranges apply in particular to the chiral dopant S-4011 or R-4011 (both from Merck KGaA) and for chiral dopants having the same or a similar HTP.
  • these preferred concentrations have to be decreased, respectively increased, proportionally according to the ratio of their HTP values relatively to that of S-4011.
  • Liquid-crystalline medium which additionally comprises one or more compounds of the formula III, in which R 31 and R 32 each, independently of one another, denote a straight- chain alkyl, alkenyl, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and denotes
  • alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms
  • alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms.
  • Particularly preferred compounds of the formula III-3 are the following:
  • Liquid-crystalline medium which additionally comprises one or more tetracyclic compounds of the formulae
  • R 14 -R 19 each, independently of one another, denote an alkyl or alkoxy radical having 1-6 C atoms; z and m each, independently of one another, denote 1-6; x denotes 0, 1, 2 or 3.
  • the medium according to the invention particularly preferably com- prises one or more compounds of the formulae Y-1 to Y-6, preferably in amounts of £ 5% by weight.
  • Liquid-crystalline medium additionally comprising one or more fluori- nated terphenyls of the formulae T-1 to T-21,
  • R denotes a straight-chain alkyl or alkoxy radical having 1-7 C atoms or alkenyl having 2-7 C atoms
  • R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, meth- oxy, ethoxy, propoxy, butoxy, pentoxy.
  • the medium according to the invention preferably comprises the ter- phenyls of the formulae T-1 to T-21 in amounts of 2-30% by weight, in particular 5-20% by weight. Particular preference is given to compounds of the formulae T-1, T-2, T-20 and T-21, very particularly T-1. In these compounds, R preferably denotes alkyl, furthermore alkoxy, each having 1-5 C atoms.
  • R preferably denotes alkyl or alkenyl, in particular alkyl.
  • R preferably denotes alkyl.
  • the terphenyls are preferably employed in the mixtures according to the invention if the Dn value of the mixture is to be 3 0.1.
  • Preferred mixtures comprise 2-20% by weight of one or more terphenyl com- pounds selected from the group of the compounds T-1 to T-21.
  • the medium according to the invention comprises one or more compounds of formula T-1 in a total concentration in the range of from 3% to 15%, more preferably from 5% to 10%.
  • Liquid-crystalline medium additionally comprising one or more bi- phenyls of the formulae B-1 to B-6,
  • alkyl and alkyl* each, independently of one another denote a straight-chain alkyl radical having 1-6 C atoms
  • alkenyl and alkenyl* each, independently of one another denote a straight-chain alkenyl radical having 2-6 C atoms
  • alkoxy denotes a straight-chain alkoxy radical having 1- 6 C atoms.
  • the proportion of the biphenyls of the formulae B-1 to B-6, preferably B-5, in the mixture as a whole is preferably at least 3% by weight, in particular 3 5% by weight, preferably in the range of from 7% to 15%.
  • the compounds of the formulae B-1 to B-4 are particularly preferred. Very particularly preferred biphenyls are
  • alkyl* denotes an alkyl radical having 1-6 C atoms.
  • the medium according to the invention particularly preferably comprises one or more compounds of the formulae B-1a and/or B-2c. f) Liquid-crystalline medium comprising at least one compound of the formulae Z-1 to Z-7,
  • R denotes a straight-chain alkyl or alkoxy radical having 1- 7 C atoms or an alkenyl radical having 2-7 C atoms
  • alkyl denotes an alkyl radical having 1-6 C atoms
  • (O)alkyl denotes alkyl or Oalkyl (alkoxy).
  • R 1 and R 2 have the meanings indicated for R 2A .
  • R 1 and R 2 preferably each, independently of one another, denote straight-chain alkyl having 1-6 C atoms or R 1 denotes straight-chain alkyl having 1-6 C atoms and R 2 denotes alkenyl having 2-6 C atoms.
  • Preferred media comprise one or more compounds of the formulae O-1, O-3, O-4, O-5, O-9, O-12, O-14, O-15, and/or O-16. Mixtures according to the invention very particularly preferably com- prise the compounds of the formulae O-9, O-12 and/or O-16 in particular in amounts of 5-30%.
  • Preferred compounds of the formula O-9 are indicated below:
  • Preferred mixtures comprise one or more indane compounds of the formula In,
  • R 13 each, independently of one another, denote a straight- chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1-6 C atoms or 2-6 C atoms respectively, R 12 and R 13 additionally denote halogen, preferably F,
  • i denotes 0, 1 or 2.
  • Preferred compounds of the formula In are the compounds of the for- mulae In-1 to In-16 indicated below:
  • the medium additionally comprises one or more compounds selected from the following formulae:
  • R Q and X Q each, inde- pendently of one another, have the meanings of R 2A in Claim 2.
  • R Q and X Q preferably denote a straight-chain alkyl radical having 1-6 C atoms, in particular having 2-5 C atoms.
  • the mixtures according to the invention preferably comprise - the compound of the formula N in combination with one or more com- pounds of the formula IIB, preferably CPY-n-Om, in particular CPY-2-O2, CPY-3-O2 and/or CPY-5-O2, preferably in concentrations > 5%, in the range of from 20 to 60%, very particularly from 30 to 50, and/or - CY-n-Om, preferably CY-3-O2, CY-3-O4, CY-5-O2 and/or CY-5-O4, pref- erably in concentrations > 5%, in particular 5-25%, very particularly 10- 15%, and/or - CCY-n-Om, preferably CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-O1 and
  • the concentration of ionic liquid of formula I in the medium is 0.25% or less, more preferably 0.2% or less, particularly preferably 0.1% or less.
  • the concentration of ionic liquid of formula I in the medium is in the range of from 0.0001% to 1%, more preferably, from 0.0005% to 0.5%, very preferably from 0.001% to 0.2% and in particular from 0.001% to 0.1%.
  • the concentration of ionic liquid of formula I in the medium is in the range of from 0.005% to 0.02%.
  • the mixtures according to the invention or the nematic host preferably exhibit very broad nematic phase ranges with clearing points 3 85°C, pref- erably 3 95°C, in particular 3 100°C, very favourable values of the capacitive threshold, relatively high values of the holding ratio and at the same time very good low-temperature stabilities at -20°C and -30°C, as well as low rotational viscosities and short response times.
  • the mixtures according to the invention are furthermore distinguished by the fact that, in addition to the improvement in the rotational viscosity g 1 , relatively high values of the elastic constants K 33 for improving the response times can be observed.
  • the liquid-crystalline medium according to the invention preferably has a nematic phase from £ -20°C to 3 85°C, particularly preferably from £ -30°C to 3 95°C, very particularly preferably from £ -40°C to 3 100°C.
  • the expression "to have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low
  • the investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical use 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.
  • the liquid-crystal mixture preferably has a nematic phase range of at least 60 K.
  • the values of the birefringence Dn in the liquid-crystal mixture are gener- ally between 0.07 and 0.25, preferably between 0.10 and 0.20.
  • the medium preferably has a birefringence Dn of 0.180 or more, more preferably of 0.190 or more, particularly preferably of 0.200 or more.
  • the liquid-crystal mixture according to the invention has a De of -0.5 to -8.0, in particular -1.0 to -6.0, where D e denotes the dielectric anisotropy.
  • the rotational viscosity g1 at 20°C is preferably £ 500 mPa ⁇ s, in particu- lar £ 250 mPa ⁇ s.
  • the liquid-crystal media according to the invention have relatively small values for the threshold voltage (V 0 ). They are preferably in the range from 1.7 V to 4.0 V, particularly preferably £ 3.0 V and very particularly prefera- bly £ 2.7 V.
  • the term "threshold voltage” relates to the capac- itive threshold (V 0 ), also known as the Freedericks threshold, unless explic- itly indicated otherwise.
  • the liquid-crystal media according to the invention have high values for the voltage holding ratio in liquid-crystal cells. In general, liquid-crystal media having a low addressing voltage or thresh- old voltage exhibit a lower voltage holding ratio than those having a higher addressing voltage or threshold voltage and vice versa.
  • dielectrically positive compounds denotes compounds having a D e > 1.0
  • dielectrically neutral com- pounds denotes those where -1.0 £ D e £ 1.0
  • dielectrically negative compounds denotes those having D e ⁇ -1.0.
  • the dielectric ani- sotropy 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 in at least one test cell in each case having a layer thickness of 20 ⁇ m with homeotropic and with homogeneous surface align- ment at 1 kHz.
  • the measurement voltage is typically 0.5 V to 1.0 V, but is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated. All temperature values indicated for the present invention are in °C.
  • the phases preferably comprise 4 to 15, in particular 5 to 12, and particularly preferably ⁇ 10, compounds of the formulae IIA, IIB and/or IIC.
  • other constituents may also be present, for example in an amount of up to 45% of the mixture as a whole, but preferably up to 35%, in particular up to 10%.
  • these liquid-crystal phases may also comprise more than 18 components, preferably 18 to 25 components.
  • the other constituents are preferably selected from nematic or nemato- genic substances, in particular known substances, from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclo- hexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acid esters.
  • R 20 and R 21 are different from one another, one of these radicals usually being an alkyl or alkoxy group.
  • Other variants of the proposed substituents are also common. Many such substances or also mixtures thereof are commercially available. All these substances can be prepared by methods known from the literature. It goes without saying for the person skilled in the art that the liquid crystalline according to the invention may also comprise compounds in which, for example, H, N, O, Cl and F have been replaced by the corres- ponding isotopes.
  • Polymerisable compounds either non-mesogenic or mesogenic, the latter referred to as reactive mesogens (RMs), for example as disclosed in US 6,861, 107, preferably non-mesogenic, may furthermore be added to the mixtures according to the invention in concentrations of preferably 10 - 50 % by weight, particularly preferably 20 - 40% by weight, based on the mixture.
  • the polymerisable compounds are preferably selected from 2- ethylhexyl acrylate (EHA), 1,3,3-trimethylhexyl acrylate (TMHA), trimethylol propane triacrylatehexanediol diacrylate (HDDA), hexanediol
  • dimethacrylate HDDMA
  • MMA metylmethacrylate
  • EA ethylacrylate
  • EMA ethylmethacrylate
  • 6CBA 6-(4'- cyanobiphenyl-4-yloxy)hexyl acrylate
  • GHPDLC guest-host polymer dispersed liquid crystals
  • a GHPDLC display is described in JP 06-324309 A.
  • a GHPDLC polymer film is published in P. Malik, K.K. Raina, Physica B 405 (2010) 161–166.
  • the prerequisite for this is that the liquid-crystal mixture itself comprises no polymerisable components which likewise polymerise under the conditions where the compounds of the formula M polymerise.
  • the polymerisation is preferably carried out under the following conditions: the polymerisable components are polymerised in a cell using a UV-A lamp of defined intensity for a defined period and applied voltage (typically 10 to 30 V alternating voltage, frequencies in the range from 60 Hz to 1 kHz).
  • the UV-A light source employed is typically a metal-halide vapour lamp or high-pressure mercury lamp having an intensity of 50 mW/cm 2 .
  • the mixtures according to the invention may furthermore comprise conven- tional additives, such as, for example, stabilisers, antioxidants, UV absorb- ers, nanoparticles, microparticles, etc.
  • the liquid crystalline medium comprises one or more chiral dopants.
  • per cent data denote per cent by weight; all tem- peratures are indicated in degrees Celsius.
  • 1,4-cyclohexylene rings and 1,4-phenyl- ene rings are depicted as follows:
  • the cyclohexylene rings are trans-1,4-cyclohexylene rings.
  • the struc- tures of the liquid-crystal compounds are indicated by means of acronyms. Unless indicated otherwise, the transformation into chemical formulae is carried out in accordance with Tables 1-3. All radicals C n H 2n+1 , C m H 2m+1 and C m‘ H 2m‘+1 or C n H 2n and C m H 2m are straight-chain alkyl radicals or alkylene radicals, in each case having n, m, m‘ or z C atoms respectively.
  • Table 1 the ring ele- ments of the respective compound are coded, in Table 2 the bridging mem- bers are listed and in Table 3 the meanings of the symbols for the left-hand or right-hand side chains of the compounds are indicated.
  • the mixtures according to the inven- tion preferably comprise one or more of the compounds from Table A indi- cated below.
  • Table A The following abbreviations are used:
  • the liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner which is conventional per se.
  • the desired amount of the components used in lesser amount is dis- solved in the components making up the principal constituent, advanta- geously at elevated temperature.
  • the dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, UV absorbers, antioxidants, nanoparticles and free-radical scavengers.
  • stabilisers or chiral dopants may be added.
  • Suitable stabilisers for the mixtures according to the invention are, in particular, those listed in Table B.
  • conductive salts preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst., Volume 24, pages 249-258 (1973)), may be added in order to improve the conductivity or substances may be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases.
  • Table B shows possible dopants which are generally added to the mixtures according to the invention.
  • the mixtures preferably comprise 0-10% by weight, in particular 0.01-5% by weight and particularly preferably 0.01-3% by weight of dopants. If the mixtures comprise only one dopant, it is em- ployed in amounts of 0.01-4% by weight, preferably 0.1-1.0% by weight.
  • Table C Stabilisers which can be added, for example, to the mixtures according to the invention in amounts of 0-10% by weight are shown below.
  • the medium according to the invention particularly preferably comprises Tinuvin ⁇ 770 (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate), preferably in amounts of 0.001– 5% by weight, based on the liquid-crystalline medium.
  • Tinuvin ⁇ 770 bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate
  • Table D Examples of preferred further dichroic dyes which may be used in the liquid crystalline media according to the invention are listed in Table D: Table D
  • m.p. denotes the melting point and C denotes the clearing point of a liquid-crystalline substance in degrees Celsius; boiling temperatures are denoted by b.p.
  • C denotes crystalline solid state
  • S denotes smectic phase (the index denotes the phase type)
  • N denotes nematic state
  • Ch denotes cholesteric phase
  • I denotes isotropic phase
  • T g denotes glass-transition temperature. The number between two symbols indicates the conversion temperature in degrees Celsius.
  • the host mixture used for determination of the optical anisotropy Dn of the compounds of the formula I is the commercial mixture ZLI-4792 (Merck KGaA).
  • the dielectric anisotropy D e is determined using commercial mix- ture ZLI-2857.
  • the physical data of the compound to be investigated are obtained from 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. In general, 10% of the compound to be investigated are dissolved in the host mixture, depending on the solubility. Unless indicated otherwise, parts or per cent data denote parts by weight or per cent by weight based on the mixture as a whole. Above and below, the symbols and abbreviations have the following mean- ings: V o threshold voltage, capacitive [V] at 20°C
  • LTS low-temperature stability (nematic phase), determined in test cells.
  • the display used for measurement of the threshold voltage has two plane- parallel outer plates at a separation of 20 ⁇ m and electrode layers with alignment layers comprising SE-1211 (Nissan Chemicals) on top on the insides of the outer plates, which effect a homeotropic alignment of the liquid crystals. All concentrations in this application, unless explicitly indicated otherwise, relate to the corresponding mixture or mixture component. All physical properties are 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 indi- cated otherwise. Mixture Examples
  • the nematic host mixtures H1 to H5 are prepared as follows: Mixture H1 CBC-33 3.0 % Clearing point [°C]: 112.5 CBC-33F 3.0 % Dn [589 nm, 20°C]: 0.1995 CCY-3-O1 3.0 % D e [1 kHz, 20°C]: -4.9 CCY-3-O2 11.0 % [1 kHz, 20°C]: 4.1 CPY-2-O2 12.0 % K 1 [pN, 20°C]: 18.0 CPY-3-O2 12.0 % K 3 [pN, 20°C]: 22.8 PGIGI-3-F 8.0 %
  • PYP-2-4 15.0 % From the host mixtures H1 to H5, Mixture Examples M1 to M9 are prepared having the compositions given in the tables below, using a dye mixture consisting of the following components Dye-1, Dye-2 and Dye-3, whose different absorption characteristics together result in a black colour, and further the ionic liquids IL-1 or IL-2, and stabiliser additives Add-1 or Add-2.
  • Example M9 component weight proportion H5 100.0 Dye 1 0.338 Dye 2 0.511 Dye 3 0.950 IL-1 0.010 ST-9-1 0.100 Use Examples
  • Transmittance and haze are measured using a commercially available hazemeter (Model NDH7000SP II, Nippon Denshoku Industries Co., Ltd., Tokyo, Japan).
  • a test cell Cell gap: 10mm (spacer in cell area), cell size: 35 x 35 mm, electrode: patterned ITO (24x24) with orientation layers for homeotropic orientation (JALS 2096-R1, from JSR (Japan Synthetic Rubber, Japan)
  • JALS 2096-R1 orientation layers for homeotropic orientation
  • the results is shown in Fig.1 and Fig.2. The following values are observed:

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Publication number Priority date Publication date Assignee Title
WO2021233797A1 (en) * 2020-05-18 2021-11-25 Merck Patent Gmbh Liquid-crystalline medium
CN115667461A (zh) * 2020-05-18 2023-01-31 默克专利股份有限公司 液晶介质

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