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WO2018104279A1 - Milieu à cristaux liquides et dispositif à cristaux liquides - Google Patents

Milieu à cristaux liquides et dispositif à cristaux liquides Download PDF

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WO2018104279A1
WO2018104279A1 PCT/EP2017/081471 EP2017081471W WO2018104279A1 WO 2018104279 A1 WO2018104279 A1 WO 2018104279A1 EP 2017081471 W EP2017081471 W EP 2017081471W WO 2018104279 A1 WO2018104279 A1 WO 2018104279A1
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phe
phel
compounds
formula
independently
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PCT/EP2017/081471
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Simon SIEMIANOWSKI
Konstantin Schneider
Peter Best
Matthias Bremer
Jana JEHN
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Merck Patent Gmbh
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Priority to DE112017006197.0T priority Critical patent/DE112017006197T5/de
Publication of WO2018104279A1 publication Critical patent/WO2018104279A1/fr

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    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0258—Flexoelectric
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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)
    • C09K2019/3009—Cy-Ph
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    • 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
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    • 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
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C09K2019/3063—Cy-Ph-C≡C-Ph
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • C09K2019/3075—Cy-COO-Ph

Definitions

  • the invention relates to a compound of formula I, R 11 -MG 11 -X 11 -Sp 11 -X 12 -MG 12 -R 12 I wherein R 11 , R 22 , MG 11 , MG 12 , Sp 11 , X 11 and X 12 have one of the meanings as given herein below.
  • the invention further relates to method of production of a compound of formula I, to the use of said compounds in LC media and to LC media comprising one or more compounds of formula I.
  • the invention relates to a method of production of such LC media, to the use of such media in LC devices, in particular in flexoelectric LC devices and to a flexoelectric LC device comprising a LC medium according to the present invention.
  • Background and Prior Art The flexoelectric effect is described, for example, by Chandrasekhar, "Liquid Crystals", 2 nd edition, Cambridge University Press (1992) and P.G. deGennes et al., "The Physics of Liquid Crystals", 2 nd edition, Oxford Science Publications (1995).
  • Flexoelectric devices utilizing the flexoelectric effect for example ULH devices and liquid crystal media that are especially suitable for flexoelectric devices and are known from EP 0971016, GB 2356629 and Coles, H.J., Musgrave, B., Coles, M.J. and Willmott, J., J. Mater. Chem., 11, p.2709-2716 (2001).
  • the Uniform Lying Helix (ULH) has high potential as a fast switching liquid crystal display mode. It is capable of sub millisecond switching at 35oC and possesses an intrinsically high aperture ratio, resulting in an energy efficient display mode.
  • the materials commonly used in media suitable for the ULH mode are typically bimesogens.
  • the corresponding LC media should exhibit favourable low ⁇ 1 values while preferably at the same time exhibiting:
  • liquid crystal means a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase (nematic, smectic, etc.) or in particular as a LC phase.
  • Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.
  • the term “mesogenic group” means in this context, a group with the ability to induce liquid crystal (LC) phase behaviour.
  • the compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds.
  • the term “liquid crystal” is used hereinafter for both mesogenic and LC materials.
  • aryl and heteroaryl groups encompass groups, which can be
  • monocyclic or polycyclic i.e. they can have one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl) or contain a combination of fused and linked rings.
  • Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se. Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings and which are optionally substituted.
  • aryl and heteroaryl groups Preference is furthermore given to 5 , 6 or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N, S or O in such a way that O atoms and/or S atoms are not linked directly to one another.
  • Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl,
  • phenanthrene pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene,
  • spirobifluorene more preferably 1,4- phenylene, 4,4’-biphenylene, 1, 4- tephenylene.
  • Preferred heteroaryl groups are, for example, 5 membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2 thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4 oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6 membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine
  • heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
  • the term“(non-aromatic) alicyclic and heterocyclic groups” encompass both saturated rings, i.e. those that contain exclusively single bonds and partially unsaturated rings, i.e.
  • Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.
  • the (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane) or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydro-naphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 3 to 25 C atoms, which optionally contain fused rings and that are optionally substituted.
  • Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane,
  • tetrahydrofuran tetrahydrothiofuran
  • pyrrolidine 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran,
  • aryl-, heteroaryl-, alicyclic- and heterocyclic groups are 1,4-phenylene, 4,4’-biphenylene, 1, 4-terphenylene, 1,4-cyclohexylene, 4,4’- bicyclohexylene and 3,17- hexadecahydro-cyclopenta[a]-phenanthrene, optionally being substituted by one or more identical or different groups L.
  • Preferred substituents of the above-mentioned aryl-, heteroaryl-, alicyclic- and heterocyclic groups (L) are, for example, solubility-promoting groups, such as alkyl or alkoxy and electron-withdrawing groups, such as fluorine, nitro or nitrile.
  • substituents are, for example, halogen, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 or OC 2 F 5 .
  • halogen denotes F, Cl, Br or I.
  • alkyl also encompass polyvalent groups, for example alkylene, arylene,
  • heteroarylene etc.
  • aryl denotes an aromatic carbon group or a group derived there from.
  • heteroaryl denotes "aryl” in accordance with the above definition containing one or more heteroatoms.
  • Preferred alkyl groups are, for example, methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, s butyl, t butyl, 2 methylbutyl, n pentyl, s pentyl, cyclo- pentyl, n hexyl, cyclohexyl, 2 ethylhexyl, n heptyl, cycloheptyl, n octyl, cyclooctyl, n nonyl, n decyl, n undecyl, n dodecyl, dodecanyl, trifluoro- methyl, perfluoro-n
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxy- ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2- methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n- decoxy, n-undecoxy, n-dodecoxy.
  • Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl.
  • Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl. Oxaalkyl, i.e.
  • Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino.
  • the term“chiral” in general is used to describe an object that is non- superimposable on its mirror image. “Achiral” (non- chiral) objects are objects that are identical to their mirror image. The terms“chiral nematic” and“cholesteric” are used synonymously in this application, unless explicitly stated otherwise.
  • the term“bimesogenic compound” relates to compounds comprising two mesogenic groups in the molecule. Just like normal mesogens, they can form many mesophases, depending on their structure.
  • bimesogenic compound may induce a second nematic phase, when added to a nematic liquid crystal medium.
  • Bimesogenic compounds are also known as“dimeric liquid crystals”.
  • the term "director” is known in prior art and means the preferred orientation direction of the long molecular axes (in case of calamitic compounds) or short molecular axes (in case of discotic compounds) of the liquid-crystalline molecules. In case of uniaxial ordering of such anisotropic molecules, the director is the axis of anisotropy.
  • the term“alignment” or“orientation” relates to alignment (orientation ordering) of anisotropic units of material such as small molecules or fragments of big molecules in a common direction named“alignment direction”.
  • the liquid- crystalline director coincides with the alignment direction so that the alignment direction corresponds to the direction of the anisotropy axis of the material.
  • plane orientation/alignment for example in a layer of an liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented substantially parallel (about 180°) to the plane of the layer.
  • the term "homeotropic orientation/alignment”, for example in a layer of a liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented at an angle ⁇ ("tilt angle") between about 80° to 90° relative to the plane of the layer.
  • the terms "uniform orientation” or “uniform alignment” of an liquid- crystalline material, for example in a layer of the material mean that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of the liquid-crystalline molecules are oriented substantially in the same direction. In other words, the lines of liquid-crystalline director are parallel.
  • the wavelength of light generally referred to in this application is 550 nm, unless explicitly specified otherwise.
  • the birefringence ⁇ n herein is defined by the following equation
  • n e is the extraordinary refractive index and n o is the ordinary refractive index and the effective average refractive index n av. is given by the following equation
  • the extraordinary refractive index n e and the ordinary refractive index n o can be measured using an Abbe refractometer.
  • the term“dielectrically positive” is used for compounds or components with “dielectrically neutral” with -1.5 and“dielectrically negative” with is determined at a frequency of 1 kHz and at 20°C.
  • the dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. In case the solubility of the respective compound in the host medium is less than 10 % its concentration is reduced by a factor of 2 until the resultant medium is stable enough at least to allow the determination of its properties.
  • the concentration is kept at least at 5 %, however, in order to keep the significance of the results a high as possible.
  • the capacitance of the test mixtures are determined both in a cell with homeotropic and with homogeneous alignment.
  • the cell gap of both types of cells is approximately 20 ⁇ m.
  • the voltage applied is a
  • permittivity of the compounds is determined from the change of the respective values of a host medium upon addition of the compounds of interest.
  • the values are extrapolated to a concentration of the compounds of interest.
  • a typical host medium is ZLI-4792 or BL-087 both commercially available from Merck, Darmstadt.
  • ZLI-4792 or BL-087 both commercially available from Merck, Darmstadt.
  • the invention relates to a compound of formula I, R 11 -MG 11 -X 11 -Sp 11 -X 12 -MG 12 -R 12 I wherein R 11 and R 22 are each independently H, F, Cl, CN, NCS or a straight- chain or branched alkyl group, which may be
  • F, Cl, CN a straight-chain or branched alkyl, alkenyl or alkoxy group which may be unsubstituted, mono- or polysubstituted by halogen or CN,
  • F, CN or OCF 3 , MG 11 and MG 12 are each independently a mesogenic group
  • each independently a mesogenic group which comprises one or more aryl-, heteroaryl-, alicyclic- and heterocyclic groups, which are optionally substituted by F, Cl, CN, OCH 3 , OCF 3 , preferably each independently a mesogenic group, which comprises two or more aryl-, heteroaryl-, alicyclic- and heterocyclic groups wherein two of these rings are optionally be linked by a linking group selected from -CO-O-, -O-CO-, -CH 2 -O-, -O-CH 2 -, -CF 2 O- and/or -OCF 2 -, Sp 11 is a spacer group comprising 1, 3 or 5 to 40 C atoms, wherein one or more non-adjacent and non-terminal CH 2 groups may also be replaced by -O-, -S-, -NH-, -N(CH 3 )-, -CO-, -O-CO-, -S-CO-, -S-
  • the unit -X 11 -Sp 11 -X 12 - denotes -CF 2 O-Sp 11 -CF 2 O-, -OCF 2 - Sp 11 -OCF 2 -, -OCF 2 -Sp 11 -CF 2 O-, -CF 2 O-Sp 11 -OCF 2 -, -CF 2 O-Sp 11 -, -OCF 2 - Sp 11 -, -Sp 11 -CF 2 O-, or -Sp 11 -OCF 2 -.
  • the compounds of formula I are preferably selected from compounds wherein the groups (R 11 -MG 11 -) and
  • R 12 -MG 12 - in formula I are identical to each other.
  • Further preferred compounds of formula I are compounds selected from the group of compounds of formulae Ia and/or Ib, R 11 -MG 11 -OCF 2 -Sp 11 -CF 2 O-MG 12 -R 12 Ia R 11 -MG 11 -Sp 11 -CF 2 O-MG 12 -R 12 Ib wherein R 11 , R 22 , MG 11 , MG 12 , Sp 11 , have one of the meanings as given above under formula I.
  • Further preferred compounds of formula I are compounds selected from the group of compounds of formulae Ia-1 and/or Ib-1 R 11 -MG 11 -OCF 2 -(CH 2 ) n -CF 2 O-MG 12 -R 12 Ia-1 R 11 -MG 11 -(CH 2 ) n -CF 2 O-MG 12 -R 12 Ib-1 wherein R 11 , R 22 , MG 11 , MG 12 have one of the meanings as given above under formula I and n denotes 1, 3 or an integer from 5 to 15, more preferably an integer from 3 to 11, most preferably an odd integer (i.e.3, 5, 7, 9 or 11). If R 11 or R 12 is an alkyl or alkoxy radical, this may be straight chain or branched.
  • It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
  • R 11 or R 12 is an alkenyl group are, this may be straight-chain or branched, preferably straight-chain, with up to 15 C atoms and more preferably, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl and corresponding isomers.
  • one of R 11 or R 12 is preferably alkenyl or alkinyl, preferably alkenyl, with up to 15 C atoms and the other is preferably alkyl, alkenyl or alkinyl, most preferably alky or alkenyl with 2 to 15 C atoms or alkoxy with 1 to 15, preferably 2 to 15, C atoms.
  • compounds of formula I containing an achiral branched group R 11 and/or R 12 may occasionally be of importance, for example, due to a reduction in the tendency towards crystallisation. Branched groups of this type generally do not contain more than one chain branch.
  • R 11 and/or R 12 are selected from CN, NO 2 , halogen, OCH 3 , OCN, SCN, COR x , COOR x or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms.
  • R x is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • Halogen is preferably F or Cl.
  • R 11 and R 12 in formula I are selected of H, alkenyl, F, Cl, CN, NO 2 , OCH 3 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 ,
  • the compounds of formula Ia-1 are selected from the following compounds: R 11 -Phe-OCF 2 -(CH 2 ) n -CF 2 O-Phe-R12
  • PheL is 1,4-phenylene, which is substituted by one, two or
  • the compounds of formula Ib-1 are selected from the following compounds: R 11 -Phe-(CH 2 ) n -CF 2 O-Phe-R 12 Ib-1- I R 11 -PheL-(CH 2 ) n -CF 2 O-Phe-R 12 Ib-1- II R 11 -Phe-(CH2)n-CF2O-PheL-R 12 Ib-1- III R 11 -PheL-(CH2)n-CF2O-PheL-R 12 Ib-1- IV R 11 -Phe-(CH 2 ) n -CF 2 O-Phe-Z-Phe-R 12 Ib-1- V R 11 -PheL-(CH2)n-CF2O-Phe-Z-Phe-R 12 Ib-1- VI R 11 -Phe-(CH2)n-CF2O-Phe-Z-PheL-R 12 Ib-1- VII R 11 -Phe-(CH 2 ) n -CF 2 O-Phe-R 12
  • R 11 , R 12 , Phe, PheL, Z and n have one of the meanings as given above.
  • Further preferred compounds of formula I are compounds in which MG 11 and MG 12 are independently from one another a group of
  • groups may be replaced by N, trans-1,4-cyclo- hexylene in which, in addition, one or two non- adjacent CH2 groups may be replaced by O and/or S, 1,4-cyclohexylene, naphthalene-2,6-diyl, decahydro- naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene- 2,6-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with F, Cl, CN or alkyl, alkoxy, alkylcarbonyl or
  • alkoxycarbonyl groups wherein one or more H atoms may be substituted by F or Cl, preferably each independently in each occurrence 1,4- phenylene, wherein in addition one or more CH groups may be replaced by N or trans-1,4-cyclo- hexylene in which, in addition, one or two non- adjacent CH 2 groups may be replaced by O and/or S, it being possible for both ring groups to be
  • alkoxycarbonyl groups wherein one or more H atoms may be substituted by F or Cl
  • k is 0, 1, 2, 3 or 4, preferably 1, 2 or 3 and, most
  • Phe in these groups is 1,4-phenylene
  • PheL is a 1,4-phenylene group which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OH, NO 2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OC 2 F 5 , in particular F, Cl, CN, CH 3 , C 2 H 5 , OCH 3 , COCH 3 and OCF 3 , most preferably F, Cl, CH 3 , OCH 3 and COCH 3 and
  • PheL is 1,4-phenylene, which is substituted by one, two or three fluorine atoms, by one or two Cl atoms or by one Cl atom and one F atom and
  • the compounds of formula Ia-1 are selected from the following compounds: R 11 -Phe-Z-Phe-OCF 2 -(CH 2 ) n -CF 2 O-Phe-Z-Phe-R12
  • R 11 , R 12 , Phe, PheL, Z and n have one of the meanings as given above.
  • the compounds of formula Ib-1 are selected from the following compounds: R 11 -Phe-Z-Phe-(CH 2 ) n -CF 2 O-Phe-Z-Phe-R 12 Ib-1- 1 R 11 -Phe-Z-PheL-OCF2-(CH2)n-Phe-Z-Phe-R 12 Ib-1- 2 R 11 -PheL-Z-Phe-OCF2-(CH2)n-Phe-Z-Phe-R 12 Ib-1- 3 R 11 -Phe-Z-PheL-(CH 2 ) n -CF 2 O-Phe-Z-Phe-R 12 Ib-1- 4 R 11 -PheL-Z-Phe-(CH2)n-CF2O-Phe-Z-Phe-R 12 Ib-1- 5 R 11 -PheL-
  • R 11 , R 12 , Phe and PheL have one of the meanings as given above and n denotes 5, 7, 9 or 11.
  • Further preferred compounds of formula Ib-1 are selected from the following compounds: R 11 -Phe-Phe-(CH2)n-CF2O-Phe-Phe-R 12 Ib-1- 1 a R 11 -Phe-PheL-OCF 2 -(CH 2 ) n -Phe-Phe-R 12 Ib-1- 2 a R 11 -PheL-Phe-OCF2-(CH2)n-Phe-Phe-R 12 Ib-1- 3 a R 11 -Phe-PheL-(CH 2 ) n -CF 2 O-Phe-Phe-R 12 Ib-1- 4 a R 11 -PheL-Phe-(CH 2 ) n -CF 2 O-Phe-Phe-R 12 Ib-1- 5 a R 11 -PheL-P
  • L is preferably F, Cl, CH 3 , OCH 3 and COCH 3 .
  • R 11 , R 12 have one of the meanings as given above, preferably both R 11 and R 12 are identical and denote both CN or F, likewise preferably R 11 and R 12 are different and at least one of them denote CN or F and n preferably denotes 7 or 9.
  • Further preferred compounds are of formula Ib-1, for example, are preferably selected from the following compounds:
  • R 11 , R 12 have one of the meanings as given above, preferably both R 11 and R 12 are identical and denote both CN or F, likewise preferably R 11 and R 12 are different and at least one of them denote CN or F and n preferably denotes 7 or 9.
  • the compounds of formula I can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the compounds of formula Ia-1 can be s nthesized accordin to or in analo to the followin s nthesis scheme:
  • the invention relates also to a method of production of compounds of formula Ia-1 com risin at least the step of reacting a compound of
  • the compounds of formula Ib-1 can be synthesized according to or in analogy to the following synthesis scheme:
  • the compounds of formula I and its subformulae can be beneficially utilized in LC media to improve the properties of such media, in particular in LC media for flexoelectric applications.
  • one of the main advantages of using compounds of formula I in LC media for flexoelectric applications is improving the switching speed in the ULH (uniform lying helix) geometry, particularly at
  • the invention also relates to the use of compounds of formula I in LC media and to a LC media comprising one or more compounds of formula I, as such.
  • the LC media in accordance with the present invention comprise one or more compounds of formula II, R 21 -A 21 -A 22 -(CH2)a-A 23 -A 24 -R 22 II wherein
  • R 21 and R 22 denote independently H, F, Cl, CN, NCS or a straight- chain or branched alkyl group, which may be
  • F, Cl, CN a straight-chain or branched alkyl or alkoxy group which may be unsubstituted, mono- or polysubstituted by halogen or CN,
  • a 21 to A 24 denote independently in each occurrence a aryl-,
  • 1,4-phenylene wherein in addition one or more CH groups may be replaced by N, trans-1,4- cyclo-hexylene in which, in addition, one or two non- adjacent CH 2 groups may be replaced by O and/or S, 1,4-cyclohexenylene, 1,4-bicyclo-(2,2,2)-octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydro- naphthalene-2,6-diyl, 1,2,3,4-tetrahydro-naphthalene- 2,6-diyl, cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6- diyl or dispiro[3.1.3.1] decane-2,8-diyl, it being possible for all these groups to be unsubstituted, mono-, di-, tri- or tetrasubstituted with F, Cl,
  • Preferred compounds of formula II are selected from compounds in which the groups (-A 21 -A 22 -) and (-A 23 -A 24 -) are each and independently selected from the following groups
  • Phe in these groups is 1,4-phenylene
  • PheL is a 1,4-phenylene group which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OH, NO 2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 ,
  • Cyc is 1,4-cyclohexylene.
  • compounds of formula II wherein the groups (R 21 -A 21 -A 22 -) and (-A 23 -A 24 -R 22 ) in formula II are identical or mirror images.
  • compounds of formula II wherein (R 21 -A 21 -A 22 -) and (-A 23 -A 24 -R 22 ) in formula II are different.
  • Preferred compounds of formula II are indicated below:
  • n denotes an integer from 1 to 15, preferably an odd (i.e.
  • the compounds of formula II can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. A preferred method of preparation can be taken from WO 2013/004333 A1.
  • the utilization of compounds of formula II beside compounds of formula I is especially useful in order to further improve the switching speeds whilst maintaining a good phase range and a favorable value for e/K.
  • the LC media in accordance with the present invention comprise one or more compounds of formula III, R 31 -A 31 -A 32 -(A 33 ) b -Z 31 -(CH 2 ) c -Z 32 -A 34 -A 35 -A 36 -R 32 III wherein
  • R 31 and R 32 have each and independently from another one of the meanings as given for R 21 and R 22 under formula II, A 31 to A 36 have each and independently from another one of the meanings as given for A 21 to A 24 under formula II, Z 31 and Z 32 are each independently in each occurrence,
  • -CH CH-COO-
  • b denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula III are selected from compounds in which c denotes 0 and the group (-A 31 -A 32 -) is selected from the groups MG-1 to MG-8 as given above. Further preferred compounds of formula III are selected from compounds in which c denotes 1 and the groups (-A 24 -A 25 -A 26 -) and (-A 21 -A 22 -A 23 -) are each and independently selected from the following groups -Cyc-Cyc-Cyc- MG-9
  • the compounds of formula III can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the utilization of compounds of formula III beside compounds of formula I is especially useful in order to achieve high stabilities, favourable high clearing points and broad phase ranges, as well as, low appearances of the nematic twist-bend phase.
  • the LC medium in accordance with the present invention comprises one or more compounds of formula IV, R 41 -A 41 -A 42 -Z 41 -(CH 2 ) d -Z 42 -A 43 -A 44 -R 42 IV wherein
  • R 41 and R 42 have each and independently one of the meanings as given above for R 21 under formula II
  • a 41 to A 44 have each and independently one of the meanings as given above for A 21 under formula II
  • Z 41 and Z 42 are each independently in each occurrence
  • -CH CH-COO-
  • d denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula IV are selected from compounds in which the groups (-A 41 -A 42 -) and (-A 43 -A 44 -) are each and independently selected from the groups of MG-1 to MG-8 as given above.
  • Especially preferred compounds of formula IV are selected from the group of compounds of the following formulae: - symmetrical ones (IVa and IVb):
  • the LC medium in accordance with the present invention additionally comprises one or more compounds of formula V, R 51 -A 51 -Z 51 -(CH 2 ) e -Z 52 -A 52 -(A 53 ) f -R 52 V wherein
  • R 51 and R 52 have each and independently one of the meanings as given above for R 21 under formula II
  • a 51 to A 53 have each and independently one of the meanings as given above for A 21 under formula II
  • Z 51 and Z 52 are each independently in each occurrence
  • -CH CH-COO-
  • e denotes an integer from 1 to 15, preferably an odd (i.e.
  • a 51 is selected from the following group of formulae Va’ to Vh’ and the mirror images of formulae Vb’, Ve’ and Vf’
  • R 51 and R 52 in formula V are selected of H, F, Cl, CN, NO2, OCH 3 , COCH 3 , COC2H5, COOCH 3 , COOC2H5, CF3, C2F5, OCF3, OCHF2 and OC 2 F 5 , in particular of H, F, Cl, CN, OCH 3 and OCF 3 , especially of H, F, CN and OCF 3.
  • Preferred compounds of formula V are selected from the group of compounds of formulae VA to VE, preferably of formulae VA and/or VD, most preferably of formula VD,
  • LG 51 is Z 51 -(CH2)z-Z 52 , (F) 0 denotes H and
  • (F) 1 denotes F. and the other parameters have the respective meanings given above including the preferred meanings.
  • Z 51 -(CH 2 ) z -Z 52 denotes -O-CO-(CH 2 ) n -CO-O-, -O-(CH 2 ) n -O- or -(CH 2 ) n -, more preferably -O-CO-(CH 2 ) n -CO-O-, wherein n denotes 3, 5, 7 or 9,
  • Particularly preferred compounds of formula VA are selected from the group of compounds of formulae VA-1 to VA-3
  • Particularly preferred compounds of formula VB are selected from the group of compounds of formulae VB-1 to VB-3
  • Particularly preferred compounds of formula VC are selected from the group of compounds of formulae VC-1 and VC-2
  • the LC medium in accordance with the present invention additionally comprises one or more compounds of formula VI, R 61 -A 61 -A 62 -(CH2)g-Z 61 -A 63 -A 64 -(A 65 )h-R 62 VI wherein R 61 and R 62 have each and independently one of the meanings as given above for R 21 under formula II, A 61 to A 64 have each and independently one of the meanings as given above for A 21 under formula II, Z 61 denotes -O-, -COO-, -OCO-, -O-CO-O-, -OCH 2 -, -CH 2 O,
  • h denotes 0 or 1
  • g denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula VI are selected from compounds in which the groups (-A 61 -A 62 -) and (-A 63 -A 64 -) are each and independently selected from the groups of MG-1 to MG-8 as given above. Further preferred are compounds of formula VI wherein h denotes 0 and the groups (-A 61 -A 62 -) and (-A 63 -A 64 -(A 65 ) h ) in formula VI are not identical or not mirror images or wherein h denotes 1 In particular preferred compounds of formula VI are selected from the group of compounds of the following formulae,
  • the compounds of formula VI can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the compounds of formula VI are synthesized according to or in analogy to methods which are disclosed for example in WO 2014/005672 A1.
  • the utilization of compounds of formula VI beside compounds of formula I is especially useful in order to achieve high clearing points and also favorable values for e/K.
  • the LC medium in accordance with the present invention additionally comprises one, two, three or more compounds of formula VII, R 71 -A 71 -Z 71 -A 72 -(Z 72 -A 73 ) i -(CH 2 ) j -(A 74 -Z 73 -) k -A 75 -Z 74 -A 76 -R 72 VII wherein
  • R 71 and R 72 have each and independently one of the meanings as given above for R 21 under formula II
  • a 71 to A 76 have each and independently one of the meanings as given above for A 21 under formula II
  • Z 71 to Z 74 each and independently denotes -COO-, -OCO-,
  • j denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula VII are selected from compounds in which at least one of the groups -A 71 -Z 71 -A 72 -(Z 72 -A 73 ) i -, -(A 74 -Z 73 -) k -A 75 -Z 74 -A 76 - are is selected from the groups of MGa to MGn (the two reference Nos.“MG i” and“MG l” being deliberately omitted to avoid any confusion) and their mirror images
  • L is in each occurrence independently of each other preferably F, Cl, CN or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, CH 3 , C2H5, OCH 3 , OC2H5, COCH 3 , COC2H5, COOCH 3 , COOC2H5, CF3, OCF3, OCHF2, OC2F5, in particular F, Cl, CN, CH 3 , C2H5, OCH 3 , COCH 3 and OCF3, most
  • F, Cl, CH 3 , OCH 3 and COCH 3 and r is in each occurrence independently of each other 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
  • R 71 and R 72 each and independently denote F or CN.
  • the compounds of formula VII can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the compounds of formula VII are synthesized according to or in analogy to methods which are disclosed for example in WO 2013/174478 A1.
  • the medium in accordance with the present invention optionally comprises one or more chiral dopants, especially when utilized in a flexoelectric device.
  • the chiral compounds induce a chiral nematic texture with a pitch (P 0 ), which is in a first approximation inversely proportional to the
  • HTP helical twisting power
  • c concentration of the chiral compound.
  • a uniform lying helix texture is realized using a chiral nematic liquid crystal with a short pitch, typically in the range from 0.2 ⁇ m to 1 ⁇ m, preferably of 1.0 ⁇ m or less, in particular of 0.5 ⁇ m or less, which is unidirectional aligned with its helical axis parallel to the substrates, e. g. glass plates, of a liquid crystal cell.
  • the helical axis of the chiral nematic liquid crystal is equivalent to the optical axis of a birefringent plate.
  • Preferred are chiral dopants with a high helical twisting power (HTP), in particular those disclosed in WO 98/00428.
  • used chiral dopants are e.g. the commercially available
  • the chiral dopants are preferably selected from formula VIII,
  • the above-mentioned chiral dopants R/S-5011 and the compounds of formula VIII and IX exhibit a very high helical twisting power (HTP) and are therefore particularly useful for the purpose of the present invention.
  • the liquid crystalline medium preferably comprises preferably 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral dopants, preferably selected from the above formula VIII, and/or formula IX and/or R-5011 or S-5011, very preferably, the chiral compound is R-5011, S- 5011.
  • the amount of chiral compounds in the liquid crystalline medium is preferably from 0.1 to 15 %, in particular from 0.5 to 10 %, very preferably 1 to 5 % by weight of the total mixture.
  • the LC medium comprises one or more nematic LC compounds selected from compounds indicated below:
  • liquid crystal media may contain further additives like for example stabilizers, inhibitors, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles in usual concentrations.
  • further additives like for example stabilizers, inhibitors, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles in usual concentrations.
  • the total concentration of these further constituents is in the range of 0.1 % to 10 %, preferably 0.1 % to 6 %, based on the total mixture.
  • the concentrations of the individual compounds used each are preferably in the range of 0.1 % to 3 %.
  • the concentration of these and of similar additives is not taken into consideration for the values and ranges of the concentrations of the liquid crystal components and compounds of the liquid crystal media in this application. This also holds for the concentration of the dichroic dyes used in the mixtures, which are not counted when the concentrations of the compounds respectively the components of the host medium are specified.
  • the concentration of the respective additives is always given relative to the final doped mixture. In general, the total concentration of all compounds in the media according to this application is 100 %.
  • the liquid crystal media according to the present invention consists of several compounds, preferably of 2 to 40, more preferably of 3 to 30 and most preferably of 4 to 25 compounds.
  • the media in accordance with the present invention exhibit high values of the elastic constant k 11 and a high flexoelectric coefficient e.
  • the liquid crystal media preferably exhibit a k 11 ⁇ 100 pN, preferably ⁇ 20 pN.
  • the liquid crystal media preferably exhibit a k 33 ⁇ 100 pN, preferably ⁇ 15 pN.
  • the liquid crystal media preferably exhibit a flexoelectric coefficient ⁇ e 11 ⁇ 0.2 pC/m, preferably ⁇ 1 pC/m.
  • the liquid crystal media preferably exhibit a flexoelectric coefficient ⁇ e 33 ⁇ 0.2 pC/m, preferably ⁇ 2 pC/m.
  • the liquid crystal media preferably exhibit a flexo-elastic ratio ( ⁇ / K) in the range from 1 to 10 V -1 , preferably in the range from 1 to 7 V -1 , more preferably in the range from 1 to 5 V -1 .
  • the media in accordance with the present invention exhibit high clearing points up to 60°C and higher, preferably up 65°C and higher and more preferably up to 70°C and higher.
  • the media in accordance with the present invention exhibit broad nematic phases of 30°C and more, preferably 35°C and more or even 40°C or more.
  • the media in accordance with the present invention exhibit N TB phases below 20°C or less, preferably below 15°C or less and more preferably below 0°C or less.
  • the media in accordance with the present invention exhibit high stabilities against crystallization at room temperature of more than 100 h, preferably more than 250 h or more than 1000 h.
  • the media in accordance with the present invention exhibit high stabilities against crystallization even at low temperatures (LTS).
  • the media do not crystallize even at temperatures down to 0°C, preferably down to -10°C, more preferably down to -20°C.
  • the LC medium comprises: ⁇ 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds of formula I, preferably selected from formulae Ia-1-2a, Ia-1-5a, Ib-1-4a and/or Ib-1-9a. The amount of
  • compounds of formula I in the liquid crystalline medium as a whole is preferably in the range from 5 to 50 %, in particular in the range from 6 to 30 %, especially in the range from 7 to 20 % by weight of the total mixture, and ⁇ optionally 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds of formula II, preferably selected from compounds compounds of formula II wherein (-A 21 -A 22 -) and (-A 23 -A 24 -) in formula II are identical or mirror images, more preferably of compounds of formulae II’a-5 and/or II’a-6.
  • the amount of compounds of formula II in the liquid crystalline medium is preferably in the range from 0 to 30 %, more preferably in the range from 1 to 20 %, even more preferably in the range from 2 to 10 % by weight of the total mixture, and/or ⁇ optionally 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds of formula III, preferably selected from symmetrical compounds of the above formulae IIIc-2 and/or IIIc-3.
  • the amount of compounds of formula III in the liquid crystalline medium, if present, is preferably in the range from 1 to 50 %, more preferably in the range from 5 to 30 %, even more preferably in the range from 10 to 20 % by weight of the total mixture, and/or
  • ⁇ optionally, 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds of formula IV, preferably selected from the symmetrical ones IVb and/or non-symmetrical ones IVc, more preferably from formulae IVb-5, IVc-2, IVc-3, IVc-12 and or IVc-15.
  • the amount of compounds of formula IV in the liquid crystalline medium, if present, is preferably in the range from 1 to 98 %, more preferably in the range from 20 to 80 %, even more preferably in the range from 30 to 60 % by weight of the total mixture, and/or ⁇ optionally, 1 to 6, in particular 2 to 5, very preferably 3 or 4
  • compounds of formula V preferably selected from the above formulae VA-1, VD-2 and/or VD-3.
  • the amount of compounds of formula V in the liquid crystalline medium is preferably in the range from 1 to 70 %, more preferably in the range from 10 to 60 %, even more preferably in the range from 20 to 50 % by weight of the total mixture, and/or ⁇ optionally 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds from the above formulae VI, preferably form compounds of formula VI-4, VI-5, VI-7 and/or VI-9.
  • the amount of compounds of formula VI in the liquid crystalline medium is preferably from 1 to 40 %, in particular from 5 to 25 %, very preferably 10 to 15 % by weight of the total mixture, and/or ⁇ optionally 1 to 10, preferably 1 to 5, more preferably 1 or 3, most preferably 1 or 2 compounds from the above formulae VII, preferably form compounds of formula VII-4, VII-5 and/or VII-8.
  • the amount of compounds of formula VII in the liquid crystalline medium, if present, is preferably from 1 to 35 %, in particular from 5 to 25 %, very preferably 10 to 15 % by weight of the total mixture,
  • the chiral compound is R-5011 or S-5011.
  • the amount of chiral compounds in the liquid crystalline medium is preferably from 1 to 15 %, in particular from 0.5 to 10 %, very preferably 0.1 to 5 % by weight of the total mixture, and/or ⁇ optionally up to 25, in particular up to 20, very preferably up to 15, different compounds selected from compounds of formula X.
  • the amount of compounds of formula X in the liquid crystalline medium as a whole is preferably from 1 to 50 %, in particular from 5 to 30 %, very preferably 10 to 25 % by weight of the total mixture, and/or ⁇ optionally further additives, such as for example stabilizers, antioxidants, etc. in usual concentrations.
  • the total concentration of these further constituents, if present, is in the range of 0.1 to 10 %, preferably 0.1 to 6 %, based on the total mixture.
  • the concentrations of the individual compounds used each are preferably in the range of 0.1 to 3 %.
  • the LC medium of the present invention consists only of compounds selected from formula I to X, very preferably the LC medium consists only of compounds selected from formula I to IX.
  • the compounds forming the LC medium in accordance with the present invention are mixed in conventional way. As a rule, the required amount of the compound used in the smaller amount is dissolved in the compound used in the greater amount. In case the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the process of dissolution. It is, however, also possible to prepare the media by other conventional ways, e.g. using so-called pre-mixtures, which can be e.g.
  • the invention also relates to a process for the production of an LC medium as described above and below.
  • the invention relates to a process for the production of an LC medium comprising the steps of mixing one or more compounds of formula I, with at least one compound selected from compounds of formulae II to X.
  • liquid crystalline media in accordance with the present invention can be used in electro optic devices, for example liquid crystal devices, such as STN, TN, AMD-TN, temperature compensation, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays, in active and passive optical elements like polarizers, compensators, reflectors, alignment layers, colour filters or holographic elements, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, diagnostics, liquid crystal pigments, for decorative and security applications, in nonlinear optics, optical information storage or as chiral dopants.
  • a LC medium comprising at least one compound of formula I in electro optic devices.
  • a flexoelectric display according to a preferred embodiment of the present invention comprises two plane parallel substrates, preferably glass plates covered with a transparent conductive layer such as indium tin oxide (ITO) on their inner surfaces, optionally alignment layers and a medium comprising one or more compounds of formula I and a chiral dopant as described above and below.
  • ITO indium tin oxide
  • the optical axis is rotated in the plane of the cell, similar as the director of a ferroelectric liquid crystal rotate as in a surface stabilized ferroelectric liquid crystal display.
  • the field induces a splay bend structure in the director, which is accommodated by a tilt in the optical axis.
  • the angle of the rotation of the axis is in first approximation directly and linearly proportional to the strength of the electrical field. The optical effect is best seen when the liquid crystal cell is placed between crossed polarizers with the optical axis in the unpowered state at an angle of 22.5° to the absorption axis of one of the polarizers.
  • This angle of 22.5° is also the ideal angle of rotation of the electric field, as thus, by the inversion the electrical field, the optical axis is rotated by 45° and by appropriate selection of the relative orientations of the preferred direction of the axis of the helix, the absorption axis of the polarizer and the direction of the electric field, the optical axis can be switched from parallel to one polarizer to the centre angle between both polarizers. The optimum contrast is then achieved when the total angle of the switching of the optical axis is 45°.
  • the arrangement can be used as a switchable quarter wave plate, provided the optical retardation, i. e. the product of the effective birefringence of the liquid crystal and the cell gap, is selected to be the quarter of the wavelength.
  • the wavelength referred to is 550 nm, the wavelength for which the sensitivity of the human eye is highest, unless explicitly stated otherwise.
  • the angle of rotation of the optical axis ( ⁇ ) is given in good
  • P 0 is the undisturbed pitch of the cholesteric liquid crystal
  • E is the electrical field strength
  • the flexoelectric effect is characterized by fast response times (T on+ T off at 35°C) typically ranging from 1 ms to 10 ms, preferably ⁇ 5ms and even more preferably ⁇ 3ms. It further features excellent grey scale capability.
  • T on+ T off at 35°C fast response times
  • E c critical field
  • inventive media in accordance with the present invention can be aligned in their cholesteric phase into different states of orientation by methods that are known to the expert, such as surface treatment or electric fields. For example, they can be aligned into the planar
  • mesogenic material in a display cell or on a substrate means that the mesogenic groups in the liquid crystal or mesogenic material are oriented substantially parallel to the plane of the cell or substrate, respectively.
  • the term“homeotropic alignment” or orientation of a liquid crystal or mesogenic material in a display cell or on a substrate means that the mesogenic groups in the liquid crystal or mesogenic material are oriented substantially perpendicular to the plane of the cell or substrate, respectively.
  • This state is also known as Grandjean state and the texture of the sample, which is observable e.g. in a polarization microscope, as Grandjean texture.
  • Planar alignment can be achieved e.g. by surface treatment of the cell walls, for example by rubbing and/or coating with an alignment layer such as polyimide.
  • a Grandjean state with a high quality of alignment and only few defects can further be achieved by heating the sample to the isotropic phase, subsequently cooling to the chiral nematic phase at a temperature close to the chiral nematic-isotropic phase transition and flow alignment by lightly pressing the cell.
  • the sample shows selective reflection of incident light, with the central wavelength of reflection depending on the helical pitch and the mean refractive index of the material.
  • the sample When an electric field is applied to the electrodes, for example with a frequency from 10 Hz to 1 kHz and an amplitude of up to 12 V rms / ⁇ m, the sample is being switched into a homeotropic state where the helix is unwound and the molecules are oriented parallel to the field, i.e. normal to the plane of the electrodes.
  • the sample In the homeotropic state, the sample is transmissive when viewed in normal daylight and appears black when being put between crossed polarizers.
  • the sample Upon reduction or removal of the electric field in the homeotropic state, the sample adopts a focal conic texture, where the molecules exhibit a helically twisted structure with the helical axis being oriented
  • a focal conic state can also be achieved by applying only a weak electric field to a sample in its planar state. In the focal conic state the sample is scattering when viewed in normal daylight and appears bright between crossed polarizers.
  • a sample of a medium in accordance with the present invention in different states of orientation exhibits different transmission of light.
  • the respective state of orientation, as well as its quality of alignment can be controlled by measuring the light transmission of the sample depending on the strength of the applied electric field. Thereby it is also possible to determine the electric field strength required to
  • the above-described focal conic state consists of many disordered
  • the LC media may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
  • T N,I clearing point
  • K crystalline
  • N nematic
  • N TB second nematic
  • S or Sm smectic
  • Ch cholesteric
  • I isotropic
  • Tg glass transition.
  • the numbers between the symbols indicate the phase transition temperatures in°C.
  • n, m and l denote an integer between 1 and 12.
  • Table A lists the symbols used for the ring elements, table B those for the linking groups and table C those for the symbols for the left hand and the right hand end groups of the molecules.
  • 2-Trimethylsilyl-1,3-dithiane 3 (52.8 g, 269 mmol) is dissolved in 190 ml tetrahydrofuran and cooled to -70°C.
  • Butyllithium (107.5 ml of a 2.5 M solution in hexanes, 269 mmol) is slowly added. After the addition is complete, the mixture is warmed to room temperature for 2 hours and then cooled again to -70°C.20 g of dialdehyde 2 in 80 ml tetrahydrofuran is slowly added at that temperature. After the addition is complete, the mixture is warmed to room temperature and worked up as usual. The residue is distilled under reduced pressure and gave 22.9 g of product 4 with a boiling point of 67-74°C at a pressure of 0.1 mbar.
  • Bis(dithiane) 4 (15.4 mmol) is suspended in 200 ml dichloromethane and cooled to -30°C.
  • Trifluoromethane sulfonic acid (2.98 ml, 34 mmol) is added dropwise while stirring and the mixture is warmed to room temperature for 30 min. It is then cooled again to -70°C, the two phenols 5 (3.1 g, 15.4 mmol) and 6 (3.3 g, 15.4 mmol) together with triethylamine (7.7 ml, 56 mmol) and 70 ml dichloromethane are added dropwise to the mixture.
  • Triethylamine trishydrofluoride (24.9 ml, 154 mmol) is added and subsequently within a period of 60 min bromine (7.9 ml, 154 mmol) in 65 ml dichloromethane. After stirring for one hour at -70°C, the mixture is allowed to warm to -30°C and morpholine (13.5 ml, 154 mmol) is added below -20°C. After warming to 0°C, the mixture is poured onto 200 ml ice water and 19.7 ml aqueous KOH (47 %). The pH is adjusted to approximately 9.0 with additional small amounts of the KOH solution. The organic phase is separated and worked up as usual. After chromatography, of compound 7 (F-PGI-QI-9-Q-PP-N) is isolated.
  • Dithiane 4 (18.3 mmol) is suspended in 230 ml dichloromethane, cooled to -30°C and trifluoromethane sulfonic acid (3.5 ml, 40.3 mmol) is added dropwise. The mixture is allowed to warm to room temperature, stirred for 30 min and cooled again to -70°C. A mixture of 4-bromophenol 9 (7 g, 40.3 mmol) and triethylamine (9.1 ml, 65.9 mmol) dissolved in 100 ml dichloromethane is added. After the addition is complete, the mixture is stirred at -70°C for one hour.
  • Triethylamine trishydrofluoride (29.5 ml, 183 mmol) is added and after one hour bromine (9.4 ml, 183 mmol) in 50 ml dichloromethane. Stirring is continued for one hour and the mixture is warmed to -30°C. Morpholine (15.9 ml, 183 mmol) is added below -20°C. Workup is carried out as described above for compound 7 and gave compound 10. Step 2.2
  • 2-Trimethylsilyl-1,3-dithiane (6.7 ml, 35.4 mmol) is dissolved in 40 ml tetrahydrofuran and cooled to -70°C.
  • Butyllithium in hexanes (23.4 ml of a 15 % solution, 37.2 mmol) is added dropwise and the mixture is warmed to -20°C and stirred for 4 hours. It is then cooled again to -70°C and 19 (37.2 mmol) dissolved in 40 ml dichloromethane is added dropwise. After warming to room temperature followed by the usual workup, 20 is obtained as a yellow oil.
  • Triethylamine trishydrofluoride (13.9 ml, 86 mmol) is added dropwise and after 1 hour 4.4 ml (86 mmol) bromine in 100 ml dichloromethane. The mixture is stirred for 1 hour at -70°C. After warming to -20°C, morpholine (7.5 ml, 86 mmol) is added and stirring is continued for 1h at 0°C. After the usual workup 21 (N-PP-QI-5-GP-N) is obtained as a white powder.
  • C H 3 B Test cells and methods Typically a 3 ⁇ m thick cell, having an anti-parallel rubbed PI alignment layer, is filled on a hotplate at a temperature at which the flexoelectric mixture in the isotropic phase. After the cell has been filled, the phase transitions including clearing point and the crystallization behavior are determined using Differential Scanning Calorimetry (DSC) and verified by optical inspection. For optical phase transition measurements, a Mettler FP90 hot-stage controller connected to a FP82 hot-stage is used to control the temperature of the cell. The temperature is increased from ambient temperature at a rate of 5 degrees C per minute, until the onset of the isotropic phase is observed.
  • DSC Differential Scanning Calorimetry
  • the texture change is observed through crossed polarizers using an Olympus BX51 microscope and the respective temperature noted. Wires are then attached to the ITO electrodes of the cell using indium metal.
  • the cell is secured in a Linkam THMS600 hot-stage connected to a Linkam TMS93 hot-stage controller.
  • the hot-stage is secured to a rotation stage in an Olympus BX51 microscope.
  • the cell is heated until the liquid crystal is completely isotropic.
  • the cell is then cooled under an applied electric field until the sample is
  • the driving waveform is supplied by a Tektronix AFG3021B arbitrary function generator, which is sent through a
  • the applied field is monitored using a HP 34401A multimeter.
  • the tilt angle is measured using the aforementioned microscope and oscilloscope.
  • the undisturbed cholesteric pitch, P 0 is measured using an Ocean Optics USB4000 spectrometer attached to a computer.
  • the selective reflection band is obtained and the pitch determined from the spectral data.
  • the media shown in the following examples are well suitable for use in ULH-displays.
  • the material containing BM-4 in accordance with the present has a significant advantage with respect to the switching speed when compared to material comprising a compound of the prior art (CM*-2).
  • the TNI is also similar, something that is surprising when considering conventional liquid crystal materials with differing switching speeds when normally a strong inverse relationship between TNI and switching speeds is observed (i.e. higher TNI leads to reduced switching speeds).
  • the material containing BM-6 in accordance with the present has a significant advantage with respect to the switching speed when compared to material comprising a compound of the prior art (CM*-3).
  • the TNI is also similar, something that is surprising when considering conventional liquid crystal materials with differing switching speeds when normally a strong inverse relationship between TNI and switching speeds is observed (i.e. higher TNI leads to reduced switching speeds).

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

L'invention concerne un composé de formule (I), R11-MG11-X11-Sp11-X12-MG12-R12 dans laquelle R11, R22, MG11, MG12, Sp11, X11 et X12 ont l'une des significations données ci-dessous. L'invention concerne en outre un procédé de production d'un composé de formule I, l'utilisation desdits composés dans des milieux à CL et les milieux à CL comprenant un ou plusieurs composés de formule I. En outre, l'invention concerne un procédé de production de tels milieux à CL, l'utilisation de tels milieux dans des dispositifs à CL, en particulier dans des dispositifs à CL flexoélectriques et un dispositif à CL flexoélectrique comprenant un milieu à CL selon la présente invention. L'invention concerne un composé de formule (I), R 11 -MG 11 -X 11 -Sp 11 -X 12 -MG 12 -R 12 I dans laquelle R 11, R 22, MG 11, MG 12, Sp 11, X 11 et X 12 ont l'une des significations données ci-dessous. L'invention concerne en outre un procédé de production d'un composé de formule (I), l'utilisation desdits composés dans des milieux à CL et les milieux à CL comprenant un ou plusieurs composés de formule (I). En outre, l'invention concerne un procédé de production de tels milieux à CL et l'utilisation de tels milieux dans des dispositifs à CL, en particulier dans des dispositifs à CL flexoélectriques et un dispositif à CL flexoélectrique comprenant un milieu à CL selon la présente invention.
PCT/EP2017/081471 2016-12-08 2017-12-05 Milieu à cristaux liquides et dispositif à cristaux liquides WO2018104279A1 (fr)

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EP0971016A1 (fr) 1998-07-08 2000-01-12 MERCK PATENT GmbH Estradiols mésogènes
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EP0971016A1 (fr) 1998-07-08 2000-01-12 MERCK PATENT GmbH Estradiols mésogènes
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Publication number Priority date Publication date Assignee Title
CN112442380A (zh) * 2019-09-04 2021-03-05 江苏集萃智能液晶科技有限公司 液晶组合物及其调光器件
US11932799B2 (en) 2019-09-04 2024-03-19 Smart Liquid Crystal Technologies Co., Ltd. Liquid crystal mixture and light modulating device

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