WO2023036746A1 - Milieu cristallin liquide - Google Patents

Milieu cristallin liquide Download PDF

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WO2023036746A1
WO2023036746A1 PCT/EP2022/074661 EP2022074661W WO2023036746A1 WO 2023036746 A1 WO2023036746 A1 WO 2023036746A1 EP 2022074661 W EP2022074661 W EP 2022074661W WO 2023036746 A1 WO2023036746 A1 WO 2023036746A1
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atoms
compounds
denotes
another
alkyl
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Min Tzu CHUANG
Randy Lin
Jer-Lin Chen
Kuang-Ting Chou
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Merck Patent Gmbh
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    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • 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
    • C09K2019/0448—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 end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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)
    • C09K2019/3004—Cy-Cy
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • 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)
    • C09K2019/301—Cy-Cy-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09K2019/3071—Cy-Cy-COO-Cy

Definitions

  • the present invention relates to chiral liquid-crystal (LC) media and to the use of the LC media for optical, electro-optical and electronic purposes, in particular in LC displays, preferably in LC displays for outdoor use.
  • LC liquid-crystal
  • LCD liquid-crystal display
  • TN twisted nematic
  • TN LCDs have the disadvantage of a strong viewing-angle dependence of the contrast.
  • VA vertical aligned
  • the LC cell of a VA display contains a layer of an LC medium between two transparent electrodes, where the LC medium usually has a negative dielectric anisotropy.
  • the molecules of the LC layer are aligned perpendicular to the electrode surfaces (homeotropically) or have a tilted homeotropic alignment.
  • an electrical voltage to the two electrodes, a realignment of the LC molecules parallel to the electrode surfaces takes place.
  • IPS in-plane switching
  • IPS in-plane switching
  • the two electrodes are arranged on only one of the two substrates and preferably have intermeshed, comb-shaped structures.
  • an electric field which has a significant component parallel to the LC layer is thereby generated between them. This causes realignment of the LC molecules in the layer plane.
  • FFS far-field switching
  • FFS displays usually contain an LC medium with positive dielectric anisotropy, and an alignment layer, usually of polyimide, which provides planar alignment to the molecules of the LC medium.
  • FFS displays can be operated as active-matrix or passive-matrix displays.
  • active-matrix displays individual pixels are usually addressed by integrated, non-linear active elements, such as, for example, transistors (for example thin-film transistors (“TFTs”)), while in the case of passive-matrix displays, individual pixels are usually addressed by the multiplex method, as known from the prior art.
  • TFTs thin-film transistors
  • FFS displays have been disclosed (see S.H. Lee et al., Appl. Phys. Lett. 73(20), 1998, 2882-2883 and S.H. Lee et al., Liquid Crystals 39(9), 2012, 1141- 1148), which have similar electrode design and layer thickness as FFS displays but comprise a layer of an LC medium with negative dielectric anisotropy instead of an LC medium with positive dielectric anisotropy.
  • the LC medium with negative dielectric anisotropy shows a more favourable director orientation that has less tilt and more twist orientation compared to the LC medium with positive dielectric anisotropy, as a result of which these displays have a higher transmission.
  • the displays further comprise an alignment layer, preferably of polyimide provided on at least one of the substrates that is in contact with the LC medium and induces planar alignment of the LC molecules of the LC medium.
  • an alignment layer preferably of polyimide provided on at least one of the substrates that is in contact with the LC medium and induces planar alignment of the LC molecules of the LC medium.
  • These displays are also known as "Ultra Brightness FFS (UB-FFS)" mode displays. These displays require an LC medium with high reliability.
  • VA displays of the more recent type uniform alignment of the LC molecules is restricted to a plurality of relatively small domains within the LC cell. Disclinations may exist between these domains, also known as tilt domains.
  • VA displays having tilt domains have, compared with conventional VA displays, a greater viewing-angle independence of the contrast and the grey shades.
  • displays of this type are simpler to produce since additional treatment of the electrode surface for uniform alignment of the molecules in the switched-on state, such as, for example, by rubbing, is no longer necessary. Instead, the preferential direction of the tilt or pretilt angle is controlled by a special design of the electrodes.
  • MVA multidomain vertical alignment
  • the slitted electrodes generate an inhomogeneous electric field in the LC cell on application of a voltage, meaning that controlled switching is still achieved.
  • the separations between the slits and protrusions can be increased, but this in turn results in a lengthening of the response times.
  • PVA patterned VA
  • protrusions are rendered completely superfluous in that both electrodes are structured by means of slits on the opposite sides, which results in increased contrast and improved transparency to light, but is technologically difficult and makes the display more sensitive to mechanical influences (“tapping”, etc.).
  • a shortening of the response times and an improvement in the contrast and luminance (transmission) of the display are demanded.
  • PS polymer sustained
  • PSA polymer sustained alignment
  • a small amount for example 0.3% by weight, typically ⁇ 1% by weight
  • the polymerisation is carried out at a temperature where the LC medium exhibits a liquid crystal phase, usually at room temperature.
  • RMs reactive mesogens
  • PS-VA, PS-OCB, PS-IPS, PS-FFS, PS-UB-FFS and PS-TN displays are known.
  • the polymerisation of the RMs preferably takes place with an applied voltage in the case of PS-VA and PS-OCB displays, and with or without, preferably without, an applied voltage in the case of PS-IPS displays.
  • the PS(A) method results in a pretilt in the cell. In the case of PS-VA displays, the pretilt has a positive effect on response times.
  • a standard MVA or PVA pixel and electrode layout can be used.
  • PS- VA displays are described, for example, in EP 1 170626 A2, US 6,861 ,107, US 7,169,449, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/0103804 A1.
  • PS-OCB displays are described, for example, in T.-J- Chen et al., Jpn. J. Appl.
  • PS-IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. 1999, 75(21), 3264.
  • PS-TN displays are described, for example, in Optics Express 2004, 12(7), 1221.
  • the PSA display typically contains an alignment layer on one or both of the substrates forming the display cell, that provides the initial alignment of the LC molecules before the polymer stabilisation step.
  • the alignment layer is usually applied on the electrodes (where such electrodes are present) such that it is in contact with the LC medium and induces initial alignment of the LC molecules.
  • the alignment layer may comprise or consist of, for example, a polyimide, which may also be rubbed, or may be prepared by a photoalignment method.
  • PSA displays can be operated as active-matrix or passive-matrix displays.
  • active-matrix displays individual pixels are usually addressed by integrated, non-linear active elements, such as, for example, transistors (for example thin-film transistors (“TFTs”)), while in the case of passive-matrix displays, individual pixels are usually addressed by the multiplex method, as known from the prior art.
  • TFTs thin-film transistors
  • the PSA method can provide significant advantages here.
  • a shortening of the response times, which correlate with a measurable pretilt in test cells can be achieved without significant adverse effects on other parameters.
  • Another problem observed in prior art is that the use of conventional LC media in LC displays, including but not limited to displays of the PSA type, often leads to the occurrence of mura in the display, especially when the LC medium is filled in the display cell manufactured using the one drop filling (ODF) method. This phenomenon is also known as "ODF mura". It is therefore desirable to provide LC media which lead to reduced ODF mura.
  • LC media for use in PSA displays do often exhibit high viscosities and, as a consequence, high switching times.
  • LC media containing alkenyl compounds often show a decrease of the reliability and stability, and a decrease of the VHR especially after exposure to UV radiation.
  • the photopolymerisation of the RMs in the PSA display is usually carried out by exposure to UV radiation, which may cause a VHR drop in the LC medium.
  • the invention is based on the object of providing novel suitable materials, in LC media comprising reactive mesogens (RM), for use in PSA displays, which do not have the disadvantages indicated above or do so to a reduced extent.
  • the invention is based on the object of LC media comprising RMs for use in PSA displays, which enable displays with high transmittance and at the same time very high specific resistance values, high VHR values, high reliability, low threshold voltages, short response times, high birefringence, show good UV absorption especially at longer wavelengths, enable quick and complete polymerisation of the RMs, allow the generation of a low pretilt angle, preferably as quickly as possible, enable a high stability of the pretilt even after longer time and/or after UV exposure, reduce or prevent the occurrence of "image sticking" and "ODF mura” in the display, and in case of the RMs polymerise as rapidly and completely as possible and show a high solubility in the LC media which are typically used as host mixtures in PSA displays.
  • PID Public information Displays
  • PIDs are particular since they are usually installed outdoors. Therefore PIDs should have higher durability to operate consistently in various environmental conditions, and should also have a broader operating temperature range compared to conventional LC displays.
  • the LC media used in PIDs should have a broad LC phase and a very high value of Tni (phase transition temperature from the nematic to the isotropic state, also known as "clearing temperature” or "clearing point”), which should preferably be 100°C or more.
  • the LC media which have hitherto been proposed for use in VA or PSA displays do usually have a Tni value of less than 100°C.
  • the invention relates to an LC medium comprising a) one or more compounds of the formula I
  • Ar denotes an aromatic or heteroaromatic hydrocarbon group having 4 to 40 C atoms, preferably 6 to 30 C atoms;
  • Sp denotes a spacer group
  • R s denotes H, alkyl having 1 to 12 C atoms or alkenyl having 2 to 12 C atoms;
  • Z s denotes single bond
  • R H denotes H, O', CH 3 , OH or OR S , preferably H or O';
  • R S1 , R S2 , R S3 and R S4 identically or differently, denote alkyl having 1 to 6 C atoms, preferably having 1 to 3 C atoms, very preferably CH 3 ;
  • G denotes H or R s or a group Z S -HA; z is an integer from 1 to 6; and q is 3 or 4; and b) one or more compounds selected from the group of compounds of the formulae IIA, I IB, IIC and IID, in which
  • R 2A , R 2B , R 2C and R 2D each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, one or more CH 2 groups in these radicals may be replaced by -O-, -S-,
  • -C C-, -CF 2 O-, -OCF 2 -, -OC-O- or -O-CO- in such a way that O atoms are not linked directly to one another;
  • L 1 and L 2 each, independently of one another, denote F, Cl, CF3 or CHF2;
  • Y denotes H, F, Cl, CF3, CHF2 or CH 3 , preferbaly H or methyl, very preferably H;
  • p denotes 0, 1 or 2;
  • q denotes 0 or 1 ;
  • v denotes 1 , 2, 3, 4, 5, or 6; and c) one or more chiral dopants; and d) optionally one or more polymerisable compounds of formula P P-Sp-A 1 -(Z 1 -A 2 ) z -R R in which the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings:
  • P a polymerisable group
  • a 1 , A 2 an aromatic, heteroaromatic, alicyclic or heterocyclic group, preferably having 4 to 25 ring atoms, which may also contain fused rings, and which is unsubstituted, or mono- or polysubstituted by L, bond,
  • the invention furthermore relates to an LC display comprising the LC medium described above.
  • the invention furthermore relates to an LC medium or LC display as described above, wherein the compounds of formula R are polymerised.
  • the invention furthermore relates to a process for preparing an LC medium as described above and below, comprising the steps of mixing one or more compounds of the formulae IIA, 11 B, IIC and/or IID, with one or more chiral dopants and one or more compounds of the formula I and optionally with one or more compounds of formula R, and optionally with further LC compounds and/or additives.
  • the invention furthermore relates to the use of LC media according to the invention in PSA displays, in particular to the use in PSA displays containing an LC medium, for the production of a tilt angle in the LC medium by in-situ polymerisation of the compound(s) of the formula R in the PSA display, preferably in an electric or magnetic field.
  • the invention furthermore relates to an LC display comprising an LC medium according to the invention, in particular a VA or PSA display, particularly preferably a VA or a PS-VA display.
  • the invention furthermore relates to the use of LC media according to the invention in polymer stabilised SA-VA displays, and to a polymer stabilised SA-VA display comprising the LC medium according to the invention.
  • the invention furthermore relates to an LC display of the VA or PSA type comprising two substrates, at least one which is transparent to light, an electrode provided on each substrate or two electrodes provided on only one of the substrates, and located between the substrates a layer of an LC medium that optionally comprises one or more polymerisable compounds and an LC component as described above and below, wherein the polymerisable compounds are polymerised between the substrates of the display.
  • the invention furthermore relates to a process for manufacturing an LC display as described above and below, comprising the steps of filling or otherwise providing an LC medium, which optionally comprises one or more polymerisable compounds as described above and below, between the substrates of the display, and optionally polymerising the polymerisable compounds.
  • the PSA displays according to the invention have two electrodes, preferably in the form of transparent layers, which are applied to one or both of the substrates. In some displays, for example in PS-VA displays, one electrode is applied to each of the two substrates.
  • the polymerisable component is polymerised in the LC display while a voltage is applied to the electrodes of the display.
  • the polymerisable compounds of the polymerisable compoment are preferably polymerised by photopolymerisation, very preferably by UV photopolymerisation.
  • liquid crystalline hosts according to the invention and of LC media comprising them in VA or PS-VA displays, enables displays with improved transmission while maintaining excellent performance regarding process relevant parameters, i.e.in the case of PSA diplays a quick and complete UV-photopolymerisation reaction in particular at longer UV wavelengths in the range from 300-380nm and especially above 320nm, even without the addition of photoinitiator, a fast generation of a large and stable pretilt angle, reduced image sticking and ODF mura in the display, a high reliability and a high VHR value after UV photopolymerisation, especially in case of LC host mixtures containing LC compounds with an alkenyl group, and generally and fast response times, a low threshold voltage and a high birefringence, as well as high reliability when exposed to the environment when used outdoors.
  • process relevant parameters i.e.in the case of PSA diplays a quick and complete UV-photopolymerisation reaction in particular at longer UV wavelengths in the range from 300-380nm and especially above
  • LC media according to the invention show the following advantageous properties when used in PSA displays:
  • Preferred aryl groups are benzene, naphthalene, anthracene, biphenyl, m-terphenyl, p-terphenyl, and (phenylalkyl)benzene in which alkyl is straight chain alkyl having 1 to 12 C atoms.
  • the compounds of formula I are preferably selected from the compounds of the formulae 1-1, I-2 and I-3:
  • R H has the meanings given above and preferably denote H or O'
  • n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7, and
  • Sp denotes a spacer group, preferably alkylene having 1 to 12 C atoms in which one or more non-adjacent -CH 2 - groups may be replaced with -O-.
  • Preferred compounds of formula 1-1 are selected from the compounds of the formula in which R H has the meanings given above and preferably denotes H or O', and n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7.
  • Preferred compounds of formula I-2 are selected from the compounds of the formula 1-2-1 : in which R H has the meanings given above and preferably denotes H or O', and n2, on each occurrence identically or differently, preferably identically, is an integer from 1 to 12, preferably 2, 3, 4, 5, or 6, very preferably 3, and R s on each occurrence identically or differently, preferably identically, denotes alkyl having 1 to 6 C atoms, preferably n-butyl.
  • Preferred compounds of formula I-3 are selected from the compounds of the formula 1-3-1: in which R H has the meanings given above and preferably denotes H or O', and n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7.
  • the medium according to the invention comprises a compound selected from the group 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 CH 2 groups in these radicals may each be replaced, -O-CO- in such a way that O atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by halogen, each occurrence, identically or differently, denotes
  • L 1 and L 2 each, independently of one another, denote F, Cl, CH 3 , CF 3 or CHF 2 , p denotes 0, 1 or 2, q denotes 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • 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-
  • 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.
  • the concentration correspondingly increases to 0.01 - 1% in the case of two compounds, based on the mixtures.
  • the total proportion of the compounds of the formulae ST-1 to ST-18, based on the mixture according to the invention, should not exceed 2%.
  • the use of chiral dopants in nematic liquid crystals is known to the skilled person. For a review see e.g. A. Taugerbeck, Ch. Booth, 2013. Design and Synthesis of Chiral Nematic Liquid Crystals. Handbook of Liquid Crystals. 3:111:14:1-63.
  • the media according to the present invention comprise one or more chiral dopants.
  • these chiral dopants have an absolute value of the helical twisting power (short: HTP) in the range of from 1 ⁇ .m -1 to 150 ⁇ .m -1 , preferably in the range of from 10 ⁇ .m -1 to 100 ⁇ .m -1 .
  • HTP helical twisting power
  • the media may comprise two or more chiral dopants, these may have opposite signs of their HTP-values. This condition is preferred for some specific embodiments, as it allows to compensate the chirality of the respective compounds to some degree and, thus, may be used to compensate various temperature dependent properties of the resulting media in the devices.
  • the chiral compounds present in the media according to the present invention have the same sign of their HTP-values.
  • 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 chiral component D) consists of two or more chiral compounds which all have the same algebraic sign of the HTP.
  • 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 multiplicity 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 CH2 groups are substituted by alkyl or alkoxy; amino acids, such as, for example, alanine, valine, phenyl
  • the optically active component D) preferably consists of chiral dopants which are selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in DE 3425 503, DE 35 34 777, DE 35 34 778, DE 35 34 779 and DE 35 34 780, DE 4342 280, EP 01 038 941 and DE 19541 820. Examples are also compounds listed in Table B below.
  • Chiral compounds preferably used according to the present invention are selected from the group consisting of the formulae shown below.
  • chiral dopants selected from the group consisting of compounds of the following formulae A-l to A-lll and Ch:
  • chiral dopants selected from the group consisting of compounds of the following formulae A-l to A-lll and A-Ch:
  • 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-, in which L 12 on each occurrence, independently of one another, denotes halogen, CN, or alkyl, alkenyl, alkoxy or alkenyloxy having up to 12 C atoms and in which one or more H atoms are optionally replaced with halogen, preferably methyl, ethyl, Cl or F, particularly preferably F, has the meanings given f has the meanings given f r alternatively denotes n2 on each occurrence, identically or differently, is 0, 1 or 2, n3 is 1, 2 or 3, and r is 0, 1, 2, 3 or 4.
  • dopants selected from the group consisting of the compounds of the following formulae: in which m 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-lll.
  • dopants are derivatives of the isosorbide, isomannitol or isoiditol of the following formula A-IV:
  • dianhydroiditol preferably dianhydrosorbitol
  • chiral ethane diols such as, for example, diphenylethanediol (hydrobenzoin), in particular mesogenic hydrobenzoin derivatives of the following formula A-V: including the (S,S) enantiomers, which are not shown, in which are each, independently of one another, 1,4-phenylene, which may also be mono-, di- or trisubstituted by L, or 1,4-cyclo- hexylene,
  • L is H, F, Cl, CN or optionally halogenated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms, c is 0 or 1 ,
  • X is CH 2 or -C(O)-
  • Z° is -COO-, -OCO-, -CH 2 CH 2 - or a single bond
  • R 0 is alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkylcarbonyloxy having 1-12 carbon atoms.
  • the compounds of the formula A-IV are described in WO 98/00428.
  • 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.
  • X 1 , X 2 , Y 1 and Y 2 are each, independently of one another, F, Cl, Br, I, CN, SCN, SFs, 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-,
  • x 1 and x 2 are each, independently of one another, 0, 1 or 2
  • y 1 and y 2 are each, independently of one another, 0, 1 , 2, 3 or 4
  • B 1 and B 2 are each, independently of one another, an aromatic or partially or fully saturated aliphatic six-membered ring in which one or more CH groups may each be replaced by N and one or more non-adjacent CH 2 groups may each be replaced by O or S,
  • W 1 and W 2 are each, independently of one another, -Z 1 -A 1 -(Z 2 -A 2 ) m -R, and one of the two is alternatively R 1 or A 3 , but both are not simultaneously H, or
  • II 1 and II 2 are each, independently of one another, CH 2 , O, S, CO or CS,
  • V 1 and V 2 are each, independently of one another, (CH 2 ) n , in which from one to four non-adjacent CH2 groups may each be replaced by O or S, and one of V 1 and V 2 and, in the case where both are a single bond, n is 1 ,2 or 3
  • R x denotes alkyl having 1 to 6 C atoms
  • 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-tetrahydronaphthalene-2,6-diyl, where each of these groups may be monosubstituted or polysubstituted by L, and in addition A 1 can be a single bond,
  • L is a halogen atom, preferably F, CN, NO2, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1-7 carbon atoms, in which one or more H atoms may each be replaced by F or Cl, m is in each case, independently, 0, 1 , 2 or 3, and
  • chiral binaphthyl derivatives of the formula A-VI-1 in which ring B and Z° have the meanings defined for the formulae A-IV and A-V, R 0 denotes alkyl having 1 to 7 C atoms and b is 0, 1 or 2, in particular to those selected from the following formulae A-VI-1a to A-VI-1c: in which R 0 ’ and Z 0 have the meanings defined for the formula A-VI-1 , and preferably R 0 denotes H or alkyl having from 2 to 5 carbon atoms, and
  • Z° is, in particular, -OC(O)- or a single bond.
  • 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.
  • S-4011 or R- 4011 both from Merck KGaA
  • these preferred concentrations have to be decreased, or increased proportionally according to the ratio of their HTP values relatively to that of S-4011.
  • the pitch p of the LC media or host mixtures according to the invention is preferably in the range of from 5 to 50 pm, more preferably from 8 to 30 pm and particularly preferably from 10 to 20 pm.
  • the cell gap d, or thickness of the LC layer of the display according to the invention is preferably in the range of from 2pm to 10 pm, more preferably 3pm to 5 pm. Based on this, according to the invention, a preferable range of the ratio d/p between the cell gap d and the chiral pitch p is set to 0.04 to 2, preferably 0.1 to 1 , very preferably 0.2 to 0.3.
  • Preferred compounds of the formulae IIA, I IB, IIC and IID are indicated below: in which the parameter a denotes 1 or 2, alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond.
  • Very preferred compounds of formula I are the compounds 1-1 to 1-14.
  • the medium comprises one or more compounds of formula 11 D-10a in which the occurring groups and parameters have the meanings given above under formula IID, and
  • Preferred compounds of formula IID-10a are the compounds IID-10a-1 to IID-10a-
  • Particularly preferred mixtures according to the invention comprise one or more compounds of the formulae IIA-2, IIA-8, IIA-10, IIA-16, IIA-18, IIA-40, IIA-41, IIA-42, IIA-43, IIB-2, IIB-10, IIB-16, IIC-1 , IID-4 and IID-10.
  • Preferred media according to the invention comprise at least one compound of the formula IIC-1 , IIC-1 in which alkyl and alkyl* have the meanings indicated above, preferably in amounts of 0.5% to 5 % by weight, in particular 1% to 3 % by weight.
  • the medium comprises one or more compounds of the formula IIA-2 selected from the following sub-formulae:
  • the medium comprises one or more compoudns of the formulae I IA-2a- 1 to IIA-
  • the medium comprises one or more compounds of the formula I IA-10 selected from the following sub-formulae:
  • the medium comprises one or more compoudns of the formulae I IA-10a-1 to IIA-10a-5:
  • the medium comprises one or more compounds of the formula IIB-10 selected from the following sub-formulae:
  • the medium comprises one or more compoudns of the formulae I IB-10a-1 to IIB-10a-5: IIB-10a-5
  • the medium according to the invention optionally comprises one or more compounds of formula III in which
  • R 11 and R 12 each, independently of one another, denote H, an alkyl or alkoxy radical having 1 to 15 C atoms, where one or more CH 2 groups in these radicals may each be replaced, independently of one another,
  • -CH CH-, by -O-, -CO-O- or -O-CO- in such a way that O atoms are not linked directly to one another, and in which one or more H atoms may be replaced by halogen,
  • Z 1 on each occurrence independently of one another denotes -CO-O-
  • L 11 and L 12 each, independently of one another, denote F, Cl, CF 3 or CHF 2 , preferably H or F, most preferably F, and
  • W denotes O or S.
  • the compounds of formula III are preferably selected from the compounds of the formula 111-1 and/or III-2 in which the occurring groups have the same meanings as given under formula III above and preferably
  • R 11 and R 12 each, independently of one another, an alkyl, alkenyl or alkoxy radical having up to 15 C atoms, more preferably one or both of them denote an alkoxy radical and
  • L 11 and L 12 each preferably denote F.
  • the compounds of the formula 111-1 selected from the group of compounds of formulae 111-1-1 to 111-1-11 , preferably of formula 111-1-6, ⁇ 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 and alkoxy* each, independently of one another, denote a straight-chain alkoxy radical having 1-6 C atoms, and L 11 and L 12 each, independently of one another, denote F or Cl, preferably both F.
  • the compounds of the formula III-2 are selected from the group of compounds of formulae 111-2-1 to 111-2-10, preferably of formula III-2-6,
  • 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 and alkoxy* each, independently of one another denote a straight-chain alkoxy radical having 1-6 C atoms
  • L 1 and L 2 each, independently of one another, denote F or Cl, preferably both F.
  • the medium comprises one or more compounds of the formula IIIA-1 and/or IIIA-2 in which L 11 and L 12 have the same meanings as given under formula III, (O) denotes O or a single bond, R IIIA denotes alkyl or alkenyl having up to 7 C atoms or a group Cy-C m H2 m+1 -, m and n are, identically or differently, 0, 1 , 2, 3, 4, 5 or 6, preferably 1 , 2 or 3, very preferably 1 ,
  • Cy denotes a cycloaliphatic group having 3, 4 or 5 ring atoms, which is optionally substituted with alkyl or alkenyl each having up to 3 C atoms, or with halogen or CN, and preferably denotes cyclopropyl, cyclobutyl or cyclopentyl.
  • the compounds of formula IIIA-1 and/or IIIA-2 are contained in the medium either alternatively or in addition to the compounds of formula III, preferably additionally.
  • IIIA-1 and IIIA-2 are the following: IIIA-1-3 alkoxy in which alkoxy denotes a straight-chain alkoxy radical having 1-6 C atoms or alternatively -(CH 2 ) n F in which n is 2,3,4, or 5, preferably C 2 H4F.
  • the medium comprises one or more compounds of formula III-3 in which
  • R 11 , R 12 identically or differently, denote H, an alkyl or alkoxy radical having 1 to
  • the compounds of formula III-3 are preferably selected from the group of compounds of the formulae 111-3-1 to 111-3-10: - ee- 0 in which R 12 denotes alkyl having 1 to 7 C-atoms, preferably ethyl, n-propyl or n- butyl, or alternatively cyclopropylmethyl, cyclobutyl methyl or cyclopentylmethyl or alternatively -(CH 2 ) n F in which n is 2,3,4, or 5, preferably C 2 H 4 F.
  • the medium comprises one or more compounds of the formulae III-4 to III-6, preferably of formula III-5, in which the parameters have the meanings given above, R 11 preferably denotes straight-chain alkyl and R 12 preferably denotes alkoxy, each having 1 to 7 C atoms.
  • the media comprise one or more compounds of the formula I selected from the group of compounds of formulae III-7 to II I-9, preferably of formula III-8, in which the parameters have the meanings given above, R 11 preferably denotes straight-chain alkyl and R 12 preferably denotes alkoxy each having 1 to 7 C atoms.
  • the medium comprises one or more compounds of the
  • R 41 denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkenyl radical having 2 to 7 C atoms, preferably an n-alkyl radical, particularly preferably having 2, 3, 4 or 5 C atoms, and
  • R 42 denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkoxy radical having 1 to 6 C atoms, both preferably having 2 to 5 C atoms, an unsubstituted alkenyl radical having 2 to 7 C atoms, preferably having 2, 3 or 4 C atoms, more preferably a vinyl radical or a 1 -propenyl radical and in particular a vinyl radical.
  • the compounds of the formula IV are preferably selected from the group of the compounds of the formulae IV-1 to IV-4, alkyl and alkyl’, independently of one another, denote alkyl having 1 to 7 C atoms, preferably having 2 to 5 C atoms, alkenyl denotes an alkenyl radical having 2 to 5 C atoms, preferably having 2 to 4 C atoms, particularly preferably 2 C atoms, alkenyl’ denotes an alkenyl radical having 2 to 5 C atoms, preferably having 2 to 4 C atoms, particularly preferably having 2 to 3 C atoms, and alkoxy denotes alkoxy having 1 to 5 C atoms, preferably having 2 to 4 C atoms.
  • the medium comprises one or more compounds selected from the compounds of the formulae IV-1-1 to IV-1-4
  • the medium according to the invention comprises one or more compounds of the formulae IV-2-1 and/or IV-2-2
  • the medium according to the invention comprises a compound of formula IV-3, in particular selected from the compounds of the formulae IV-3-1 to IV-3-5
  • the medium according to the invention comprises a compound of formula IV-4, in particular selected from the compounds of the formulae IV-4-1 and IV-4-2
  • the medium according to the invention comprises one or more compounds of formula I selected from the compounds of the formulae 1-1 to I-4 in combination with one or more compounds selected from the group of compounds of the formulae IA-1 to IA-18: in which alkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or n- pentyl.
  • the liquid-crystalline medium preferably additionally comprises one or more compounds of the formula IVa,
  • R 41 and R 42 each, independently of one another, denote a straight-chain alkyl, alkoxy, alkenyl, alkoxyalkyl or alkoxy radical having up to 12 C atoms, and
  • alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms.
  • the medium according to the invention preferably comprises at least one compound of the formula IVa-1and/or formula IVa-2.
  • the proportion of compounds of the formula IVa in the mixture as a whole is preferably less than 5 % by weight, very preferably less than 2% by weight.
  • the medium comprises one or more compounds of formula IVb-1 to IVb- 3 alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2 to 6 C atoms.
  • the proportion of the biphenyls of the formulae IV-1 to IV-3 in the mixture as a whole is preferably less than 3 % by weight, in particular less than 2 % by weight.
  • the compounds of the formula IVb-2 are particularly preferred.
  • biphenyls are in which alkyl* denotes an alkyl radical having 1 to 6 C atoms and preferably denotes n-propyl.
  • the medium according to the invention particularly preferably comprises one or more compounds of the formulae IVb-1-1 and/or IVb-2-3.
  • the medium according to the invention comprises one or more compounds of formula V in which
  • the compounds of the formula V are selected from the group consisting of the formulae
  • the compounds of formula V are preferably selected from the compounds of the in which R 51 and R 52 have the meanings indicated for Formula V above.
  • R 51 and R 52 preferably each, independently of one another, denote straight-chain alkyl having 1 to 7 C atoms or alkenyl having 2 to 7 C atoms.
  • Preferred media comprise one or more compounds of the formulae V-1 , V-3, V-4, V- 6, V-7, V-10, V-11, V-12, V-14, V-15, and/or V-16, very preferably V-3.
  • the medium additionally comprises one or more compounds of the formulae VI-1 to VI-21 ,
  • R denotes a straight-chain alkyl or alkoxy radical having 1 to 6 C atoms
  • (O) denotes -O- or a single bond
  • m is 0, 1 , 2, 3, 4, 5 or 6
  • n is 0, 1 , 2, 3 or 4.
  • R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy.
  • the medium additionally comprises one or more compounds of the formulae VI 1-1 to VII-9
  • R 7 denotes a straight-chain alkyl or alkoxy radical having 1 to 6 C atoms, or a straight chain alkenyl radical having 2 to 6 C atoms, and w is an integer from 1 to 6.
  • mixtures comprising at least one compound of the formula V-9.
  • R preferably denotes alkyl, furthermore alkoxy, each having 1 to 5 C atoms.
  • R preferably denotes alkyl or alkenyl, in particular alkyl.
  • R preferably denotes alkyl.
  • Liquid-crystalline medium comprising at least one compound of the formulae
  • Preferred liquid-crystalline media according to the invention comprise one or more substances which contain a tetrahydronaphthyl or naphthyl unit, such as, for example, the compounds of the formulae N-1 to N-5, in which R 1N and R 2N each, independently of one another, have the meanings indicated for R 2A , preferably denote straight-chain alkyl, straight-chain alkoxy or straight-chain alkenyl, and
  • Preferred mixtures comprise one or more compounds selected from the group of the difluorodibenzochroman compounds of the formula BC, chromans of the formula CR, and fluorinated phenanthrenes of the formulae PH-1 and PH-2, in which R B1 , R B2 , R CR1 , R CR2 , R 1 , R 2 each, independently of one another, have the meaning of R 2A .
  • c is 0, 1 or 2.
  • R 1 and R 2 preferably, independently of one another, denote alkyl or alkoxy having 1 to 6 C atoms.
  • Particularly preferred compounds of the formulae BC and CR are the compounds BC-1 to BC-7 and CR-1 to CR-5, in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straightchain alkenyl radical having 2 to 6 C atoms.
  • mixtures comprising one, two or three compounds of the formula BC-2, BF-1 and/or BF-2.
  • Preferred mixtures comprise one or more indane compounds of the formula In, in which
  • R 11 , R 12 , and R 13 each, independently of one another, denote a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1 to 6 C atoms, R 12 and R 13 alternatively denote halogen, preferably F, i denotes 0, 1 or 2.
  • Preferred compounds of the formula In are the compounds of the formulae ln-
  • Preferred mixtures additionally comprise one or more compounds of the formulae L-1 to L-5,
  • R, R 1 and R 2 each, independently of one another, have the meanings indicated for R 2A in formula IIA above, and alkyl denotes an alkyl radical having 1 to 6 C atoms.
  • the parameter s denotes 1 or 2.
  • the compounds of the formulae L-1 to L-9 are preferably employed in concentrations of 5 to 15 % by weight, in particular 5 to 12 % by weight and very particularly preferably 8 to 10 % by weight.
  • Preferred mixtures additionally comprise one or more compounds of formula IIA- Y in which R 11 and R 12 have one of the meanings given for R 2A in formula IIA above, and L 1 and L 2 , identically or differently, denote F or Cl.
  • Preferred compounds of the formula IIA-Y are selected from the group consisting of the following sub-formulae in which, Alkyl and Alkyl* each, independently of one another, denote a straightchain alkyl radical having 1-6 C atoms, Alkoxy denotes a straight-chain alkoxy 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, and O denotes an oxygen atom or a single bond.
  • Particularly preferred compounds of the formula IIA-Y are selected from the group consisting of following sub-formulae:
  • Alkoxy IIA-Y6b in which Alkoxy and Alkoxy* have the meanings defined above and preferably denote methoxy, ethoxy, n- propyloxy, n-butyloxy or n-pentyloxy.
  • the term "reliability” as used herein means the quality of the performance of the display during time and with different stress loads, such as light load, temperature, humidity, voltage, and comprises display effects such as image sticking (area and line image sticking), mura, yogore etc. which are known to the skilled person in the field of LC displays.
  • VHR voltage holding ration
  • PSA is used hereinafter when referring to displays of the polymer sustained alignment type in general, and the term “PS” is used when referring to specific display modes, like PS-VA, PS-TN and the like.
  • RM is used hereinafter when referring to a polymerisable mesogenic or liquid-crystalline compound.
  • active layer and “switchable layer” mean a layer in an electrooptical display, for example an LC display, that comprises one or more molecules having structural and optical anisotropy, like for example LC molecules, which change their orientation upon an external stimulus like an electric or magnetic field, resulting in a change of the transmission of the layer for polarized or unpolarized light.
  • the tilt angle here denotes the average angle ( ⁇ 90°) between the longitudinal molecular axes of the LC molecules (LC director) and the surface of the plane-parallel outer plates which form the LC cell.
  • ⁇ 90° the average angle
  • a low value for the tilt angle i.e. a large deviation from the 90° angle
  • tilt angle values disclosed above and below relate to this measurement method.
  • the terms “reactive mesogen” and “RM” will be understood to mean a compound containing a mesogenic or liquid crystalline skeleton, and one or more functional groups attached thereto which are suitable for polymerisation and are also referred to as “polymerisable group” or “P”. llnless stated otherwise, the term “polymerisable compound” as used herein will be understood to mean a polymerisable monomeric compound.
  • low-molecular-weight compound will be understood to mean to a compound that is monomeric and/or is not prepared by a polymerisation reaction, as opposed to a "polymeric compound” or a "polymer”.
  • unpolymerisable compound will be understood to mean a compound that does not contain a functional group that is suitable for polymerisation under the conditions usually applied for the polymerisation of the RMs.
  • mesogenic group as used herein is known to the person skilled in the art and described in the literature, and means a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquidcrystal (LC) phase in low-molecular-weight or polymeric substances.
  • Compounds containing mesogenic groups do not necessarily have to have an LC phase themselves. It is also possible for mesogenic compounds to exhibit LC phase behaviour only after mixing with other compounds and/or after polymerisation. Typical mesogenic groups are, for example, rigid rod- or discshaped units.
  • optically active and “chiral” are synonyms for materials that are able to induce a helical pitch in a nematic host material, also referred to as “chiral dopants”.
  • spacer group hereinafter also referred to as "Sp”, as used herein is known to the person skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 2001 , 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.
  • the terms "spacer group” or “spacer” mean a flexible group, for example an alkylene group, which connects the mesogenic group and the polymerisable group(s) in a polymerisable mesogenic compound. Above and below, denotes a trans- 1 ,4-cyclohexylene ring.
  • the single bond shown between the two ring atoms can be attached to any free position of the benzene ring.
  • organic group denotes a carbon or hydrocarbon group.
  • Carbon group denotes a mono- or polyvalent organic group containing at least one carbon atom, where this either contains no further atoms (such as, for example, -C ⁇ C-) or optionally contains one or more further atoms, such as, for example, N, O, S, B, P, Si, Se, As, Te or Ge (for example carbonyl, etc.).
  • hydrocarbon group denotes a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as, for example, N, O, S, B, P, Si, Se, As, Te or Ge.
  • Halogen denotes F, Cl, Br or I, preferably F or Cl.
  • a carbon or hydrocarbon group can be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups.
  • a carbon or hydrocarbon radical having more than 3 C atoms can be straight-chain, branched and/or cyclic and may also contain spiro links or condensed rings.
  • alkyl also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.
  • aryl denotes an aromatic carbon group or a group derived therefrom.
  • heteroaryl denotes “aryl” as defined above, containing one or more heteroatoms, preferably selected from N, O, S, Se, Te, Si and Ge.
  • Preferred carbon and hydrocarbon groups are optionally substituted, straight-chain, branched or cyclic, alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 20, very preferably 1 to 12, C atoms, optionally substituted aryl or aryloxy having 5 to 30, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 5 to 30, preferably 6 to 25, C atoms, wherein one or more C atoms may also be replaced by hetero atoms, preferably selected from N, O, S, Se, Te, Si and Ge.
  • hetero atoms preferably selected from N, O, S, Se, Te, Si
  • carbon and hydrocarbon groups are C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 allyl, C 4 -C 20 alkyldienyl, C 4 -C 20 polyenyl, C 6 -C 20 cycloalkyl, C 4 - C 15 cycloalkenyl, C 6 -C 30 aryl, C 6 -C 30 alkylaryl, C 6 -C 30 arylalkyl, C 6 -C 30 alkylaryloxy, C 6 -C 30 arylalkyloxy, C 2 -C 30 heteroaryl, C 2 -C 30 heteroaryloxy.
  • C 1 -C 12 alkyl Particular preference is given to C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 6 -C 25 aryl and C 2 -C 25 heteroaryl.
  • R x preferably denotes H, F, Cl, CN, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which, in addition, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- and in which one or more H atoms may be replaced by F or Cl, or denotes an optionally substituted aryl or aryloxy group with 6 to 30 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group with 2 to 30 C atoms.
  • Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2- trifluoroethyl, perfluorooctyl, perfluorohexyl, etc.
  • Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, etc.
  • Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, etc.
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, 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, etc.
  • Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.
  • Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e. they can contain one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently bonded (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.
  • aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted.
  • Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1 ,1':3',1"]terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, 9,10- dihydro-phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.
  • 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, 1 ,2,4-triazine, 1
  • aryl and heteroaryl groups mentioned above and below may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
  • the (non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings, i.e. those containing exclusively single bonds, and also partially unsaturated rings, i.e. those which may also contain multiple bonds.
  • 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, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 5 to 25 ring atoms, which optionally contain fused rings and 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, tetrahydrothiopyran, 1 ,3-dioxane, 1 ,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1 ,3-diyl, bicyclo[2.2.2]octane- 1 ,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4, 7-
  • Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy, e I ectron-wi th drawing groups, such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) in the polymer, in particular bulky groups, such as, for example, t-butyl or optionally substituted aryl groups.
  • solubility-promoting groups such as alkyl or alkoxy
  • e I ectron-wi th drawing groups such as fluorine, nitro or nitrile
  • substituents for increasing the glass transition temperature (Tg) in the polymer in particular bulky groups, such as, for example, t-butyl or optionally substituted aryl groups.
  • Y 1 denotes halogen.
  • "Substituted silyl or aryl” preferably means substituted by halogen, -CN, R 0 , -OR 0 , -CO-R 0 , -CO-O-R 0 , -O-CO-R 0 or -O-CO-O-R 0 , wherein R 0 denotes H or alkyl with 1 to 20 C atoms.
  • substituents L are, for example, F, Cl, CN, NO2, 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 , furthermore phenyl.
  • a 1 and A 2 very preferably denote in which L has one of the meanings indicated above and r denotes 0, 1 , 2, 3 or 4, in particular
  • the polymerisable group P is a group which is suitable for a polymerisation reaction, such as, for example, free-radical or ionic chain polymerisation, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain.
  • a polymerisation reaction such as, for example, free-radical or ionic chain polymerisation, polyaddition or polycondensation, or for a polymer-analogous reaction, for example addition or condensation onto a main polymer chain.
  • groups which are suitable for polymerisation with ring opening such as, for example, oxetane or epoxide groups.
  • Very preferred groups P are selected from the group consisting of
  • W 1 denotes H, F, Cl, CN, CF 3 , phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH 3 , W 2 and W 3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W 4 , V ⁇ and W 6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W 7 and W 8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1 ,4-pheny
  • polymerisable groups P are selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably from acrylate and methacrylate.
  • the spacer group Sp is different from a single bond, it is preferably of the formula Sp"-X", so that the respective radical P-Sp- conforms to the formula R-Sp"-X"-, wherein
  • Sp denotes linear or branched alkylene having 1 to 20, preferably 1 to 12, C atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN and in which, in addition, one or more non-adjacent CH 2 groups may each be replaced, independently of one another, by -O-, -S-,
  • X denotes -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R 0 )-, -N(R 0 )-CO-, -N(R 0 )-CO-N(R 00 )-, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CF 2 O-, -OCF 2 -, -CF 2 S-, -SCF 2 -, -CF 2 CH 2 -, -CH 2 CF 2 -, -CF 2 CF 2 -, -CH 2 -, -CH 2 -, -CH 2 -, -CH 2 -, -CH 2 CF 2 -, -CH 2 -, -CH 2 -, -CH 2 CF 2 -, -CH 2 -, -CH 2 -,
  • Y 2 and Y 3 each, independently of one another, denote H, F, Cl or CN.
  • X" is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR 0 -CO-, -NR 0 -CO-NR 0 °- or a single bond.
  • Typical spacer groups Sp and -Sp"-X"- are, for example, -(CH 2 ) P1 -, -(CH 2 ) P1 -O-, - (CH 2 ) P1 -O-CO-, -(CH 2 ) P1 -CO-O-, -(CH 2 ) P1 -O-CO-O-, -(CH 2 CH 2 O) q1 -CH 2 CH 2 -, - CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH 2 -NH-CH 2 CH 2 - or -(SiR 0 R 0 °-O) p1 -, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 0 and R 0 ° have the meanings indicated above.
  • Particularly preferred groups Sp and -Sp"-X"- are -(CH 2 ) P1 -, -(CH 2 ) P1 -O-, -(CH 2 ) P1 -O- CO-, -(CH 2 ) P1 -CO-O-, -(CH 2 ) P1 -O-CO-O-, in which p1 and q1 have the meanings indicated above.
  • Particularly preferred groups Sp" are, in each case straight-chain, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.
  • the compounds of formula P and its subformulae contain a spacer group Sp that is substituted by one or more polymerisable groups P, so that the group Sp-P corresponds to Sp(P) s , with s being ⁇ 2 (branched polymerisable groups).
  • Preferred compounds of formula P according to this preferred embodiment are those wherein s is 2, i.e. compounds which contain a group Sp(P) 2 .
  • Very preferred compounds of formula P according to this preferred embodiment contain a group selected from the following formulae:
  • X has one of the meanings indicated for X", and is preferably O, CO, SO 2 , O-CO-, CO-O or a single bond.
  • Preferred spacer groups Sp(P) 2 are selected from formulae S1 , S2 and S3.
  • Very preferred spacer groups Sp(P)2 are selected from the following subformulae:
  • P is preferably selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide, most preferably from acrylate and methacrylate.
  • R preferably denotes P-Sp-.
  • Sp denotes a single bond or -(CH 2 ) P i-, -O-(CH 2 ) P1 -, -O- CO-(CH 2 ) P1 , or -CO-O-(CH 2 ) P1 , wherein p1 is 2, 3, 4, 5 or 6, and, if Sp is -O-(CH 2 ) P1 -, -O-CO-(CH 2 ) P1 or -CO-O-(CH 2 ) P1 the O-atom or CO-group, respectively, is linked to the benzene ring.
  • At least one group Sp is different from a single bond, and is preferably selected from -(CH 2 ) P1 -, -O-(CH 2 ) P1 -, -O-CO-(CH 2 ) P1 , or -CO-O-(CH 2 ) P1 , wherein p1 is 2, 3, 4, 5 or 6, and, if Sp is -O-(CH 2 ) P1 -, -O-CO-(CH 2 ) P1 or -CO-O- (CH 2 ) P1 the O-atom or CO-group, respectively, is linked to the benzene ring.
  • Very preferred groups -A 1 -(Z-A 2 ) z - in formula P are selected from the following formulae wherein at least one benzene ring is substituted by at last one group L and the benzene rings are optionally further substituted by one or more groups L or P-Sp-.
  • Preferred compounds of formula P and their subformulae are selected from the following preferred embodiments, including any combination thereof:
  • the compounds contain exactly two polymerizable groups (represented by the groups P),
  • the compounds contain exactly three polymerizable groups (represented by the groups P),
  • - P is selected from the group consisting of acrylate, methacrylate and oxetane, very preferably acrylate or methacrylate,
  • - Sp when being different from a single bond, is -(CH 2 ) P 2-, -(CH 2 ) P 2-O-,
  • - Sp is a single bond or denotes -(CH 2 ) P 2-, -(CH 2 ) P 2-O-, -(CH 2 ) P 2-CO-O-, -(CH 2 ) P 2-O- CO-, wherein p2 is 2, 3, 4, 5 or 6, and the O-atom or the CO-group, respectively, is connected to the benzene ring,
  • - R does not denote or contain a polymerizable group and denotes straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH 2 -groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a manner that O- and/or S- atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F, Cl or L a ,
  • Suitable and preferred compounds of formula P are selected from the following formulae:
  • Sp 1 , Sp 2 and Sp 3 each, independently of one another, denote a single bond or a spacer group having one of the meanings indicated above and below for Sp, and particularly preferably denote -(CH 2 ) P1 -, -(CH 2 ) P1 -O-, -(CH 2 ) P1 -CO-O-, -(CH 2 ) P1 -O-CO- or -(CH 2 ) P1 -O-CO-O-, in which p1 is an integer from 1 to 12, where, in addition, one or more of the radicals P 1 -Sp 1 -, P 2 -Sp 2 - and P 3 -Sp 3 - may denote R aa , with the proviso that at least one of the radicals P 1 -Sp 1 -, P 2 - Sp 2 - and P 3 -Sp 3 - present is different from R aa ,
  • R y and R z each, independently of one another, denote H, F, CH 3 or CF3,
  • X 1 , X 2 and X 3 each, independently of one another, denote -CO-O-, -O-CO- or a single bond,
  • Z 1 denotes -O-, -CO-, -C(R y R z )- or -CF 2 CF 2 -,
  • Z 2 and Z 3 each, independently of one another, denote -CO-O-, -O-CO-, -CH 2 O-, - OCH 2 -, -CF 2 O-, -OCF 2 - or -(CH 2 ) n -, where n is 2, 3 or 4,
  • L on each occurrence denotes F, Cl, CN or straightchain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F,
  • L' and L" each, independently of one another, denote H, F or Cl, k denotes 0 or 1 , r denotes 0, 1 , 2, 3 or 4, s denotes 0, 1 , 2 or 3, t denotes 0, 1 or 2, x denotes 0 or 1 .
  • trireactive compounds R15 to R30 in particular R17, R18, R19, R22, R23, R24, R25, R26, R30, R31 and R32.
  • L on each occurrence identically or differently, has one of the meanings given above or below, and is preferably F, Cl, CN, NO2, CH 3 , C 2 H 5 , C(CH 3 )3, CH(CH 3 ) 2 , CH 2 CH(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 , OCHF2, OC 2 F5 or P-Sp-, very preferably F, Cl, CN, CH 3 , C 2 H 5 , OCH 3 , COCH 3 , OCF 3 or P-Sp-, more preferably F, Cl, CH 3 , OCH 3 , COCH 3 Oder OCF 3 , especially F or CH 3 .
  • the polymerisable compounds cointained in the LC medium are polymerised or crosslinked (if one compound contains two or more polymerisable groups) by in-situ polymerisation in the LC medium between the substrates of the LC display, optionally while a voltage is applied to the electrodes.
  • the structure of the PSA displays according to the invention corresponds to the usual geometry for PSA displays, as described in the prior art cited at the outset. Geometries without protrusions are preferred, in particular those in which, in addition, the electrode on the colour filter side is unstructured and only the electrode on the TFT side has slots. Particularly suitable and preferred electrode structures for PS-VA displays are described, for example, in US 2006/0066793 A1.
  • a preferred PSA type LC display of the present invention comprises: a first substrate including a pixel electrode defining pixel areas, the pixel electrode being connected to a switching element disposed in each pixel area and optionally including a micro-slit pattern, and optionally a first alignment layer disposed on the pixel electrode, a second substrate including a common electrode layer, which may be disposed on the entire portion of the second substrate facing the first substrate, and optionally a second alignment layer, an LC layer disposed between the first and second substrates and including an LC medium comprising a polymerisable component comprising one or more compounds of formula R and a chiral nematic liquid crystal host including as described above and below, wherein the polymerisable component may also be polymerised.
  • the first and/or second alignment layer controls the alignment direction of the LC molecules of the LC layer.
  • the alignment layer is selected such that it imparts to the LC molecules homeotropic (or vertical) alignment (i.e. perpendicular to the surface) or tilted alignment.
  • Such an alignment layer may for example comprise a polyimide, which may also be rubbed, or may be prepared by a photoalignment method.
  • the LC layer with the LC medium can be deposited between the substrates of the display by methods that are conventionally used by display manufacturers, for example the so-called one-drop-filling (ODF) method.
  • ODF one-drop-filling
  • the polymerisable component of the LC medium is then polymerised for example by UV photopolymerisation.
  • the polymerisation can be carried out in one step or in two or more steps.
  • the PSA display may comprise further elements, like a colour filter, a black matrix, a passivation layer, optical retardation layers, transistor elements for addressing the individual pixels, etc., all of which are well known to the person skilled in the art and can be employed without inventive skill.
  • the electrode structure can be designed by the skilled person depending on the individual display type. For example for PS-VA displays a multi-domain orientation of the LC molecules can be induced by providing electrodes having slits and/or bumps or protrusions in order to create two, four or more different tilt alignment directions.
  • the polymerisable compounds Upon polymerisation the polymerisable compounds form a crosslinked polymer, which causes a certain pretilt of the LC molecules in the LC medium.
  • a crosslinked polymer which causes a certain pretilt of the LC molecules in the LC medium.
  • at least a part of the crosslinked polymer, which is formed by the polymerisable compounds will phaseseparate or precipitate from the LC medium and form a polymer layer on the substrates or electrodes, or the alignment layer provided thereon.
  • Microscopic measurement data like SEM and AFM have confirmed that at least a part of the formed polymer accumulates at the LC/substrate interface.
  • the polymerisation can be carried out in one step. It is also possible firstly to carry out the polymerisation, optionally while applying a voltage, in a first step in order to produce a pretilt angle, and subsequently, in a second polymerisation step without an applied voltage, to polymerise or crosslink the compounds which have not reacted in the first step ("end curing").
  • Suitable and preferred polymerisation methods are, for example, thermal or photopolymerisation, preferably photopolymerisation, in particular UV induced photopolymerisation, which can be achieved by exposure of the polymerisable compounds to UV radiation.
  • one or more polymerisation initiators are added to the LC medium.
  • Suitable conditions for the polymerisation and suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature.
  • Suitable for free-radical polymerisation are, for example, the commercially available photoinitiators Irgacure651®, Irgacure184®, lrgacure907®, Irgacure369® or Darocurel 173® (Ciba AG).
  • a polymerisation initiator is employed, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.
  • the polymerisable compounds according to the invention are also suitable for polymerisation without an initiator, which is accompanied by considerable advantages, such, for example, lower material costs and in particular less contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof.
  • the polymerisation can thus also be carried out without the addition of an initiator.
  • the LC medium thus does not contain a polymerisation initiator.
  • the the LC medium may also comprise one or more stabilisers in order to prevent undesired spontaneous polymerisation of the RMs, for example during storage or transport.
  • Suitable types and amounts of stabilisers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilisers from the Irganox® series (Ciba AG), such as, for example, Irganox® 1076. If stabilisers are employed, their proportion, based on the total amount of RMs or the polymerisable component (component P), is preferably 10-500,000 ppm, particularly preferably 50-50,000 ppm.
  • the polymerisable compounds of formula R do in particular show good UV absorption in, and are therefore especially suitable for, a process of preparing a PSA display including one or more of the following features:
  • UV-1 step a first UV exposure step
  • UV-2 step a second UV exposure step
  • UV lamps also known as “green UV lamps”.
  • These lamps are characterized by a relative low intensity (1/100-1/10 of a conventional UV1 lamp) in their absorption spectra from 300-380nm, and are preferably used in the UV2 step, but are optionally also used in the UV1 step when avoiding high intensity is necessary for the process.
  • the polymerisable medium is exposed to UV light in the display generated by a UV lamp with a radiation spectrum that is shifted to longer wavelengths, preferably 340nm or more, to avoid short UV light exposure in the PS-VA process.
  • a preferred embodiment of the present invention relates to a process for preparing a PSA display as described above and below, comprising one or more of the following features: - the polymerisable LC medium is exposed to UV light in a 2-step process, including a first UV exposure step ("UV-1 step”) to generate the tilt angle, and a second UV exposure step (“UV-2 step”) to finish polymerization,
  • the polymerisable LC medium is exposed to UV light generated by a UV lamp having an intensity of from 0.5 mW/cm 2 to 10 mW/cm 2 in the wavelength range from 300-380nm, preferably used in the UV2 step, and optionally also in the UV1 step,
  • the polymerisable LC medium is exposed to UV light having a wavelength of 340 nm or more, and preferably 400 nm or less.
  • This preferred process can be carried out for example by using the desired UV lamps or by using a band pass filter and/or a cut-off filter, which are substantially transmissive for UV light with the respective desired wavelength(s) and are substantially blocking light with the respective undesired wavelengths.
  • a band pass filter and/or a cut-off filter which are substantially transmissive for UV light with the respective desired wavelength(s) and are substantially blocking light with the respective undesired wavelengths.
  • UV exposure can be carried out using a wide band pass filter being substantially transmissive for wavelengths 300nm ⁇ ⁇ ⁇ 400nm.
  • UV exposure can be carried out using a cut-off filter being substantially transmissive for wavelengths ⁇ > 340 nm.
  • “Substantially transmissive” means that the filter transmits a substantial part, preferably at least 50% of the intensity, of incident light of the desired wavelength(s). “Substantially blocking” means that the filter does not transmit a substantial part, preferably at least 50% of the intensity, of incident light of the undesired wavelengths.
  • “Desired (undesired) wavelength” e.g. in case of a band pass filter means the wavelengths inside (outside) the given range of ⁇ , and in case of a cut-off filter means the wavelengths above (below) the given value of ⁇ .
  • This preferred process enables the manufacture of displays by using longer UV wavelengths, thereby reducing or even avoiding the hazardous and damaging effects of short UV light components.
  • UV radiation energy is in general from 6 to 100 J, depending on the production process conditions.
  • the LC medium according to the present invention essentially consist of a polymerisable component P) comprising or one or more polymerisable compounds of formula R, and an LC host mixture, and an optically active component comprising one or more chiral dopants, as described above and below.
  • the LC medium may additionally comprise one or more further components or additives, preferably selected from the list including but not limited to co-monomers, polymerisation initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricating agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.
  • further components or additives preferably selected from the list including but not limited to co-monomers, polymerisation initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricating agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.
  • the LC media according to the invention comprise one, two or three chrial dopants, very preferably one chiral dopant.
  • LC media comprising one, two or three polymerisable compounds of formula R.
  • the proportion of compounds of formula R in the LC medium is from >0 to ⁇ 5%, very preferably from >0 to ⁇ 1%, most preferably from 0.01 to 0.5%.
  • the medium according to the invention comprises
  • one or more compounds of the formula I IB preferably of the fromula I IB-10, in a total concentration in the range of from 5% to 25%, more preferably from 9% to 22% and very preferably from 12% to 20%;
  • - one or more compounds of formula IIA and one or more compounds of formula II B in a total concentration of 50% or more, more preferably of 55% or more, and very preferbly of 60% or more;
  • - one or more compounds of formula IIA and one or more compounds of formula II B and one or more compounds of formula V in a total concentration of 60% or more, more preferably of 65% or more, very preferbly of 70% or more and in particular of 73% or 74% or more;
  • one or more compounds of the formula IV in a total concentration in the range of from 15% to 45%, more preferably from 18% to 38%, still more preferably from 21% to 30% and very preferably from 22% to 28% or from 22% to 26%;
  • one or more compounds of the formula IV-3, preferably IV-3-4 and IV-3-1 in a total concentration in the range of from 10% to 35%, more preferably from 12% to 32%, still more preferably from 16% to 28% and very preferably from 18% to 22%;
  • the compound of the formula IV-3-4 in a total concentration in the range of from 5% to 25%, more preferably from 10% to 22% and very preferably from 13% to 17%;
  • the compound of the formula IV-3-1 in a total concentration in the range of from 1% to 12%, more preferably from 2% to 10%, and very preferably from 3% to 7%;
  • one or more compounds of the formula V in a total concentration in the range of from 15% to 40%, more preferably from 17% to 38%, still more preferably from 19% to 30% and very preferably from 20% to 26%;
  • one or more compounds of the formula V-10 in a total concentration in the range of from 5% to 30%, more preferably from 10% to 25% and very preferably from 12% to 18%.
  • liquid-crystalline medium according to the invention prefferably have a nematic phase from ⁇ -20°C to ⁇ 100°C, particularly preferably from ⁇ -30°C to ⁇ 110°C, very particularly preferably from ⁇ -40°C to ⁇ 120°C.
  • the medium according to the invention has a clearing temperature of 90°C or more, preferably of 100°C or more, more preferably of 105°C or more and in particular of 110°C or more.
  • the expression "have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that clearing (phase transition to the isotropic phase) still does not occur on heating from the nematic phase.
  • the investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical use for at least 100 hours.
  • the medium is referred to as stable at this temperature.
  • the corresponding times are 500 h and 250 h respectively.
  • 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 and a flow viscosity V20 of at most 30 mm 2 • s -1 at 20°C.
  • the mixture is nematic at a temperature of -20°C or less, preferably at -30°C or less, very preferably at -40°C or less.
  • the medium has a birefringence in the range of from 0.085 to 0.110, preferably from 0.090 to 0.105, in particular from 0.095 to 0.100.
  • the liquid-crystal mixture according to the invention has a dielectric anisotropy ⁇ of -2.5 to -5.0, preferably of -2.8 to - 4.0, in particular -3.0 to -3.5,
  • the rotational viscosity ⁇ 1 at 20°C is preferably in the range of from 150 to 250 mPas, more preferably from 170 to 210 mPa s.
  • the liquid-crystal media according to the invention have relatively low values for the threshold voltage (Vo). They are preferably in the range from 1.7 V to 3.0 V, particularly preferably ⁇ 2.8 V and very particularly preferably ⁇ 2.6 V.
  • threshold voltage relates to the capacitive threshold (Vo), also called the Freedericks threshold, unless explicitly indicated otherwise.
  • liquid-crystal media according to the invention have high values for the voltage holding ratio in liquid-crystal cells.
  • liquid-crystal media having a low addressing voltage or threshold 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 ⁇ > 1.5
  • dielectrically neutral compounds denotes those having -1.5 ⁇ ⁇ ⁇ 1.5
  • dielectrically negative compounds denotes those having ⁇ ⁇ -1.5.
  • the dielectric anisotropy of the compounds is determined here by dissolving 10 % of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture in at least one test cell in each case having a layer thickness of 20 pm with homeotropic and with homogeneous surface alignment at 1 kHz.
  • the measurement voltage is typically 0.5 V to 1.0 V but it is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
  • the liquid crystal medium according to the invention has negative dielectric anisotropy ( ⁇ ).
  • the mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, VAN, MVA, (S)-PVA, ASV, PSA (polymer sustained VA) and PS-VA (polymer stabilized VA). They are furthermore suitable for IPS (in-plane switching) and FFS (fringe field switching) applications having negative As. It goes without saying for the person skilled in the art that the VA, IPS or FFS mixture according to the invention may also comprise compounds in which, for example, H, N, O, Cl and F have been replaced by the corresponding isotopes.
  • the compounds according to the present invention can be synthesized by or in analogy to known methods described in the literature (for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), under reaction conditions which are known and suitable for said reactions. Use may also be made here of variants which are known per se, but are not mentioned here. In particular, they can be prepared as described in or in analogy to the following reaction schemes. Further methods for preparing the inventive compounds can be taken from the examples.
  • Table A shows the codes for the ring elements of the nuclei of the compound
  • Table B lists the bridging units
  • Table C lists the meanings of the symbols for the left- and right-hand end groups of the molecules.
  • the acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right- hand end group.
  • Table D shows illustrative structures of compounds together with their respective abbreviations.
  • Table C End groups in which n and m are each integers, and the three dots are placeholders for other abbreviations from this table.
  • the mixtures according to the invention optionally comprise one or more compounds of the compounds mentioned below.
  • the following abbreviations are used:
  • n, m, k and I are, independently of one another, each an integer, preferably 1 to 9 preferably 1 to 7, k and I possibly may be also 0 and preferably are 0 to 4, more preferably 0 or 2 and most preferably 2, n preferably is 1 , 2, 3, 4 or 5, in the combination “-nO-” it preferably is 1 , 2, 3 or 4, preferably 2 or 4, m preferably is 1 , 2,
  • the combination “-IVm” preferably is “2V1”.
  • threshold voltage for the present invention relates to the capacitive threshold (Vo), also known as the Freedericks threshold, unless explicitly indicated otherwise.
  • the optical threshold may also, as generally usual, be quoted for 10% relative contrast (V10).
  • the process of polymerising the polymerisable compounds in the PSA displays as described above and below is carried out at a temperature where the LC medium exhibits a liquid crystal phase, preferably a nematic phase, and most preferably is carried out at room temperature.
  • the display used for measurement of the capacitive threshold voltage consists of two plane-parallel glass outer plates with a distance of 25 pm, each of which has on the inside an electrode layer and an unrubbed polyimide alignment layer on top, which effect homeotropic alignment of the liquid-crystal molecules.
  • the display or test cell used for measurement of the tilt angles consists of two plane-parallel glass outer plates at a separation of 4 pm, each of which has on the inside an electrode layer and a polyimide alignment layer on top, where the two polyimide layers are rubbed antiparallel to one another and effect a homeotropic edge alignment of the liquid-crystal molecules.
  • the polymerisable compounds are polymerised in the display or test cell by irradiation with UV light of defined intensity for a prespecified time, with a voltage simultaneously being applied to the display (usually 10 V to 30 V alternating current, 1 kHz).
  • a fluorescent lamp and an intensity of 0 to 20 mW/cm 2 is used for polymerisation. The intensity is measured using a standard meter (Ushio Accumulate UV meter with central wavelength of 313nm).
  • the transmission measurements are performed in test cells with fishbone electrode layout (from Merck Ltd., Japan; 1 pixel fishbone electrode (ITO, 10x10 mm, 47.7° angle of fishbone with 3pm line/3pm space), 3.2 pm cell gap, AF-glass, tilt angle 1°).
  • fishbone electrode layout from Merck Ltd., Japan; 1 pixel fishbone electrode (ITO, 10x10 mm, 47.7° angle of fishbone with 3pm line/3pm space), 3.2 pm cell gap, AF-glass, tilt angle 1°).
  • the nematic LC host mixtures H1 to H9 are formulated as follows:
  • the chiral nematic mixtures are prepared from the nematic host mixture N1 above by adding the chiral dopant S-811 , S-2011 or S-4011 , resp.
  • the following polymerisable chiral nematic mixtures are prepared from the chiral nematic mixtures given in Table 1 by adding a reactive mesogen (RM) selected from the group of compounds of the formulae RM1 , RM2, RM3 and RM4 in the amount given in Table 4 (% RM).
  • RM reactive mesogen

Abstract

La présente invention concerne un milieu cristallin liquide (CL) chiral comprenant a) un ou plusieurs composés de formule I, b) un ou plusieurs composés choisis dans le groupe des composés de formules IIA, IIB, IIC et IID telles que définies dans la revendication 1 et c) un ou plusieurs dopants chiraux ; ainsi que l'utilisation des milieux CL à des fins optiques, électro-optiques et électroniques, en particulier dans des affichages CL, de préférence des affichages CL pour utilisation en extérieur.
PCT/EP2022/074661 2021-09-08 2022-09-06 Milieu cristallin liquide WO2023036746A1 (fr)

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Publication number Priority date Publication date Assignee Title
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