WO2019121438A1 - Composé à cristaux liquides et milieu à cristaux liquides - Google Patents

Composé à cristaux liquides et milieu à cristaux liquides Download PDF

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WO2019121438A1
WO2019121438A1 PCT/EP2018/085101 EP2018085101W WO2019121438A1 WO 2019121438 A1 WO2019121438 A1 WO 2019121438A1 EP 2018085101 W EP2018085101 W EP 2018085101W WO 2019121438 A1 WO2019121438 A1 WO 2019121438A1
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phe
chex
phel
compounds
denotes
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PCT/EP2018/085101
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Simon SIEMIANOWSKI
Matthias Bremer
Jana JEHN
Konstantin Schneider
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Merck Patent Gmbh
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Priority to GB2010827.0A priority Critical patent/GB2583649A/en
Publication of WO2019121438A1 publication Critical patent/WO2019121438A1/fr

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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
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    • 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
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—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-)
    • C09K2019/122—Ph-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004—Cy-Cy
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/301—Cy-Cy-Ph
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph
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    • C09K19/08—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

Definitions

  • the invention relates to compounds of formula I,
  • R 1 1 , R 12 , A 1 1 to A 14 , Z 1 1 , Z 13 , X 1 1 , X 12 , Sp 1 1 , p and q have one of the meanings as given herein below.
  • the invention further relates to method of production of compounds of formula I, to the use of said
  • the invention relates to a method of production of such LC media, to the use of such media in electro optical device, in particular, in flexoelectric electro optical device and to a flexoelectric electro optical device, as such.
  • Flexoelectric devices utilizing the flexoelectric effect for example ULFI devices and liquid crystal media that are especially suitable for
  • the Uniform Lying Hel ix (ULFI) has high potential as a fast switching
  • liquid crystal display mode It is capable of sub millisecond switching at 35°C and possesses an intrinsically high aperture ratio, resulting in an energy efficient display mode.
  • 35 structure is unstable, because there is a strong tendency for the ULFI texture to transform into the stable Grandjean texture (uniform standing P17310 SL
  • the ULH texture can be irreversibly damaged by external factors, such as dielectric coupling.
  • dielectric coupling becomes strong, the helix could be partially or completely unwound depending on the magnitude of
  • the cholesteric liquid crystal possesses a positive dielectric anisotropy sD «.0d, the unwound state will be homeotropic and thus totally black when the cell is placed between crossed polarizers.
  • the helix unwinding is a quadratic effect in contrast to the flexoelectric-optic effect which is a polar and linear effect. It should be noted that the helix
  • PS polymer stabilised
  • a small amount of a polymerisable compound is added to the LC medium and, after introduction into the LC cell, is polymerised or crosslinked in situ, usually by UV photopolymerisation.
  • a polymerisable mesogenic or liquid-crystalline compounds also known as
  • RMs reactive mesogens
  • PS-ULH displays are described, for example, in WO 2005/072460 A2;
  • RM in PS-ULH type displays is typically higher (0.5-20%) than commonly known display mode such as PSA (polymer-sustained alignment) type displays (0.3-0.5%).
  • one aim of the invention is to provide alternative, or preferably
  • liquid crystal means a compound
  • Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.
  • liquid crystal 5 ability to induce liquid crystal (LC) phase behaviour.
  • the compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds.
  • liquid crystal is used hereinafter for both mesogenic and LC
  • aryl and heteroaryl groups encompass groups, which can be
  • phenyl or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl) or contain a combination of fused and linked rings.
  • Heteroaryl groups contain one or more heteroatoms, preferably selected
  • tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings and which are optionally substituted.
  • Preference is furthermore given to 5 , 6 or 7-membered aryl and heteroaryl groups, in which, in
  • one or more CH groups may be replaced by N, S or O in such a way that O atoms and/or S atoms are not linked directly to one another.
  • Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl,
  • phenanthrene pyrene, dihydropyrene, chrysene, perylene, tetracene,
  • spirobifluorene more preferably 1 ,4- phenylene, 4,4’-biphenylene, 1 , 4- tephenylene.
  • Preferred heteroaryl groups are, for example, 5 membered rings, such as
  • 5 tetrazine, 1 , 2, 3, 5-tetrazine or condensed groups such as indole, iso- indole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphth- imidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phen- anthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran,
  • heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
  • heterocyclic rings contain one or more heteroatoms
  • the (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane) or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydro-naphthalene or bicyclooctane). Preference is furthermore given to mono-, bi- or tricyclic groups having 3
  • Preferred alicyclic and heterocyclic groups are, for
  • 5-membered groups such as cyclopentane, tetrahydrofuran, P17310 SL
  • groups are 1 ,4-phenylene, 4,4’-biphenylene, 1 , 4-terphenylene, 1 ,4- cyclohexylene, 4,4’- bicyclohexylene and 3,17-hexadecahydro- cyclopenta[a]-phenanthrene, optionally being substituted by one or more identical or different groups L.
  • Preferred substituents of the above-mentioned aryl-, heteroaryl-, alicyclic- and heterocyclic groups (L) are, for example, solubility-promoting groups, such as alkyl or alkoxy and electron-withdrawing groups, such as fluorine, nitro or nitrile.
  • substituents are, for example, halogen, CN, NO 2 , CHs, C2H5, OCHs, OC2H5, COCH3, COC2H5, COOCHs, COOC2H5, CFs, OCFs, OCHF2 or OC2F5.
  • halogen denotes F, Cl, Br or I.
  • alkyl also encompass polyvalent groups, for example alkylene, arylene,
  • aryl denotes an aromatic carbon group or a group derived there from.
  • heteroaryl denotes “aryl” in accordance with the above
  • Preferred alkyl groups are, for example, methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, s butyl, t butyl, 2 methylbutyl, n pentyl, s pentyl, cyclo- pentyl, n hexyl, cyclohexyl, 2 ethylhexyl, n heptyl, cycloheptyl, n octyl, cyclooctyl, n nonyl, n decyl, n undecyl, n dodecyl, dodecanyl, trifluoro-
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxy- ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-
  • Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl.
  • Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl.
  • Oxaalkyl i.e. where one Chte group is replaced by -0-, is preferably
  • Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino.
  • “Achiral” (non- chiral) objects are objects that are identical to their mirror image.
  • mesogenic compound relates to compounds comprising two mesogenic groups in the molecule. Just like normal mesogens, they can form many mesophases, depending on their structure. In particular,
  • 5 bimesogenic compound may induce a second nematic phase, when
  • Bimesogenic compounds are also known as“dimeric liquid crystals”.
  • the director is the axis of anisotropy.
  • alignment or“orientation” relates to alignment (orientation ordering) of anisotropic units of material such as small molecules or fragments of big molecules in a common direction named“alignment direction”.
  • the liquid- crystalline director coincides with the alignment direction so that the
  • alignment direction corresponds to the direction of the anisotropy axis of the material.
  • planar orientation/alignment for example in a layer of an liquid-crystalline material, means that the long molecular axes (in case of
  • liquid-crystalline material means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented at an angle Q ("tilt angle") between about 80° to 90° relative to the plane of the layer.
  • uniform orientation or “uniform alignment” of an liquid- crystalline material, for example in a layer of the material, mean that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of the liquid-crystalline
  • the wavelength of light generally referred to in this application is 550 nm, unless explicitly specified otherwise.
  • the extraordinary refractive index n e and the ordinary refractive index n 0 can be measured using an Abbe refractometer.
  • dielectrically positive is used for compounds or components with De > 3.0,“dielectrically neutral” with -1 .5
  • De 25 ⁇ De ⁇ 3.0 and“dielectrically negative” with De ⁇ -1 .5.
  • De is determined at a frequency of 1 kHz and at 20°C.
  • the dielectric anisotropy of the respective compound is determined from the results of a solution of 10 % of the respective individual compound in a nematic host mixture. In case the solubility of the respective compound in the host medium is less than
  • the medium is stable enough at least to allow the determination of its properties.
  • the concentration is kept at least at 5 %, however, in order to keep the significance of the results a high as possible.
  • the capacitance of the test mixtures are determined both in a cell with
  • the voltage applied is a P17310 SL
  • the dielectric permittivity of the compounds is determined from the change of the respective values of a host medium upon addition of the compounds of interest. The values are extrapolated to a concentration of the
  • a typical host medium is ZLI-4792 or
  • trans-1 ,4-cyclohexylene denote 1 ,4-phenylene.
  • the invention relates to a compound of formula I
  • R 1 1 denotes P-Sp
  • P denotes a polymerisable group
  • Sp denotes a spacer group or a single bond
  • R 12 denotes F, Cl, CN, NO2, NCO, NCS or a straight-chain or branched alkyl group, which may be unsubstituted,
  • a 1 1 to A 14 each independently in each occurrence denote, 1 ,4-
  • N, trans-1 ,4-cyclo- hexylene in which, in addition, one or two non- adjacent CFI2 groups may be replaced by O and/or S, 1 ,4-cyclohexylene, naphthalene-2, 6-diyl, decahydro-
  • alkoxycarbonyl groups wherein one or more H atoms may be substituted by F or Cl,
  • alkoxycarbonyl groups wherein one or more FI atoms may be substituted by F or Cl,
  • p and q is each and independently 0, 1 , 2, 3 or 4, preferably 0,
  • Sp 11 is a spacer group comprising 1 , 3 or 5 to 40 C atoms, wherein one or more non-adjacent and non-terminal CFI2 groups may also be replaced by -O-, -S-, -NFH-, -N(CH 3 )-, -CO-, -O-CO-, -S-CO-, -O-COO-, -CO-S-, -CO-O-, -CF2-, -CF2O-, -OCF2- -C(OH)-, -CH(alkyl)-,
  • X 11 and X 12 are independently from one another selected from a single bond, -CO-O-, -O-CO-, -O-COO-, -0-,
  • Preferred polymerisable groups are selected from the group consisting of
  • W 1 denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CFI3, W 2 and W 3 each,
  • FI or alkyl having 1 to 5 C atoms in particular FI, methyl, ethyl or n-propyl, W 4 , W 5 and W 6 each, P17310 SL
  • k3 preferably denotes 1
  • k 4 is an integer from 1 to 10.
  • the polymerisable compounds of the formulae I * and II * and sub-formulae thereof contain, instead of one or more radicals R-Sp-, one or more branched radicals
  • R x has the above-mentioned meaning and preferably denotes R° as 20 defined above, aa and bb each, independently of one another, denote 0, 1 , 2, 3, 4, 5 or 6,
  • X has one of the meanings indicated for X', and
  • P 1 5 each, independently of one another, have one of the meanings indicated above for P.
  • Preferred spacer groups Sp are selected from the formula Sp'-X', so that 30 the radical "P-Sp-" conforms to the formula "P-Sp'-X'-", where
  • Sp' denotes alkylene having 1 to 20, preferably 1 to 12 C
  • 35 adjacent CFh groups may each be replaced, independently of one another, by -O-, -S-, -NH-, -NR X -, -SiR x R xx -, -CO-, P17310 SL
  • X' denotes -0-, -S-, -CO-, -COO-, -OCO-, -0-C00-,
  • R x and R xx each, independently of one another, denote FI or alkyl
  • Y 2 and Y 3 each, independently of one another, denote FI, F, Cl or CN.
  • X' is preferably
  • Typical spacer groups Sp' are, for example, -(CH 2 ) PI -, -(CFI 2 CFI 2 0)qi- CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH 2 -NH-CH 2 CH 2 - or -(SiR x R xx -0) Pi -, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R x 25 and R xx have the above-mentioned meanings.
  • Particularly preferred groups -X'-Sp'- are -(CFH 2 ) P I-, -0-(CFI 2 ) pi -, -OCO- (CH 2 ) P I-, -OCOO-(CH 2 ) P I-.
  • Particularly preferred groups Sp' are, for example, in each case straight- chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethyl- ene-N-methyliminoethylene, 1 -methylalkylene, ethenylene, propenylene 35 and butenylene.
  • P17310 SL straight- chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethyl- ene-N-methylimin
  • R 12 is selected from
  • R x is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms.
  • Halogen is preferably F or Cl.
  • R 11 and R 12 are identical.
  • Z in each case independently has one of the meanings of Z 11 as given under formula I and if present twice, preferably one of Z is -COO-, -OCO-, -CF2-O- or
  • a smaller group of preferred groups -A 11 (-Z 11 -A 12 -) p - or -(A 13 -Z 12 -) q A 14 - comprising only 6-membered rings is listed below.
  • Phe in these groups is 1 ,4-phenylene
  • PheL is a 1 ,4-phenylene
  • L which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OH, NO2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO2, CH3,
  • CHex is 1 ,4-cyclohexylene, preferably trans-1 ,4- cyclohexylene,
  • PheL is 1 ,4-phenylene, which is substituted by one, two or three fluorine atoms, by one or two Cl atoms or by one Cl atom and one F atom and
  • Z has one of the meanings of Z 11 as given under partial
  • At least one is preferably selected from -COO-, -OCO-, -OCH2-, -CH2O-, -OCF2- or -CF2O-.
  • PheL preferably denotes the
  • L is preferably F, Cl, CH3, OCH3 and COCH3 .
  • a 14 - each comprise two six-atomic rings or
  • -A 11 (-Z 11 -A 12 -) p - comprises two six-atomic rings and -(A 13 -Z 12 -) q
  • a 14 - comprises three six-atomic rings or -A 11 (-Z 11 -A 12 -) p - comprises three 25 six-atomic rings and or -(A 13 -Z 12 -) q
  • a 14 - comprises two six-atomic rings.
  • -A 11 (-Z 11 -A 12 -) p - or -(A 13 -Z 12 -) q A 14 - are selected as such that both mesogenic groups are mirror images of each other, for example if -A 11 (-Z 11 -A 12 -) p - denotes -Phe-PheL- then
  • Sp 11 denotes -(CFl2)n- with
  • n an integer from 1 to 15, wherein one or more -Chte- groups may be replaced by -CO-, preferably an uneven integer, more preferably 3, 5, 7, 9, 11 or 13,
  • -X 1 1 -Sp 1 1 -Xi2. is -Sp 11 -, -Sp 11 -0-, -Sp 11 -C0-0-, -Sp 11 -0-C0-,
  • 20 -X 11 -sp 11 -x i2 _ denotes -Sp 11 -, -0-Sp 11 -0-, -0CF 2 -Sp 11 -CF 2 0-, or
  • L denotes each and independently in each occurrence F, Cl,
  • r denotes an integer between 0 and 4, preferably 0, 1 or 2
  • n denotes 3, 5, 7, 9, 11 or 13
  • L denotes each and independently in each occurrence F, Cl,
  • n denotes 3, 5, 7, 9, 11 or 13, preferably 7, 9 or 11 , and
  • P denotes acrylate or methacrylate.
  • Especially preferred compounds of formula I are selected from the substructure, 1-2-1 to I-2-3, 1-4-1 to I-4-3, 1-6-1 to I-6-3 and 1-8-1 to I-8-3, 25 preferably from , 1-2-1 , 1-2-3, 1-4-1 , I-4-3, 1-6-1 , I-6-3, 1-8-1 and l-8-3,more preferably from 1-2-1 , 1-4-1 , 1-6-1 and 1-8-1 , wherein L, if present, denotes F, n denotes 7, 9 or 11 and P denotes acrylate or methacrylate.
  • the compounds of formula I can be synthesized according to or in 30 analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Flouben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the compounds of formula I can be polymerised or cross-linked (if a 35 compound contains two or more polymerisable groups) by in-situ
  • Suitable and preferred polymerisation methods are, for example, thermal or photopolymerisation, preferably photopolymerisa- tion, in particular UV photopolymerisation. If necessary, one or more initiators may also be added here. Suitable conditions for the polymerisa-
  • Suitable for free-radical polymerisation are, for example, the commercially available photoinitiators Irgacure651 ® , Irgacure184 ® , Irgacure907®, Irgacure369 ® or Darocurel 173 ® (Ciba AG). If an initiator is employed, its proportion in
  • the mixture as a whole is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1 % by weight.
  • the polymerisation can also take place without addition of an initiator.
  • the LC medium does not comprise a polymerisation initiator.
  • the liquid-crystalline 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
  • stabilisers of the Irganox ® series (Ciba AG). If stabilisers are employed, their proportion, based on the total amount of RMs or polymerisable compounds, is preferably 10 - 5000 ppm, particularly preferably 50 - 500 ppm.
  • the compounds of formula I are also suitable for polymerisation without initiator, which is associated with considerable advantages, such as, 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 compounds of formula I can be added individually to the liquid- crystalline medium, but it is also possible to use mixtures comprising two or more polymerisable compounds. On polymerisation of mixtures of this type, copolymers are formed.
  • the invention also relates to the use of compounds of formula I in LC media and to a LC media comprising one or more compounds of formula I, as such.
  • the LC media in accordance with the present 10 invention comprise one or more compounds of formula II,
  • R 21 and R 22 denote independently H, F, Cl, CN, N0 2 , NCS or a
  • 25 preferably F, Cl, CN, a straight-chain or branched alkyl or alkoxy group which may be unsubstituted, mono- or polysubstituted by halogen or CN,
  • a 21 to A 24 denote independently in each occurrence a aryl-
  • FI atoms may be substituted by F or Cl
  • a denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula II are selected from compounds in which the groups (-A 21 -A 22 -) and (-A 23 -A 24 -) are each and independently selected from the following groups
  • Phe in these groups is 1 ,4-phenylene
  • PheL is a 1 ,4-phenylene group which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OFI, NO2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1
  • 35 to 7 C atoms very preferably F, Cl, CN, OFI, NO2, CFI3,
  • Cyc is 1 ,4-cyclohexylene.
  • 30 n denotes an integer from 1 to 15, preferably an odd (i.e.
  • the compounds of formula II can be synthesized according to or in analogy to methods which are known per se and which are described in
  • the LC media in accordance with the present 10 invention comprise one or more compounds of formula III,
  • R 31 and R 32 have each and independently from another one of the meanings as given for R 21 and R 22 under formula II,
  • a 31 to A 36 have each and independently from another one of the meanings as given for A 21 to A 24 under formula II,
  • Z 31 and Z 32 are each independently in each occurrence
  • -CF CF-
  • -CH CH-COO-
  • -OCO-CH CH- or -CoC-
  • b denotes an integer from 1 to 15, preferably an odd (i.e.
  • C denotes 0 or 1 , preferably 0.
  • Preferred compounds of formula III are selected from compounds in
  • Phe, PheL an L have one of the meanings given above for the groups MG-1 to MG-4.
  • the compounds of formula III can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl,
  • the LC medium in accordance with the present invention comprises one or more compounds of formula IV,
  • R 41 and R 42 have each and independently one of the meanings as given above for R 21 under formula II,
  • a 41 to A 44 have each and independently one of the meanings as given above for A 21 under formula II,
  • Z 41 and Z 42 are each independently in each occurrence
  • d denotes an integer from 1 to 15, preferably an odd (i.e.
  • Especially preferred compounds of formula IV are selected from the
  • the compounds of formula IV are either known or can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-
  • the LC medium in accordance with the present invention additionally comprises one or more compounds of formula V,
  • R 51 and R 52 have each and independently one of the meanings as 25 given above for R 21 under formula II,
  • a 51 to A 53 have each and independently one of the meanings as given above for A 21 under formula II,
  • e denotes an integer from 1 to 15, preferably an odd (i.e.
  • a 51 is selected from the following group of formulae Va’ to Vf and the mirror images of formulae Vd’ and Ve’
  • R 51 and R 52 in formula V are selected of H, F, Cl, CN, NO 2 , OCHs, COCH3, COC2H5, COOCHs, COOC2H5, CFs, C2F5, OCFs, OCHF2 and OC 2 F 5 , in particular of FI, F, Cl, CN, OCFI3 and OCF3, especially of
  • Preferred compounds of formula V are selected from the group of compounds of formulae VA to VD, preferably of formulae VA and/or VC, most preferably of formula VC,
  • LG 51 is Z 51 -(CH 2 ) Z -Z 52 ,
  • Z 51 -(CH 2 ) z -Z 52 denotes -0-C0-(CH 2 ) n -C0-0-, -0-(CH 2 ) n -0- or -(CFI 2 ) n -, more preferably -0-C0-(CFI 2 ) n -C0-0-, wherein n denotes 3, 5, 7 or 9,
  • Particularly preferred compounds of formula VA are selected from the group of compounds of formulae VA-1 to VA-3
  • Particularly preferred compounds of formula VB are selected from the group of compounds of formulae VB-1 to VB-3
  • Compounds of formula VC are very much preferred. And of these particularly preferred compounds are selected from the group of compounds of formulae VC-1 to VC-3
  • the compounds of formula V can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben- Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. A 5 preferred method of preparation is disclosed for example in
  • the LC medium in accordance with the present invention additionally comprises one or more compounds of 10 formula VI,
  • R 61 and R 62 have each and independently one of the meanings as given above for R 21 under formula II,
  • a 61 to A 64 have each and independently one of the meanings as given above for A 21 under formula II,
  • Z 61 denotes -0-, -COO-, -OCO-, -0-C0-0-, -OCH2-, -CH2O,
  • 9 denotes an integer from 1 to 15, preferably an odd (i.e.
  • Preferred compounds of formula VI are selected from compounds in which the groups (-A 61 -A 62 -) and (-A 63 -A 64 -) are each and independently selected from the groups of MG1 to MG4 as given above.
  • the compounds of formula VI can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • Houben-Weyl Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the LC medium in accordance with the present invention additionally comprises one, two, three or more compounds of formula VII,
  • R 71 and R 72 have each and independently one of the meanings as given above for R 21 under formula II,
  • a 71 to A 76 have each and independently one of the meanings as given above for A 21 under formula II,
  • Z 71 to Z 74 each and independently denotes -COO-, -OCO-,
  • j denotes an integer from 1 to 15, preferably an odd (i.e.
  • i and k each and independently denotes 0 or 1.
  • Preferred compounds of formula VII are selected from compounds in which at least one of the groups -A 71 -Z 71 -A 72 -(Z 72 -A 73 ),-,
  • L is in each occurrence independently of each other preferably F, Cl, CN or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, CFb, C2FI5, OCFI3, OC2FI5, COCFI3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, in particular F, Cl, CN, CFI3, C2FI5, OCFI3, COCFI3 and OCF3, most preferably F, Cl, CFI3, OCFI3 and COCFI3 and r is in each occurrence independently of each other 0, 1 , 2, 3 or 4, preferably 0, 1 or 2.
  • L is preferably F, Cl, CFb, OCH3 and COCH3 .
  • i and k both denote 1 , more preferably one of i and k denotes 0 and the other 1 , most 10 preferably i and k both denote 0.
  • Especially preferred compounds of formula VII are selected from the group of compounds of the following formulae,
  • R 71 and R 72 each and independently denote F or CN.
  • the compounds of formula VII can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • Houben-Weyl Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
  • the medium in accordance with the present invention optionally comprises one or more chiral dopants
  • the chiral compounds induce a chiral nematic texture with a pitch (Po), which is in a first approximation inversely proportional to the
  • HTP helical twisting power
  • a uniform lying helix texture is realized using a chiral nematic liquid crystal with a short pitch, typically in the range from 0.2 pm to 1 pm, preferably of 1.0 pm or less, in particular of 0.5 pm or less,
  • the helical axis of the chiral nematic liquid crystal is equivalent to the optical axis of a birefringent plate.
  • chiral dopants with a high helical twisting power in particular those disclosed in WO 98/00428.
  • used chiral dopants are e.g. the commercially available
  • the chiral dopants are preferably selected from formula VIII,
  • E and F are each independently 1 ,4-phenylene or trans-1 ,4- cyclohexylene, v is 0 or 1 , Z° is -COO-, -OCO-, -CH2CH2- or a single bond and R is alkyl, alkoxy or alkanoyl with 1 to 12 C atoms.
  • the liquid crystalline medium preferably comprises preferably 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral dopants, preferably selected
  • R-5011 or S-5011 very preferably, the chiral compound is R-5011 , or S-5011.
  • the amount of chiral compounds in the liquid crystalline medium is 20 preferably from 0.1 to 15 %, in particular from 0.5 to 10 %, very
  • the LC medium comprises one or more nematic LC
  • L 1 and L 2 each, independently of one another, denote F, Cl, CF3 or CFIF 2 , preferably each denote F,
  • the liquid crystal media may contain further additives like for example stabilizers, inhibitors, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive
  • the total concentration of these further constituents is in the range of 0.1 % to 10 %, preferably 0.1 % to 6 %, based on the total mixture.
  • concentrations of the individual compounds used each are preferably in the range of 0.1 % to 3 %.
  • the liquid crystal media according to the present invention consists of several compounds, preferably of 2 to 40, more preferably of 3 to 30 and
  • 25 most preferably of 4 to 25 compounds.
  • the media in accordance with the present invention exhibit high values of the elastic constant kn and a high flexoelectric coefficient e.
  • the liquid crystal media preferably exhibit a kn ⁇ 100 pN, preferably ⁇ 20 pN.
  • the liquid crystal media preferably exhibit a k 3 3 £ 100 pN, preferably ⁇ 15 pN.
  • the liquid crystal media preferably exhibit a flexoelectric coefficient
  • the liquid crystal media preferably exhibit a flexoelectric coefficient
  • the liquid crystal media preferably exhibit a flexo-elastic ratio (e / K) in
  • V 1 the range from 1 to 10 V 1 , preferably in the range from 1 to 7 V 1 , more preferably in the range from 1 to 5 V 1 .
  • the media in accordance with the present invention exhibit high clearing points up to 60°C and higher, preferably up 65°C and higher and more
  • the media in accordance with the present invention exhibit broad nematic phases of 30°C and more, preferably 35°C and more or even 40°C or more.
  • the media in accordance with the present invention exhibit NTB phases below 20°C or less, preferably below 15°C or less and more preferably below 0°C or less.
  • the media in accordance with the present invention exhibit high
  • the media do not crystallize even at temperatures down to 0°C, preferably down to -10°C, more preferably down to -20°C.
  • the LC medium comprises:
  • the amount of compounds of formula I in the liquid crystalline medium as a whole is preferably in the range from 1 to 50 %, in particular in the range from 2 to 30
  • 10 medium if present, is preferably in the range from 0 to 30 %, more preferably in the range from 1 to 20 %, even more preferably in the range from 2 to 10 % by weight of the total mixture, and/or
  • 20 crystalline medium if present, is preferably in the range from 1 to
  • crystalline medium if present, is preferably in the range from 1 to 98 %, more preferably in the range from 20 to 80 %, even more preferably in the range from 30 to 60 % by weight of the total mixture,
  • formula V in the liquid crystalline medium is preferably in the range from 1 to 70 %, more preferably in the range from 10 to 60 %, even more preferably in the range from 20 to 50 % by weight of the total mixture,
  • the amount of compounds of formula VI in the liquid crystalline medium is preferably from 1 to 40 %, in particular from 5 to 25 %, very preferably 10 to 15 % by weight of the total mixture,
  • the amount of compounds of formula VII in the liquid crystalline medium is preferably from 1 to 35 %, in particular from 5 to 25 %, very preferably 10 to 15 % by weight of the total mixture,
  • 35 in the liquid crystalline medium is preferably from 1 to P17310 SL
  • the amount of compounds of formula X in the liquid crystalline medium as a whole is preferably from 1 to 50 %, in
  • additives such as for example, polymerisation initiatore, stabilizers, antioxidants, etc. in usual concentrations.
  • the total concentration of these further constituents, if present, is in the range of 0.1 to 10 %, preferably 0.1 to 6 %, based on the total mixture.
  • concentrations of the individual compounds is in the range of 0.1 to 10 %, preferably 0.1 to 6 %, based on the total mixture.
  • the LC medium of the present invention consists only of compounds selected from formula I to X, very preferably the LC medium consists only of compounds selected from
  • the LC medium of the present invention consists only of compounds selected from formula I to X wherein none of the compounds contains a CN group. It is well know that
  • the compounds forming the LC medium in accordance with the present invention are mixed in conventional way. As a rule, the required amount of the compound used in the smaller amount is dissolved in the
  • the clearing point of the compound used in the higher concentration it is particularly easy to observe completion of the process of dissolution. It is, however, also possible to prepare the media by other conventional ways, e.g. using so-called pre-mixtures, which can be e.g. homologous or eutectic media of compounds or using so-called multi-bottle-systems, the
  • invention also relates to a process for the production of an LC medium as described above and below.
  • the invention relates to a process for the production of an
  • liquid crystalline media in accordance with the present invention can be any liquid crystalline media in accordance with the present invention.
  • liquid crystal devices such as STN, TN, AMD-TN, temperature compensation, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays, in active and passive optical elements like polarizers, compensators, reflectors, alignment layers, colour filters or
  • LC medium comprising at least one
  • the liquid crystal device in accordance with the present invention is particularly beneficially for flexoelectric liquid crystal display applications, such as, for example, devices of the ULH or USH mode.
  • the liquid crystal device is preferably a PS-display, particularly preferably a PS-ULH or PS-USH.
  • Another object of the present invention is a electro optical device
  • flexoelectric device 5 preferably a flexoelectric device, obtainable or obtained by the process described above.
  • the construction of the flexoelectric electro optical device according to the invention corresponds to the usual geometry for ULH or USH
  • a flexoelectric electro optical device according to a preferred
  • embodiment of the present invention comprises two plane parallel substrates, preferably glass plates covered with a transparent conductive
  • ITO indium tin oxide
  • the optical axis is rotated in the plane of the cell, similar as the
  • the field induces a splay bend structure in the director, which is
  • the angle of the rotation of the axis is in first approximation directly and linearly proportional to the strength of the electrical field.
  • the optical effect is best seen when the liquid crystal cell is placed between crossed polarizers with the optical axis in the unpowered state at an angle of 22.5° to the absorption axis of
  • This angle of 22.5° is also the ideal angle of
  • the optical axis is rotated by 45° and by appropriate selection of the relative orientations of the preferred direction of the axis of the helix, the absorption axis of the polarizer and the direction of the electric field, the
  • 35 optical axis can be switched from parallel to one polarizer to the centre angle between both polarizers.
  • the optimum contrast is then achieved P17310 SL
  • the arrangement can be used as a switchable quarter wave plate, provided the optical retardation, i. e. the product of the effective birefringence of the liquid crystal and the cell gap, is selected to be the
  • the wavelength referred to is 550 nm, the wavelength for which the sensitivity of the human eye is highest, unless explicitly stated otherwise.
  • e / K is called the flexo-elastic ratio.
  • This angle of rotation is half the switching angle in a flexoelectric switching element.
  • g is the effective viscosity coefficient associated with the distortion of the helix.
  • the flexoelectric effect is characterized by fast response times (T 0n+ T 0ff at 35°C) typically ranging from 1 ms to 10 ms, preferably ⁇ 5ms and even more preferably ⁇ 3ms. It further features excellent grey scale capability.
  • De is the dielectric anisotropy of the liquid crystal.
  • inventive media in accordance with the present invention can be aligned in their cholesteric phase into different states of orientation by methods that are known to the expert, such as surface treatment or electric fields. For example, they can be aligned into the planar
  • planar alignment or orientation of a liquid crystal
  • mesogenic material in a display cell or on a substrate means that the mesogenic groups in the liquid crystal or mesogenic material are
  • the term“homeotropic alignment” or orientation of a liquid crystal or mesogenic material in a display cell or on a substrate means that the
  • the sample is placed into a cell comprising two plane-parallel glass plates coated with electrode layers, e.g. ITO layers and aligned in its cholesteric phase into a planar state
  • This state is also known as Grandjean state and the texture of the sample, which is observable e.g. in a polarization microscope, as Grandjean texture.
  • Planar alignment can be achieved e.g. by surface treatment of the cell walls, for example by rubbing and/or coating with an alignment layer
  • a Grandjean state with a high quality of alignment and only few defects can further be achieved by heating the sample to the isotropic phase, subsequently cooling to the chiral nematic phase at a temperature close
  • the sample shows selective reflection of incident light, with the central wavelength of reflection depending on the helical pitch
  • the sample When an electric field is applied to the electrodes, for example with a frequency from 10 Hz to 1 kHz and an amplitude of up to 12 V rms /pm, the sample is being switched into a homeotropic state where the helix is
  • the sample is transmissive when viewed in normal daylight and appears black when being put between crossed polarizers.
  • the sample Upon reduction or removal of the electric field in the homeotropic state, the sample adopts a focal conic texture, where the molecules exhibit a helically twisted structure with the helical axis being oriented
  • a focal conic state can also be achieved by applying only a weak electric
  • the respective state of orientation, as well as its quality of alignment can be controlled by measuring the light transmission of the sample depending on the strength of the applied electric field. Thereby it is also possible to determine the electric field strength required to
  • the above-described focal conic state consists of many disordered
  • this texture is also called uniformly lying helix (ULH) texture. This texture is required to characterize the flexoelectric properties of the inventive compound.
  • the inventive media can be subjected to
  • the field frequency may
  • the invention relates to a process of preparing such electro optical device comprising the steps of
  • the LC medium is provided as a layer between two substrates forming a cell.
  • the LC medium is filled into the cell.
  • Conventional filling methods can be used which are known to the skilled person, like for example the so-called “one-drop filling” (ODF), which are preferably carried out in a vacuum.
  • ODF one-drop filling
  • the LC medium is heated above the clearing point of the mixture into its isotropic phase.
  • the LC medium is heated 1 °C or more above the clearing point, more preferably 5°C or more above the clearing point and even more preferably 10°C above the
  • the LC medium is cooled below the clearing point of the mixture.
  • the LC medium is cooled 1 °C or less below the clearing point, more preferably 5°C or less below the clearing
  • the cooling rate is preferably -10°C/min or less, more preferably - 5°C/min or less, in particular -2°C/min or less.
  • a voltage preferably an AC voltage
  • Suitable and preferred field strength are in the range from 1 Vprrr 1 to 15 Vprrr 1 , preferably from 3 Vprrr 1 to 10 Vprrr 1 .
  • the applied voltage stays constant during the following irradiation step. It is likewise preferred, that the applied voltage is increased or decreased.
  • step c the electro optical device is exposed to photoradiation that causes photopolymerisation of the polymerisable functional groups of the compounds of formula I contained in the LC medium.
  • steps c the electro optical device is exposed to photoradiation that causes photopolymerisation of the polymerisable functional groups of the compounds of formula I contained in the LC medium.
  • these compounds are polymerised or crosslinked (in case of compounds with two or more polymerisable groups) in situ within
  • the polymerisation is induced for example by exposure to UV radiation.
  • the wavelength of the photoradiation should not be too low, in order to
  • the wavelength of the photoradiation should not be too high, so as to allow quick and complete UV
  • component A should be not higher than, preferably the same as or lower than the UV absorption maximum of the polymerisable component (component A).
  • Suitable wavelengths are from 300 to 450 nm, for example 305, 320 or 340, 376 or 410 nm.
  • the irradiation or exposure time should be selected such that
  • Suitable and preferred exposure times are in the range from 30 seconds to 20 minutes, preferably from 1 minute to 15 minutes.
  • Suitable and preferred radiation intensities are in the range from 1 to 300 mW/cm 2 , preferably from 2 to 200 mW/cm 2 , preferably from 3 to
  • a voltage preferably an AC voltage
  • Suitable and preferred electric fields are in the range from 0.3 to 10 Vprrr 1 , preferably from 1 to 7 Vprrr 1 .
  • the steps c) and d) can be repeated once, twice or more than two times.
  • step d can be the same as or different from that of step c). If a voltage is applied in step d), it is preferably the same or lower than in step c).
  • the media in accordance with the present invention are also suitable for other types of displays and other optical and electro optical applications, such as optical
  • the LC media may also comprise compounds in which, for example, H, N, O, Cl, F
  • T N,I clearing point
  • K crystalline
  • N nematic
  • NTB second nematic or twist-bend nematic phase

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Abstract

L'invention porte sur des composés de formule (I) : R11-A11-(Z11-A12)p-X11-Sp11-X12-(A13-Z13)q-A14-R12, dans laquelle les R11, R12, A11 à A<u>14</u>, Z11, Z13, X11, X12, Sp11, p et q ont l'une des significations telles qu'indiquées dans la description ci-dessous. L'invention porte en outre sur un procédé de production des composés de formule (I), l'utilisation desdits composés dans des milieux à cristaux liquides (CL) et des milieux à CL comprenant un ou plusieurs composés de formule (I). En outre, l'invention porte sur un procédé de production de tels milieux à CL, l'utilisation de tels milieux dans un dispositif électro-optique, en particulier dans un dispositif électro-optique flexoélectrique, et un dispositif électro-optique flexoélectrique, en tant que tel.
PCT/EP2018/085101 2017-12-18 2018-12-17 Composé à cristaux liquides et milieu à cristaux liquides WO2019121438A1 (fr)

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