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Definitions

• the present invention describes new compounds.
• LCDs such as multiplexed Twisted Nematic TN-LCDs, Super Twisted Nematic STN-LCDs, Super Birefringent SBE-LCDs, Electrically Controlled Birefringence ECB-LCDs, or flexoelectric LCDs are currently used or being developed for computer monitors, laptop or notebook computers, portable telephones, video telephones, personal digital assistants, etc.
• the optical, electrical and temporal performance, e.g., contrast, threshold and driving voltages, and response times, of such displays depends crucially on the ratios of the elastic constants (k 33 , k 22 , k ) and the cell gap, d.
• trans- 1 ,4- disubstituted-cyclohexyl derivatives with a terminal alkenyl chain (i.e., incorporating a carbon-carbon double bond) directly attached to the cyclohexane ring in order to produce the necessary elastic constant ratios for short response times, high multiplexing rates and low driving voltages.
• Such materials are costly and difficult to synthesise due to the requirement for a trans configuration of the 1 ,4-disubstituted cyclohexane ring and the necessity of synthesising the carbon-carbon double bond stepwise from this trans ,4-disubstituted- cyclohexyl intermediate.
• the carbon-carbon double bond is substituted at both carbon atoms, it must have a trans (E) configuration in order to exhibit an advantageous combination of elastic constants and to have an acceptably high nematic-isotropic transition temperature (N-l).
• the trans configuration is then generally produced by isomerisation of the cis (Z) form generated by the preceding Wittig reaction.
• TN-LCDs using thin film transistors (TFTs) as the backplate for active addressing require nematic liquid crystal mixtures with a positive dielectric anisotropy ( ⁇ ) and a very high resistivity (holding ratio >98%) in order to avoid dielectric breakdown and inferior display performance. It has been shown that standard nematic liquid crystals with a terminal cyano group are unsuitable for TN-TFT-LCDs since they lead to low resisitivity values due in part to their ability to solvate ions present in the alignment layers and electrodes. This has led to the wide-spread use of
• N-l nematic-isotropic transition temperatures
• Liquid crystals with a trifluoromethyl group are known and are described in for example P. Le Barney, G. Ravaux, J. C. Dubois and J. P. Parneix, Mol. Cryst. Liq. Cryst, (1985), Vol. 127, pp 413 and EPA 0 480 217.
• Liquid crystal materials comprising fluorine containing end-groups are described in WO 98/13321 , WO 96/05159, WO 90/13610, DE 4415882 and DE 4222371.
• the present invention seeks to overcome or alleviate some of the above problems.
• n may be 0, 1 or 2
• A-,, A 2 , A 3 are independently chosen from 1 ,4-disubstituted benzene, 2,5-disubstituted pyrimidine, 2,5-disubstituted pyridine, 2,6-disubstituted naphthalene; laterally substituted 1 ,4-disubstituted benzene, laterally substituted 2,5-disubstituted pyrimidine, laterally substituted 2,5-disubstituted pyridine, laterally substituted 2,6- disubstituted naphthalene wherein the lateral substituents are independently selected from F, Cl, Br or CN and may be present in any of the available substitution positions; 1 ,4-disubstituted bicyclo(2.2.2)octane, trar/s-1 ,4-disubstituted cyclohexane, trans-2,5- disubstituted dioxane, 1
• R may be alkyl, alkoxy, alkenyl, alkenyloxy, alkanoyloxy, alkenoyloxy or OC m F 2m+1 , R may contain 1 to 20 carbon atoms and may be branched or a straight chain; m is 1-20.
• n is 0 or 1 ;
• a ⁇ A 2 , A 3 are 1 ,4-disubstituted benzene, 2,5-disubstituted pyrimidine, trans-2,5- disubstituted dioxane, 1 ,4-disubstituted piperidine, or trans- 1 ,4-disubstituted cyclohexane;
• R is alkyl, alkoxy, alkenyl or alkenyloxy and has one to seven carbon atoms.
• R is alkyl, alkoxy, alkenyl or alkenyloxy and has one to seven carbon atoms.
• Especially preferred structures for formula I are those listed below:
• R is alkyl, alkoxy, alkenyl or alkenyoxy and contains 1-7 carbon atoms.
• Compounds of formula I can be prepared by various routes.
• the ethers can be prepared by the Mitsunobu reaction (Synthesis, (1981) pp 1) of a phenol with an ⁇ , ⁇ , ⁇ - trifluoroalcohol in the presence of triphenyl phosphine, a dehydrating agent, such as diethyl azodicarboxylate, and a suitable solvent, such as tetrahydrofuran or N,N'- dimethylformamide.
• ⁇ , ⁇ , ⁇ -trifluoroalkyl bromide or the tosylate of the appropriate ⁇ , ⁇ , ⁇ -trifluoroalkanol in the presence of a suitable base, such as potassium carbonate, and a suitable solvent, such as ethyl methyl ketone or cyclohexanone in a Williamson ether synthesis.
• a suitable base such as potassium carbonate
• a suitable solvent such as ethyl methyl ketone or cyclohexanone in a Williamson ether synthesis.
• the dioxanes can be prepared by reaction of an aldehyde with a 2-substituted 1 ,3-diol in an appropriate solvent such as toluene catalysed by a small amount of an acid such as sulphuric acid or toluene-4- sulphonic acid under azeotropic removal of water.
• N-Arylpiperidines can be obtained by condensation of a 4-substituted piperidine with an aryl fluoride with an appropriate base such as potassium carbonate in a suitable solvent such as acetonitrile or hexamethylphosphoric triamide (Synthesis, (1981), pp 606).
• the (£)-5,5,5-trifluropent-1-enyl substituted compounds can be prepared using a Wittig reaction involving a 4,4,4-trifluorobutanal and appropriate Wittig salts (EPA 0 480 217 A2) in a suitable solvent such as tetrahydrofuran or dimethoxyethane with an appropriate base such as potassium tert.-butoxide or butyl lithium.
• the corresponding 5,5,5-trifluoropentyl substituted compounds can be prepared by hydrogenation of the (E)-5,5,5-trifluropent-1-enyl substituted compounds with hydrogen over a suitable catalyst such as palladium on charcoal in an appropriate solvent such as toluene or ethyl acetate.
• 1 ,2-Disubstituted acetylenes and tolanes can be prepared by metal catalysed cross-coupling reactions of mono-substituted acetylenes with aryl and cyclohexyl halides or triflates in the presence of an appropriate base such as triethylamine and appropriate metal based catalysts such as tetrakis(t phenylphosphine)palladium(0) and copper(l)iodide or palladium(ll) acetate and triorthotoluylphosphine ligands (Mol. Cryst. Liq. Cryst., (1990), Vol. 148, pp 193; Mol. Cryst.
• esters can be prepared by esterification (Angewandte Chemie (1978) Vol. 90, pp 556) of the appropriate phenol or secondary alcohol with an alkanoic acid or alkenoic acid in the presence of 4-(dimethylamino)pyridine, a dehydrating agent, such as N, N'- dicyclohexylcarbodiiimide, and a suitable solvent, such as dichloromethane or N, N'- dimethylformamide.
• a dehydrating agent such as N, N'- dicyclohexylcarbodiiimide
• suitable solvent such as dichloromethane or N, N'- dimethylformamide.
• alkanoic or alkenoic acid chloride produced, for example, from the corresponding alkanoic or alkenoic acid by the action of thionyl chloride or oxalyl chloride
• a base such as pyridine or triethylamine
• a suitable solvent such as toluene or dichloromethane
• Figure 1 is a plan view of a matrix multiplex addressed liquid crystal display
• Figure 2 is a cross-section of a display such as Figure 1 used in a transmissive mode
• Figure 3 is similar to Figure 2 but operates in a reflective mode.
• K refers to the crystalline state
• N the nematic phase
• SmB a smectic B phase
• SmX an undefined crystal smectic phase.
• Values contained in brackets [ ] are nematic-isotropic transition temperatures extrapolated from mixtures of individual compounds and the commercially available (Merck, Darmstadt) nematic mixture ZLI 3086.
• the (E)-4,4,4-trifluorobut-2-enyl toluene-4-sulfonate required as starting material could be prepared as follows:
• the 1-fluoro-4-[4,4,4-trifluorobutyloxy]benzene required as starting material could be prepared as follows:
• a mixture of potassium tert.-butylate (2.9 g) is added portionwise to a mixture of 4,4,4- trifluorobutanal (1.0 g), 4-(trar/s-4-propylcyclohexyl)phenyl)methylphosphoniumbromide (3.1 g) and tetrahydrofuran (100 cm 3 ) at 0 °C.
• the reaction is stirred for a further 2 h at room temperature and then poured into water (500 cm 3 ).
• the organic layer is separated off and the aqueous layer extracted with diethyl ether (4 x 100 cm 3 ).
• the combined organic layers were washed with brine (2 x 200 cm 3 ), dried (MgSO 4 ), filtered and then evaporated down.
• 1-enyl]cyclohexane is dissolved in a mixture of ethanol (50 cm 3 ), water (1 cm 3 ) and freshly prepared benzene sulphinic acid (2 g), heated at 65 °C for 48 h and then poured into water
• the 4,4,4-trifluorobutanal required as starting material could be prepared as follows
• % palladium on charcoal (0.2 g) and toluene (20 cm 3 ) is hydrogenated until the absorption of hydrogen is completed.
• the inorganic material was removed by filtration and the filtrate evaporated down.
• the residue is purified by column chromatography on silica gel using a 95:5 hexane/ethyl acetate mixture as eluent and recrystallisation from ethanol to yield 0.7 g of 1-(trans-4-propylcyclohexyl)-4-(5,5,5-trifluoropentyl)benzene.
• the crude product is purified by column chromatography on silica gel using a 9:1 petroleum ether (40-60°C)/ethyl acetate mixture as eluent, followed by recrystallisation from ethanol to yield 1-(4-[(E)-hex-2-enoyloxy]phenyl)-2- (4-[4,4,4-trifluorobutyloxy]phenyl)acetylene (0.26 g).
• the 1-(4-hydroxyphenyl)-2-(4-[4,4,4-trifluorobutyloxy]phenyl)acetylene required as starting material could be prepared as follows:
• the compounds were individually doped 10% into the host and the clearing points determined.
• the structure of the compounds and the phase behaviour of the mixtures is detailed in Table 1.
• a compound WD30 is shown for comparison.
• Table 2 The birefringence and refractive indices of the mixtures were determined and the results are shown in Table 3 with DOP-017 for comparison.
• twisted nematic (TN) device which uses a thin layer of a nematic material between glass slides.
• the slides are unidirectionally rubbed and assembled with the rubbing directions orthogonal.
• the rubbing gives a surface alignment to the liquid crystal molecules resulting in a progressive 90° twist across the layer.
• polarisers with their optical axis perpendicular or parallel to a rubbing direction the device rotates the plane of polarised light in its OFF state and transmits without rotation in the ON state.
• Small amounts of cholesteric material may be added to the nematic material to ensure the 90° twist is of the same sense across the whole area of the device as explained in UK patents 1 ,472,247 and 1 ,478,592.
• the display of Figures 1 and 2 comprises a liquid crystal cell 1 formed by a layer 2 of cholesteric liquid crystal material contained between glass walls 3,4.
• a spacer ring 5 maintains the walls typically 6 ⁇ m apart.
• passive matrix devices strip like row electrodes 6-, to 6 m , e.g. of SnO 2 are formed on one wall 3 and similar column electrodes 7, to 7 n formed on the other wall 4. With m-row electrodes and n-column electrodes this forms an mxn matrix of addressable elements. Each element is formed by the interaction of a row and column electrode.
• a discrete nonlinear device eg a transistor or diode is associated with each pixel.
• a row driver supplies voltage to each row electrode 6.
• a column drive 9 supplies voltages to each column electrode 7.
• Control of applied voltages is from a control logic 10 which receives power from a voltage source 11 and timing from a clock 12.
• TFT AMLCD thin film transistor active matrix liquid crystal device
• three types of electrodes are present, pixel, scanning and signal electrodes as well as a common electrode on the opposite side of the liquid crystal.
• the control electrode operates the gate such that the voltage on the signal electrode is applied to the relevant pixel electrode.
• the liquid crystal device consists of two transparent plates, 3 and 4, for example made from glass, in the case of an active matrix device these will usually be ofaluminosilicate (alkali free) glass often with a passivation layer of SiO 2 .
• active matrix display the active devices eg thin film transistors, are fabricated and the colour filter layer is added for a full colour display.
• These plates are coated on their internal face with transparent conducting electrodes 6 and 7, often ITO which is patterned using photolithography techniques.
• An alignmentlayer is introduced onto the internal faces of the cell so that a planar orientation of the molecules making up the liquid crystalline material will be approximately parallel to the glass plates 3 and
• the alignment directions are orthogonal. Prior to the construction of the cell the alignment layers are rubbed with a roller covered in cloth (for example made from velvet) in a given direction, the rubbing directions being arranged parallel
• a spacer 5 e.g. ofpolymethyl methacrylate separates the glass plates 3 and 4 to a suitable distance e.g. 2-7 microns preferably 4-6 microns.
• Liquid crystal material 2 is introduced between glass plates 3,4 by filling the space in between them. This may be done by flow filling the cell using standard techniques.
• the spacer 5 is sealed with an adhesive in a vacuum using an existing technique.
• Polarisers 13 may be arranged in front of and behind the cell.
• Alignment layers may be introduced onto one or more of the cell walls by one or more of the standard surface treatment techniques such as rubbing, oblique evaporation or as described above by the use of polymer aligning layers.
• the substrates with the aligning layers on them are heated and sheared to induce alignment
• the substrates with the aligning layers are thermally annealed above the glass transition temperature and below the liquid crystal to isotropic phase transition in combination with an applied field.
• Further embodiments may involve a combination of these aligning techniques. With some of these combinations an alignment layer may not be necessary. It is also possible to use so-called non-contact alignment layers in both passive and active devices described by the current invention.
• the device may operate in atransmissive or reflective mode.
• atransmissive or reflective mode In the former, light passing through the device, e.g. from a tungsten bulb, is selectively transmitted or blocked to form the desired display.
• a mirror, or diffuse reflector, (16) is placed behind the second polariser 13 to reflect ambient light back through the cell and twopolarisers.
• the alignment layers have two functions, one to align contacting liquid crystal molecules in a preferred direction and the other to give a tilt to these molecules - a so called surface tilt - of a few degrees typically around 4° or 5°.
• the alignment layers may be formed by placing a few drops of the polyimide on to the cell wall and spinning the wall until a uniform thickness is obtained.
• the polyimide is then cured by heating to a predetermined temperature for a predetermined time followed by unidirectional rubbing with a roller coated with a nylon cloth.
• a single polariser and dye material may be combined.
• the materials of the current invention may also be used in LCDs with an actively addressed matrix e.g. thin film transistors (TFT-LCDs) or a passively addressed matrix e.g., dual scan

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Liquid Crystal Substances (AREA)
• Pyridine Compounds (AREA)
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• 1998
  • 1998-12-24 GB GBGB9828427.6A patent/GB9828427D0/en not_active Ceased
• 1999
  • 1999-12-17 JP JP2000590975A patent/JP2004507438A/ja not_active Withdrawn
  • 1999-12-17 EP EP99962342A patent/EP1150937A1/de not_active Withdrawn
  • 1999-12-17 WO PCT/GB1999/004292 patent/WO2000039062A1/en not_active Application Discontinuation

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