WO1995009379A1 - Retardation layer having a dispersion adapted to the active liquid-crystalline cell - Google Patents

Retardation layer having a dispersion adapted to the active liquid-crystalline cell Download PDF

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Publication number
WO1995009379A1
WO1995009379A1 PCT/EP1994/003246 EP9403246W WO9509379A1 WO 1995009379 A1 WO1995009379 A1 WO 1995009379A1 EP 9403246 W EP9403246 W EP 9403246W WO 9509379 A1 WO9509379 A1 WO 9509379A1
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Prior art keywords
liquid
crystalline
dispersion
retardation layer
molecular weight
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PCT/EP1994/003246
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French (fr)
Inventor
Martin Bosma
Jan Willem Venema
Stephen James Picken
Gustaaf Ronald MÖHLMANN
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Akzo Nobel N.V.
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Priority to EP94929500A priority Critical patent/EP0721602B1/en
Priority to KR1019960701692A priority patent/KR100314320B1/en
Priority to JP7510117A priority patent/JPH09504382A/en
Priority to DE69421407T priority patent/DE69421407T2/en
Priority to US08/619,613 priority patent/US5760859A/en
Publication of WO1995009379A1 publication Critical patent/WO1995009379A1/en

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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/12Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1347Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
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    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/22Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and nitrogen atoms as chain links, e.g. Schiff bases
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    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/28Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and sulfur atoms as chain links, e.g. thioesters
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    • C09K19/00Liquid crystal materials
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    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
    • C09K19/3086Cyclohexane rings in which at least two rings are linked by a chain containing nitrogen atoms
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    • C09K19/38Polymers
    • C09K19/3833Polymers with mesogenic groups in the side chain
    • C09K19/3876Polyoxyalkylene polymers
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    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60Pleochroic dyes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3016Polarising elements involving passive liquid crystal elements
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • G02F1/133636Birefringent elements, e.g. for optical compensation with twisted orientation, e.g. comprising helically oriented LC-molecules or a plurality of twisted birefringent sublayers
    • GPHYSICS
    • G11INFORMATION STORAGE
    • G11BINFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/25Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing liquid crystals
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/06Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
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    • C09K2323/00Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/06Substrate layer characterised by chemical composition
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363Birefringent elements, e.g. for optical compensation
    • G02F1/133637Birefringent elements, e.g. for optical compensation characterised by the wavelength dispersion

Definitions

  • the invention is in the field of retardation layers comprising high- molecular weight liquid-crystalline material. Such retardation layers are used in displays.
  • Figure 1 is a schematic depiction of the construction of a display.
  • Figure 1 shows a cross-section of a display comprising an active twisted layer (4), the active cell, which can be switched on and off by means of transparent electrodes (6), and a retardation layer (3), with substrates (2) disposed on either side of the two layers (3) and (4).
  • substrates (2) disposed on either side of the two layers (3) and (4).
  • polarisers (1) At the outer sides of the two outermost substrates there are polarisers (1), and underneath the polariser situated under the active twisted layer is positioned a mirror (5).
  • the mirror can be omitted in some displays.
  • the invention is directed in particular to the retardation layer (3) of a display.
  • Retardation layers serve to compensate for the undesirable birefringence effect that occurs in the active cell in the display.
  • the retardation layer use may be made of a twisted nematic layer composed of low-molecular weight liquid-crystalline material such as is described in, e.g., Kirk Othmer's Encyclopedia of Technology, 3rd ed. (New York: Wiley & Sons) Vol. 7, p. 728.
  • low-molecular weight liquid-crystalline material gives good compensation when used, it is attended with the drawback of being low- viscous. For that reason, the low-molecular weight material is sealed between inflexible substrates by means of spacers in order to attain a twisted, form-retaining structure. In other words, a closed, rigid cell has to be made.
  • birefringent films e.g., a film of drawn polymer such as a birefringent polycarbonate film.
  • a birefringent polycarbonate film is described in Jap. J. Appl . Physics, Vol. 30, No. 4 (April 1991), 682-686.
  • birefringent polycarbonate films By using birefringent polycarbonate films a liquid-crystalline display of reduced thickness and weight may be obtained.
  • said birefringent polycarbonate films fail to provide optimum contrast. The reason for this poor contrast is as follows:
  • retardation layers serve to compensate for the undesirable birefringence effect that occurs in the active cell of a display.
  • This birefringence effect depends on the retardation value, the angle of twist, and the direction of twist of the layer of liquid- crystalline molecules in the active cell of the display.
  • the retardation of a birefringent layer is defined as the product of the birefringence value ( ⁇ ) and the layer thickness.
  • the birefringence value
  • the birefringence effect of the active cell of the display can be completely compensated for by using a retardation layer that has equal retardation, and an equal as well as an opposite angle of rotation compared with the active cell. For full compensation these conditions should apply for the entire visible part of the wavelength spectrum. This requirement can only be realised if the dependence of the birefringence on the wavelength, also known as the dispersion, of the material of the retardation layer is equal to that of the LC material used in the active cell of the display.
  • birefringent polycarbonate films This is not the case for birefringent polycarbonate films.
  • the dispersion of birefringent polycarbonate films is lower than liquid crystalline active cells which are co rnercially used. Therefore, their retardation can only be set (by setting the layer thickness) to match the retardation of the active cell at 550 nm. As a consequence, over the rest of the visible wavelength area the retardation fails to match that of the active cell of the display, especially in the wavelength area of 400-550 nm the dispersion appears to be too low. This results in a less than optimal contrast.
  • a retardation layer of high-molecular material which has a retardation virtually matching that of the active cell over the whole visible wavelength area.
  • the invention is directed to a retardation layer for a liquid-crystalline display comprising high-molecular weight liquid- crystalline material, wherein the dispersion has been adapted to that of the active liquid-crystalline cell by varying the mesogenic groups of the high-molecular weight liquid-crystalline material, so that the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1, preferrabley not more than 0.03.
  • high-molecular weight liquid-crystalline material are meant: relatively low-molecular weight liquid-crystalline polymers, oligomers, and liquid-crystalline glasses.
  • the molecular weight for liquid-crystalline glasses and oligomers varies from 1000 to 4000, for liquid-crystalline polymers it varies 1000 to 20000.
  • High-molecular weight liquid-crystalline material has a higher mechanical strength than low-molecular weight liquid-crystalline material. Therefore, it is not necessary to seal the liquid-crystalline material in a rigid cell. Because liquid-crystalline material is used, and the mesogenic groups of liquid-crystalline material can easily be varied, it is possible to obtain a retardation layer which has approximately the same dispersion as that of the active cell.
  • the dispersion is defined here as the retardation (or the birefringence) at a certain wavelength divided by the retardation (or the birefringence) at 550 nm.
  • mesogenic groups By using mesogenic groups with large conjugated systems the dispersion of liquid-crystalline material is increased, whereas smaller conjugated systems lower the dispersity, especially in the wavelength area of 400-550 nm.
  • mesogenic groups have the following general formula: - (CH 2 ) m - 0 - ⁇ .- (Q) n ⁇ 2 -Ri
  • the mesogenic group has a large conjugated system.
  • the conjugation is decreased.
  • the conjugation can be further decreased by using -0-R* or R* for the R ⁇ end group of the mesogenic group.
  • the dispersity will be lower than when aromatic compounds are used.
  • mesogenic groups with polar moieties the dispersion of the liquid-crystalline material is increased. For instance, if mesogenic groups according to formula 1 are used with -N0 as Ri instead of 0-R* or R* , the dispersion is increased. Halogenation of the mesogenic group also gives an increase of dispersion.
  • the artisan can easily adjust the dispersion of the retardation layer via the measures described above.
  • the birefringence at a certain wavelength can easily be measured with a refractometer, and from birefringences at various wavelengths the dispersion can be calculated.
  • the retardation of a commercially available cell can be measured with various optical techniques known to the artisan. From the retardation at a certain wavelength and the retardation at 550 nm the dispersion at a certain wavelength can be calculated.
  • liquid- crystalline material For accurate matching of the dispersion of an active cell, liquid- crystalline material may be used wherein both mesogenic groups having a large conjugated system and mesogenic groups having a small conjugated system are present. By varying the ratio of the two kinds of mesogenic groups the dispersion can be accurately matched with the active cell .
  • cyclic or aromatic compounds ⁇ I and ⁇ * examples include:
  • R* stands for an alkyl group having 1-5 carbon atoms.
  • R groups examples include:
  • R* groups contain an asymmetrical carbon atom.
  • the use of chiral (exclusively laevorotatory or dextrorotatory) R* groups may be advantageous in LCD retardation layers, as will be explained below. It was found that the dispersion of high-molecular weight liquid- crystalline material is mainly dependent on the mesogenic group. A specific mesogenic group gives the virtually same dispersion irrespective of the liquid-crystalline polymer, oligomer or glass into which it is incorporated.
  • high-molecular weight material has a higher mechanical strength than low-molecular weight material. This makes it possible to place the liquid-crystalline material between glass substrates having a thickness of 20-500 micrometers instead of thick glass substrates.
  • the liquid-crystalline material may even be placed between or coated on flexible plastic substrates such as PET and polycarbonate.
  • the retardation layer To obtain full compensation for the birefringence effect of the active cell, it is also necessary for the retardation layer to have an equal as well as an opposite angle of rotation compared with the active cell.
  • a twisted structure is obtained by placing the liquid- crystalline material between two orienting substrates, giving one of the substrates a different orientation direction from that of the other substrate.
  • the substrate itself may be rubbed in a single direction.
  • the substrate in that case may be made of, e.g., polyimide, polyvinyl alcohol, glass, etc.
  • the substrate may be provided with a thin orienting layer.
  • This. may be a thin polymer layer which can be rubbed, e.g., polyimide, polyvinyl alcohol, etc.
  • this thin orienting layer may be a SiO x layer evaporated at an angle of less than 90°, usually of 60° or 86°.
  • a substrate of poor flexibility, such as glass or quartz is used for SiO x evaporation.
  • the liquid-crystalline material is frequently mixed with a chiral material: the so-called chiral dopant.
  • chiral dopant any optically active compound may be used to this end.
  • cholesterol derivatives and 4-(4-hexyloxy-benzoyloxy) benzene acid 2-octyl -ester.
  • up to 5 wt.% of chiral dopant is employed in relation to the total amount of liquid-crystalline material.
  • the liquid crystalline material itself may be provided with chiral centres.
  • this is done by providing the mesogenic group with a chiral chain (group R*) or spacer, since in this way the transition temperatures will hardly if at all be adversely affected.
  • group R* chiral chain
  • Examples of mesogenic groups with chiral chains have been described above.
  • the angle of rotation of an STN display cell typically is 240° but may be any other appropriate value.
  • the film In the case of an angle of rotation of 90° (or -90°), the film is generally called "twisted nematic.”
  • an angle of rotation of 90° (or -90°) is required. If the angle of rotation is greater, the film is called “supertwisted nematic.”
  • this invention also concerns retardation layers with a smaller angle of rotation, from 0° (no twist) to 90° (or -90°). For convenience these layers are also called “twisted nematic" here. In the case of an angle of rotation of 0°, the arrangement of the liquid-crystalline layer will be uniform planar.
  • the invention is also directed to retardation layers having more than one pitch (even more than 5 pitches) .
  • the high molecular-weight liquid-crystalline film can be placed between the substrate of the display cell and another substrate.
  • the LC polymer film is placed between the polariser and a substrate.
  • a second substrate is not necessary and the thickness and weight of the retardation layer are reduced further.
  • the invention is further directed to a liquid-crystalline display comprising an active liquid-crystalline cell and a retardation layer of high-molecular weight liquid-crystalline material, wherein the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1.
  • Liquid-crystalline glasses were prepared from mesogenic group- containing epoxides and diamines.
  • a mixture of 1 eq. of diamine and 4 eq. of epoxy was heated for 5 hours under a nitrogen atmosphere at a temperature of 130°C.
  • the melt was cooled down and dissolved in THF, and the solution of approximately 20% (m/M) was precipitated in a 10-fold excess of ethanol .
  • the yields were in the range of 75 to 90%.
  • LC 1 The epoxide of cyanobiphenyl was used to prepare an LC glass (LC 1) by the general method for the synthesis of LC glasses specified above, using m-xylylene diamine (m-XDA), ex Fluka ® .
  • m-XDA m-xylylene diamine
  • the molecualar weight was found to be 1140 , Tg: 64/70°C, Tc: 127°C.
  • a liquid-crystalline glass (LC 2) was prepared by the general method for the synthesis of LC glasses specified above using methylene diamine, ex Fluka®. The molecular weight turned out to be 1398, Tg: 66/72°C, Tc: 127°C.
  • Liquid-crystal l ine polyethers were prepared from mesogenic group- containing epoxides and mesogeni c group-containing diol s.
  • the epoxide of methoxyphenyl benzoate was used, to prepare a liquid- crystalline polyether (LC 3) by the general method for the synthesis of LC polyethers specified above, using methoxyphenyl-(2,3 dihydroxypropyloxy)benzoate with an epoxy/OH ratio of 5:1.
  • the diol was prepared in the same manner as the hexyloxy analogon in EP-A2-0550 105.
  • the molecular weight turned out to be 2984, Tg: 46/52°C, Tc: 146°C.
  • This product was recrystallised from 250 ml of glacial acetic acid.
  • 32 g (0.18 mole) of the dried 4(allyloxy)benzoic acid were dissolved in 150 ml of thionyl chloride, whereupon 2 drops of dimethyl formamide were added and the whole was boiled with refluxing.
  • Thionyl chloride was distilled off, and after being cooled the residue was incorporated into 100 ml of dry dichloromethane. After filtration the dichloromethane solution was added, with vigorous stirring, over 1 hour and at a temperature of 5-10°C, to a solution of 23 g of nitrophenol (0.166 mole) in a mixture of 135 ml of dichloromethane and 34.2 ml of pyridine.
  • LC 4 liquid- crystalline polyether
  • LC 4 liquid- crystalline polyether
  • the diol was prepared in the same manner as the hexyloxy analogon in EP-A2-0550 105.
  • the molecular weight turned out to be 3173, Tg: 58/63°C, Tc: 130°C.
  • the epoxide of methoxycyclohexyl benzoate was used together with the epoxide of methoxyphenyl benzoate to prepare a liquid crystalline polyether (LC 5) by using the general method for the synthesis of liquid crystalline polyethers specified above, using methoxy phenyl-(2,3 dihydroxypropyloxy) benzoate with an epoxy/OH ratio of 5:1. It appeared that the cyclohexyl group containing epoxide was present for 16 mole % in the polyether.
  • the layer thickness obtained was 4 micrometers.
  • the two films of LC material 3 were dried in a vacuum oven for 16 hours at 20°C. They were then placed one on top of the other under a 60° difference in orientation direction and moulded at a temperature of 160°C. Next, the sample was cooled to 115°C, and after 5 minutes to room temperature. The quality of the resulting retardation film was determined with the aid of various optical techniques based on the theory described in E.P. Raynes, "Molecular Crystals,” Liquid Crystals Letters 4(3-4) (1987), 69-75.
  • the dispersion of the high-molecular weight liquid-crystalline material was measured by fitting transmission spectra of the retardation layers between two polarisers to the formulae given in Raynes.
  • the dispersion (defined as the retardation at a certain wavelength divided by the retardation at 550 nm) was given for LC 3, a birefingent polycarbonate film such as described in Jap. J. Appl Physics,VOl.30, No.4 (APril 1991), 682-686, and a commercially available low-molecular weight liquid-crystalline active cell as used in the Sharp wordprocessor WD A 330®, and an active cell containing a commercially available liquid crystal mixture ZLI 4544, ex Merck ® .
  • the dispersion of LC 4 according to the invention is nearly the same as that of a commercially available active cell (a difference in dispersion of less than 0.1) over the whole wavelength area of 400-800 nm, whereas the dispersion of the birefringent polycarbonate film only matches that of the commercially available active cell at 550 nm , by definition, and shows large deviations, especially in the shorter wavelength area of 400-550 nm.
  • the dispersion of LC 5 is nearly the same as that of the active cell containing ZLI 4544 over the whole wavelength area of 400-800 nm.

Abstract

The invention is in the field of retardation layers comprising high-molecular weight liquid-crystalline material for liquid-crystalline displays. The invention is directed to a retardation layer for a liquid-crystalline display comprising high-molecular weight liquid-crystalline material, wherein the dispersion has been adapted to that of the active liquid-crystalline cell by varying the mesogenic groups of the high-molecular weight liquid-crystalline material, so that the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1.

Description

RETARDATION LAYER HAVING A DISPERSION ADAPTED TO THE ACTIVE LIQUID-CRYSTALLINE CELL
The invention is in the field of retardation layers comprising high- molecular weight liquid-crystalline material. Such retardation layers are used in displays. Figure 1 is a schematic depiction of the construction of a display.
Figure 1 shows a cross-section of a display comprising an active twisted layer (4), the active cell, which can be switched on and off by means of transparent electrodes (6), and a retardation layer (3), with substrates (2) disposed on either side of the two layers (3) and (4). At the outer sides of the two outermost substrates there are polarisers (1), and underneath the polariser situated under the active twisted layer is positioned a mirror (5).
In practice, the mirror can be omitted in some displays. The invention is directed in particular to the retardation layer (3) of a display. Retardation layers serve to compensate for the undesirable birefringence effect that occurs in the active cell in the display. For the retardation layer use may be made of a twisted nematic layer composed of low-molecular weight liquid-crystalline material such as is described in, e.g., Kirk Othmer's Encyclopedia of Technology, 3rd ed. (New York: Wiley & Sons) Vol. 7, p. 728. Although low-molecular weight liquid-crystalline material gives good compensation when used, it is attended with the drawback of being low- viscous. For that reason, the low-molecular weight material is sealed between inflexible substrates by means of spacers in order to attain a twisted, form-retaining structure. In other words, a closed, rigid cell has to be made.
Alternatively, use may be made of birefringent films, e.g., a film of drawn polymer such as a birefringent polycarbonate film. Such a birefringent polycarbonate film is described in Jap. J. Appl . Physics, Vol. 30, No. 4 (April 1991), 682-686. By using birefringent polycarbonate films a liquid-crystalline display of reduced thickness and weight may be obtained. However, said birefringent polycarbonate films fail to provide optimum contrast. The reason for this poor contrast is as follows:
As stated above, retardation layers serve to compensate for the undesirable birefringence effect that occurs in the active cell of a display. This birefringence effect depends on the retardation value, the angle of twist, and the direction of twist of the layer of liquid- crystalline molecules in the active cell of the display. The retardation of a birefringent layer is defined as the product of the birefringence value (ΔΠ) and the layer thickness. At a given wavelength, the birefringence effect of the active cell of the display can be completely compensated for by using a retardation layer that has equal retardation, and an equal as well as an opposite angle of rotation compared with the active cell. For full compensation these conditions should apply for the entire visible part of the wavelength spectrum. This requirement can only be realised if the dependence of the birefringence on the wavelength, also known as the dispersion, of the material of the retardation layer is equal to that of the LC material used in the active cell of the display.
This is not the case for birefringent polycarbonate films. The dispersion of birefringent polycarbonate films is lower than liquid crystalline active cells which are co rnercially used. Therefore, their retardation can only be set (by setting the layer thickness) to match the retardation of the active cell at 550 nm. As a consequence, over the rest of the visible wavelength area the retardation fails to match that of the active cell of the display, especially in the wavelength area of 400-550 nm the dispersion appears to be too low. This results in a less than optimal contrast.
In the present invention a retardation layer of high-molecular material is provided which has a retardation virtually matching that of the active cell over the whole visible wavelength area. Accordingly, the invention is directed to a retardation layer for a liquid-crystalline display comprising high-molecular weight liquid- crystalline material, wherein the dispersion has been adapted to that of the active liquid-crystalline cell by varying the mesogenic groups of the high-molecular weight liquid-crystalline material, so that the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1, preferrabley not more than 0.03.
By high-molecular weight liquid-crystalline material are meant: relatively low-molecular weight liquid-crystalline polymers, oligomers, and liquid-crystalline glasses. The molecular weight for liquid-crystalline glasses and oligomers varies from 1000 to 4000, for liquid-crystalline polymers it varies 1000 to 20000. High-molecular weight liquid-crystalline material has a higher mechanical strength than low-molecular weight liquid-crystalline material. Therefore, it is not necessary to seal the liquid-crystalline material in a rigid cell. Because liquid-crystalline material is used, and the mesogenic groups of liquid-crystalline material can easily be varied, it is possible to obtain a retardation layer which has approximately the same dispersion as that of the active cell.
The dispersion is defined here as the retardation (or the birefringence) at a certain wavelength divided by the retardation (or the birefringence) at 550 nm.
It appears that the dispersion of a liquid-crystalline material can be varied by the following measures:
By using mesogenic groups with large conjugated systems the dispersion of liquid-crystalline material is increased, whereas smaller conjugated systems lower the dispersity, especially in the wavelength area of 400-550 nm. Usually, mesogenic groups have the following general formula: - (CH2)m - 0 - φ.- (Q)n ψ 2 -Ri
wherein: stands for an integer from 0-6,
Q stands for -C(0)-0-, -C=C-, -ON-, -N=C-, -0-C(0)-,
Figure imgf000006_0001
Ri stands for -0-R*. -N02 -CN, -HC=C(CN)2, -C(CN)=C(CN)2 or -R*, . . . φi stands for a substituted or unsubstituted cyclic, aromatic or heterocyclic compound having 4-10 carbon atoms, φ* stands for a cyclic, aromatic or heterocyclic compound having 4-10 carbon atoms, n stands for 0 or 1.
If for Q groups such as -C=C-, -C=N-, -N=C- or -C≡C- are used, or if n is 0, the mesogenic group has a large conjugated system. By using -C(0)-0- or -0-C(0)- the conjugation is decreased. The conjugation can be further decreased by using -0-R* or R* for the Rι end group of the mesogenic group.
If for φi or φ2 a non-aromatic cyclic compound is used, the dispersity will be lower than when aromatic compounds are used.
By using mesogenic groups with polar moieties the dispersion of the liquid-crystalline material is increased. For instance, if mesogenic groups according to formula 1 are used with -N0 as Ri instead of 0-R* or R* , the dispersion is increased. Halogenation of the mesogenic group also gives an increase of dispersion.
When the dispersion of a commercially available active cell is known, the artisan can easily adjust the dispersion of the retardation layer via the measures described above. The birefringence at a certain wavelength can easily be measured with a refractometer, and from birefringences at various wavelengths the dispersion can be calculated. The retardation of a commercially available cell can be measured with various optical techniques known to the artisan. From the retardation at a certain wavelength and the retardation at 550 nm the dispersion at a certain wavelength can be calculated.
For accurate matching of the dispersion of an active cell, liquid- crystalline material may be used wherein both mesogenic groups having a large conjugated system and mesogenic groups having a small conjugated system are present. By varying the ratio of the two kinds of mesogenic groups the dispersion can be accurately matched with the active cell .
Examples of the cyclic or aromatic compounds ΦI and Φ* include:
Figure imgf000007_0001
wherein R* stands for an alkyl group having 1-5 carbon atoms.
Examples of R groups include:
-(CH2)x-0-C(0)-C(CH3)=CH2,
-(CH2)x-0-C(0)-CH=CH2,
-(CH2)X-CH3,
-CH2-CH(CH3)-(CH2)X-CH3, -CH(CH3)-(CH2)X-CH3, wherein x= 1-14.
Some of these R* groups contain an asymmetrical carbon atom. The use of chiral (exclusively laevorotatory or dextrorotatory) R* groups may be advantageous in LCD retardation layers, as will be explained below. It was found that the dispersion of high-molecular weight liquid- crystalline material is mainly dependent on the mesogenic group. A specific mesogenic group gives the virtually same dispersion irrespective of the liquid-crystalline polymer, oligomer or glass into which it is incorporated.
As mentioned above, high-molecular weight material has a higher mechanical strength than low-molecular weight material. This makes it possible to place the liquid-crystalline material between glass substrates having a thickness of 20-500 micrometers instead of thick glass substrates. The liquid-crystalline material may even be placed between or coated on flexible plastic substrates such as PET and polycarbonate.
To obtain full compensation for the birefringence effect of the active cell, it is also necessary for the retardation layer to have an equal as well as an opposite angle of rotation compared with the active cell. A twisted structure is obtained by placing the liquid- crystalline material between two orienting substrates, giving one of the substrates a different orientation direction from that of the other substrate.
Various techniques are known for making an orienting substrate. For instance, the substrate itself may be rubbed in a single direction. The substrate in that case may be made of, e.g., polyimide, polyvinyl alcohol, glass, etc. Alternatively, the substrate may be provided with a thin orienting layer. This.may be a thin polymer layer which can be rubbed, e.g., polyimide, polyvinyl alcohol, etc. Alternatively, this thin orienting layer may be a SiOx layer evaporated at an angle of less than 90°, usually of 60° or 86°. Generally, a substrate of poor flexibility, such as glass or quartz, is used for SiOx evaporation. These orienting techniques are known to the skilled person and require no further elucidation here. Of course, it is also possible to employ other orienting techniques.
To control the direction of rotation of the director (to the left or to the right) and/or to obtain an angle of rotation greater than 90°, the liquid-crystalline material is frequently mixed with a chiral material: the so-called chiral dopant. In principle, any optically active compound may be used to this end. As examples may be mentioned cholesterol derivatives and 4-(4-hexyloxy-benzoyloxy) benzene acid 2-octyl -ester. Ordinarily speaking, up to 5 wt.% of chiral dopant is employed in relation to the total amount of liquid-crystalline material. Alternatively, the liquid crystalline material itself may be provided with chiral centres. Preferably, this is done by providing the mesogenic group with a chiral chain (group R*) or spacer, since in this way the transition temperatures will hardly if at all be adversely affected. Examples of mesogenic groups with chiral chains have been described above.
The angle of rotation of an STN display cell typically is 240° but may be any other appropriate value. In the case of an angle of rotation of 90° (or -90°), the film is generally called "twisted nematic." For a TFT-TN compensation layer an angle of rotation of 90° (or -90°) is required. If the angle of rotation is greater, the film is called "supertwisted nematic." In addition, this invention also concerns retardation layers with a smaller angle of rotation, from 0° (no twist) to 90° (or -90°). For convenience these layers are also called "twisted nematic" here. In the case of an angle of rotation of 0°, the arrangement of the liquid-crystalline layer will be uniform planar. At angles of rotation exceeding 360° the structure goes through more than one full rotation within a single layer. The length covered by the structure in a full rotation is called the pitch. The invention is also directed to retardation layers having more than one pitch (even more than 5 pitches) . The value of optical retardation (=ΔΠ (birefringence) X d (thickness of the (S)TN layer) may be adjusted by choosing an appropriate value for the thickness of the layer. This can be done by using spacers of appropriate size. In general, glass spheres, polymer spheres or silica spheres are used as spacers.
Alternatively, the high molecular-weight liquid-crystalline film can be placed between the substrate of the display cell and another substrate. In a further embodiment of the invention the LC polymer film is placed between the polariser and a substrate. In these embodiments of the invention a second substrate is not necessary and the thickness and weight of the retardation layer are reduced further.
The invention is further directed to a liquid-crystalline display comprising an active liquid-crystalline cell and a retardation layer of high-molecular weight liquid-crystalline material, wherein the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1.
The invention will be further illustrated with reference to the following unlimitative Examples.
EXAMPLES
Example 1
Liquid-crystalline glasses were prepared from mesogenic group- containing epoxides and diamines.
Synthesis of LC glasses (general method):
A mixture of 1 eq. of diamine and 4 eq. of epoxy was heated for 5 hours under a nitrogen atmosphere at a temperature of 130°C. The melt was cooled down and dissolved in THF, and the solution of approximately 20% (m/M) was precipitated in a 10-fold excess of ethanol . The yields were in the range of 75 to 90%.
epoxide of cyanobiphenyl
A mixture of 39.0 g (0.20 mole) of hydroxycyanobiphenyl, 100 ml (1.25 moles) of epichlorohydrin, and 0.44 g (2.4 mmoles) of benzyl trimethyl ammonium chloride was heated to 70°C. Next, a solution of 17 g (0.42 mole) of sodium hydroxide in 100 ml water was dispensed in 3 hours. Following this addition there was one extra hour of stirring at 70°C. The reaction mixture was cooled to 20°C, and 200 ml of dichloromethane were added. The organic layer was separated from the aqueous one and washed with, successively, NaCl solution (twice) and water (twice). After drying on magnesium sulphate and concentration by evaporation the crude product was converted to the crystallised form from 450 ml of methanol . The yield was 38.30 g (76%).
The epoxide of cyanobiphenyl was used to prepare an LC glass (LC 1) by the general method for the synthesis of LC glasses specified above, using m-xylylene diamine (m-XDA), ex Fluka®. The molecualar weight was found to be 1140 , Tg: 64/70°C, Tc: 127°C.
epoxide of methoxyphenyl benzoate
Preparation of 4-methoxyphenol-4'oxybenzoate
74.5 g (0.6 mole) of 4-methoxyphenol , 55.3 (0.40 mole) of hydroxybenzoic acid, and 1.24 g (20 mmoles) of boric acid were dissolved in 750 ml of toluene. Next, 2.0 g (20.4 mmoles) of H2S04 were added dropwise, and the mixture was refluxed for 26 hours with the formed water being distilled off azeotropically. The toluene was evaporated, and the reaction product was washed twice in 200 ml of diethyl ether/petroleum ether (1:1 (V:V)). The product was twice converted to the crystallised form from 400 ml of acetonitrile and then dried. The yield was 56.1 g (49%).
A mixture of 42.0 g (0.17 mole) of 4-methoxyphenol-4'oxybenzoate, 100 ml (1.25 moles) of epichlorohydrin, and 0.35 g of benzyl trimethyl ammonium chloride was heated to 70°C. Next, a solution of 6.4 g (0.16 mole) of sodium hydroxide in 32 ml of water was dispensed in 2 hours. Following this addition stirring continued for 2 more hours at 70°C. The reaction mixture was cooled to 20°C, and the organic layer was separated from the aqueous one and washed with 50 ml of water. The excess epichlorohydrin was removed by means of vacuum evaporation at a temperature below 50°C. The residue was dissolved in 250 ml of butanol/toluene (1:2 (V:V)) and stirred for 1 hour at 30°C in the presence of a 20%-solution of NaOH (1.49 g) . The organic layer was washed with water several times. After vacuum evaporation the crude product was twice converted to the crystallised form from methanol. The yield was 28.5 g (55%).
A liquid-crystalline glass (LC 2) was prepared by the general method for the synthesis of LC glasses specified above using methylene diamine, ex Fluka®. The molecular weight turned out to be 1398, Tg: 66/72°C, Tc: 127°C.
Example 2
Liquid-crystal l ine polyethers were prepared from mesogenic group- containing epoxides and mesogeni c group-containing diol s.
Synthesis of LC polyethers (general method) : 11
To a mixture of OH-containing compound and 5% of BF3Et20 in dichloromethane there was slowly added dropwise, at room temperature, epoxide dissolved in dichloromethane. In the case of acrylate alcohols being used, a pinch of Ionol®, ex Shell, was added. The polymerisation mixture was stirred overnight and then neutralised with solid CaO. After one hour the CaO was filtered off. The polyether was precipitated in ether, washed with ether, and dried under vacuum. The yield was 75-90%.
The epoxide of methoxyphenyl benzoate was used, to prepare a liquid- crystalline polyether (LC 3) by the general method for the synthesis of LC polyethers specified above, using methoxyphenyl-(2,3 dihydroxypropyloxy)benzoate with an epoxy/OH ratio of 5:1. The diol was prepared in the same manner as the hexyloxy analogon in EP-A2-0550 105. The molecular weight turned out to be 2984, Tg: 46/52°C, Tc: 146°C.
epoxide of nitrophenyl benzoate
Preparation of 4-nitrophenyl 4'oxybenzoyl epoxypropyl ether
To a solution of 56 g (1 mole) of potassium hydroxide in 225 ml of water were added 69 g (0.5 mole) of p-hydroxybenzoic acid. To this solution were slowly added dropwise, at room temperature, 42 g (0.55 mole) of allyl chloride. Following the addition of the allyl chloride there was refluxing for a further 18 hours. After cooling the reaction mixture separated into two layers. A solution of 28 g (0.5 mole) of potassium hydroxide in 240 ml of water was added, and the whole was heated until a homogeneous reaction mixture had formed. After renewed cooling and acidification with concentrated hydrochloric acid 4(allyloxy)benzoic acid was precipitated. This product was recrystallised from 250 ml of glacial acetic acid. 32 g (0.18 mole) of the dried 4(allyloxy)benzoic acid were dissolved in 150 ml of thionyl chloride, whereupon 2 drops of dimethyl formamide were added and the whole was boiled with refluxing. Thionyl chloride was distilled off, and after being cooled the residue was incorporated into 100 ml of dry dichloromethane. After filtration the dichloromethane solution was added, with vigorous stirring, over 1 hour and at a temperature of 5-10°C, to a solution of 23 g of nitrophenol (0.166 mole) in a mixture of 135 ml of dichloromethane and 34.2 ml of pyridine. There was 2 hours of afterstirring at room temperature. 250 ml of dichloromethane were added to the reaction mixture; the whole was washed twice with dilute hydrochloric acid and then washed until neutral. After distilling off of the solvents the residue was converted to the crystallised form from methanol. The yield was 37.6 g (70%).
10 g (33 mmoles) of 4-nitrophenyl 4'oxybenzoyl allyl ether were dissolved in 50 ml of dichloromethane, and 11.2 g (45.5 mmoles) of m- chloroperbenzoic acid were added under nitrogen. After 24 hours' stirring at room temperature 250 ml of dichloromethane were added, and the solution was washed with sodium carbonate solution and then with water until neutral. After drying and distilling off of the solvent the residue was converted to the crystallised form from 250 ml of ethanol . The yield was 8.1 g (77%).
The epoxide of nitrophenyl benzoate was used to prepare a liquid- crystalline polyether (LC 4) by using the general method for the synthesis of LC polyethers specified above, using nitrophenyl-(2,3 dihydroxypropyloxy)benzoate with an epoxy/OH ratio of 5:1. The diol was prepared in the same manner as the hexyloxy analogon in EP-A2-0550 105. The molecular weight turned out to be 3173, Tg: 58/63°C, Tc: 130°C. Epoxide of methoxycyclohexyl benzoate
4(2,3 epoxypropyloxy)phenyl 4'methoxycyclohexyl carboxylate
76 g (480 mmoles) of 4 methoxycyclohexane carboxylic acid (cis/trans mixture) were boiled for 7 hours with refluxing in 350 ml of thionyl chloride to which several drops of dimethyl formamide had been added. The obtained 4 methoxycyclohexane carboxylic acid chloride was composed almost completely of the trans compound. After distilling off of the thionyl chloride the residue was incorporated into 75 ml of dry tetrahydrofuran. At a temperature of from 0° to 5°C this solution was slowly added dropwise to a solution of 158,4 g (1440 mmoles) of hydroquinone in 650 ml of tetrahydrofuran and 375 ml of pyridine. When, after this addition, the mixture had attained room temperature, it was poured onto ice and concentrated sulphuric acid. Extraction wi ch dichloromethane, evaporation of the dichloromethane, and, in succession, conversion of the evaporation residue to the crystallised form from an ethanol-water mixture and from toluene gave a yield of 24,45 g (20%) of pure trans 4 hydroxyphenyl 4'methoxycyclohexyl carboxylate.
24,3 g (97 mmoles) of the above compound were boiled, with refluxing, for 24 hours with 17,6 g of allyl bromide (145 mmoles) and 13,4 g (97 mmoles) of potassium carbonate in 350 ml of methylethyl ketone. After cooling the reaction mixture was poured into 1 1 of ice water, which was extracted with the aid of diethyl ether. After drying and evaporation of the diethyl ether 28,9 g (97%) of 4 allyloxyphenyl 4'methoxycyclohexyl carboxylate were obtained.
To 28,7 g (99 mmoles) of said compound in 250 ml of dichloromethane there were added 32,9 g of chloroperbenzoic acid, and the mixture was stirred for 24 hours under an atmosphere of nitrogen. After being diluted with dichloromethane the reaction mixture was washed with sodium carbonate solution and water. After drying the dichloromethane was distilled off, and the residue was purified on a column filled with silica gel and eluted with a hexane-ethyl acetate mixture (75/25). The yield was 20,8 g (66%) of 4(2,3 epoxypropyloxy)phenyl 4'methoxycyclohexyl carboxylate.
The epoxide of methoxycyclohexyl benzoate was used together with the epoxide of methoxyphenyl benzoate to prepare a liquid crystalline polyether (LC 5) by using the general method for the synthesis of liquid crystalline polyethers specified above, using methoxy phenyl-(2,3 dihydroxypropyloxy) benzoate with an epoxy/OH ratio of 5:1. It appeared that the cyclohexyl group containing epoxide was present for 16 mole % in the polyether.
Example 3
Procedure for making the retardation layers:
Used were two glass substrates of a thickness of 100 micrometers. These were coated with Merck Liquicoat® PA, pre-cured at 60°C for 15 minutes, cured at 300°C for 1 hour, and then rubbed in the appropriate direction on a felt cloth, in accordance with the instructions provided by Merck®. To ensure proper adhesion of the PI layer the glass substrates were cleaned in advance using the following procedure:
- ultra-sonic cleaning with a detergent (Q9, Purum GmbH) - KOH (1 M), 50°C/1 hr
- HN03/H2S0 /H 0 (1:1:10), 60°C/1 hr
- reflux in isopropyl alcohol vapour for 30 minutes or more.
Between each cleansing step a rinsing with demineralised water was performed. This is a variation on the method as described by W.H. de Jeu in Physical properties of Liquid Crystals, 1st edition (Gordon and Breach Science Publishers), p. 23. LC 3 was dissolved in cyclopentanone together with 5 wt.% of chiral dopant (Merck CB 15®). To the filtered solution 0.5 wt.% (calculated on LC material 3) of cross-linked polymer spheres (Dynospheres DL-1060®, ex JSR) was added as spacers. The solution of LC material 3 with spacers was spin-coated onto the two pretreated glass substrates. The layer thickness obtained was 4 micrometers. The two films of LC material 3 were dried in a vacuum oven for 16 hours at 20°C. They were then placed one on top of the other under a 60° difference in orientation direction and moulded at a temperature of 160°C. Next, the sample was cooled to 115°C, and after 5 minutes to room temperature. The quality of the resulting retardation film was determined with the aid of various optical techniques based on the theory described in E.P. Raynes, "Molecular Crystals," Liquid Crystals Letters 4(3-4) (1987), 69-75.
The dispersion of the high-molecular weight liquid-crystalline material was measured by fitting transmission spectra of the retardation layers between two polarisers to the formulae given in Raynes. In Figure 2 the dispersion (defined as the retardation at a certain wavelength divided by the retardation at 550 nm) was given for LC 3, a birefingent polycarbonate film such as described in Jap. J. Appl Physics,VOl.30, No.4 (APril 1991), 682-686, and a commercially available low-molecular weight liquid-crystalline active cell as used in the Sharp wordprocessor WD A 330®, and an active cell containing a commercially available liquid crystal mixture ZLI 4544, ex Merck®.
From Figure 2 it can be seen that the dispersion of LC 4 according to the invention is nearly the same as that of a commercially available active cell (a difference in dispersion of less than 0.1) over the whole wavelength area of 400-800 nm, whereas the dispersion of the birefringent polycarbonate film only matches that of the commercially available active cell at 550 nm , by definition, and shows large deviations, especially in the shorter wavelength area of 400-550 nm. The dispersion of LC 5 is nearly the same as that of the active cell containing ZLI 4544 over the whole wavelength area of 400-800 nm.
In Figure 3 the dispersion is given for various LC materials according to the invention. From Figure 3 it can be seen that using mesogenic groups with a by more conjugated system such as cyanobiphenyl gives a higher dispersion than when LC material having mesogenic groups with a less conjugated system such as phenyl benzoate groups are used. A comparison between LC material having nitrophenyl benzoate mesogenic groups and LC material having methoxyphenyl benzoate mesogenic groups showed that the latter, i.e., the least conjugated material, has the lowest dispersion. When replacing some of the phenyl groups for cyclohexyl groups in the mesogenic groups, the dispersion is lowered even further. These examples show that the dispersion can be set by varying the mesogenic groups of the LC material.

Claims

Claims
1. A retardation layer for a liquid-crystalline display comprising high-molecular weight liquid-crystalline material, wherein the dispersion has been adapted to that of the active liquid- crystalline cell by varying the mesogenic groups of the high- molecular weight liquid-crystalline material, so that the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1, preferrably not more than 0.03.
2. A retardation layer according to claim 1, wherein both mesogenic groups having a large conjugated system and mesogenic groups having a small conjugated system are present.
3. A method for preparing a retardation layer according to claim 1 for liquid-crystalline displays, wherein the high-molecular weight liquid-crystalline material is placed between two orienting substrates, giving one of the substrates a different orientation direction from that of the other substrate.
4. A liquid-crystalline display comprising an active liquid- crystalline cell and a retardation layer of high-molecular weight liquid-crystalline material, wherein the difference in dispersion between the active cell and the retardation layer in the wavelength area of 400-800 nm is not more than 0.1.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997023805A1 (en) * 1995-12-22 1997-07-03 Akzo Nobel N.V. Temperature matched retardation layer
WO1998004651A1 (en) * 1996-07-26 1998-02-05 Merck Patent Gmbh Combination of optical elements
EP0851269A1 (en) * 1996-12-24 1998-07-01 Sharp Kabushiki Kaisha Liquid crystal display device
EP0871059A3 (en) * 1997-04-07 1999-09-15 Sharp Kabushiki Kaisha Liquid crystal display device
US6084651A (en) * 1997-03-05 2000-07-04 Sharp Kabushiki Kaisha Liquid crystal display device having liquid crystal layer divided at different ratios in each pixel
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6351299B2 (en) * 1996-04-15 2002-02-26 Ricoh Company, Ltd. Liquid crystal display device
JPH11509650A (en) * 1996-05-17 1999-08-24 フィリップス エレクトロニクス ネムローゼ フェンノートシャップ Compensation layer, liquid crystal display and retardation foil
TW515925B (en) * 1996-12-25 2003-01-01 Sharp Kk Liquid crystal display device
GB9713981D0 (en) * 1997-07-03 1997-09-10 Sharp Kk Optical device
US6606143B1 (en) * 1998-03-13 2003-08-12 Sharp Kabushiki Kaisha Liquid crystal display device with phase element
US6400433B1 (en) * 1998-11-06 2002-06-04 Fuji Photo Film Co., Ltd. Circularly polarizing plate comprising linearly polarizing membrane and quarter wave plate
US6853423B2 (en) * 1998-11-06 2005-02-08 Fuji Photo Film Co., Ltd. Quarter wave plate comprising two optically anisotropic layers
JP2001066596A (en) * 1999-08-24 2001-03-16 Nec Corp Liquid crystal display device
DE60302698T2 (en) * 2002-04-26 2006-08-24 Optrex Corp. A nematic liquid crystal display device of the double-layer type
GB2394718B (en) * 2002-09-05 2007-03-07 Merck Patent Gmbh Polymerised liquid crystal film with retardation pattern
JP4475515B2 (en) * 2004-09-03 2010-06-09 国立大学法人東京工業大学 Photo diode
JP2006284928A (en) * 2005-03-31 2006-10-19 Seiko Epson Corp Liquid crystal display device, method for manufacturing liquid crystal display device, and electronic apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0380338A2 (en) * 1989-01-26 1990-08-01 Nippon Oil Co., Ltd. Compensator for liquid crystal display
EP0382460A2 (en) * 1989-02-06 1990-08-16 Sharp Kabushiki Kaisha Liquid crystal display device
DE3925382A1 (en) * 1989-06-14 1991-01-03 Merck Patent Gmbh ELECTROOPTIC SYSTEM WITH COMPENSATION FILM
EP0524028A1 (en) * 1991-07-19 1993-01-20 Nippon Oil Co. Ltd. Viewing angle compensator for liquid crystal display
EP0550105A2 (en) * 1991-12-30 1993-07-07 Akzo Nobel N.V. Liquid-crystalline polyurethanes, compositions of said liquid-crystalline polyurethanes, and a device for optical data storage comprising a liquid-crystalline polyurethane

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01206318A (en) * 1988-02-03 1989-08-18 Matsushita Electric Ind Co Ltd Liquid crystal display device
US4954288A (en) * 1988-12-05 1990-09-04 Hoechst Celanese Corp. Side chain liquid crystalline polymers exhibiting nonlinear optical response
EP0379315B1 (en) * 1989-01-19 1994-05-18 Seiko Epson Corporation Electro-optical liquid crystal device
US5380459A (en) * 1990-04-20 1995-01-10 Ricoh Company, Ltd. Liquid crystal display device with improved viewing angle dependence of color
JP2711585B2 (en) * 1990-06-26 1998-02-10 日本石油株式会社 Compensator for active matrix liquid crystal display
JP2916331B2 (en) * 1991-11-08 1999-07-05 株式会社日立製作所 Liquid crystal display
KR950009315A (en) * 1993-09-29 1995-04-21 피이터 코르넬리스 샬크비즈크; 귄터 페트 Compensation Layer with Thin Glass Substrate
JP4098695B2 (en) * 2003-09-30 2008-06-11 株式会社デンソー Valve timing adjustment device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0380338A2 (en) * 1989-01-26 1990-08-01 Nippon Oil Co., Ltd. Compensator for liquid crystal display
EP0382460A2 (en) * 1989-02-06 1990-08-16 Sharp Kabushiki Kaisha Liquid crystal display device
DE3925382A1 (en) * 1989-06-14 1991-01-03 Merck Patent Gmbh ELECTROOPTIC SYSTEM WITH COMPENSATION FILM
EP0524028A1 (en) * 1991-07-19 1993-01-20 Nippon Oil Co. Ltd. Viewing angle compensator for liquid crystal display
EP0550105A2 (en) * 1991-12-30 1993-07-07 Akzo Nobel N.V. Liquid-crystalline polyurethanes, compositions of said liquid-crystalline polyurethanes, and a device for optical data storage comprising a liquid-crystalline polyurethane

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6088077A (en) * 1995-12-22 2000-07-11 Akzo Nobel Nv Temperature matched retardation layer
CN1097744C (en) * 1995-12-22 2003-01-01 德吉玛泰克有限公司 Temp. matched retardation layer
WO1997023805A1 (en) * 1995-12-22 1997-07-03 Akzo Nobel N.V. Temperature matched retardation layer
JP2000512768A (en) * 1995-12-22 2000-09-26 アクゾ ノーベル ナムローゼ フェンノートシャップ Temperature matching retardation layer
EA000614B1 (en) * 1995-12-22 1999-12-29 Акцо Нобель Н.В. Temperature matched retardation layer
USRE41281E1 (en) 1996-07-01 2010-04-27 Merck Patent Gesellschaft Mit Beschrankter Haftung Liquid crystal display device
GB2331813A (en) * 1996-07-26 1999-06-02 Merck Patent Gmbh Combination of optical elements
US7175890B2 (en) 1996-07-26 2007-02-13 Merck Patent Gmbh Combination of optical elements
GB2331813B (en) * 1996-07-26 2000-06-07 Merck Patent Gmbh Combination of optical elements
USRE39605E1 (en) * 1996-07-26 2007-05-01 Merck Patent Gmbh Combination of optical elements
KR100484085B1 (en) * 1996-07-26 2005-04-20 메르크 파텐트 게엠베하 Combination of Optical Elements
US6544605B1 (en) 1996-07-26 2003-04-08 Merck Patent Gesellschaft Mit Beschrankter Haftung Combination of optical elements
WO1998004651A1 (en) * 1996-07-26 1998-02-05 Merck Patent Gmbh Combination of optical elements
EP1403690A1 (en) * 1996-12-24 2004-03-31 Sharp Kabushiki Kaisha Liquid crystal display device
US6163354A (en) * 1996-12-24 2000-12-19 Sharp Kabushiki Kaisha Liquid crystal display device including liquid crystal display material preventing generation of viewing-angle-dependent coloration of display screen
EP0851269A1 (en) * 1996-12-24 1998-07-01 Sharp Kabushiki Kaisha Liquid crystal display device
US6084651A (en) * 1997-03-05 2000-07-04 Sharp Kabushiki Kaisha Liquid crystal display device having liquid crystal layer divided at different ratios in each pixel
US6535258B1 (en) 1997-04-07 2003-03-18 Sharp Kabushiki Kaisha Liquid crystal display device with low dispersion LC and high dispersion compensator
US6137556A (en) * 1997-04-07 2000-10-24 Sharp Kabushiki Kaisha Liquid crystal display device
US6937309B2 (en) 1997-04-07 2005-08-30 Sharp Kabushiki Kaisha Liquid crystal display/optical retardation compensator combination in which variations in the dispersion of light in the liquid crystal and/or in the compensator materials minimize undesired screen coloration
EP0871059A3 (en) * 1997-04-07 1999-09-15 Sharp Kabushiki Kaisha Liquid crystal display device
US7245340B2 (en) 1997-04-07 2007-07-17 Sharp Kabushiki Kaisha Liquid crystal display device having controlled refractive index anisotropy of the liquid crystal layer and the retardation compensator plate

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DE69421407D1 (en) 1999-12-02
CN1132557A (en) 1996-10-02
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EP0721602B1 (en) 1999-10-27
ATE186125T1 (en) 1999-11-15
JPH09504382A (en) 1997-04-28
KR960705254A (en) 1996-10-09
KR100314320B1 (en) 2001-12-28
US5760859A (en) 1998-06-02
DE69421407T2 (en) 2000-05-04
CN1047003C (en) 1999-12-01
EP0721602A1 (en) 1996-07-17

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