WO1994017441A1 - Liquid crystal devices - Google Patents
Liquid crystal devices Download PDFInfo
- Publication number
- WO1994017441A1 WO1994017441A1 PCT/GB1994/000089 GB9400089W WO9417441A1 WO 1994017441 A1 WO1994017441 A1 WO 1994017441A1 GB 9400089 W GB9400089 W GB 9400089W WO 9417441 A1 WO9417441 A1 WO 9417441A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chevron
- liquid crystal
- angle
- alignment layer
- surface alignment
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/137—Devices 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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/139—Devices 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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
- G02F1/141—Devices 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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent using ferroelectric liquid crystals
- G02F1/1416—Details of the smectic layer structure, e.g. bookshelf, chevron, C1 and C2
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133734—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by obliquely evaporated films, e.g. Si or SiO2 films
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL 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
- G02F1/00—Devices 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
- G02F1/01—Devices 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
- G02F1/13—Devices 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133746—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for high pretilt angles, i.e. higher than 15 degrees
Definitions
- EP-A-0032362 discloses a surface stabilised FLC device which possesses bistability and fast switching. However, in most real devices as cooled from the isotropic phase to the S c * phase, instead of a structure consisting of smectic layers normal to the substrate interface as disclosed in EP-A-0032362, a tilted layer structure called a chevron is obtained. Consequently, this gives rise to a relatively small effective bistable switching angle which tends to reduce the overall optical
- chevron structure provides an alignment texture consisting of visible defects called 'zig-zags'. These defects usually degrade the appearance of the device.
- GB2183054 B discloses the application of a high voltage, low frequency electrical signal to a ferro-electric liquid crystal device to irreversibly reduce the chevron angle so that at the end of the electrical treatment, a layer structure known
- ⁇ c is usually arranged to be «22.5° and from X-ray diffraction measurements, ⁇ is typically 90% of ⁇ c i.e. «20°.
- both C1 and C2 chevrons are stable i.e. both ⁇ c + ⁇ > ⁇ and ⁇ c - ⁇ > ⁇ can be satisfied respectively.
- the bistable switching angle (2 ⁇ S ) which is defined as the angle between the projection of the optic axis of the two memory states onto the substrate plane is given approximately by cos ⁇ s ⁇ cos ⁇ c /cos ⁇
- ⁇ is very similar in value to ⁇ c
- ⁇ s is typically between 6° and 10°.
- bistable states can be switched by electrical pulses, two types of bistable states can be switched by electrical pulses, two types of bistable states.
- bistable twisted states correspond to the switching of the director only at the chevron interface.
- bistable planar states correspond to the switching of the director only at the chevron interface.
- QBG Quasi Bookshelf Geometry
- a ferro-electric liquid crystal device comprising a substrate having a surface alignment layer, the surface alignment layer
- chevron angle ⁇ in the range of 2° ⁇ 15°, the C2 chevron being such that ⁇ c - ⁇ > ⁇ , wherein ⁇ is said pre-tilt angle, ⁇ c is one half of chiral smectic cone angle and ⁇ is a chevron angle and wherein a bistable switching angle ⁇ s of the device is > 12°.
- the surface alignment layer is a rubbed polymer layer.
- the surface alignment layer may be formed of silicon monoxide or magnesium fluoride.
- ferro-electric liquid crystal device which comprises the steps of providing a liquid crystal device having said surface alignment layer and C1 chevron structure only and applying a low frequency ( ⁇ 500 Hz) and low voltage ( ⁇ 35)AC wave
- the liquid crystal device embodying the invention has increased bistable switching angle, and consequently improved the optical performance, without a large increase in electrical threshold, and has a uniform alignment texture.
- the surface alignment layer may provide a pre-tilt angle of ⁇ in the range ⁇ >10° when measured with a nematic liquid crystal such as E7 and the natural alignment in the S c * phase has been modified by the method embodying the present invention such that a configuration is obtained in which the chevron angle, ⁇ is in the range 2° ⁇ 15 0 , and the condition ⁇ c - ⁇ is satisfied and the bistable switching angle ⁇ s >12°.
- the C2 chevron In a ferro-electric liquid crystal device with a surface alignment that provides a high pre-tilt angle only the C1 chevron is stable, the C2 chevron is naturally unstable because ⁇ c - ⁇ > ⁇ cannot be satisfied.
- the C2 Chevron can be rendered stable. Normally under such conditions, one would expect the zig-zag defects which are not desired will return because of the presence of both C1 and C2 Chevrons.
- the use of the high pre-tilt surface alignment layer leads to a higher degree of twist of the LC director through the thickness of the cell in the C1 chevron than for the C2 chevron. Consequently, the C2 chevron will be more stable than the C1 chevron, and under these favourable
- the C1 chevron can be eliminated and replaced by C2 chevron.
- C2 chevron with a high pre-tilt and a small chevron angle are that it provides a relatively large (up to 35°) switching angle between the bistable states, which in turn provides a high contrast bright display, a defect free alignment texture is obtained and switching between the two stable states can be achieved by the use of relatively low voltage pulses.
- a sample prepared with a high pre-tilt polyimide surface alignment layer gives a pre-tilt angle of about 15° for a nematic liquid crystal.
- the alignment as cooled from the isotropic liquid of the ferro-electric liquid crystal to S c ⁇ consists of only twisted C1 chevron states.
- a low frequency, low voltage ( ⁇ 25V) electrical signal is applied to the ferro-electric liquid crystal which should have a spontaneous polarisation vaue in the range >7nC/cm 2 .
- the alignment structure in the present invention may be extended to other values of the pre-tilt angle when the following conditions are met:
- the appropriate treatment is preferably the application of a low
- the ferro-electric liquid crystal phase may be a chiral smectic C phase.
- the less ordered liquid crystal phase may be a smectic A phase or may be a nematic phase.
- the pre-tilt angle between the director and the surface of the substrate may be provided by the use of a rubbed polymer layer, or may be provided by the use of a layer of obliquely evaporated silicon
- the device embodying the present invention may be used to provide a display with memory.
- Figure 1 illustrates geometrical conditions of chevron structures in a ferro ⁇ electric crystal device
- Figure 2 illustrates a ferro-electric crystal device according to the present invention
- Figure 3 illustrates a device for determining a pre-tilt angle ⁇ of the device illustrated in Figure 2;
- Figure 4 illustrates change of C1 chevrons to and C2 chevrons and their orientations in the device embodying the invention
- Figure 5 illustrates a curve showing the minimum pulse width required for a given voltage for switching C2 chevron states between the bistable states.
- a liquid crystal device illustrated in Figure 2 comprises upper and lower glass
- substrates 1 and 9 The inner surfaces of these substrates carry transparent electrodes or conductive coatings, 2 and 8 of indium tin oxide.
- Protecting films 3 and 7 of Si0 2 (Liquicoat by Merck Ltd) having a thickness of 100-1000A 0 are formed on electrodes 2 and 8 by spin coating.
- Spacers 5 and 12 are used to provide spacing of 2 ⁇ m between surfaces 4a and 6a of layers 4 and 6.
- the plate substrates 1 and 9 (comprising the layers 2, 3, 4, 6, 7 and 8) are assembled as shown in Figure 2 such that the alignment layers 4 and 6 have the same rubbing directions 19 and 20 parallel to the layers 4 and 6.
- the alignment layers 4 and 6 cause the liquid crystal directions 10 and 11 to be fixed at a surface pre-tile angle ⁇ to the plane by the substrates 1 and 9.
- the surface pre-tilt angle ⁇ is determined by using another liquid crystal cell (refer to Figure 3 for cross sectional view).
- spacers 23 and 26 are provided. Each spacer is of 25 ⁇ m in size.
- the tilt angle cell of Figure 3 comprises substrates similar to the substrate of Figure 2 except that the protective films of Rgure 2 are not provided.
- 28 and 29 are the glass substrates
- 21 and 25 are the indium tin oxide films
- 22 and 24 are the orientation layers of LQ1800.
- the orientation layers 22, 24 are rubbed in opposite directions 30 and 31.
- the two substrates 28 and 29 are assembled together with spacers 23 and 26.
- This tilt angle cell is injected with a nematic liquid crystal fluid E7 manufactured by Merck Company.
- the pre-tilt angle ⁇ of liquid crystal molecules in the nematic phase is measure by an optical null method (Mosley et al. Displays 8, 17- 21 (1987).).
- the values of ⁇ obtained for LQ1800 are between 13° and 15°.
- the device shown in Figure 2 is injected with a ferro-electric fluid ZL1 -4655-000 (Manufactured by Merck).
- the LC alignment as cooled from the isotropic phase to the smectic C* phase consists of only twisted C1 chevron states, 14, (Rgure 4) given by
- This director profiles shown in Figure 4 provides very low contrast devices.
- a low frequency (10Hz), low voltage ( ⁇ 30V) electrical signal is applied across the liquid crystal in the direction normal to
- the alignment structure thus formed has a uniform C2 chevron states 15 as shown by director profiles 15a and 15b.
- the resultant uniform C2 chevron states are separated from the twisted C1 chevron
- the active region i.e. the pixels of displays should contain only uniform C2 chevron states. These states are referred to as uniform because they extinct when viewed between crossed polarisers.
- Figure 5 shows the switching behaviour of treated sample.
- the curve represents the minimum pulse width required for a given voltage to switch the uniform C2 chevron states clearly between the bistable states 15a and 15b.
- the threshold voltage of these states are approximately 10V.
- the bistable switching angle is in the order of 30° and this can provide a transmissive contrast ratio of up to 30:1 between crossed polarisers and a corresponding transmission of >25% with respect to parallel polarisers.
- the Merck liquid crystal ZL1 -4655-000 may be replaced with mixtures containing p% of ZL1 -4655-000 and q% of ZL1 -4655-100 (Merck fluid) where
- orientation layer LQ1800 may be replaced by a layer produced by thermal evaporation at an angle of 5° to the plane of the substrates 1 and 9. Further ZL1-4655 mixtures may be replaced by Merck liquid crystal 91-678.
- the ferro-electric liquid crystal structure according to the present invention provides large bistable switching angle combined with low electrical switching voltage requirement.
- the present invention is also advantageous in that it provides a relatively stabie C2 chevron with very few visible defects.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6516781A JPH07505236A (en) | 1993-01-20 | 1994-01-17 | lcd device |
US08/302,938 US5528394A (en) | 1993-01-20 | 1994-01-17 | Ferroelectric liquid crystal device having frequency ≦500 Hz and voltage ≦35 volts that switches a C1 chevron structure to a C2 chevron structure |
EP94904272A EP0631672B1 (en) | 1993-01-20 | 1994-01-17 | Liquid crystal devices |
DE69409039T DE69409039T2 (en) | 1993-01-20 | 1994-01-17 | LIQUID CRYSTAL DEVICES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9301051.0 | 1993-01-20 | ||
GB939301051A GB9301051D0 (en) | 1993-01-20 | 1993-01-20 | Liquid crystal devices |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994017441A1 true WO1994017441A1 (en) | 1994-08-04 |
Family
ID=10728990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1994/000089 WO1994017441A1 (en) | 1993-01-20 | 1994-01-17 | Liquid crystal devices |
Country Status (6)
Country | Link |
---|---|
US (1) | US5528394A (en) |
EP (1) | EP0631672B1 (en) |
JP (1) | JPH07505236A (en) |
DE (1) | DE69409039T2 (en) |
GB (2) | GB9301051D0 (en) |
WO (1) | WO1994017441A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5781266A (en) * | 1993-09-27 | 1998-07-14 | Matsushita Electric Industrial Co., Ltd. | Ferroelectric liquid crystal display device and method for producing the same |
US5726725A (en) * | 1994-03-31 | 1998-03-10 | Canon Kabushiki Kaisha | Liquid crystal device and process for production thereof with polyimide alignment film rubbed and then baked |
GB9604461D0 (en) * | 1996-03-01 | 1996-05-01 | Secr Defence | Alignment of ferroelectric liquid crystal displays |
GB2324619A (en) * | 1996-03-01 | 1998-10-28 | Secr Defence | Alignment of ferroelectric liquid crystal devices |
SG50846A1 (en) * | 1996-06-12 | 1998-07-20 | Rolic Ag | Liquid crystalline display switching or image processing apparatus |
US6020947A (en) * | 1996-11-06 | 2000-02-01 | Sharp Kabushiki Kaisha | Liquid crystal devices |
GB9713544D0 (en) * | 1997-06-26 | 1997-09-03 | Sharp Kk | Ferroelectric liquid crystal device manufacture |
EP0967510A4 (en) * | 1997-12-05 | 2005-11-02 | Citizen Watch Co Ltd | Method of preventing and remedying image persistence of ferroelectric liquid crystal apparatus |
SE517919C2 (en) * | 1998-07-08 | 2002-08-06 | Ecsibeo Ab | Liquid crystal device and method for its preparation and use |
SE0200910D0 (en) * | 2002-03-22 | 2002-03-22 | Ecsibeo Ab | A liquid crystal device, a method for producing a liquid crystal device and a method for controlling liquid crystal device |
JP2004151578A (en) * | 2002-10-31 | 2004-05-27 | Fujitsu Display Technologies Corp | Liquid crystal display device and method for manufacturing the same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0307959A2 (en) * | 1987-09-17 | 1989-03-22 | Canon Kabushiki Kaisha | Ferroelectric smectic liquid crystal device |
EP0444705A2 (en) * | 1990-03-02 | 1991-09-04 | Canon Kabushiki Kaisha | Liquid crystal element and liquid crystal apparatus using the same |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2590392B1 (en) * | 1985-09-04 | 1994-07-01 | Canon Kk | FERROELECTRIC LIQUID CRYSTAL DEVICE |
JP2558447B2 (en) * | 1985-09-18 | 1996-11-27 | セイコー電子工業株式会社 | Ferroelectric liquid crystal electro-optical element |
JPS62129813A (en) * | 1985-11-29 | 1987-06-12 | Olympus Optical Co Ltd | Optical apparatus having stereoscopic parallax utilizing liquid crystal |
JP3071204B2 (en) * | 1989-02-10 | 2000-07-31 | 株式会社リコー | Liquid crystal display device |
CA2022880A1 (en) * | 1989-08-18 | 1991-02-19 | Toyozi Shimizu | Carboxylate compounds, liquid crystal compositions containing said compounds and liquid crystal element |
GB9002105D0 (en) * | 1990-01-31 | 1990-03-28 | Stc Plc | Ferro electric liquid crystal cells |
US5184237A (en) * | 1990-03-27 | 1993-02-02 | Ricoh Company, Ltd. | Super-twisted nematic type liquid crystal display device |
US5250214A (en) * | 1990-04-09 | 1993-10-05 | Ricoh Company, Ltd. | Liquid crystal color display device provided with a color filter film and an optical phase plate comprising liquid crystal polymer |
US5380459A (en) * | 1990-04-20 | 1995-01-10 | Ricoh Company, Ltd. | Liquid crystal display device with improved viewing angle dependence of color |
EP0484972B1 (en) * | 1990-11-09 | 1997-03-12 | Canon Kabushiki Kaisha | Liquid crystal device, display apparatus using same and display method using same |
US5347381B1 (en) * | 1991-01-25 | 1997-07-01 | Sharp Kk | Ferroelectric liquid crystal display device with molecules between hairpin and lightning defects following the lightning defects |
JP3164321B2 (en) * | 1991-03-26 | 2001-05-08 | キヤノン株式会社 | Liquid crystal element and display device, and display method using them |
JP2713513B2 (en) * | 1991-08-29 | 1998-02-16 | シャープ株式会社 | Liquid crystal display |
-
1993
- 1993-01-20 GB GB939301051A patent/GB9301051D0/en active Pending
-
1994
- 1994-01-17 JP JP6516781A patent/JPH07505236A/en active Pending
- 1994-01-17 GB GB9400753A patent/GB2274519B/en not_active Expired - Fee Related
- 1994-01-17 WO PCT/GB1994/000089 patent/WO1994017441A1/en active IP Right Grant
- 1994-01-17 US US08/302,938 patent/US5528394A/en not_active Expired - Fee Related
- 1994-01-17 EP EP94904272A patent/EP0631672B1/en not_active Expired - Lifetime
- 1994-01-17 DE DE69409039T patent/DE69409039T2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0307959A2 (en) * | 1987-09-17 | 1989-03-22 | Canon Kabushiki Kaisha | Ferroelectric smectic liquid crystal device |
EP0444705A2 (en) * | 1990-03-02 | 1991-09-04 | Canon Kabushiki Kaisha | Liquid crystal element and liquid crystal apparatus using the same |
Non-Patent Citations (1)
Title |
---|
KODEN M ET AL: "Four states of surface-stabilized ferroelectric liquid crystal with parallel rubbing", JAPANESE JOURNAL OF APPLIED PHYSICS, PART 1., vol. 31, no. 11, November 1992 (1992-11-01), TOKYO JP, pages 3632 - 3635, XP000414731 * |
Also Published As
Publication number | Publication date |
---|---|
GB9400753D0 (en) | 1994-03-16 |
GB9301051D0 (en) | 1993-03-10 |
US5528394A (en) | 1996-06-18 |
EP0631672B1 (en) | 1998-03-18 |
DE69409039D1 (en) | 1998-04-23 |
GB2274519A (en) | 1994-07-27 |
JPH07505236A (en) | 1995-06-08 |
GB2274519B (en) | 1996-08-21 |
EP0631672A1 (en) | 1995-01-04 |
DE69409039T2 (en) | 1998-07-02 |
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