GB2163273A - Liquid crystal device - Google Patents

Liquid crystal device Download PDF

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Publication number
GB2163273A
GB2163273A GB08517546A GB8517546A GB2163273A GB 2163273 A GB2163273 A GB 2163273A GB 08517546 A GB08517546 A GB 08517546A GB 8517546 A GB8517546 A GB 8517546A GB 2163273 A GB2163273 A GB 2163273A
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Prior art keywords
liquid crystal
phase
cholesteric
chiral smectic
base plate
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GB08517546A
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GB8517546D0 (en
GB2163273B (en
Inventor
Kazuharu Katagiri
Kazuo Yoshinaga
Shinjiro Okada
Junichiro Kanbe
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Canon Inc
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Canon Inc
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Priority claimed from JP14621184A external-priority patent/JPS6125127A/en
Priority claimed from JP14649884A external-priority patent/JPS6125128A/en
Priority claimed from JP19079084A external-priority patent/JPS6167828A/en
Priority claimed from JP19078984A external-priority patent/JPS6167827A/en
Priority claimed from JP19292084A external-priority patent/JPS6170529A/en
Application filed by Canon Inc filed Critical Canon Inc
Publication of GB8517546D0 publication Critical patent/GB8517546D0/en
Publication of GB2163273A publication Critical patent/GB2163273A/en
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Publication of GB2163273B publication Critical patent/GB2163273B/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
    • C09K19/0225—Ferroelectric
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021—Compounds containing at least one asymmetric carbon atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/50—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing steroidal liquid crystal compounds
    • 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
    • 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
    • G02F1/133765—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers without a surface treatment
    • 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
    • G02F1/133773—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers the alignment material or treatment being different for the two opposite substrates
    • 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
    • G02F1/1341—Filling or closing of cells

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Liquid Crystal (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

A bistable liquid crystal device having a liquid crystal composition which contains a liquid crystal showing at least a chiral smectic phase and a liquid crystal showing at least a cholesteric phase. At least one of the base plates has a face which orients the axes of the liquid crystal molecules contacting the face in one direction. Preferably one or other of the liquid crystals is capable of passing through a number of phases e.g. isotropic, cholesteric, smectic A, chiral smectic as a result of changes in temperature.

Description

1 GB 2 163 273A 1
SPECIFICATION
Liquid crystal device BACKGROUND OF THE INVENTION The present invention relates to a liquid crystal device for use in a liquid crystal display device, an optical shutter array, etc., and more particularly to a liquid crystal device having improved display and driving characteristics, because of improved initial alignment or orientation of liquid crystal molecules. -
Hitherto, there have been well known liquid crystal devices using TN (twisted nematic) type 10 liquid crystal as shown, for example, in -Voltage-Dependent Optical Activity of a Twisted Nematic Liquid Crystalby M. Schadt and W. Helfrich, Applied Physics Letters Vol. 18, No. 4 (Feb. 15, 1971) pp. 127-128. In this type of liquid crystal devices, the number of picture elements have been restricted, because there is a problem that a crosstalk phenomenon occurs when a device of a matrix electrode structure with a high density of picture elements is driven 15 according to a time-sharing or time-division driving scheme.
As another type of liquid crystal device, there has been known one comprising a plurality of picture elements each connected to and subject to switching by a thin film transistor as a switching element. This type of liquid crystal device, however, is accompanied with problems such that production of thin film transistors on a substrate is very complicated, and production 20 of a display device with a large picture area or screen is difficult.
In order to obviate the above-mentioned drawbacks of the conventional types of liquid crystal devices, Clark and Lagerwall have proposed the use of a liquid crystal device using a bistable liquid crystal (Japanese Laid-Open Patent Application No. 107216/1981, U. S. Patent No.
4367924, etc.). The bistable liquid crystal to be used may be a ferroelectric liquid crystal having a chiral smectic C (SmC) phase or another phase such as chiral smectic H (SmH) phase, chiral smectic F (SmF) phase, chiral smectic 1 (Smi) phase or chiral smectic G (SmG) phase.
Such a ferroelectric liquid crystal has bistability, i.e., has two stable states comprising a first stable state and a second stable state. Accordingly, different from the conventional TN-type liquid crystal in the abovementioned device, the liquid crystal is oriented to the first stable state 30 in response to one electric field vector and to the second stable state in response to the other electric field vector. Further, this type of liquid crystal very quickly assumes either one of the above-mentioned two stable states in reply to an electric field applied thereto and retains the state in the absence of an electric field. By utilizing these properties, essential improvements can be attained with respect to the above-mentioned difficulties involved in the conventional TN-type 35 liquid crystal device. This point will be explained hereinafter in further detail in connection with the present invention.
However, in order that an optical modulation device using the liquid crystal having bistability could show desired operation performances, the liquid crystal interposed between a pair of parallel base plates is required to be placed in such a state of molecular arrangement that the 40 transition between the two stable states can effectively occur, as a matter different from or a precondition of the application of an electric field. With respect to, for example, a ferroelectric liquid crystal having an SmC or other phases, there must be formed a monodomain wherein the layers of the liquid crystal molecules are perpendicular to the face of the base plate and therefore the axes of the liquid crystal molecules are almost in parallel with the base plate face.
However, in the optical modulation devices using a bistable liquid crystal, an orientation or alignment state of a liquid crystal having such a monodomain structure cannot satisfactorily be formed, whereby the optical modulation device cannot actually show sufficient performances.
For example, several methods have been proposed to give such an orientation state, including a method of applying a magnetic field and a method of applying a shearing force. These methods have not necessarily provided satisfactory results. For example, the rnethod of applying a magnetic field requires a large size of apparatus and is not readily compatible with a thin layer cell which is generally excellent in operation performances. On the other hand, the method of applying a shearing force is not compatible with a process where a cell structure is first formed and then a liquid crystal is poured thereinto.
SUMMARY OF THE INVENTION
A principal object of the present invention is, in view of the above mentioned circumstances, to provide an improvement in monodomain formability or initial alignment, of which an improvement has been desired, to an optical modulation device using a bistable liquid crystal, 60 which is potentially suited for a display device with a high response speed, picture elements arranged at a high density and a large display area or an optical shutter having a high shutter speed, thereby to allow the optical modulation device to fully exhibit their excellent character istics.
We have made a further study with the above object, noting the orientation characteristics of 65 1 2 GB2163273A 2 a liquid crystal during a temperature decreasing stage for causing transition from another phase (e.g., a higher temperature phase such as an isotropic phase) of the liquid crystal to a lower temperature phase such as a smectic phase, e.g., SmA (smectic A phase). As the result, we have observed that a monodomain where liquid crystal molecules of, e.g., smectic A phase are aligned in one direction can be formed by using a liquid crystal composition comprising a liquid crystal showing at least a chiral smectic phase such as chiral smectic C (SmC) phase, chiral smectic H (SmH) phase, chiral smectic F (SmF) phase, chiral smectic 1 (Smi) phase or chiral smectic G (SmG) phase and a liquid crystal showing at least a cholesteric phase, and by imparting a function of orienting molecular axes of the liquid crystal molecules preferentially in one direction to a face of a base plate contacting the liquid crystal composition, whereby a liquid 10 crystal device having operation characteristics based on the bistability of the liquid crystal and a monodomain formation characteristic of the liquid crystal layer in combination is provided.
The liquid crystal device according to the present invention is based on the above finding and, more particularly, comprises a pair of base plates and a liquid crystal composition interposed between the pair of base plates; the liquid crystal composition comprising a liquid crystal showing at least chiral smectic phase and a liquid crystal showing at least cholesteric phase; a face of at least one of the pair of base plates having been provided with a function of preferentially orienting the axes of the liquid crystal molecules contacting the face in one direction.
These and'other objects, features and advantages of the present invention will become more 20 apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 and 2 are schematic perspective views illustrating the basic operation principle of a 25 liquid crystal cell used in the present invention, Figure 3A is a plan view showing an example of the liquid crystal device according to the present invention, Fig. 313 is a sectional view taken along the line A-A in Fig. 3A, Figure 4 is a sectional view showing another example of the liquid crystal device according to the present invention, Figure 5 is a sectional view schematically showing a tilt or oblique vapor deposition apparatus for use in production of the liquid crystal device according to the present invention, Figure 6 is a schematic plan view showing an electrode arrangement of a liquid crystal device used in the present invention, Figures 7A to 7D illustrate signals for driving a liquid crystal device used in the present 35 invention, Figures BA to BD illustrate waveforms applied to respective picture elements.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The liquid crystal composition used in the present invention is one which comprises a liquid 40 crystal showing at least a chiral smectic phase such as SmC, SmH, SmF, Smi or SmG and a liquid crystal showing at least a cholesteric phase and shows a ferroelectricity.
Specific examples of the liquid crystal showing a chiral smectic phase and the liquid crystal showing a cholesteric phase available for the present invention are shown in Table 1 and Table 2, respectively.
Table 1
Specific examples of liquid crystal showing chiral smectic phase (compound name, structural formula and phase transition temperature) (1) CH 3 C 10 H 21 0 -&CH=N -@CH=CH-C0uk-;tl 2 kiL 2 H 5 p-decyloxybenzyiidene-p'-amino-2-methyibutyl cinnamate (DOBAMBC) 3 GB2163273A 3 76 OC crystal /63 C SmH CIC 1170C SMC;- o SmA -C 0 isotropic phase (2) cl 1 C 6 H 13 0 CH=N CH=CH-COuk;kI 2 CHLAI 3 p-hexyloxybenzyiidene-p-amino-2-chforopropyI cinnamate, (HOBACPC) 600C 64 OC 78 OC SmA isotropic crystal SmH SMC f phase (3) CN CH 3 1 1 C 10 H 2 0 CH=N =C _Cuut-;M 2 LAIL; H 1 2 5 p-decyloxybenzyiidene-p'-amino-2-methyibutyl-a-cyanocinnamate (DOBAMBCC) crystal 920C 1040C SMA. isotropic phase 700C /750C SMH (4) CN CH 3 1 1 C H 0 -@-CH=N 2 CHU 2 H 5 14 29 p-tetradecyloxybenzy] idene-p'-a m i no-2-methyl butyi-a-cya noci n na mate (TDOBAMBCC) 78 Oc 104 OC crystal > SmA isotropic phase 470C '1'7 0 0 C SMC (5) cl CH C H 0-CH=N-(jm 1 1 3 =;-(.;UULH2(jHU2H5 8 17 p-octyloxybenzyi idene-p'-a m i no-2-methy[butyi-a-ch loroci n na mate (OOBAMBCC) 4 GB2163273A 4 41 OC crystal SmA 7 -C^ X.1 8 0 C SMC 660C f % isotropic phase (6) CH 3 CH 3 1 C H 0- CH=N CH=C-CO0CH 2 CH2C 2 H 5 8 17 @- -@p-octyloxybenzyiidene-p'-amino-2-methyibutyi-a-methylcinnamate 49 OC crystal -e (7) CH 3 1 58 OC SMC -C > SmA 940C isottopic phate CH 3 1 C H LAICII 0CO-CH=CH 0 N=N CH=CH-COUCki 2 kAI(; 2 H 5 2 5 2 _@1 -@- 0 4,41-azoxycinnamic acid-bis(2-methyibutyi)ester 1210C 1340C 1680C crystal SMC SmA isotropic phase (8) CH 1 C 2 H 5 CHCH 2 0 -@ CH =N -8 H 17 OH 4-0-(2-methyi)-butyiresorcylidene-4'-octylaniline (MBRA 8) 2800C crystal SMC Table 2
550C 620c SniA _ 5 isotropic phase Specific examples of liquid crystals showing cholesteric phase (compound name, structured formula and phase transition temperature) GB 2 163 273A 5 (A) Cholesteryl propionate 1070C 1170C crystal cholesteric isotropic 5 phase phase 10 (B) Cholesteryl nonamate 780C 920C crystal cholesteric isotropic phase phase 15 (C) Cholesteryl palmitate 20 770C 830C crystal cholesteric isotropic phase phase 25 (D) Cholesteryl benzoate 30 148c'C 1760C crystal cholesteric isotropic phase phase 35 (E) CH 3 1 C H CHCH CN 2 5 2 40 4-(2"-methylbutyl)-4'-cyanobiphenyl 40C isotropic crystal -540C 1 phase SMA cholesteric 0//-30 OC phase (G) CH 1 3 c ki 5 CHCH coo coo c 8 H 17 2 2-@- -@- -@- 4-octylphenyl-4'-(4-0-methylbenzoyloxy)benzoate c crystal 72.6 OC cholesteric phase 154.3 OC isotropic phase 6 GB2163273A 6 (H) CH 1 3 C2ki 5 CHCH2-@-N=CH W 4-cyanobenzylidene-41-(2-methylbutyl)aniline 51 OC crystal P isotropic phase 26.5'C cholesteric phase (I) CH 1 3 C2 ki 5 HCH2-'N..,:N-0C6H 13 4-(2-methylbutyl)-4'-hexyloxyazobenzene 35.9 OC crystal cholesteri phase (i) CH 3 c F, 0 -coo 2 ti;t1IL; 2 ri 5 21 _@) 58.2 OC 4-(2-methylbutyl)phenyl-41-decyloxybenzoate crystal. - 45.30C 41.80C 42.20C SmA cholesteric phase isotropic phase isotropic 25 phase 7 GB2163273A 7 (K) CH 3 1 c 2 H 5 CHCH 0 COO--oc H 2 -@)- 6 13 4-hexyloxy-41-(2-methylbutyl)benzoate 220C crystal - P isotropic phase -1.
cholesteric phase 7 C The above mentioned liquid crystals showing a chiral smectic phase and liquid crystals 35 showing a cholesteric phase may respectively be used in combination of two or more species from each group.
While the proportion between the two types of liquid crystals can vary depending on particular liquid crystals used, the liquid crystal showing a cholesteric phase may generally be used in an amount of 0. 1 to 50 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the liquid crystal showing a chiral smectic phase.
In a preferred embodiment, a liquid crystal causing successive phase transition of isotropic phase, cholesteric phase, SmA phase and chiral smectic phase, in the order named, on temperature decrease, may be used in place of the liquid crystals shown in Table 1. Specific examples of such a liquid crystal are enumerated in Table 3 below.
Table 3
Specific examples of liquid crystal showing chiral smectic phase (compound name, structural formula and phase transition temperature) CH 3 1 C H 0 coo CH 2 Lli(; 2 ki 5 8 17- -@- 4-(2 '-methyl butyl)pheny14 1-octyloxybi phenyl-4-carboxylate 8 GB 2 163 273A 8 780C 800C 128.30C crystal Sm3 SmC 4- (unknown phase) 171 OOC (2) cholesteric phase 174.20C CH 1 c 2 H 5 CH-tCH 2+3_ coo C H @- -@- 7 15 4-heptylphenyi-4-(4"-methyihexyl)biphenyl-4'-carboxylate crystal ----------- 1 SMA isotropic phase 91.50C SMC 1310C isotropic phase 0 930C 1120C SMA cholesteri phase (3) p-n-octyloxybenzoic acid-p'-(2-methyibutyloxy)phenyI ester CH 3 1 C H 0 coo O-CH 2-CH-C 2 H 5 8 17 -& 40.50C 420C 580C crystal -c SMC.E S mA,-) cholesteric phase 650C 4 3,isotropic phase The liquid crystals shown in Table 3 may also be used in two or more species in combination.
In another preferred embodiment of the present invention, a liquid crystal causing successive 45 phase transition of isotropic phase, cholesteric phase and chiral smectic phase, in the order named, on temperature decrease, may be used in place of the liquid crystals showing chiral smectic phase as mentioned above. Specific examples of such a liquid crystal are enumerated in Table 4 below.
Table 4 Specific examples of liquid crystals showing chiral smectic phase (compound name, structural formula and phase transition temperature) (1) CH 1 3 2 ki 5 Ltik;kl 2 -&COO -&OC 6 H 13 4-hexyloxyphenyi-4-(2"-methyibutyi)biphenyl-4-carboxylate 9 G82163273A 9 crystal 163.50C 68.80C 80.20C SMC Iket cholesteric phase isotropic phase (2) CH 3 - 10 C H CHCH 0 0 coo OC H 2 5 2 8 17 15 4-octyloxyphenyi-4-(2 "-methyl butyi)biphenyi-4'-carboxylate 76 OC 88.6 OC crystal 3. SMC.6 cholesteric phase 155.4 OC 36 isotropic phase (3) CH 3 1 C n CH --- tCH CH=H-@ N=CH 2 5 2+5-@ CH 1 3 -@-O(CH 2)5 CHC 2 H 5 3: 350C 930C 1450C 35 crystal SMC cholesteric isotropic 0 --C phase phase The liquid crystals of the type as shown in the Table 4 may be used in combination of two or 40 more species.
According to a still preferred embodiment of the present invention, the liquid crystal composition is composed as a ferroelectric composition comprising at least two liquid crystals which show at least a chiral smectic phase; at least one of the liquid crystals showing further a cholesteric phase. More specifically the chiral smectic phase may be SmC, SrnF, Smi or 45 SmG.
Specific examples of the liquid crystals constituting this embodiment of the liquid crystals are shown in Tables 1, 3 and 4 described above. These liquid crystals selected from each group may also be used in combination of two or more species.
In this embodiment of the composition, while the proportion of the two types of the liquid crystals can vary depending on particular liquid crystals used, the liquid crystal showing cholesteric phase as well as a chiral smectic phase may generally be used in a proportion of 0. 1 to 50 parts by weight, preferably 0. 1 to 10 parts by weight, with respect to 1 part by weight of the liquid crystal showing a chiral smectic phase but not a cholesteric phase.
According to a further preferred embodiment of the present invention, the liquid crystal 55 composition may be composed of a combination of a liquid crystal (referred to as---liquidcrystal A-) causing successive phase transition of isotropic phase, cholesteric phase, smectic A phase and chiral smectic phase (inclusive of SrnW, SmH, SrnF, Smi, SmX, SmK, Sm1% SrnG) in the order named on temperature decrease, and a liquid crystal (referred to as -liquid crystal 13---) causing successive phase transition of isotropic phase, cholesteric phase and chiral smectic phase. Specific examples of the liquid crystals A and B are shown in Tables 3 and 4, respectively. The composition of this embodiment, when sandwiched between base plates to a face of which has been imparted a function of orienting molecular axes of the liquid crystal molecules preferentially in one direction, provides a monodomain wherein liquid crystal molecules are aligned uniformly in one direction, whereby a liquid crystal device having GB2163273A 10 operation characteristics based on the bistability of the liquid crystal and a monodomain formation characteristic of the liquid crystal layer in combination is provided.
In this embodiment, a composition further comprising a liquid crystal (referred to as -liquid crystal C-) which causes successive phase transition of isotropic phase, smectic phase and chiral smectic phase, in the order named, on temperature decrease, provides a still better orientation 5 stability for a longer period of time than the above mentioned composition.
The liquid crystal device according to this embodiment of the invention may be expressed as one comprising a pair of base plates and a liquid crystal composition interposed therebetween; the liquid crystal composition comprising a liquid crystal A, a liquid crystal B and, preferably, a liquid crystal C; a face of at least one of the pair of base plates having been provided with a function of preferentially orienting the axes of the liquid crystal molecules contacting the face in one direction.
The proportions of the liquid crystals A and B in the liquid crystal composition can vary depending on particular liquid crystals used but generally be such that the liquid crystal A is used in 0.05 to 20 parts by weight, preferably 0.5 to 2 parts by weight with respect to 1 part 15 by weight of the liquid crystal B. The proportion of the liquid crystal C, when used, is such that it constitutes 0.1 to 40% by weight, preferably 5 to 20% by weight, of the resultant liquid crystal composition.
The liquid crystal composition according to the present invention may preferably be so composed that it will cause successive phase transition of isotropic phase, cholesteric phase, 20 smectic A phase and chiral smectic phase, in the order named, on temperature decrease.
When a device is constituted using these materials, the device may be supported with a block of copper, etc., in which a heater is embedded in order to realize a temperature condition where the liquid crystal composition assumes a desired chiral smectic phase.
Referring to Fig. 1, there is schematically shown an example of a ferroelectric liquid crystal 25 cell for explanation of the operation thereof. Reference numerals 11 and 11 a denote base plates (glass plates) on which a transparent electrode of, e.g., 1n203, Sn02, ITO (Indium-Tin Oxide), etc., is disposed respectively. A liquid crystal of a chiral smectic phase such as SmC, SmW, SrnP, Smi or SmG in which liquid crystal molecular layers 12 are oriented perpendicular to surfaces of the glass plates is hermetically disposed therebetween. A full line 13 shows liquid 30 crystal molecules. Each liquid crystal molecule 13 has a dipole moment (P, ) 14 in a direction perpendicular to the axis thereof. When a voltage higher than a certain threshold level is applied between electrodes formed on the base plates 11 and 11 a, a helical structure of the liquid crystal molecule 13 is loosened or unwound to change the alignment direction of respective liquid crystal molecules 13 so that the dipole moments (P,) 14 are all directed in the direction of 35 the electric field. The liquid crystal molecules 13 have an elongated shape and show refractive anisotropy between the long axis and the short axis thereof. Accordingly, it is easily understood that when, for instance, polarizers arranged in a cross nicol relationship, i.e., with their polarizing directions crossing each other, are disposed on the upper and the lower surfaces of the glass plates, the liquid crystal cell thus arranged functions as a liquid crystal optical 40 modulation device of which optical characteristics vary depending upon the polarity of an applied voltage.
The liquid crystal layer in the liquid crystal device of the present invention may be rendered sufficiently thin in thickness (e.g., less than 10 1L). As the thickness of the liquid crystal layer is decreased, the helical structure of the liquid crystal molecules is loosened even in the absence of 45 an electric field whereby the dipole moment assumes either of the two states i.e., P in an upper direction 24 or Pa in a lower direction 24a as shown in Fig. 2. When electric field E or Ea higher than a certain threshold level and different from each other in polarity as shown in Fig. 2 is applied to a cell having the abovementioned characteristics, the dipole moment is directed either in the upper direction 24 or in the lower direction 24a depending on the vector of the 50 electric field E or Ea. In correspondence with this, the liquid crystal molecules are oriented in either of a first stable state 23 and a second stable state 23a.
When the above-mentioned ferroelectric liquid crystal is used as an optical modulation element, it is possible to obtain two advantages as briefly touched on hereinbefore. First is that the response speed is quite fast. Second is that the orientation of the liquid crystal shows 55 bistability. The second advantage will be further explained, e.g., with reference to Fig. 2. When the electric field E is applied to the liquid crystal molecules, they are oriented in the first stable stage 23. This state is kept stable even if the electric field is removed. On the other hand, when the electric field Ea of which direction is opposite to that of the electric field E is applied thereto, the liquid crystal molecules are oriented to the second stable state 23a, whereby the directions of molecules are changed. This state is similarly kept stable even if the electric field is removed.
Further, as long as the magnitude of the electric field E being applied is not above a certain threshold value, the liquid crystal molecules are placed in the respective orientation states. In order to effectively realize high response speed and bistability, it is preferable that the thickness of the cell is as thin as possible.
11 GB2163273A 11 The most serious problem encountered in forming a device using such a ferroeiectric liquid crystal has been, as briefly mentioned hereinbefore, that it is difficult to form a cell having a highly uniform mono-domain wherein liquid crystal layers having a chiral smectic phase such as SmC, SmH, SrnF, Sm] or SmG are aligned perpendicular to the base plate phases and the liquid crystal molecules are aligned almost in parallel with the base plate phases. A principal object of the invention is to provide a solution to this problem.
Figs. 3A and 3B illustrate an example of the liquid crystal device according to the present invention. Fig. 3A is a plan view of the example and Fig. 313 is a sectional view taken along the line A-A in Fig. 3A.
A cell structure 100 shown in Fig. 3 comprises a pair of base plates 10 1 and 10 1 a made of 10 glass plates or plastic plates which are held with a predetermined gap with spacers 104 and sealed with an adhesive 106 to form a cell structure. On the base plate 10 1 is further formed an electrode group (e.g., an electrode group for applying scanning voltages of a matrix electrode structure) comprising a plurality of transparent electrodes in a predetermined pattern, e.g., of a stripe pattern. On the base plate 101 is formed another electrode group (e.g., an electrode group for applying signal voltages of the matrix electrode structure) comprising a plurality of transparent electrodes 102a crossing the transparent electrodes 102.
On the base plate provided with such transparent electrodes may be further formed an orientation controlling film 105 composed of an inorganic insulating material such as silicon monoxide, silicon dioxide, aluminurn oxide, zirconia, magnesium fluoride, cerium oxide, cerium 20 fluoride, silicon nitride, silicon carbide, and boron nitride, or an organic insulating material such as polyvinyl alcohol, polyimide, polyamide-imide, polyester-imide, polyparaxylylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyamide, polystyrene, cellulose resin, melamine resin, urea resin and acrylic resin.
The orientation controlling film 105 may be formed by first forming a film of an inorganic 25 insulating material or an organic insulating material as described above and then rubbing the surface thereof in one direction with velvet, cloth, paper, etc.
In another preferred embodiment according to the present invention, the orientation control ling film 105 may be formed as a film of an inorganic insulating material such as SiO or S'02 on the base plate 10 1 a by the oblique or tilt vapor deposition.
In an apparatus shown in Fig. 5, a bell jar 501 is placed on an insulting base plate 503 provided with a suction hole 505 and the bell jar 501 is made vacuum by operating a vacuum pump (not shown) connected the suction hole 505. A crucible 507 made of tungsten or molybdenum is place inside and at the bottom of the bell jar 501. In the crucible 507 is paced several grams of a crystal such as SiO, S'02 or MgF2. The crucible 507 has two downwardly extending arms 507a and 507b, which are respectively connected to lead wires 509 and 510.
A power source 506 and a 504 are connected in series to the lead wires 509 and 510 outside the bell jar 501. A base plate 502 is disposed inside the bell jar 501 and right above the crucible 507 so that it forms an angle of 0 with respect to the vertical axis of the bell jar 501.
First, the bell jar 501 is evacuated to a vacuum of about 10-5 mmHg while the switch 504 is 40 open. Then the switch 504 is closed to supply a power while adjusting an output of the power source 506 until the crucible is heated to an incandescent state of an appropriate temperature for evaporating the crystal 508. About 100 amps. of current is required for giving an appropriate temperature range (700-1 0OWC). The crystal 508 is then evaporated off to form an unward molecular stream denoted by S in the figure. The stream S is incident on the base 45 plate 502 with an angle thereto of 0 to coat the base plate 502. The angle 0 is the above mentioned incident angle and the direction of the stream S is the oblique or tilt vapor deposition direction---. The thickness of the film is determined based on the calibration of the thickness with respect to the operation time which is effected prior to the introduction of the base plate 502 into the bell jar 501. After an appropriate thickness of the film is formed, a power supply from the source 506 is decreased, the switch 504 is opened, and the bell jar 501 and the interior thereof are cooled. Then, the pressure in the bell jar is raised to atmospheric pressure and the base plate 502 is taken out from the bell jar 501.
In still another embodiment, the orientation controlling film 105 may be formed by first forming a uniform film of the above-mentioned inorganic or organic insulating material on, i.e., 55 in contact with or above, the base plate 10 1 a and then subjecting the surface of the film to the oblique or tilt etching to provide the surface with an orientation controlling effect.
It is preferred that the orientation controlling film 105 is also cuased to function as an insulating film For this, purpose, the orientation controlling film may preferably have a thickness in the range'of 100 A to 1 g, especially 500 A to 5000 A. The insulating film also has a function of preventing the occurrence of an electric current which is generally caused due to minor quantities of impurities contained in the liquid crystal layer 103, whereby deterioration of the liquid crystal compoundsis prevented even on repeating operations.
In the liquid crystal device according to the present invention, it is possible to form an orientation controlling film similar to the orientation controlling film 105 also on the order base 65 12 GB2163273A 12 plate 101.
A similar orientation controlling effect can also be imparted to the side walls of spacers 104 in the structure shown in Fig. 3, for example, by rubbing.
In the cell structure shown in Fig. 3, the liquid crystal layer 103 may be formed into a chiral smectic phase such as SmW, SmH, SmP, Smi or SmG. The liquid crystal layer 103 having a chiral smectic phase is formed by first forming an SmA (smectic A) phase through phase transition from a cholesteric phase, particularly a cholesteric phase with a grandjean texture, on cooling and by further phase transition on cooling into a chiral smectic phase such as Smc or SmH.
One important aspect of the present invention is that, when a liquid crystal composition 10 containing a liquid crystal showing a cholesteric phase is transformed from a higher temperature phase into SmA phase, the axes of the liquid crystal molecules of the SmA phase are aligned or oriented in the orientation controlling direction imparted to the orientation controlling film, whereby a uniform monodomain is formed.
Fig. 4 shows another embodiment of the liquid crystal device according to the present invention. In the liquid crystal device shown in Fig. 4, a plurality of spacer members 201 are disposed between a pair of base plates 10 1 and 10 1 a. The spacer members 201 can be provided, for example, by forming a film of an inorganic compound such as SiO, S'02, A1203 and Ti02, or a resin such as polyvinyl alcohol, polyimide, polyamide-imide, polyester-imide, polyparaxylylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, 20 polyamide, polystyrene, cellulose resin, melamine resin, urea resin, acrylic resin and a photwesist resin on the base plate 101 on which an orientation controlling film 105 has not been provided, and by etching the film to leave the spacer members 201 at appropriate parts.
A similar orientation effect as explained withh reference to the surface of the base plate 101 or 101 a can also be imparted to the side wall of the spacer members 104 and 201.
Such a cell structure 100 having base plates 10 1 and 10 1 a as shown in Fig. 3 or Fig. 4 is sandwiched between a pair of polarizers 107 and 108 to form an optical modulation device causing optical modulation when a voltage is applied between electrodes 102 and 102a.
Next, a process for producing the liquid crystal device according to the present invention by orientation-controlling the liquid crystal layer 103 is explained more specifically, with reference 30 to Fig. 3. ' First, a cell 100 containing a liquid crystal according to the present invention is set in such a heating case (not shown) that the whole cell 100 is uniformly heated therein. Then, the cell 100 is heated to a temperature where the liquid crystal in the cell assumes as isotropic phase. The temperature of the heating case is decreased, whereby the liquid crystal composition is subjected to a temperature decreasing stage. In the temperature decreasing stage, the liquid crystal composition in the isotropic phase is transformed into SmA either directly or through a cholesteric phase having a grandjean texture. Herein, the axes of the liquid crystal molecules in the SmA phase are algined in the rubbing direction.
Then, the liquid crystal in the SmA phase is transformed into a chiral smectic phase such as 40 SmC on further cooling, whereby a monodomain of the chiral smectic phase with a non-spiral structure is formed if the cell thickness is of the order of, for example, 1 gm.
Referring to Fig. 6, there is schematically shown an example of a cell 41 having a matrix electrode arrangement in which a ferroelectric liquid crystal compound is interposed between a pair of groups of electrodes oppositely spaced from each other. Reference numerals 42 and 43 45 respectively denote a group of scanning electrodes to which scanning signals are applied and a group of signal electrodes to which information signals are applied. Referring to Figs. 7A and 713, there are respectively shown electric signals applied to a selected scanning electrode 42(s) and electric signals applied to the other scanning electrodes (non- selected scanning electrodes) 42(n). On the other hand, Figs. 7C and 7 D show electric signals applied to the selected signal 50 electrode 43(s) and electric signals applied to the non-selected signal electrodes 43(n), respectively. In Figs. 7A to 7D, the abscissa and the ordinate represent a time and a voltage, respectively. For instance, when displaying a motion picture, the group of scanning electrodes 42 are sequentially and periodically selected. If a threshold voltage for giving a first stable state of the liquid crystal having bistability is referred to as V1h, and a threshold voltage for giving a 55 second stable stage thereof as - V,, an electric signal applied to the selected scanning electrode 42(s) is an alternating voltage showing V at a phase (time) t, and - V at a phase (time) t, as shown in Fig. 7A. The other scanning electrodes 42(n) are grounded as shown in Fig. 7B. Accordingly, the electric signals appearing thereon show zero volt. On the other hand, an electric signal applied to the selected signal electrode 43(s) shows V as indicated in Fig. 7C 60 while an electric signal applied to the nonselected signal electrode 43(n) shows - V as indicated in Fig. 7D. In this instance, the voltage V is set to a desired value which satisfies V<Vthl <2V and - V> - VW> - 2V. Voltage waveforms applied to each picture element when such electric signals are given are shown in Fig. 8. Waveforms shown in Figs. 8A, 8B, 8C 65 and 81) correspond to picture elements A, B, C and D shown in Fig. 6, respectively. Namely, as 65 13 GB2163273A 13 seen from Fig. 8A, a voltage of 2 V above the threshold level VIM is applied to the ferroelectric liquid crystal electrically connected to the picture elements A on the selected scanning line at a phase Of t2. Further, a voltage of - 2 V above the threshold level - Vh2 is applied to the ferroelectric liquid crystal electrically connected to the picture elements B on the same scanning line at a phase of t, Acordingly, depending upon whether a signal electrode is selected or not on a selected scanning electrode line, the orientation of liquid crystal molecules changes.
Namely, when a certain signal electrode is selected, the liquid crystal molecules are oriented to the first stable state, while when not selected, oriented to the second stable state. In either case, the orientation of the liquid crystal molecules is not related to the previous states of each picture element.
On the other hand, as indicated by the picture elements C and D on the non-selected scanning lines, a voltage applied to all picture elements C and D is + V or - V, each not exceeding the threshold level. Accordingly, the ferroelectric liquid crystal molecules electrically connected to the respective picture elements C and D are placed in the orientations correspond ing to signal states produced when they have been last scanned without change in orientation. 15 Namely, when a certain scanning electrode is selected, signals corresponding to one line are written and thus writing of signals corresponding to one frame is completed. The signal state of each picture element can be maintained until the line is subsequently selected. Accordingly, even if the number of scanning lines increases, the duty ratio does not substantially change, resulting in no possibility of lowering in contrast, occurrence of crosstalk, etc. In this instance, 20 the magnitude of the voltage V and length of the phase (t, + t,) = T usually ranges from 3 volts to 70 volts and from 0. 1 gsec. to 2 msec., respectively, although they change depending upon the thickness of a liquid crystal material or a cell used. In this way, the electric signals applied to a selected scanning electrode can cause either direction of change in state, i.e., from a first stable state (defined herein as---bright-state when converted to corresponding optical signals) 25 to a second stable state (defined as---dark-state when converted to corresponding optical signals), or vice versa.
Compared with a case where a liquid crystal sowing a chiral smectic phase such as DOBAMBC cinnamate, HOBACPC, or MBRA 8 is used alone, the liquid crystal composition used, in the present invention containing a liquid crystal showing a cholesteric phase has a better 30 orientation characteristic and gives an orientation or alignment state free of orientation defects.
As for the extent of orientation controlling treatment, it is preferred to impart such an orientation controlling treatment or layer to only one of the pair of base plates in order to give a faster response speed because a weaker constraining force acting on liquid crystal molecules on 1he surface of the base plate (or a weaker orientation controlling effect imparted to the base plate) favors a. better switching characteristic (faster response speed), especially when a thin cell is used or a chiral smectic phase such a SmC, SmW, SrnF, Smi or SmG having bistability (memory characteristic) is formed. For example, with respect to a cell having a thickness of 2 jum or less, a cell in which only one base plate has been subjected to orientation controlling treatment gives about twice as fast a response speed as that obtained by a cell in which both 40 base plates have been treated for orientation control.
The present invention will be further explained with reference to working examples.
Example 1 45 On a square glass base plate were formed ITO (Indium-TinOxide) electrode films in the form 45 of stripes with a width of 62.5 lim at a pitch of 1 00jum. In an apparatus for the oblique vapor deposition as shown in Fig. 5, the base plate was disposed with its face having the ITO film being directed downward and a crystal of S'02 was set in a crucible of molybdenum. Then the vapor deposition apparatus was evacuated to a vacuum of the order of 10-5 mmHg and S'02 50 was obliquely vapordeposited in a prescribed manner to form an electrode plate with an 800 g50 thick oblique vapor deposition film (A electrode plate). On the other hand, on a similar glass plate provided with stripe-form ITO electrode films was applied a polyimide-forming solution (---PIG-: polyimideisoindoiquinazoline-dione, produced by Hitachi Kasei Kogyo K.K.; Nonvolatile content: 14.5 wt.5) by means of a spinner coater, which 55 was then heated at WC for 30 minutes, at 20WC for 60 minutes and at 35WC for 30 minutes to form a film of 800 A in thickness (B electrode plate). Then, a heat-setting epoxy adhesive was applied to the periphery of the A electrode plate except for the portion forming an injection port by screen printing process. The A electrode plate and the B electrode plate were superposed with each other so that their stripe-pattern electrodes crossed each other with right angles and secured to each other with a polyimide spacer while 60 leaving the gap of 2 [L therebetween, thereby to form a cell (blank cell).
Separately, a liquid crystal composition was prepared by mixing 5 parts by weight of cholesteryl nonanate with 100 parts by weight of p-decyloxybenzylidene-p- amino-2-methyibutyI cinnamate (DOBAMBC).
The liquid crystal composition was heated into the isotropic phase and injected through the 65 1 14 GB 2 163 273A 14 injection port of the above-prepared cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of G.WC/hr and, at a constant temperature of about WC, was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase whose spiral had been loosened was found to be formed.
Example 2
On a square glass plate provided with stripe-form [TO electrode films as used in Example 1 was applied a polyimide-forming solution (---PlW: produced by Hitachi Kasei Kogyo K.K.; Non volatile content: 14.5 wt.%) by means of a spinner coater, which was then heated at WC for 10 minutes, at 20WC for 60 minutes and at 35WC for 30 minutes to form a film of 800 A in thickness (A electrode plate).
A similar electrode plate provided with a polyimide film was subjected to a rubbing treatment to produce a B electrode plate.
Then, a heat-setting epoxy adhesive was applied to the periphery of the A electrode plate 15 except for the portion forming an injection port by screen printing process. The A electrode plate and the B electrode plate were superposed with each other so that their stripe-pattern electrodes crossed each other with right angles and secured to each other with a polyimide spacer while leaving the gap of 2 g therebetween, thereby to form a cell (blank cell).
Separately, a liquid crystal composition was prepared by mixing 10 parts by weight of 4-(2- 20 methyl butyi)phenyi-4-decyloxybenzoate with 100 parts by weight of DOBAMBC.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of the above-prepared cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and, at a constant temperature of about WC, was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of an SmC phase whose spiral had been loosened was found to be formed.
Example 3
A blank cell as used in Example 1 was provided.
Separately, a liquid crystal composition was prepared by mixing 8 parts by weight of 4hexyloxyphenyi-4-(2 "-methyl butyl) biphenyl-4-ca rboxylate with 100 parts by weight of DOBAMBC.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of the above-prepared cell, and the injection port was sealed. The liquid crystal cell 35 thus formed was gradually cooled at a rate of 0.5'C/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicok relationship, whereby a monodomain of SmC phase whose spiral had been loosened was found to be formed.
Example 4
A blank cell as used in Example 1 was provided.
Separately, a liquid crystal composition was prepared by mixing 5 parts by weight of 4 heptylphenyl-4-(4"-methylhexyi)biphenyl-4'-carboxylate with 100 parts by weight of DOBAM BC.
The liquid crystal composition was heated into the isotropic phase and injected through the 45 injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase whose spiral had been loosened was found to be formed.
Example 5
A blank cell as used in Example 1 was provided.
Separately, a liquid crystal composition was prepared by mixing 5 parts by weight of cholesteryl nonanate with 100 parts by weight of 4-hexyloxyphenyi-4-(2 "- methyl butyl) biphenyl- 55 4'-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of 0.5'C/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, 60 whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 500 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the 65 GB 2 163 273A 15 same manner as described above except that the cholesteryl nonanate was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 500 hours of durability test.
Example 6
A blank cell as used in Example 2 was provided.
Separately, a liquid crystal composition was prepared by mixing 10 parts by weight of 4-(2methyl butyi)phenyi-4'-decyloxybenzoate with 100 parts by weight of 4-octyloxyphenyl-4-(2"- methyl butyi)bi phenyl-4-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of the above provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of 0.5T/hr and, at a constant temperature of about WC, was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase whose spiral had been loosened was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 700 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the 20 same manner as described above except that the 4-(2-methyibutyi)pheny]-4'- decyloxybenzoate was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 700 hours of durability test.
Examples 7-9
Liquid crystal devices were prepared in the same manner as in Example 6 except that the 4- (2-methyibutyi)phenyi-4'-decyloxybenzoate was replaced by 4-(2 "-methyl butyl)4'-cya nobi phenyl (Example 7), cholesteryl benzoate (Example 8) and 4-(2 "-methyl butyloxy)- 4'-cya nobi phenyl 30 (Example 9), respectively. The liquid crystal devices were subjected to similar microscopic observation, whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 6.
Example 10
A transparent electrode film consisting primarily of indium oxide was formed on a polyethy]- ene terephthalate base film of 100 gm in thickness with the surface temperature of the base film being suppressed to below 1 20C by means of a low-temperature sputtering apparatus, thereby to provide a plastic substrate. A solution having the following composition (Solution Composition 40 (1)) was applied on the plastic substrate and dried at 1 2WC for 30 minutes to form a coating film.
Solution composition (1) 45 Acetomethoxyaluminum diisopropylate Polyester resin (Bylon 30P, mfd. by Toyobo K. K.) Tetrahydrofuran 1 9 0.5 g 100 M1 The coating film on the plastic substrate was then rubbed in one direction under the pressure 50 of 100 g/CM2. A pair of the thus rubbing-treated plastic substrate were superposed each other so that their rubbing directions were in parallel with each other and secured to each other with a gap of 1 it therebetween by sealing the periphery except for a port for liquid crystal injection, whereby a blank cell was prepared.
Separately, a liquid crystal composition was prepared by mixing 4 parts by weight of 4-(2- 55 methyl butyl)-4'-hexyl oxyazobenzene with 100 parts by weight of 4- hexyloxyphenyl-4-(2"-me thylbutyi)biphenyi-4'-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injection through'the injection port of and into the above-provided cell under vacuum, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was 60 observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with non- spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 500 hours and then subjected to similar microscopic observation, whereby the 65 16 GB 2 163 273A 16 SmC phase with non-spiral structure was observed to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the same manner as described above except that the 4-(2methylbutyi)-4'-hexyloxyazobenzene was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage, whereas the monodomain of SmC phase was not retained after the 500 hours of durability test.
Example 11
A glass plate, on which stripes of ITO electrode film were provided in a width of 62.5 gm and 10 at a pitch of 100 gm, was further coated with a coating solution having the following solution composition (6).
Solution composition (6) Tetraisopropoxytitanium Condensation product of pyromellitic anhydride and 4,4-diaminodiphenyl ether 0.59 as a polyimide precursor (polyamide acid) (solid) lsopropyl alcohol 50 M1 Ethanol 50 M1 1 9 is The thus coated glass substrate was further heated at 2WC for 1 hour to cause a dehydration-ring closure reaction, thereby to convert the coating film into a polyimide film.
The polyimide film on the glass substrate was then rubbed in one direction under the pressure of 100 g/CM2. A pair of the thus rubbing-treated plastic substrate were superposed each other 25 so that their rubbing directions were in parallel with each other and secured to each other with a gap of 1 g therebetween by sealing the periphery except for a port for liquid crystal injection, whereby a blank cell was prepared.
Separately, a liquid crystal composition was prepared by mixing 4 parts by weight of 4 cyanobenzyiidene-4'-(2-methylbutyi)aniline with 100 parts by weight of 4- octyloxypheny]-4-(2"- 30 methyibutyi)biphenyi-41-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of and into the above-provided cell under vacuum, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of 0.5,C/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in 35 the cross nicol relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 800 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the same manner as described above except that the 4cyanobenzyiidene-4'-(2-methylbutyl)aniline was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 800 hours of durability test.
Example 12
A blank cell as used in Example 1 was provided.
Separately, a liquid crystal composition was prepared by mixing 5 parts by weight of cholesteric nonanate with 100 parts by weight of 4-(2- rnethyl butyi)phenyi-4'-octyloxybi phenyl4-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was observed though a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with nonspiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 500 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the same manner as described above except that the cholesteryl nonanate was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 500 hours of durability test.
17 GB2163273A 17 Example 13
A blank cell as used in Example 2 was provided.
Separately, a liquid crystal composition was prepared by mixing 10 parts by weight of 4-(2 methyl butyi)phenyi-4'-decyloxybenzoate with 4-(2'-methyibutyl)phenyl-4- octyloxybiphenyi-4-car- 5 boxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of and into the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of 0.5T/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol 10 relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 700 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the same manner as described above except that the 4-(2methyibutyi)phenyl-4'-decyloxybenzoate was omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 700 hours of 20 durability test.
Examples 14 and 15 Liquid crystal devices were prepared in the same manner as in Example 13 except that the 4 (2-methylbutyl)phenyi-4'-oetyloxybipheny]-4-carboxylate was replaced by 4pentylphenyl-4-(4'- 25 methyl hexyi)pheny]-4'-carboxylate (Example 14), and p-n-octyloxybenzoic acid-p'-(2-methylbuty loxy)phenyl ester (Example 15), respectively. The liquid crystal devices were subjected to similar microscopic observation whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 13.
Examples 16-18 Liquid crystal devices were prepared in the same manner as in Example 13 except that the 4- (2-methyibutyi)phenyi-4'-decyloxybenzoate was replaced by 4-(2 "-methyl butyl)-4'-cyanobi phenyl (Example 16), cholesteryl benzoate (Example 17) and 4-(2-rnethyl butyloxy)-4-cyanobi phenyl 35 (Example 18), respectively. The liquid crystal devices were subjected to similar microscopic observation whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 13.
Example 19
A blank cell as used in Example 10 was provided.
Separately, a liquid crystal composition was prepared by mixing 4 parts by weight of 4-(2 methyl butyl)-4'-hexyloxyazo benzene with 100 parts by weight 4-(2'- methyibutyi)phenyi-4-octy- loxybiphenyi-4-carboxylate.
The liquid crystal composition was heated into the isotropic phase andinjected through the injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 500 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as a comparative experiment, a liquid crystal device was prepared in the same manner as described above except that the 4-(2-methyibutyi)-4- hexyloxyazobenzene was 55 omitted. The liquid crystal device was subjected to similar microscopic observation. As a result, a monodomain of SmC phase with non-spiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 500 hours of durability test.
Examples 20-22 Liquid crystal devices were prepared in the same manner as in Example 19 except that the 4- (2-methyibutyi)4'-hexyloxyazobenzene was replaced by 4-(2 "-methyl buty14'-cya nobiphenyl (Example 20), cholesteryl benzoate (Example 21) and 4-(2 "-methyl butyloxy)-4'-cya nob i phenyl (Example 22), respectively. The liquid crystal devices were subjected to similar microscopic 18 GB2163273A 18 observation whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 500 hours of the durability test as carried out in Example 19.
Example 23
A blank cell as used in Example 1 was provided.
Separately, a liquid crystal composition was prepared by mixing 75 parts by weight of 4hexyloxyphenyi-4-(2"-methyibutyi)bipheny]-41-carboxylate with 100 parts by weight of 4-(21methy[butyi)phenyi-4'-octyloxybipheny]-4carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the 10 injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the 15 condition for 700 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as comparative experiments, liquid crystal devices were prepared in the same manner as described above except that the two liquid crystals used in the above liquid crystal device were separately used. The liquid crystal devices were subjected to similar microscopic observation. As a result, in each case, a monodomain of SmC phase with nonspiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 700 hours of durability test.
Further, when 20 parts by weight of DOBAMBC was added to 100 parts by weight of the above mentioned liquid crystal composition to obtain a liquid crystal composition. The thus obtained liquid crystal composition was used to prepare a liquid crystal device in the same manner. The liquid crystal device was subjected to similar microscopic observation, whereby a - monodomain of SmC phase with non-spiral structure was found to be formed and observed to be retained after the durability test for a prolonged time which was 1000 hours longer than that in the above mentioned example.
Example 24
A blank cell as used in Example 2 was provided.
Separately, a liquid crystal composition was prepared by mixing 70 parts by weight of 4 (octyloxyphenyi)-4-(2 "-methyl butyi)bi phenyl-4'-carboxylate with 100 parts by weight of 4pentylpheny]-4-(4"-methyihexyl)biphenyl-4'-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the injection port of and into the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of O.WC/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the condition for 700 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as comparative experiments, liquid crystal devices were prepared in the same manner as described above except that the two liquid crystals used in the above liquid crystal device were separately used. The liquid crystal devices were subjected to similar microscopic observation. As a result, in each case, a monodomain of SmC phase with non spiral structure was found to be formed at the initial stage, whereas the monodomain of SmC 50 phase was not retained after the 700 hours of durability test.
Further, when 20 parts by weight of DOBAMBC was added to 100 parts by weight of the above mentioned liquid crystal composition to obtain a liquid crystal composition. The thus obtained liquid crystal composition was used to prepare a liquid crystal device in the same manner. The liquid crystal device was subjected to similar microscopic observation whereby a 55 monodomain of SmC phase with non-spiral structure was found to be formed and observed to be retained after the durability test for a prolonged time which was 1000 hours longer than that in the above mentioned example.
Examples 25 and 26 Liquid crystal devices were prepared in the same manner as in Example 23 except that the 4(2-methyibutyi)phenyi-4'-octyloxybipheny]-4-carboxylate was replaced by 4pentylphenyi-4-(4" methyihexyi)biphenyi-4'-carboxylate (Example 25), and p-n-octyloxybenzoic acid-p-(2-methyibu tyloxy)phenyl-ester (Example 26). The liquid crystal devices were subjected to similar micro scopic observation whereby a monodomain of SmC phase with non-spiral structure was 65 19 GB 2 163 273A 19 respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 23.
Further, two liquid crystal devices respectively containing threecomponent liquid crystal compositions were prepared in the same manner as explained in Example 23 except that HOBACIPC was used in place of DOBAMBC. The liquid crystal devices were subjected to similar 5 microscopic observation, whereby a monodomain of SmC with non-spiral structure was observed to be formed at the initial stage and retained after the durability for 1 7GO hours for each device.
Example 27
A blank cell as used in Example 10 was provided.
Separately, a liquid crystal composition was prepared by mixing 80 parts by weight of 4 hexyloxypheny14-(2 "-methyl butyi)bi phenyl-41-carboxylate with 100 parts by weight of 4-(2' methyl butyi)phenyi-4'-octyloxybi phenyl-4-carboxylate.
The liquid crystal composition was heated into the isotropic phase and injected through the 15 injection port of the above-provided cell, and the injection port was sealed. The liquid crystal cell thus formed was gradually cooled at a rate of 0.5C/hr and was observed through a microscope while being sandwiched between a pair of polarizers arranged in the cross nicol relationship, whereby a monodomain of SmC phase with non-spiral structure was found to be formed.
The device containing the liquid crystal composition in the SmC phase was held under the 20 condition for 500 hours and then subjected to similar microscopic observation, whereby the SmC phase with non-spiral structure was found to be retained.
On the other hand, as comparative experiments, liquid crystal devices were prepared in the same manner as described above except that the two liquid crystals used in the above liquid crystal device were separately used. The liquid crystal devices were subjected to similar microscopic observation. As a result, in each case, a monodomain of SmC phase with nonspiral structure was found to be formed at the initial stage whereas the monodomain of SmC phase was not retained after the 500 hours of durability test.
Further, when 20 parts by weight of OOBAMBCC was added to 100 parts by weight of the above mentioned liquid crystal composition to obtain a liquid crystal composition. The thus obtained liquid crystal composition was used to prepare a liquid crystal device in the same manner. The liquid crystal device was subjected to similar microscopic observation whereby a monodomain of SmC with non-spiral structure was found to be formed at the initial stage and observed to be retained after the durability test for a prolonged time which was 800 hours longer than that in the above mentioned example.
Examples 28 and 29 Liquid crystal devices were prepared in the same manner as in Example 27 except that the 4 (2'-methyibutyi)phenyi-4'-octyloxybiphenyi-4-carboxylate was replaced by 4-pentyiphenyi-4-(4" methyl hexyi)b i phenyl4'-ca rboxylate (Example 28) and p-n- octyloxybenzoic acid-p'-(2-methyibuty- 40 loxy)phenyl ester.
The liquid crystal devices were subjected to similar microscopic observation whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 24.
Further, two liquid crystal devices respectively containing threecomponent liquid crystal compositions were prepared in the same manner as explained in Example 23 except that DOBAMBC was used in place of OOBAMBCC. The liquid crystal devices were subjected to similar microscopic observation, whereby a monodomain of SmC with non- spiral structure was observed to be formed at the initial stage and retained after the durability for 2000 hours for each device.
Examples 30 and 31 Liquid crystal devices were prepared in the same manner as in Example 24 except that the 4 pentylphenyi-4-(4"-methylhexyi)biphenyl-4'-carboxylate used in Example 24 was replaced by 4 (2 '-methyl butyi)phenyi-4'-octyl oxybi phenyl-4-ca rboxylate (Example 30) and p-n-octyloxybenzoic 55 acid-p'-(2-methyibutyloxy)phenyI ester. The liquid crystal devices were subjected to similar microscopic observation whereby a monodomain of SmC with non-spiral structure was respectively found to be formed and observed to be retained after the 700 hours of the durability test as carried out in Example 24.
Further, two liquid crystal devices respectively containing threecomponent liquid crystal 60 compositions were prepared in the same manner as explained in Example 23 except that MBRA 8 was used in place of DOBAMBC. The liquid crystal devices were subjected to similar microscopic observation, whereby a monodomain of SmC with non-spiral structure was observed to be formed at the initial stage and retained after the durability for 1500 hours for each device.
GB 2 163 273A 20 The liquid crystal devices produced in the above examples were driven for wiring with voltage signals having waveforms as shown in Fig. 8 (driving voltage 30 V, pulse width 500 msec), whereby the writen images were memorized without inversion for a duration of one frame.

Claims (30)

1. A liquid crystal device comprising a pair of base plates and a liquid crystal composition interposed between the pair of base plates; said liquid crystal composition comprising a liquid crystal showing at least a chiral smectic phase and a liquid crystal showing at least a cholesteric phase; a face of at least one of said pair of base plates having been provided with a function of preferentially orienting the axes of the liquid crystal molecules contacting the face in one 10 direction.
2. A device according to claim 1 wherein said liquid crystal composition comprises at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase, smectic A phase and chiral smectic phase on temperature decrease, and at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase and crystalline 15 phase or of isotropic phase, cholesteric phase, smectic phase and crystalline phase respectively on temperature decrease.
3. A device according to claim 1 wherein said liquid crystal composition comprises at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase and chiral smectic phase on temperature decrease, and at least one liquid crystal causing successive 20 phase transition of isotropic phase, cholesteric phase and crystalline phase or of isotropic phase, cholesteric phase, smectic phase and crystalline phase respectively on temperature decrease.
4. A device according to claim 1 wherein said liquid crystal composition comprises at least two liquid crystals showing a chiral smectic phase, at least one of which further shows a cholesteric phase.
5. A liquid crystal device according to claim 1 wherein said liquid crystal composition comprises at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase, smectic A phase and chiral smectic phase on temperature decrease, and at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase and chiral smectic phase on temperature decrease.
6. A liquid crystal device according to claim 1 wherein said liquid crystal composition comprises at least one liquid crystal causing successive phase transition of isotropic phase, smectic A phase and chiral smectic phase on temperature decrease, at least one liquid crystal causing successive phase transition of isotropic phase, cholesteric phase, smectic A phase and chiral srnectic phase on temperature decrease, and at least one liquid crystal causing successive 35 phase transition of isotropic phase, cholesteric phase and chiral smectic phase.
7. A device according to claim 1 wherein said liquid crystal composition causes successive phase transition from smectic A phase to chiral smectic phase on temperature decrease.
8. A device according to claim 7 wherein said chiral smectic phase is C phase, H phase, F phase, 1 phase, K phase, J phase or G phase.
9. A device according to claim 7 or 8 wherein said chiral smectic phase is in a state where a non-spiral structure is formed.
10. A device according to any preceding claim wherein one of the pair of base plates has a function of preferentially orienting the axes of the liquid crystal in one direction and the other does not have the function.
11. A device according to any preceding claim wherein the function of preferentially orienting the axes of the liquid crystal molecules in one direction has been provided by rubbing the face of a base plate.
12. A device according to claim 11 wherein said face of a base plate is formed by a film of an organic insulating material or an inorganic insulating material.
13. A device according to claim 12 wherein said organic insulating material comprises at least one resin selected from polyvinyl alcohol, polyimides, polya m ide- im ides, polyester-i m ides, polyparaxylylene, polyesters, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl ace tate, polyamides, polystyrene, cellulose resins, melamine resins, urea resins, acrylic resins and a photoresist resins.
14. A device according to claim 12 wherein said inorganic insulating material is SiO, Si02 or Ti02.
15. A device according to any of claims 1 to 10 wherein the function of preferentially orienting the axes of the liquid crystal molecules in one direction has been provided to the face of a base plate by forming a film having the face on the base plate by the oblique vapor 60 deposition of an inorganic insulating material.
16. A device according to claim 15 wherein said inorganic insulating material is SiO or S'02.
17 A device according to any of claims 1 to 10 wherein the function of preferentially orienting the axes of the liquid crystal molecules in one direction has been provided on the face 65 21 GB2163273A 21 of a base plate by oblique etching of a face of the base plate.
18. A device according to claim 17 wherein said face of a base plate is given by a film of an organic or inorganic insulating material formed on the base plate or the base plate per se.
19. A device according to claim 18 wherein said organic insulating material is as specified in claim 13.
20. A device according to claim 18 wherein said inorganic insulating material is glass, SiO, Si02 or Ti02.
2 1. A device according to claim 10 wherein said the other base plate is provided with a spacer member which has been provided by first forming a film of an insulating material and then etching the film except a selected portion thereof.
22. A device according to claim 21 wherein said spacer member is in the form of a stripe.
23. A device according to claim 21 or 22 including a plurality of spacer members.
24. A liquid crystal device comprising a plurality of picture elements arranged in a plurality of rows and columns, and a ferroelectric liquid crystal electrically connected to the picture elements and placed in the bistable state, the orientation state of the ferroelectric liquid crystal being controlled for each picture element to effect writing, wherein said ferroelectric liquid crystal is in the form of a composition comprising a liquid crystal showing at least chiral smectic phase and a liquid crystal showing at least cholesteric phase and is in contact with a base plate face which has been provided with a function of preferentially orienting the axes of the liquid crystal molecules contacting the face in one direction.
25. A device according to claim 24 wherein the written state of a written picture element is memorized for a duration of one field on one frame.
26. A device according to claim 24 or 25 which comprises a plurality of picture elements arranged in a plurality of rows and columns, and a ferroelectric liquid crystal electrically 25 connected to the picture elements and placed in the bistable state, each row of the picture elements being electrically connected to a scanning line and each column of the picture elements being electrically connected to a data line, a scanning signal being applied line by line to the scanning lines while a data signal is applied to the data lines in synchronism with the scanning signals thereby to effect writing by changing the orientation states of the ferroelectric 30 liquid crystal electrically connected to the scanning lines in correspondence with the data signal.
27. A device according to any of claims 24 to 26 wherein data signals comprising a first signal and a second signal are applied to the data lines in synchronism with the scanning signals thereby to effect writing by orienting the ferroelectric liquid crystal in the bistable state to its first stable state in correspondence with the first data signal and to its second stable state in correspondence with the second data signal.
28. A device according to any of claims 24 to 27 wherein said ferroelectric liquid crystal is in the form of a liquid crystal composition as specified in any of claims 2 to 6.
29. A liquid crystal device substantially as described herein with reference to the accom panying drawings.
30. A liquid crystal device substantially as described herein with reference to any one of the Examples.
Printed in the United Kingdom for Her Majesty's Stationery Office, Dd 8818935, 1986, 4235. Published at The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
GB08517546A 1984-07-13 1985-07-11 Liquid crystal device Expired GB2163273B (en)

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GB2188742A (en) * 1986-04-01 1987-10-07 Stc Plc Ferroelectric liquid crystal cells
US4778260A (en) * 1985-04-22 1988-10-18 Canon Kabushiki Kaisha Method and apparatus for driving optical modulation device
US4859035A (en) * 1986-05-26 1989-08-22 Nec Corporation Ferroelectric liquid crystal light shutter device and method of controlling the driving of the same
US4878742A (en) * 1986-08-04 1989-11-07 Canon Kabushiki Kaisha Liquid crystal optical modulator
US4997264A (en) * 1986-04-03 1991-03-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Ferroelectric liquid crystal devices having a high surface tilt
US5398042A (en) * 1987-11-18 1995-03-14 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Method and apparatus for multiplex addressing of a ferro-electric liquid crystal display
US5594575A (en) * 1989-03-22 1997-01-14 Hoechst Aktiengesellschaft Ferroelectric liquid-crystal systems having three or more chiral additives with different signs of the helical twist in the cholesteric phase
USRE37509E1 (en) 1986-04-03 2002-01-15 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britian And Northern Ireland Smectic liquid crystal devices

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CA1258512A (en) * 1985-10-28 1989-08-15 John W. Goodby Ferroelectric liquid crystal optical devices

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US3716289A (en) * 1970-08-31 1973-02-13 Texas Instruments Inc Electro-optical display devices using smectic-nematic liquid crystal mixtures

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US4367924A (en) * 1980-01-08 1983-01-11 Clark Noel A Chiral smectic C or H liquid crystal electro-optical device
US4781441A (en) * 1983-11-25 1988-11-01 Canon Kabushiki Kaisha Method of controlling orientation of liquid crystal, device used therein and liquid crystal device produced thereby
FR2557719B1 (en) * 1984-01-03 1986-04-11 Thomson Csf MEMORY DISPLAY DEVICE USING FERROELECTRIC MATERIAL

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4778260A (en) * 1985-04-22 1988-10-18 Canon Kabushiki Kaisha Method and apparatus for driving optical modulation device
GB2188742A (en) * 1986-04-01 1987-10-07 Stc Plc Ferroelectric liquid crystal cells
US4799775A (en) * 1986-04-01 1989-01-24 Stc Plc Ferroelectric liquid crystal cells having a helical liquid crystal structure
US4997264A (en) * 1986-04-03 1991-03-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Ferroelectric liquid crystal devices having a high surface tilt
EP0299970B1 (en) * 1986-04-03 1994-01-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Liquid crystal devices
USRE37509E1 (en) 1986-04-03 2002-01-15 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britian And Northern Ireland Smectic liquid crystal devices
US4859035A (en) * 1986-05-26 1989-08-22 Nec Corporation Ferroelectric liquid crystal light shutter device and method of controlling the driving of the same
US4878742A (en) * 1986-08-04 1989-11-07 Canon Kabushiki Kaisha Liquid crystal optical modulator
US5398042A (en) * 1987-11-18 1995-03-14 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Method and apparatus for multiplex addressing of a ferro-electric liquid crystal display
US5497173A (en) * 1987-11-18 1996-03-05 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Method and apparatus for multiplex addressing of a ferro-electric liquid crystal display
US5594575A (en) * 1989-03-22 1997-01-14 Hoechst Aktiengesellschaft Ferroelectric liquid-crystal systems having three or more chiral additives with different signs of the helical twist in the cholesteric phase

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FR2567533B1 (en) 1994-04-15
GB2163273B (en) 1987-12-09

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