WO2011115611A1 - Formulations et structures de cristaux liquides pour dispositifs optiques smectiques a - Google Patents

Formulations et structures de cristaux liquides pour dispositifs optiques smectiques a Download PDF

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WO2011115611A1
WO2011115611A1 PCT/US2010/027328 US2010027328W WO2011115611A1 WO 2011115611 A1 WO2011115611 A1 WO 2011115611A1 US 2010027328 W US2010027328 W US 2010027328W WO 2011115611 A1 WO2011115611 A1 WO 2011115611A1
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composition
liquid crystal
smectic
cell
dye
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PCT/US2010/027328
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English (en)
Inventor
Terry Victor Clapp
William Alden Crossland
Anthony Bernard Davey
Martin Grassman
Jonathan Paul Hannington
Russell Keith King
Mike Pivnenko
Steven Robson
Huan Xu
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Cambridge Enterprise Limited
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Priority to PCT/US2010/027328 priority Critical patent/WO2011115611A1/fr
Priority to KR1020127026906A priority patent/KR101801722B1/ko
Priority to CA2792334A priority patent/CA2792334A1/fr
Priority to US13/635,334 priority patent/US8956548B2/en
Priority to CN201180014289.7A priority patent/CN102959049B/zh
Priority to EP11718175.0A priority patent/EP2547749B1/fr
Priority to JP2013500152A priority patent/JP5771682B2/ja
Priority to PCT/US2011/028495 priority patent/WO2011115976A1/fr
Publication of WO2011115611A1 publication Critical patent/WO2011115611A1/fr

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    • 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
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
    • C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
    • 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
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
    • C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
    • C09K19/408—Polysiloxanes
    • 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
    • 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
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group

Definitions

  • the present invention relates to liquid crystal compositions having a smectic A structure, cells containing such a composition sandwiched between a pair of electrodes, an optical device containing multiple cells and a method of switching the optical properties of the composition by applying an electric field thereto.
  • phase sequences In the phases of matter normally considered by the lay person there are a series of material characteristics typified, in a cooling sequence, by a gas phase, a liquid phase and a solid phase.
  • a gas phase For materials such as simple organic liquids (e.g. methanol, hexane etceteras) this is normally sufficient.
  • simple organic liquids e.g. methanol, hexane etceteras
  • the phases of liquid crystals are many and complex but may be readily (albeit broadly and non-comprehensively) described as a generalised sequence of states that such a molecular fluid may pass through on the way from being an isotropic liquid until it freezes as a solid.
  • such molecules will be typified by strong anisotropy.
  • the form that this anisotropy takes may be complex, but for the present purposes, cases can be considered where the molecule is typified by a high aspect ratio (much longer than wide, thus "rod” or “lathe” like), and may have dipole character, and anisotropic polarisability. In these cases the average direction of molecular orientation is referred to as the "director".
  • anisotropy very often such properties of anisotropy are well aligned with each other, but significant cases exist where the forms of anisotropy of a molecule do not have the same principle axes within a Cartesian coordinate system. Such molecules are of profound significance in a very large class of materials of biological and physical scientific interest.
  • Nematic liquid crystals typify the commonest liquid crystalline materials and are commonly used in liquid crystal flat screen devices and flat-panel displays. They are typically fairly short (bi- phenyl) aromatic cores with a charge transfer character (in the extreme), a strong electron donor and acceptor group serving to enhance polarisability, and with modest head or tail extensions which enhance their mesogenic character (molecular aspect ratio, internal heterogeneous character). Such nematic materials typically display a uniaxial order whereby they have an anisotropy displayed along a certain axis and the plane normal to this axis has little or no anisotropy.
  • the nematics are still relatively fluid and if they have strong dipolar and polarisable character they may be aligned with an electnc field (or magnetic field) dielectric re-orientation axis. This is the principle behind many of their most valued applications. They may also be ordered by alignment agents, physical flow and other mechanical processes, and, in various applications, these processes are very often used to set a pre -determined initial condition or a state to which they will return after perturbation. Generally, in the absence of strong alignment agents, or a situation wherein the nematic is constrained in an anisotropic field, then upon removal of an imposed field the nematic liquid crystals will relax to poly- domains that are locally anisotropic, and thus appear optically "light scattering".
  • mCB mCB
  • mOCB mCB
  • m stands for an integer and refers to the number of carbon atoms in the alkyl or alkoxyl chain in 4-cyano-4'-n-alkylbiphenyl and 4-cyano-4'-n-alkoxybiphenyl, respectively; for example:
  • 8CB 4-cyano-4'-octylbiphenyl
  • 80CB 4-cyano-4'-octyloxybiphenyl
  • Other abbreviations used in the specification are set out in the Tables at the end of the specification.
  • the molecules forming SmA phases have similar properties to those forming nematic phases. They are rod-like and usually have a positive dielectric anisotropy. The introduction of a strong transverse dipole in order to induce a negative dielectric anisotropy tends to destabilise the SmA phase and may lead to increased chemical instability.
  • SmA liquid crystal compositions form a layered structure.
  • the layers of the liquid crystals in the different regions of the body may be more ordered with respect to each other or less ordered, (i.e. more disordered)
  • ordered and disordered refer to the alignment of the layers within a body of SmA liquid ciystal composition.
  • disordered state the composition is broken up into fragments (or domains) and the orientation of the layers within each fragment is not influenced by its surroundings, including the orientation of the layers in neighboring fragments.
  • the liquid crystal system will have constraints upon it, such as the j uxtaposition of walls containing the composition, especially field electrodes, and these will cause some deviation from a truly random (stochastic) alignment of the layers in the fragments of the layered phase.
  • the layer orientation after the composition has been disturbed is often parameterised by reference to mathematical definitions of "order parameter" (e.g. see reference 15).
  • order parameter e.g. see reference 15
  • a thin glass cell may be formed by taking planar sheets, generally of glass (similar to small microscope slides), and applying to these a transparent conducting layer, typically made of indium tin oxide. These two sheets may be formed into a thin cell for example separated by beads of uniform diameter (typically, say, 5-15 micrometers, dependent on desired cell thickness). This cell is normally edge sealed with glue allowing apertures for filling (only one for small cells vacuum filled, but two or more in flow or pumped filling systems) with the liquid crystal.
  • Such simple glass cells are very often used for liquid crystal characterisation and are similar in form to the much larger glass panels used in display devices (for nematic liquid crystals, these generally have much thinner cell- gaps).
  • a SmA liquid crystal layer may be formed by filling the cell (typically at an elevated temperature above the isotropic transition for the material).
  • the cell typically at an elevated temperature above the isotropic transition for the material.
  • no alignment layers need be used in such materials, in strong contrast to nematic display-type devices where uniform alignment of the cell is a requisite of their operation.
  • the liquid crystal will exhibit textures that are typical for the phases.
  • SmA materials may have their electro-optic responses measured.
  • the application of wires to contact the conducting glass coating allows the field across the liquid crystal layer to be established and modulated.
  • an alternating (AC) field is normally applied.
  • the dielectric anisotropy of the LC will cause the re-arrangement, of the initially randomly aligned poly-domains, to align the mesogen with the field direction (normal to the glass surface).
  • the cell viewed in transmission or normal to its surface
  • the average orientation of the anisotropic molecules is normal to the glass layer.
  • the SmA layer is now in a mono- domain, that is oriented with layers parallel to the glass plates. For most SmA materials this situation is only reversible by re-heating the cell to destroy the SmA alignment.
  • SmA materials have a positive dielectric anisotropy, i.e. the average direction of the long axis of the molecules will align with an electric field.
  • a film of smectic A liquid crystal aligned m this manner between glass plates has the average orientation of the long molecular axis (called the 'director') aligned orthogonal to the glass plates. This orientation is referred to as 'homeotropic alignment'.
  • liquid crystals with a negative dielectric anisotropy at low frequencies and a positive dielectric anisotropy at higher frequencies (so-called two frequency materials) as described by Crossland et al 1978 (refs 6 and P4) and in this instance, it is possible to reversihly switch such a waveplate using dielectric re-orientation.
  • the molecular structures required, inducing negative dielectric anisotropy at low frequency usually conflict with the requirements for stable SmA phases and reduces significantly the value of the positive dielectric anisotropy at higher frequencies (so both re-orientations require relatively high drive voltages and are relatively slow).
  • a suitable ionic dopant is dissolved in the smectic A liquid crystal host, then under the influence of DC or low frequency (e.g. ⁇ 500 Hz) electric fields, two orthogonal forces attempt to orient the smectic A director.
  • Dielectric re-orientation as described above attempts to align the smectic A director (indicating the average direction of the long molecular axis) in the field direction.
  • the movement of ions through the smectic A electrolyte attempts to align the smectic A director in the direction in which ions find it easer to travel. In smectic A materials this is within the layers i.e. orthogonal to the field direction (i.e.
  • the materials have a positive dielectric anisotropy and a negative conductivity anisotropy).
  • the two competing forces give rise to an electro- hydrodynamic instability in the liquid crystal fluid that is referred to as 'dynamic scattering'.
  • 'dynamic scattering' In smectic A materials the dynamic scattering state strongly scatters light and (in contrast to the similar state in nematic materials) the disruption of the smectic A structure that it produces remains after the electrical pulse causing it has terminated.
  • dielectric re-orientation into a clear transparent state
  • dynamic scattering into a strongly light scattering state
  • a suitably doped SmA phase possessing a positive dielectric anisotropy and a negative conductivity anisotropy
  • High frequencies (variable, typically >1000 Hz) drive the SmA layer into an optically clear state
  • low frequencies (variable, typically ⁇ 500 Hz) drive it into the light scattering state.
  • a key feature of such a display is that both these optical states are set up using short electrical pulses, and both persist indefinitely, or until they are re- addressed electrically.
  • This invention relates to displays as described in which a disordered state is produced by the process of SmA dynamic scattering and a clear, uniform state is induced by dielectric re-orientation.
  • SmA dynamic scattering a disordered state is produced by the process of SmA dynamic scattering and a clear, uniform state is induced by dielectric re-orientation.
  • SDS smectic A dynamic scattering
  • SmA materials offer several significant intrinsic advantages, hi particular SmA materials are very attractive for information displays where video performance is not requisite and high energy efficiency, and quite possibly unlit operation, is desired (reflective display systems).
  • a typical example is provided by the consideration of metropolitan information systems (e.g. displays of road-traffic information, public transport timetables, visitor information etceteras). Such will need to operate in a quasi continuous up-date mode, with some sites requiring full exposure to sunlight, others being sited where frequent maintenance is difficult. Such applications will thus require refresh rates that are reasonable and provide a readable experience (for comparison, consider the experience of reading and turning a page of a book or magazine). Similarly with continuously refreshed, paged, data, the expectation for acceptable lifetime must suggest that the screen can be refreshed many times, say, for a service life of 3 to 5 years (if we assume pages will be refreshed every 10 seconds then this would imply that the display must operate between 10 and 15 Million refresh cycles).
  • the use of dyed or un-dyed systems is viable, in the latter case a printed back-drop may be used to present a colour when the material is cleared.
  • the scattering texture is critical to the visual quality of the display.
  • the contrast is between the (normally) white of the back-drop and the achieved extinction of the light from the dyed scattering texture.
  • the contrast perceived is through the achieved background scattering 'brightness' (of the native scattering texture) and the contrast between that and the revealed back-drop.
  • the texture which develops in the scattering state and the ability to clear that state back to 'transparency' are critical application parameters.
  • Light scattering depends upon both the refractive index anisotropy of the material and the scale of the micro-structure developed in the scattering state. In liquid crystals these are related through several equations which tie dielectric anisotropy and other parameters together with field driven character.
  • w is a characteristic length scale (domain size)
  • K is the effective elastic modulus
  • E is the applied field.
  • Dynamic scattering relies on the competing forces of 'flow alignment' due to the passage of ions and dielectric re-orientation attempting to align the liquid crystal director in orthogonal directions.
  • the voltage required to cause scattering scales with a relationship derived by Geurst and Goosens. In their paper they relate the threshold voltage V, to the ratio of the product of the effective elastic tensor component, K, (for smectic A liquid crystals this is the splay component, Kl l) and the cell thickness; divided by the product of the dielectric modulus (reduced by a factor related to the conductivity anisotropy) multiplied by the characteristic length, ⁇ , of the smectic layer, thus,
  • CN-101533162 and WO 2009/1 11919 disclose an electrically controlled medium for modulating light includes two plastic thin film layers and a mixture layer is provided between the two thin film layers.
  • the mixture layer consists of smectic liquid crystals, polymeric molecule materials and additives.
  • Conductive electrode layers 4 are provided on the sides of the two plastic thin film layers and the liquid crystal molecules exhibit different alignment states by controlling the size, frequency and acting time of the voltage applied to the conductive electrode layers , so that the electrically controlled medium for modulating light may be switched between a blurredly shielding state and a fully transparent state and even may be switched among a plurality of gradual states of different gray levels.
  • the aspects of the present invention specifically exclude the arrangement disclosed in this specification, Disclosure of the Invention
  • the present invention provides a thermotropic liquid crystal smectic A composition exhibiting a smectic type A phase made up of multiple layers and capable of forming a liquid crystal optical device, e.g. a display, when sandwiched between a pair of electrodes as set out in the following claims as well as cells containing such a composition.
  • the present invention also provides an optical device containing multiple cells and a method of switching the optical properties of the composition by applying an electric field thereto.
  • the present invention provides a viable SmA formulation, which may be the basis in reflective (or lit) display systems, and related applications, are described.
  • the formulation enables scattering displays suitable for a diversity of reflective display applications and it is believed that, for the first time, there is provided a commercially viable material for SmA based devices.
  • thermotropic liquid ciystal smectic A composition exhibiting a smectic type A phase made up of multiple layers and capable of forming a liquid crystal optical device, e.g. a display, when sandwiched between a pair of electrodes, wherein:
  • the alignment of the layers of the composition can become more ordered or more disordered
  • the composition has stable states in which the alignment of the layers of the composition are differently ordered including an ordered state, a disordered state and intermediate states, the composition being such that, once switched to a given state by an electric field, it remains substantially in that state when the field is removed,
  • composition comprises, in weight %:
  • p 1 to 10, e.g. 1 to 3,
  • A is a phenyl or cyclohexyl ring which may be the same or different and are bonded together in para positions,
  • R a C alkyl group, e.g. methyl, which may be the same or different,
  • X a C alkyl group
  • Z F, CI, Br, I, CN, N3 ⁇ 4, N ⁇ 3 ⁇ 4, NMe 2 , NCS, CH 3 , or OC3 ⁇ 4, CF 3 , OCF 3 ,
  • Rl, R2 and R3, which may be the same or different, are C,. 4 alkyl, e.g. methyl or ethyl,
  • T a methyl group or a silyl or siloxane group
  • Q is an oxidatively stable ion, especially a CIO4 ion
  • D stands for a CM 6 straight chained alkyl or alkoxy group optionally containing one or more double bonds
  • A' is a phenyl, cyclohexyl, pynmidine, 1,3-dioxane, or 1,4- bicyclo[2,2,2]octyl ring, wherein each A may be the same or different and are bonded together in para positions, the terminal ring attached to Y optionally being a phenyl and
  • Y is located in the para position of the terminal ring of the group A' K and is selected from Z (as defined above in connection with Formula I), CM 6 straight chained alkyl, Ci. 16 straight chained alkoxy, OCHF 2 , NMe 2 , CH 3 ,
  • a, b and c each independently have a value of 0 to 100 and are such that a+b+c has an average value in the range 3 to 200, e.g. 5 to 20; and a is such that the chain units of the formula Y-R 2 SiO-[SiR 2 -0] a represents 0 to 25 mole percentage of the compound of the general formula IV, and c is such that the units of the formula chain -[SiHR- 0] c -R 2 SiO-Y represents 0 to 15 mole percentage of the compound of the general formula IV,
  • n 3 to 20, eg. 4 to 12;
  • A is a phenyl or cyclohexyl ring which may be the same or different and the rings are bonded together in para positions,
  • R a Ci alkyl group, e.g. methyl, each of which may be the same or different, and
  • Y a Ci alkyl group, a chromophore or a calamitic liquid crystal group and each of which may be the same or different, and
  • Figure 1 is an illustration of a simple schematic of the sub-structure that forms in phase partitioned smeetic-A layered systems when driven by siloxane-derivatized mesogens showing its layering and sub-structure
  • Figure 2 is a micrograph of a pure organic nematic composition
  • Figure 3 is a micrograph of pure Si2-80CB mesogen
  • Figure 4 is a micrograph of a polymer formulation agent
  • Figure 5 is a micrograph of a according to the present invention.
  • Fig. 6 are Differential
  • Figure 7 are further Differential Scanning Calorimetry (DSC) thermograms for the same liquid crystalline components and formulations as in Figure 6 - re -heating of the cooled samples.
  • DSC Differential Scanning Calorimetry
  • Figures 8 and 9 show the small angle X-ray scattering data for: the pure siloxane mesogen; and the same for a formulation with an organic, nematic host and an oligomer.
  • Figure 10 shows a comparison of conductivity anisotropy for 8CB (top line of dots), pure
  • Si280CB bottom line of dots
  • a formulation test sample middle line of dots
  • Figure 1 1 shows the theoretical scattering efficiency of particles of different dimensions, treated as spheres.
  • Figure 12 shows the formulated smectic A scattering texture of the composition in accordance with the present invention in scattered state and translucent state
  • Figure 13 shows the scattering texture measurements and direct comparative brightness measured through an identical optical system for each of a powder electro-phoretic material, white paper and a formulated smectic A liquid Crystals accordmg to the present invention.
  • Figure 14 is a graph for a silicon augmented SmA formulation MM22066-58B doped with
  • Figure 15 is a cyclic field addressing (voltammetry) depiction of an accelerated aging of a formulated SmA (as per this invention) showing consistent operation over in excess of 1 Million cycles.
  • Figure 16 is similar to Figure 15 but using the organic smectic, 80CB using the same ionic dopant used in the formulation of Figure 15).
  • Figure 17 is a graph of the transmittance of a high birefringence composition (top 3 plots) and a composition whose refractive index has been reduced substantially,
  • Figure 18 is a schematic view of a cell shown in cross section. Detailed Description of the Invention
  • composition of the present invention has several components, which will be described in turn.
  • the first component is least one siloxane of the general formula I defined above.
  • This mesogen is siloxane tagged to drive the phase partitioning.
  • Other organic mesogens (not necessarily themselves having any smectic character) form part of the composition - see discussion of component (c) below).
  • the resultant smectic A host is designed to operate via an internal phase partitioning, which drives the phase condensation and properties and it is, in this way, possible to achieve smectic order, layering, that has unusual stability relative the norm in simple organic systems. This is explained in further detail below.
  • the degree of stability of the phases and the preferred phase properties and consequent thermal stability etceteras may be pre-determined by selection of the cyclo (aromatic or non-aromatic) core [A]k and the aliphatic tail length (CH2)q of the mesogen of the Formula I above, in balance with the siloxane adduct.
  • the aliphatic tail is preferably not too short since they are harder to synthesise due to competition in side reactions; similarly the sources of synthons at suitable price and purity favours certain choices over others.
  • a shorter aliphatic unit say, in the range 7-9 carbon
  • 1,1,1,3,3-pentamethyldisiloxane will drive layering and some favourable properties. Increasing the aliphatic length, excessively will eventually frustrate mesogenicity (if there is sufficient transverse dipole strength then it may introduce Smectic C , or other character). If the siloxane is increased in length or made more bulky, it may similarly be observed that new phase behaviours become observable up to some limit whereupon the phase is destabilised.
  • Figure 1 is an illustration of a simple schematic of the sub-structure that forms in phase partitioned smectic-A layered systems when driven by siloxane-denvatized mesogens showing its layering and sub-structure.
  • the mesogenic molecules of component (a) have the properties usually associated with the formation of liquid crystal phases, but have a siloxane oligomeric moiety integrated into the molecule. This has been demonstrated in previous filings for example (Coles, Hannington et al., US5455697A; US5547604A). However, this property may be further enhanced if the mesogen is synthesised to have an optimum ratio between the mesogenic core and a silicon- containing 'tail' moiety. Compounds of the two formulae below, illustrate such a phase depiction and representative molecules, showing the key performance directing factors in the mesogen design.
  • 8CB is one of a homologous series of mesogens that are nematic when the aliphatic chain is shortened and show smectic phases at higher chain lengths prior to losing mesogenicity.
  • Such simple aliphatic tailed mesogens are characterised by fairly small Smectic A phase ranges:
  • 8CB is marginally smectic over 2oC to around 40oC;
  • 9CB has the recorded behaviour, Cr-->42oC-->SmA-->48oC-->N-->49.5oC-->I;
  • phase partitioning silicon augmented molecule e.g. Si2-80CB, (8-(4- cyanobiphen-4-oxy)octyl) pentamethyldisiloxane
  • Si2-80CB is an example of a siloxane derivatised SmA material; note the marked dipole character imbued by the terminal CN coupled with strong molecular form anisotropy, the phase partitioning siloxane moiety terminal to the organic spacer chain, attached para to the CN on the biphenyl aromatic core. Many other such molecules have been made and, if conveying similar design attributes, offer value in the formulations described herein.
  • the ionic dopant migrates through the composition when low frequency electric (or dc) fields are applied across the composition, thereby disrupting the order to the composition. Order in the composition can be restored by applying a higher frequency field that does not allow the dopant time to migi'ate significantly and yet causes the mesogens to align with each other.
  • Smectic A phases usually have a positive' dielectric anisotropy and an ionic dopant is added to disrupt and re-align the layer structure of SmA liquid crystal as the dopant migrates through the composition under the influence of certain electric fields (generally low frequency or non-alternating fields) applied across the liquid crystal composition.
  • the electro-hydrodynamic instability of the liquid crystals necessary to bring about dynamic scattering can only occur if the conductivity anisotropy is negative, i.e. the direction of easy conductivity of the dopant ions is in the plane of the layers and orthogonal to the average direction of the long axis of the molecules.
  • a wide range of negative conductivity anisotropics has been measured in the composition of the present invention, ranging from just above unity to greater than 10. The value depends on both the electrolyte (the smectic A phase) and the dopants used.
  • ionic dopants Three issues dominate the choice of the ionic dopants: ) The ability of the ions to disrupt and re-align the layer structure of SmA liquid crystal. Small ions exhibit conductivity anisotropy, but do not cause dynamic scattering in the liquid crystal host. It is usually the cation (the positive ion) that causes scattering and quaternary ammonium compounds are suitable for this purpose in the context of the present invention; Crossland et al 1976 (PI) have already proposed the use of quaternary ammonium compounds as ionic dopants, as has a detailed study carried out with halide counter ions in 1987 (Coates, Davey et al ref 4). The ionic compounds are of the form
  • R R 2 , R3 or R may be alkyl " groups, which may be the same or different.
  • R4 needs to be an alkyl hydrocarbon chain with greater than 8 carbon atoms, preferably 12 - 18, in order to promote disordering of the mesogens.
  • the nature of the remaining three groups can control the retention of the substituted ammonium ion at surfaces in contact with the composition.
  • R] R 2 , 3 are unsubstantial (i.e. they are H atoms), then there is a danger that the absorption of ions at the electrodes (and other surfaces) will deplete their concentration in the bulk.
  • Crossland et al 1976 disclosed the use of selected hexadecyl tri -methyl ammonium salts with halide counterions, and this has been followed by most subsequent workers (e.g. Coles et al 2007 ref 7).
  • tri-methyl derivatives might still be absorbed over long periods of time and display operation, in which case R 2 and/or R 3 might be replaced with C 2 , C 3 or C 4 alkyl groups.
  • 100 to 400 ppm of hexadecyl butyl di-methyl ammonium salt gives efficient scattering in a range of smectic A hosts.
  • solubility of such dopants in smectic A hosts is excellent and they show very little tendency to be electro-chemically reduced.
  • the present invention also provides the use of a dopant (component (b)) that is a quaternary ammonium salt.
  • the counterion is oxidatively stable in a liquid crystal optical device, e.g. in a display having a thickness of 5-15 ⁇ across which is applied a field of 2 -
  • Perchlorate anions provide an especial advantage in SmA compositions since they have been found unexpectedly to increase the lifetime of SmA displays using quaternary ammonium ionic dopants.
  • perchlorate ions are known in non-SmA liquid crystal formulations, especially with respect to oxidation stability (see for examples refs 13, 14), neither of references 13 and 14 teaches that the use of a perchlorate dopant might increase the lifetime of SmA compositions.
  • Our tests have established that perchlorate counter ions (C10 4 ”) display improved performance relative to other possible counter ions (such as bromide) and strong evidence of electro-chemical stability to oxidation in the hosts herein described (at least in part due to their already highly oxidised state). Within an appropriate choice of smectic host they can certainly survive greater than 10 x 10 6 scattering operations.
  • Quaternary ammonium compounds with long hydrocarbon chains are surfactants and adsorb onto glass surfaces with the hydrocarbon chain oriented orthogonal to the surface. As such they align liquid crystals with their director orthogonal to the surface (homeotropic alignment).
  • This can be controlled by varying the size of the substituents R 2 , R3 and R4 in order to avoid depletion of the dissolved dopant from the liquid crystal solvent and, on the other hand to promote homeotropic alignment and therefore lower the voltages required to give efficient cleanng of light scattering textures.
  • R 2 , R 3 and R4 should not all have the same length, e.g. R 2 may be a C 2 , C 3 or C 4 alkyl group and R 3 and R4 may be methyl.
  • preferred dopants are quaternary ammonium perchlorates of the form:
  • dopants are designed to:
  • nematic liquid crystal phases that may or may not exhibit a smectic phase at lower temperatures, can be converted to a stable wide temperature range SmA phase by the simple addition of silicon based compounds (component (a)), notably siloxane small molecules and oligomers, that may not have complementary liquid crystal phases, and in some cases lack the normal features that result in liquid crystal formation.
  • component (a) silicon based compounds
  • the nematic liquid crystal phases treated in this manner can be complex eutectic mixtures that have been formulated to achieve special properties (e.g. high or low birefringence, high dielectric anisotropy etc). To some extent, these special properties may be carried over into the induced SmA phase.
  • the polarisable linear molecule having an alkyl chain of component (c) can be incorporated into the SmA structure formed by the siloxane of component (a) and can alter the properties of component (a), especially its birefringence.
  • the present invention provides a way of producing a SmA liquid crystal composition tailored to have particular properties.
  • Siloxane derivatised small molecules and oligomers (component (a)), whose organic moiety is of a nature complementary to the guest component (c) organic (formerly nematic), in the SmA phases, are particularly efficient at inducing SmA phases.
  • siloxane modified SmA-directing species has been shown to allow many nematic molecular systems to be rendered layered. This opens the door to strategies that can exploit the veiy rich landscape of nematic mixtures and by judicious formulation with appropriate siloxane species and ionics new SmA formulations may be formed.
  • complementary species it is possible to considerably broaden the range of smectic ordered liquid crystals starting from a simple organic nematic base component (c) and employing formulations with phase directing siloxane adduct species component (a).
  • the characteristic length (the factor, ⁇ , in Equation 5, above) will be slightly larger than that in simpler molecular systems.
  • the reasons for this include the fact that these materials are expected to be slightly more compressible due to the poorer volume packing.
  • the layer spacing tends to be higher in such systems, for similar organic species the layer spacing (for 8CB) is about 30nm which can be compared with the formulation which has a spacing of 34-37nm (40nm for pure siloxane mesogen), see graphs provided below).
  • component (a) can be a hybrid oligosiloxane cyanobiphenyl, which has a lower birefringence than the corresponding cyanobiphenyl, in conjunction with a low birefringence component (c), e.g. a cyclohexyl phenyl, to produce a low birefringence SmA formulation which would not be obtainable using an all organic (i.e. no siloxane) formulations.
  • a low birefringence component (c) e.g. a cyclohexyl phenyl
  • Tables 1 and 3 set out some high birefringence materials and low birefringence materials that can be used in the present invention.
  • components (a) to (c) allows such systems to be further moderated. They can be considered as binding together the layers, both within a given layer and between layers. This allows the composition to be tailored further, especially in providing a higher clearing temperature, and controlling the domain size in the relatively disordered states; it also moderates ionic conduction of the dopant (component (b)). In addition, it allows the amount of component (c) that can be contained within the composition without losing the SmA structure to be increased.
  • Figure 2 the nematic liquid crystal phase texture of Merck BL003 commercial nematic liquid crystal formulation, as observed using a polarized light optical microscope, at room temperature;
  • Figure 3 Smectic A liquid crystal phase texture of the oligosiloxane modified mesogen Si2- 80CB, as observed using a polarized light optical microscope, cooled from the isotropic phase to the biphasic SmA+I region.
  • Figure 4 Smectic A liquid crystal phase texture of a side chain liquid crystal polysiloxane used in the claimed formulations oligosiloxane, as observed using a polarized light optical microscope, cooled from the isotropic phase to the biphasic SmA+I region.
  • Figure 5 Smectic A liquid crystal phase texture of a formulation comprising an oligosiloxane modified mesogen Si2-80CB, Merck BL003, and a side chain liquid crystal polysiloxane, as observed using a polarized light optical microscope, cooled from the isotropic phase to the biphasic SmA+I region. Apart from the dopant, this composition is in accordance with the present invention.
  • a suitable siloxane oligomer of the AB or ABA type may be seen to construct a layered SmA system of particular spacing and "strength".
  • the role of the low molar mass nematic mesogen may be considered to be that of a "plasticiser” which moderates the layer “strength”; while simultaneously providing tuneability to the properties of the composition, e.g. its refractive index or dielectric anisotropy.
  • compositions can be considered as binding together the layers, both within a given layer and between layers. This allows the composition to be tailored further, especially in providing a higher clearing temperature, and controlling the domain size in the relatively disordered states; it also moderates ionic conduction of the dopant (component (b)). In addition, it allows the amount of component (c) that can be contained within the composition without losing the SmA structure to be increased. .
  • the constituents (a) to (d) thus form a formulation design space enabling applications in respect of dynamic scattering. Guest chromophores may then be selected compatible with design targets and similarly complementary to the formulation.
  • novel formulations according to the present invention result in stable and robust SmA phases: small angle X-ray scattering has established their layered nature, differential scanning calorimetry establishes their phase sequences and optical microscopy has demonstrated that they exhibit the classic textures of smectic A phases (see above, albeit they are exceptional in many ways).
  • composition has particular application in displays and the features of the prior art cells and displays, as discussed above, are applicable to contain the composition of the present invention.
  • the overall electrolytic solutions may need to be modified to meet the particular requirements of the specific electronic drive circuits used to address the display in the chosen display configurations, in particular, the balance between clearing and scattering, the relative response times and the display lifetimes all depend on this formulation.
  • Any dye may be used that will orientate itself with the mesogens in the composition and produce different colourations of the composition depending on whether the dyes are aligned perpendicular to the electrodes (when the composition is in an ordered state) or at an angle to them (in a relatively disordered state).
  • the ability of smectic A materials to achieve grey-scale in scattering is enabling of this when combined with pleochroic dyes.
  • the liquid crystal elements in the stack are able to switch between a clear state and a coloured state that has a reduced level of scattering and preferably minimal scattering (otherwise light will be back-scattered towards the viewer before reaching the lower coloured layers in the stack).
  • the surface energy and viscosity must be controlled accurately.
  • the material can flow into the aperture and not separate (into its constituent parts) during the filling and spreading out across the full areal extent.
  • a schematic cell is shown in Figure 18.
  • Spacer beads or fibres 16 separate a pair of glass or plastic substrates 12,13 and define the cell thickness.
  • An edge seal 18 is used to retain the liquid crystal composition 17 in the cell.
  • the liquid crystal electro-optic devices of the present invention typically have a cell gap designed to be in the range of 0.5 microns to 10 microns.
  • a transparent conductor layer 14,15 e.g. indium tin oxide, is applied to each of the substrates 12.13 to form electrodes.
  • the lower substrate 13 may be reflective or may emit light in a back-lit display.
  • a mixture of a dispersion side chain liquid crystal polymer may be made by hydrosilation of an alkyl cyano-biphenyl mesogenic moiety.
  • the hydrosilation agent may be, for example a siloxane such as Dow Corning 1 107, which is polymethylhydrogensiloxane of the formula:
  • composition consisting of:
  • composition was placed into a test cell having a pair of glass plates having indium tin oxide electrodes spaced apart by 7.5 ⁇ .
  • the best response times at 30°C, using an alternating current with a 100V peak voltage were:
  • Example 2 (comparative) Short siloxane derivatised mesogens plus nematic mixtures.
  • a formulation of materials based upon the mesogens based upon penta-methyl di-siloxane substituted alkyl-oxy-cyano-biphenyls with pentyl- cyano-biphenyl may be made (see for example ref. Coles et al, J. Phys. D: Appl. Phys. 39 (2006) 4948 ⁇ 1955).
  • Example 3 Short siloxane derivatised mesogens plus nematic mixtures plus Phase Modification using Side Chain Liquid Crystal Polysiloxanes.
  • test nematic species (component (c)) was done on the basis of availability of certain very well characterised mixtures, Merck/BDH BL003, for example, along with E7 were explored to see how the complexity of commercial mixtures engineered for use in nematic display applications performed within the oligosiloxane templated Smectic A phases.. Comparisons between these commercial eutectic mixtures and relatively simple nematic formulations, prepared in-house, led to the elucidation of simplified organic nematic mixtures which were equally able to meet the applications demands of the smectic-A scattering displays.
  • the combined Si2-80CB/SCLCPolysiloxane systems are capable of accepting high concentrations of a range of nematic organic species. It was further shown that nematic pre- formulations can readily be designed to impart favoured property profiles (birefringence, viscosity, temperature ranges) in the siloxane formulations.
  • birefringence can be tuned down utilizing 4-(trans-4-pentylcyclohexyl)benzonitrile and similar component (c) species which do not, themselves, exhibit Smectic A phases, but which have been shown to be compatible with siloxane host systems comprising cyanobiphenyl moieties and similar component (a) species, this being accommodated in the phase-segregated smectic sub-structure.
  • DSC differential scanning calorimetry
  • the liquid SmA phase of Si2-80CB can be greatly improved by adding either individual nematic mesogens, or eutectic nematic mixtures (component (c)), such as BL003, which is a composition commercially from Merck.
  • component (c) eutectic nematic mixtures
  • the DSC data for an Si2-8OCB/BL003 blend reveals that the undesirable low temperature phase behaviour of the Si2-80CB can be suppressed, allowing the SmA phase to exist down to -40°C, a temperature which represents the lower end of a storage temperature range which would be required for deployment of devices. While this blend has a good phase range it has too low an upper temperature for transition to the isotropic state. Furthermore, such mixtures have been shown to suffer from poor bistability, or multi-stability; i.e. they tend to relax to an equilibrium state after switching.
  • the DSC for the Side chain Liquid Crystal Polysiloxane reveals a SmA phase which extends down to -3°C, where the material forms a glassy, layered phase.
  • the formulation comprising the Si2-80CB, nematic BL003 and the side chain liquid crystal polysiloxane, i.e. a composition according to the present invention, but without the ionic dopant, exhibits a very broad SmA phase with a glass transition below -50°C and a clearing temperature of > 65°C.
  • This formulation exhibits a broad SmA range, multi-stability and response times which are acceptable for the intended applications.
  • the response times of the present invention to both clear and scattering state can be less than 300ms and values lower than 200 ms have been achieve, even down to 2ms (clearing) and 20ms (scattering).
  • compositions in accordance with the present invention are set out in Tables 2 and 4.
  • Si280CB was made already partially from the prior work on such species.
  • Figures 8 and 9 show the small angle X-ray scattering data for: the pure siloxane mesogen; and the same for a formulation with an organic, nematic host and an oligomer. This clearly illustrates the ability to formulate a material with all of the design attributes required. Moreover the ability to formulate outside of the bounds taught within the published literature.
  • Figure 8 shows the strong layer formation observed for (8-(4-cyanobiphen-4-oxy)octyl) pentamethyldisiloxane, Si2-80CB. Note that "+xx” defines the temperature of the experimental run in °C.
  • Figure 9 shows the layering in a formulated material (composition MM22066-58A) where 50% of the material is formally an organic nematogen, and a further 10% is a polymeric additive. Note that "+xx" defines the temperature of the experimental run in °C.
  • Example 5 Advantages of silicon augmented SmA phases doped with preferred ionic dopants.
  • the conductivity anisotropy is important in controlling the SDS process (e.g. equation 2 above).
  • the magnitude of the conductivity is important since high conductivities are likely to lead to irreversible electrode reactions and therefore threaten the liftetime of devices.
  • silicon augmented SmA phases doped with the appropriate ionic materials to induce scattering tend to have a lower conductivity and a higher conductivity anisotropy.
  • the former property is helpful in prolonging the life-time of electrically switched devices, since it minimises potential problems regarding the reversibility of the electrode reactions during the passage of current.
  • the enhanced conductivity anisotropy is likely to be another consequence of the micro-phase segregation that is forcing the formation of smectic layering in these materials. High values reduce the electrical scattering threshold as suggested by equation 3.
  • the performance of SDS devices is presumptive of achieving a good dielectric anisotropy (and a higher absolute value of the dielectric constant parallel to the molecular long axis in the smectic A phase).
  • the plots are for particles having the following dimensions, identified by their values at lambda 0.4 and starting from the top: 2.0 ⁇ , ⁇ . ⁇ , ⁇ . ⁇ (wavy line), 5.0 ⁇ , 0.5 ⁇ and 0.2. ⁇ .
  • Figure 12 shows the formulated smectic A scattering texture of the composition in accordance with the present invention in scattered state and translucent state, illustrating the uniform texture and the scale which spans a few micrometres down to ⁇ 0.5 micrometre. This gives an exceptionally flat and un-coloured white scattering.
  • This scattering texture is the product of the ionic electro-hydrodynamic vortices effect upon the layered mesogen.
  • driving a very fine texture development due, in part, to the effective elastic tensor and its interplay via the conductivity anisotropy that creates very short range ionic paths before the structure is disrupted.
  • the fine structure developed is evident in the pictures of Figure 1 1, however, Figure 12 shows how the consequence of this is to create a paperlike scattering whose metrics are superior to that of other contemporary reflective display offerings (such as e-ink).
  • Figure 13 we see the realization of the display metric promised by the formulation MM21 48-7A which has a composition that is equivalent to composition MM22066-58A (see Table 2).
  • Figure 13 shows the scattering texture measurements, direct comparative brightness measured through an identical optical system for each of a powder electro-phoretic material, white paper and a formulated smectic A liquid Crystals (after the present invention), i.e. an advantage of these formulations is that they scatter efficiently, with a finer scattering texture than that found with non siloxane based materials, e.g. the typical organic mesogens.
  • Silicon augmented SmA electrolytes of the present invention described above have the property that they modify the internal glass/mdium-tin oxide surfaces of the liquid crystal cells by blocking access to at least the more reactive surface adsorption sites.
  • the low frequency waveforms that cause scattering are usually applied to the whole display panel for a period of milliseconds or tens of milliseconds. This sets up a 'blank page', onto which the information can be written (line-at-time) by dielectric re-orientation using a higher frequency waveform.
  • the power consumption is very low because electrical waveforms need only be applied whilst the information being written as a result of the bi (or multi-) stability of the composition of the present invention in the ordered (clear) and disordered (scattering) states.
  • the lifetime depends on changes in the scattering conditions.
  • the current flowing during the brief tenure of the scattering pulse is a key factor.
  • the lifetime can be measured in terms of the number of scatter and clear operations that the device can sustain, since between such operations the device is stable for any period of time.
  • the number of such cycles can be considered as the number of pages of infonnation that can be presented on a display, or the number of times a window panel can be switched.
  • myristyl or cetyl trimethyl ammonium perchiorate are used such that we have anions that will not be oxidised (unlike the commonly used bromide ion) and efficient (e.g. myristyl or cetyl tri methyl ammonium) scattering cations.
  • efficient scattering cations are AC waveforms with very little DC content and that the low frequency scatter-waveform always starts and finishes at a zero transition.
  • the failure mode of SDS devices is usually failure to scatter uniformly following depletion of the ionic dopant (especially the scattering cation). This results in partial scattering and lack of uniformity.
  • One substantial contribution toward this process is the occurrence of non-reversible reaction at the electrodes; another is adsorption of ions on the interior surfaces of the liquid crystal cells in which the formulation is contained.
  • the scattering is also considered to be inadequate if it will not withstand the continuous application of the waveform used to clear the scattering (e.g. a 2 to 10 KHz square wave) with one third of the peak voltage actually used for scattering. This is because in electrically addressing large arrays of pixels row-at-a-time with the clear waveform, this error voltage appears on all the pixels during all of the time period during which a page is being addressed.
  • the waveform used to clear the scattering e.g. a 2 to 10 KHz square wave
  • Silicon augmented SmA phases have been observed to have a life time (measured in the number of clear to scattering switching operations, which corresponds to the number of pages on information switched) that can be close to an order of magnitude longer than the best figures we have observed with organic Sma materials.
  • Cells of this type have shown good uniform scattering out to approaching 20 x 106 operations. They continue to scatter uniformly with currents densities below 180 micro amps per cm sq and have shown life times close to 20 x 106 operations. After impurity and contaminant ions have been electrolytically removed the scattering current remains 200micro amps per cm sq over 20 million operations and the scattering threshold and uniformity remain excellent.
  • Figures 15 and 16 show comparative accelerated ageing curves for ionic doped smectic A materials, in these examples a formulated siloxane augmented smectic A system in accordance with the present invention is compared with the (very similar mesogenic moiety) organic 80CB.
  • the enhanced lifetime of the composition of the present invention ( Figure 15) as against a known 80CB system is evident.
  • Figure 15 shows cyclic field addressing (voltammetry) depiction of an accelerated aging of a formulated SmA (as per this invention) showing consistent operation over in excess of 1 Million cycles.
  • the cyclic voltammetry depiction of organic smectic, 80CB shows the classical signatures of electrolytic decomposition. Comparing the two sets of curves we see a tendency in the siloxane based formulation for the ionic species to be consistent with no broadening of the peak ion, nor shifts of the baseline slope indicative of degradation.
  • Addition of black (K) is desirable in certain applications; the coloration using dyes may be done in combination with coloured back-planes, and other practices known to those skilled in the art, to yield a coloured reflective display or, alternatively, a lit display to provide the performance required in diverse applications.
  • the standard complementary colours cyan, magenta and yellow layers may be used, optionally with a black layer, And provide good brightness.
  • Figure 17 is a graph illustrating a simple example of a formulation where the refractive index has been reduced substantially to allow demonstration of this principle.
  • the transmittance is shown of a smectic liquid crystal cell, 12 ⁇ thick, filled with MM22066-142C in isotropic (top line), transparent (line 2nd from the top) and scattering (line 2nd from the bottom) state.
  • the isotropic state of this composition MM22066-142C was used as a reference.
  • the corresponding transmission of the scattering state of a similar cell filled with a low birefringence composition MM22268-30A (bottom line) is also shown.
  • composition as claimed in claim 1, includes components (a) to (d); it also optionally includes:
  • At least one molecule e.g. a lathe-shaped molecule, that is not a liquid crystal, but which can be incorporated into the formulation, without degrading the smectic A layer quality or structure of the composition (component (g) - see claim 10), and
  • the present invention also provides a composition with a novel dopant in the form of a quaternary ammonium salt of the general formula VI (see claim 29).
  • the amounts of the dopant in the composition of claim 29 may be 0,001 - 1 wt%, e.g. 0.01 - 0.5 wt% or 0.05 - 0.1 wt%.
  • Oligosiloxanes (component (a): A basic synthesis is given for example materials in the literature, for example our publication: J. Materials Chemistry, 1994, 4(6), 869-874.
  • Siloxane modified Ionic dopants (component (b): their synthesis is straightforward to a skilled LC chemist.
  • Dichroic dyes these are commercially available.

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Abstract

La présente invention a pour objet des compositions de cristaux liquides ayant une structure smectique A destinées à être utilisées dans un dispositif optique dans lequel la composition est prise en sandwich entre une paire d'électrodes (12-15). En essence, la composition comprend un oligomère de siloxane (composant (a)) qui peut être vu pour construire un système SmA stratifié d'un espacement et d'une « résistance » particuliers. Au sein de cette structure, un mésogène nématique de faible masse molaire (composant (c)) est prévu, lequel peut être considéré comme étant celui d'un « plastifiant » qui modère la « résistance » de la couche, tandis qu'il fournit simultanément une adaptabilité aux propriétés de la composition, par exemple son indice de réfraction ou son anisotropie diélectrique. L'ajout d'un polysiloxane cristallin liquide à chaîne latérale (composant (d)) permet à de tels systèmes d'être encore plus modérés étant donné qu'ils peuvent être considérés comme liant les couches ensemble, à la fois au sein d'une couche donnée et entre les couches. Un dopant ionique (composant (b)) est également compris dans la composition, qui migre dans la composition lorsque des champs électriques basse fréquence sont appliqués à la composition par les électrodes, ce qui rompt l'ordre de la composition. L'ordre dans la composition peut être restauré par l'application d'un champ de fréquence supérieure qui ne laisse pas au dopant le temps de migrer de manière significative. Des chromophores peuvent aussi être compris dans la formulation.
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US13/635,334 US8956548B2 (en) 2010-03-15 2011-03-15 Liquid crystal formulations and structures for smectic A optical devices
CN201180014289.7A CN102959049B (zh) 2010-03-15 2011-03-15 用于近晶a光学器件的液晶制剂和结构
EP11718175.0A EP2547749B1 (fr) 2010-03-15 2011-03-15 Structures et formulations de cristaux liquides pour dispositifs optiques a structure smectique a
JP2013500152A JP5771682B2 (ja) 2010-03-15 2011-03-15 スメクチックａ光学素子のための液晶配合および構造
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WO2014036766A1 (fr) 2012-09-10 2014-03-13 苏州汉朗光电有限公司 Nouveau matériau à cristaux liquides en phase smectique a
CN115505404A (zh) * 2022-08-30 2022-12-23 联创电子科技股份有限公司 液晶组合物、液晶透镜以及液晶显示装置

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