Patent Application
20170357131
The invention relates to a light modulation element comprising a polymer stabilized cholesteric liquid crystalline medium sandwiched between two substrates (1), provided with a common electrode structure (2) and a driving electrode structure (3) individually, wherein the substrate with driving and/or common electrode structure is additionally provided with an alignment electrode structure (4) which is separated from the driving and or common electrode structure on the same substrate by an dielectric layer (5), characterized in that the light modulation element comprises at least one alignment layer (6) directly adjacent to the liquid crystalline medium.
The invention is further relates to a method of production of said light modulation element and to the use of said light modulation element in various types of optical and electro-optical devices, such as electro-optical displays, liquid crystal displays (LCDs), non-linear optic (NLO) devices, and optical information storage devices.
Liquid Crystal Displays (LCDs) are widely used to display information. LCDs are used for direct view displays, as well as for projection type displays. The electro-optical mode, which is employed for most displays, still is the twisted nematic (TN)-mode with its various modifications. Besides this mode, the super twisted nematic (STN)-mode and more recently the optically compensated bend (OCB)-mode and the electrically controlled birefringence (ECB)-mode with their various modifications, as e.g. the vertically aligned nematic (VAN), the patterned ITO vertically aligned nematic (PVA)-, the polymer stabilized vertically aligned nematic (PSVA)-mode and the multi domain vertically aligned nematic (MVA)-mode, as well as others, have been increasingly used. All these modes use an electrical field, which is substantially perpendicular to the substrates, respectively to the liquid crystal layer. Besides these modes there are also electro-optical modes employing an electrical field substantially parallel to the substrates, respectively the liquid crystal layer, like e.g. the In Plane Switching (short IPS) mode (as disclosed e.g. in DE 40 00 451 and EP 0 588 568) and the Fringe Field Switching (FFS) mode. Especially the latter mentioned electro-optical modes, which have good viewing angle properties and improved response times, are increasingly used for LCDs for modern desktop monitors and even for displays for TV and for multimedia applications and thus are competing with the TN-LCDs.
Further to these displays, new display modes using cholesteric liquid crystals having a relatively short cholesteric pitch have been proposed for use in displays exploiting the so-called “flexoelectric” effect, which is described inter alia by Meyer et al., Liquid Crystals 1987, 58, 15; Chandrasekhar, “Liquid Crystals”, 2nd edition, Cambridge University Press (1992); and P. G. deGennes et al., “The Physics of Liquid Crystals”, 2nd edition, Oxford Science Publications (1995).
Displays exploiting flexoelectric effect are generally characterized by fast response times typically ranging from 500 μs to 3 ms and further feature excellent grey scale capabilities.
In these displays, the cholesteric liquid crystals are e.g. oriented in the “uniformly lying helix” arrangement (ULH), which also give this display mode its name. For this purpose, a chiral substance, which is mixed with a nematic material, induces a helical twist whilst transforming the material into a chiral nematic material, which is equivalent to a cholesteric material.
The uniform lying helix texture is realized using a chiral nematic liquid crystal with a short pitch, typically in the range from 0.2 μm to 2 μm, preferably of 1.5 μm or less, in particular of 1.0 μm or less, which is unidirectional aligned with its helical axis parallel to the substrates of a liquid crystal cell. In this configuration, the helical axis of the chiral nematic liquid crystal is equivalent to the optical axis of a birefringent plate.
If an electrical field is applied to this configuration normal to the helical axis, the optical axis is rotated in the plane of the cell, similar as the director of a ferroelectric liquid crystal rotate as in a surface stabilized ferroelectric liquid crystal display.
The field induces a splay bend structure in the director, which is accommodated by a tilt in the optical axis. The angle of the rotation of the axis is in first approximation directly and linearly proportional to the strength of the electrical field. The optical effect is best seen when the liquid crystal cell is placed between crossed polarizers with the optical axis in the unpowered state at an angle of 22.5° to the absorption axis of one of the polarizers. This angle of 22.5° is also the ideal angle of rotation of the electric field, as thus, by the inversion the electrical field, the optical axis is rotated by 45° and by appropriate selection of the relative orientations of the preferred direction of the axis of the helix, the absorption axis of the polarizer and the direction of the electric field, the optical axis can be switched from parallel to one polarizer to the center angle between both polarizers. The optimum contrast is then achieved when the total angle of the switching of the optical axis is 45°. In that case, the arrangement can be used as a switchable quarter wave plate, provided the optical retardation, i.e. the product of the effective birefringence of the liquid crystal and the cell gap, is selected to be the quarter of the wavelength. In this context, the wavelength referred to is 550 nm, the wavelength for which the sensitivity of the human eye is highest.
The angle of rotation of the optical axis (Φ) is given in good approximation by formula (1)
tan Φ=ēP0E/(2πK) (1)
wherein
This angle of rotation is half the switching angle in a flexoelectric switching element.
The response time (τ) of this electro-optical effect is given in good approximation by formula (2)
τ=[P0/(2π)]2·γ/K (2)
wherein
There is a critical field (Ec) to unwind the helix, which can be obtained from equation (3)
E
c=(π2/P0)·[k22/(∈0·Δ∈)]1/2 (3)
wherein
However, the main obstacle preventing the mass production of a ULH display is that its alignment is intrinsically unstable and no single surface treatment (planar, homeotropic or tilted) provides an energetically stable state. Due to this, obtaining a high quality dark state is difficult as a large amount of defects are present when conventional cells are used.
Specifically, the severe problem in the flexo electric-optic effect is that the ULH structure is unstable, because there is a strong tendency for the ULH texture to transform into the stable Grandjean texture (uniform standing helix, USH) over time. For example, the ULH texture can be irreversibly damaged by external factors, such as dielectric coupling. At higher electric fields, when the dielectric coupling becomes strong, the helix could be partially or completely unwound depending on the magnitude of the applied voltage. If the cholesteric liquid crystal possesses a positive dielectric anisotropy, the unwound state will be homeotropic and thus totally black when the cell is placed between crossed polarizers. The helix unwinding is a quadratic effect in contrast to the flexoelectric-optic effect which is a polar and linear effect. It should be noted that the helix unwinding by the applied electric field usually destroys irreversibly the ULH texture thus resulting in deterioration of the flexoelectric-optic mode of the device. In order to be practical, an electro-optic device based on the flexoelectric-optic effect must withstand a large temperature and field variation and still work functionally. This means, that such a device requires a stable ULH texture which after unwinding by the applied electric field, for instance, will be able to recover completely after switching off the field. The same should be valid for exposing the sample to high temperatures.
Attempts to improve ULH alignment mostly involving polymer structures on surfaces or bulk polymer networks, such as, for example described in,
Another attempt to improve ULH alignment was suggested by Carbone et al. in Mol. Cryst. Liq. Cryst. 2011, 544, 37-49. The authors utilized a surface relief structure created by curing an UV curable material by a two-photon excitation laser-lithography process in order to promote the formation of a stable ULH texture.
However, all above-described attempts require unfavorable processing steps, which are especially not compatible with the commonly known methods for mass production of LC devices.
Another attempt to improve ULH alignment was suggested by Qasim et al. in Applied. Phys. Lett. 2012, 100, 063501. The authors utilized an IPS electrode structure in order to promote the formation of a stable ULH texture. By using an IPS electrode as alignment and driving electrode, the alignment voltage need to be much higher than utilizing a FFS like alignment electrode to provide same electric field strength, and cannot fully switch the display, where as a consequence, the transmittance is unfavorable lower.
A further development are the so-called PS (polymer stabilised) displays. In these, a small amount of a polymerisable compound is added to the LC medium and, after introduction into the LC cell, is polymerised or crosslinked in situ, usually by UV photopolymerisation. The addition of polymerisable mesogenic or liquid-crystalline compounds, also known as “reactive mesogens” (RMs), to the LC mixture has proven particularly suitable in order to stabilize the ULH texture.
PS-ULH displays are described, for example, in WO 2005/072460 A2; U.S. Pat. No. 8,081,272 B2; U.S. Pat. No. 7,652,731 B2; Komitov et al. Appl. Phys. Lett. 2005, 86, 161118; or in Rudquist et al. Liquid Crystals 1998, 24, 3, p. 329-334.
No matter which polymer stabilization method is used for the stabilization of the ULH texture, the polymer stabilization process requires generally longer curing times in comparison to other polymer stabilization processes since the total concentration of reactive mesogenic monomers (RM) in PS-ULH type displays is typically higher (0.5˜20%) than commonly known display mode such as PSA (polymer-sustained alignment) type displays (0.3˜0.5%). In order to reduce the curing time and to increase the polymerization rate of the polymerisable monomers, typically the utilized liquid crystal media comprise a photo-initiator. However the utilization of photo-initiators often causes reliability problems, such as image sticking or VHR drop in the final display device.
In summary, the attempts of prior art are connected with several disadvantages such as, an increase of the operational voltage, a reduction of the switching speed, decreasing contrast ratio or unfavourable processing steps, which are especially not compatible with commonly known methods for the mass production of corresponding LC devices.
Thus, one aim of the invention is to provide an alternative or preferably improved liquid crystal (LC) light modulation elements and a process of preparing such liquid crystal light modulation elements of the PS-ULH (polymer stabilised ULH) type, which does not have the drawbacks of the prior art, and preferably have the advantages mentioned above and below.
These advantages are amongst others favourable high switching angles, favourable fast response times, favourable low voltage required for addressing, compatible commonly known methods for the mass production, compatible, and finally, a favourable really dark “off state”, which should be achieved by an long term stable alignment of the ULH texture.
Other aims of the present invention are immediately evident to the person skilled in the art from the following detailed description.
Surprisingly, the inventors have found out that one or more of the above-defined aims can be achieved by providing a light modulation element comprising a polymer stabilized cholesteric liquid crystalline medium sandwiched between two substrates (1), provided with a common electrode structure (2) and a driving electrode structure (3) individually, wherein the substrate with driving and/or common electrode structure is additionally provided with an alignment electrode structure (4) which is separated from the driving and or common electrode structure on the same substrate by an dielectric layer (5), characterized the light modulation element comprises at least one alignment layer (6) directly adjacent to the liquid crystalline medium.
The invention also relates to a process of preparing a light modulation element comprising the steps of
a) providing a layer of the cholesteric liquid crystalline medium comprising one or more bimesogenic compounds, one or more chiral compounds, and one or more polymerisable compounds between two substrates, wherein at least one substrate is transparent to light and electrodes are provided on one or both of the substrates,
b) heating the cholesteric liquid crystalline medium to its isotropic phase,
c) cooling the cholesteric liquid crystalline medium below its clearing point while applying an AC field between the electrodes, which is sufficient to switch the liquid crystal medium between switched states,
d) exposing said layer of the cholesteric liquid crystalline medium to photo radiation that induces photopolymerisation of the polymerisable compounds, while applying an AC field between the electrodes.
e) cooling the cholesteric liquid crystalline medium to room temperature with or without applying an electric field or thermal controlling.
f) exposing said cholesteric liquid crystalline medium to photo radiation that induces photopolymerisation of any remaining polymerisable compounds that were not polymerised in step d), optionally while applying an AC field between said electrodes.
The following meanings apply above and below:
The term “liquid crystal”, “mesomorphic compound”, or “mesogenic compound” (also shortly referred to as “mesogen”) means a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase (nematic, smectic, etc.) or in particular as a LC phase. Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.
The term “mesogenic group” means in this context, a group with the ability to induce liquid crystal (LC) phase behaviour. The compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds. For the sake of simplicity, the term “liquid crystal” is used hereinafter for both mesogenic and LC materials.
Throughout the application, the term “aryl and heteroaryl groups” encompass groups, which can be monocyclic or polycyclic, i.e. they can have one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently linked (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se. Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 2 to 25 C atoms, which optionally contain fused rings, and which are optionally substituted. Preference is furthermore given to 5-, 6- or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N, S or 0 in such a way that 0 atoms and/or S atoms are not linked directly to one another. Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1′:3′,1″]terphenyl-2′-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, more preferably 1,4-phenylene, 4,4′-biphenylene, 1, 4-tephenylene.
Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6-membered rings, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups, such as indole, iso-indole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphth-imidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxa-linimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxa-zole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups. The heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.
In the context of this application, the term “(non-aromatic) alicyclic and heterocyclic groups” encompass both saturated rings, i.e. those that contain exclusively single bonds, and partially unsaturated rings, i.e. those that may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se. The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 3 to 25 C atoms, which optionally contain fused rings and that are optionally substituted. Preference is furthermore given to 5-, 6-, 7- or 8-membered carbocyclic groups in which, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent CH2 groups may be replaced by —O— and/or —S—. Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl, more preferably 1,4-cyclohexylene 4,4′-bicyclohexylene, 3,17-hexadecahydro-cyclopenta[a]phenanthrene, optionally being substituted by one or more identical or different groups L. Especially preferred aryl-, heteroaryl-, alicyclic- and heterocyclic groups are 1,4-phenylene, 4,4′-biphenylene, 1, 4-terphenylene, 1,4-cyclohexylene, 4,4′-bicyclohexylene, and 3,17-hexadecahydro-cyclopenta[a]-phenanthrene, optionally being substituted by one or more identical or different groups L.
Preferred substituents (L) of the above-mentioned aryl-, heteroaryl-, alicyclic- and heterocyclic groups are, for example, solubility-promoting groups, such as alkyl or alkoxy and electron-withdrawing groups, such as fluorine, nitro or nitrile. Particularly preferred substituents are, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2 or OC2F5.
Above and below “halogen” denotes F, Cl, Br or I.
Above and below, the terms “alkyl”, “aryl”, “heteroaryl”, etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc. The term “aryl” denotes an aromatic carbon group or a group derived there from. The term “heteroaryl” denotes “aryl” in accordance with the above definition containing one or more heteroatoms.
Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclo-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoro-methyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, etc.
Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxy-ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy.
Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl.
Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl.
Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino.
The term “chiral” in general is used to describe an object that is non-superimposable on its mirror image.
“Achiral” (non-chiral) objects are objects that are identical to their mirror image.
The terms “chiral nematic” and “cholesteric” are used synonymously in this application, unless explicitly stated otherwise.
The pitch induced by the chiral substance (P0) is in a first approximation inversely proportional to the concentration (c) of the chiral material used. The constant of proportionality of this relation is called the helical twisting power (HTP) of the chiral substance and defined by equation (4)
HTP≡1/(c·P0) (4)
wherein
The term “bimesogenic compound” relates to compounds comprising two mesogenic groups in the molecule. Just like normal mesogens, they can form many mesophases, depending on their structure. In particular, bimesogenic compound may induce a second nematic phase, when added to a nematic liquid crystal medium. Bimesogenic compounds are also known as “dimeric liquid crystals”.
The term “alignment” or “orientation” relates to alignment (orientation ordering) of anisotropic units of material such as small molecules or fragments of big molecules in a common direction named “alignment direction”. In an aligned layer of liquid-crystalline material, the liquid-crystalline director coincides with the alignment direction so that the alignment direction corresponds to the direction of the anisotropy axis of the material.
The term “planar orientation/alignment”, for example in a layer of an liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented substantially parallel (about 180°) to the plane of the layer.
The term “homeotropic orientation/alignment”, for example in a layer of a liquid-crystalline material, means that the long molecular axes (in case of calamitic compounds) or the short molecular axes (in case of discotic compounds) of a proportion of the liquid-crystalline molecules are oriented at an angle θ (“tilt angle”) between about 80° to 90° relative to the plane of the layer.
The wavelength of light generally referred to in this application is 550 nm, unless explicitly specified otherwise.
The birefringence Δn herein is defined in equation (5)
Δn=ne−no (5)
wherein ne is the extraordinary refractive index and no is the ordinary refractive index, and the average refractive index nav, is given by the following equation (6).
n
av.=[(2no2+ne2)/3]1/2 (6)
The extraordinary refractive index ne and the ordinary refractive index no can be measured using an Abbe refractometer. Δn can then be calculated from equation (5).
In the present application the term “dielectrically positive” is used for compounds or components with Δ∈>3.0, “dielectrically neutral” with −1.5≦Δc≦3.0 and “dielectrically negative” with Δ∈<−1.5. Δ∈ is determined at a frequency of 1 kHz and at 20° C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10% of the respective individual compound in a nematic host mixture. In case the solubility of the respective compound in the host medium is less than 10% its concentration is reduced by a factor of 2 until the resultant medium is stable enough at least to allow the determination of its properties. Preferably, the concentration is kept at least at 5%, however, in order to keep the significance of the results as high as possible. The capacitance of the test mixtures are determined both in a cell with homeotropic and with homogeneous alignment. The cell gap of both types of cells is approximately 20 μm. The voltage applied is a rectangular wave with a frequency of 1 kHz and a root mean square value typically of 0.5 V to 1.0 V, however, it is always selected to be below the capacitive threshold of the respective test mixture.
Δ∈ is defined as (∈∥−∈⊥), whereas ∈av., is (∈∥+2∈⊥)/3.
The dielectric permittivity of the compounds is determined from the change of the respective values of a host medium upon addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%. The host mixture is disclosed in H. J. Coles et al., J. Appl. Phys. 2006, 99, 034104 and has the composition given in the table 1.
The term “substantially parallel” encompasses also stripe patterns having small deviations in their parallelism to each other, such as deviations less than 10°, preferably less than 5°, in particular less than 2° with respect to their orientation to each other.
The term “stripes” relates in particular to stripes having a straight, curvy or zig-zag-pattern but is not limited to this. Furthermore, the outer shape or the cross-section of the stripes encompasses but is not limited to triangular, circular, semi-circular, or quadrangular shapes.
The term “substrate array” relates in particular to an ordered layer structure such as, in this order, substrate layer, 1st electrode layer, dielectric layer, 2nd electrode layer, and optionally alignment layer, or substrate layer, electrode layer, optionally alignment layer, or substrate layer electrode layer.
Furthermore, the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply to non-defined terms related to liquid crystal materials in the instant application.
In a preferred embodiment of the invention the utilized substrates are substantially transparent. Transparent materials suitable for the purpose of the present invention are commonly known by the skilled person. In accordance with the invention, the substrates may consist, inter alia, each and independently from another of a polymeric material, of metal oxide, for example ITO and of glass or quartz plates, preferably each and independently of another of glass and/or ITO, in particular glass/glass.
Suitable and preferred polymeric substrates are for example films of cyclo olefin polymer (COP), cyclic olefin copolymer (COC), polyester such as polyethyleneterephthalate (PET) or polyethylene-naphthalate (PEN), polyvinylalcohol (PVA), polycarbonate (PC) or triacetylcellulose (TAC), very preferably PET or TAC films. PET films are commercially available for example from DuPont Teijin Films under the trade name Melinex®. COP films are commercially available for example from ZEON Chemicals L.P. under the trade name Zeonor® or Zeonex®. COC films are commercially available for example from TOPAS Advanced Polymers Inc. under the trade name Topas®.
The substrate layers can be kept at a defined separation from one another by, for example, spacers, or projecting structures in the layer. Typical spacer materials are commonly known to the expert and are selected, for example, from plastic, silica, epoxy resins, etc.
In a preferred embodiment, the substrates are arranged with a separation in the range from approximately 1 μm to approximately 50 μm from one another, preferably in the range from approximately 1 μm to approximately 25 μm from one another, and more preferably in the range from approximately 1 μm to approximately 15 μm from one another. The layer of the cholesteric liquid-crystalline medium is thereby located in the interspace.
The light modulation element in accordance with the present invention comprises a common electrode structure (2) and driving electrode structure (3) each provided directly on the opposing substrates (1), which are capable to allow the application of an electric field, which is substantially perpendicular to the substrates or to the cholesteric liquid-crystalline medium layer.
Additionally, the light modulation element comprises an alignment electrode structure (4) and a driving electrode structure (3) each provided on the same substrate and separated from each other by a dielectric layer (5), which are capable to allow the application of an electric fringe field.
Preferably, the common electrode structure is provided as an electrode layer on the entire substrate surface of one substrate.
Suitable transparent electrode materials are commonly known to the expert, as for example electrode structures made of metal or metal oxides, such as, for example transparent indium tin oxide (ITO), which is preferred according to the present invention.
Thin films of ITO are commonly deposited on substrates by physical vapour deposition, electron beam evaporation, or sputter deposition techniques.
In a preferred embodiment, the light modulation element comprises at least one dielectric layer, which is provided either only on the driving electrode structure, or on the common electrode structure, or both on the driving electrode structure and the common electrode structure.
In another preferred embodiment, the light modulation element comprises at least two dielectric layers, which are provided on the opposing electrode structures.
Typical dielectric layer materials are commonly known to the expert, such as, for example, SiOx, SiNx, Cytop, Teflon, and PMMA.
The dielectric layer materials can be applied onto the substrate or electrode layer by conventional coating techniques like spin coating, roll-coating, blade coating, or vacuum deposition such as PVD or CVD. It can also be applied to the substrate or electrode layer by conventional printing techniques which are known to the expert, like for example screen printing, offset printing, reel-to-reel printing, letter press printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat-seal printing, ink-jet printing or printing by means of a stamp or printing plate.
In another preferred embodiment, the light modulation element in accordance with the present invention comprises at least one alignment electrode structure (4), which is provided on the dielectric layer (5), which separates the driving electrode structure from the alignment electrode structure.
However it is likewise preferred, that the light modulation element in accordance with the present invention comprises at least two alignment layers, which are provided on each of the dielectric layers (5) provided on the driving electrode layer and the common electrode layer.
Thus, the resulting structured substrate, comprising the substrate itself, the driving electrode structure, the dielectric layer and the alignment electrode structure forms a substrate array, preferably a FFS-type structured substrate array as it is commonly known by the expert.
Preferably, the alignment electrode structure comprises a plurality of substantially parallel stripe electrodes wherein the gap between the stripe electrodes is in a range of approximately 500 nm to approximately 10 μm, preferably in a range of approximately 1 μm to approximately 5 μm, the width of each stripe electrode is in a range of approximately 500 nm to approximately 10 μm, preferably in a range of approximately 1 μm to approximately 5 μm, and wherein the height of each stripe electrode is preferably in a range of approximately 10 nm to approximately 10 μm, preferably in a range of approximately 40 nm to approximately 2 μm.
Thus, the resulting structured substrate, comprising the substrate itself, the driving electrode structure, the dielectric layer and the alignment electrode structure forms a substrate array, preferably a FFS-type structured substrate array as it is commonly known by the expert.
Suitable electrode materials are commonly known to the expert, as for example electrode structures made of metal or metal oxides, such as, for example transparent indium tin oxide (ITO), which is preferred according to the present invention.
Thin films of ITO are commonly deposited on substrates by physical vapor deposition, electron beam evaporation, or sputter deposition techniques.
In a preferred embodiment, the light modulation element comprises at least one alignment layer which is provided on the common electrode layer.
In another preferred embodiment the alignment layer is provided on the alignment electrode structure.
In a further preferred embodiment at least one alignment layer is provided on the alignment electrode structure and at least one alignment layer is provided on the common electrode structure.
In another preferred embodiment at least one alignment layer is provided on the alignment electrode structure and at least one alignment layer is provided on the opposing the alignment electrode structure.
Preferably the alignment layer induces a homeotropic alignment, tilted homeotropic or planar alignment to the adjacent liquid crystal molecules, and which is provided on the common electrode structure and/or alignment electrode structure as described above.
Preferably, the alignment layer(s) is/are made of homeotropic and/or planar alignment layer materials, which are commonly known to the expert, such as, for example, layers made of alkoxysilanes, alkyltrichlorosilanes, CTAB, lecithin or polyimides, such as for example SE-5561, commercially available for example from Nissan, AL-3046 or AL-5561, commercially available for example from JSR Corporation.
Further suitable methods to achieve homeotropic alignment are described for example in J. Cognard, Mol. 78, Supplement 1, 1-77 (1981).
The alignment layer materials can be applied onto the substrate array or electrode structure by conventional coating techniques like spin coating, roll-coating, dip coating or blade coating. It can also be applied by vapour deposition or conventional printing techniques which are known to the expert, like for example screen printing, offset printing, reel-to-reel printing, letter press printing, gravure printing, rotogravure printing, flexographic printing, intaglio printing, pad printing, heat-seal printing, ink-jet printing or printing by means of a stamp or printing plate.
In a preferred embodiment, the alignment layer are preferably rubbed by rubbing techniques known to the skilled person in the art.
If two alignment layers are present, which are each provided on opposing common electrode structure and/or alignment electrode structures, it is likewise preferred, that the rubbing direction of one of the alignment layers is preferably in the range of +/−45°, more preferably in the range of +/−20°, even more preferably in the range of +/−10, and in particular in the range of the direction+/−5° with respect to the longitudinal axis of the stripe pattern of the alignment electrode structure or the length of the stripes and the rubbing direction of the opposing alignment layer is substantially antiparallel.
The term “substantially antiparallel” encompasses also rubbing directions having small deviations in their antiparallelism to each other, such as deviations less than 10°, preferably less than 5°, in particular less than 2° with respect to their orientation to each other.
In a further preferred embodiment, the alignment layer substitutes the dielectric layer and the alignment layer is provided on the side of the alignment electrode.
In a preferred embodiment of the invention, the light modulation element comprises two or more polarisers, at least one of which is arranged on one side of the layer of the cholesteric liquid-crystalline medium and at least one of which is arranged on the opposite side of the layer of the liquid-crystalline medium. The layer of the cholesteric liquid-crystalline medium and the polarisers here are preferably arranged parallel to one another.
The polarisers can be linear polarisers. Preferably, precisely two polarisers are present in the light modulation element. In this case, it is furthermore preferred for the polarisers either both to be linear polarisers. If two linear polarisers are present in the light modulation element, it is preferred in accordance with the invention for the polarisation directions of the two polarisers to be crossed.
It is furthermore preferred in the case where two circular polarisers are present in the light modulation element for these to have the same polarisation direction, i.e. either both are right-hand circular-polarised or both are left-hand circular-polarised.
The polarisers can be reflective or absorptive polarisers. A reflective polariser in the sense of the present application reflects light having one polarisation direction or one type of circular-polarised light, while being transparent to light having the other polarisation direction or the other type of circular-polarised light. Correspondingly, an absorptive polariser absorbs light having one polarisation direction or one type of circular-polarised light, while being transparent to light having the other polarisation direction or the other type of circular-polarised light. The reflection or absorption is usually not quantitative; meaning that complete polarisation of the light passing through the polariser does not take place.
For the purposes of the present invention, both absorptive and reflective polarisers can be employed. Preference is given to the use of polarisers, which are in the form of thin optical films. Examples of reflective polarisers which can be used in the light modulation element according to the invention are DRPF (diffusive reflective polariser film, 3M), DBEF (dual brightness enhanced film, 3M), DBR (layered-polymer distributed Bragg reflectors, as described in U.S. Pat. No. 7,038,745 and U.S. Pat. No. 6,099,758) and APF (advanced polariser film, 3M).
Examples of absorptive polarisers, which can be employed in the light modulation elements according to the invention, are the Itos XP38 polariser film and the Nitto Denko GU-1220DUN polariser film. An example of a circular polariser, which can be used in accordance with the invention, is the APNCP37-035-STD polariser (American Polarizers). A further example is the CP42 polariser (ITOS).
The light modulation element may furthermore comprise filters, which block light of certain wavelengths, for example, UV filters. In accordance with the invention, further functional layers commonly known to the expert may also be present, such as, for example, protective films and/or compensation films.
Suitable cholesteric liquid crystalline media for the light modulation element according to the present invention typically comprise one or more bimesogenic compounds, one or more polymerisable liquid-crystalline compounds, and one or more chiral compound.
In view of the bimesogenic compounds for the ULH-mode, the Coles group published a paper (Coles et al., 2012 (Physical Review E 2012, 85, 012701)) on the structure-property relationship for dimeric liquid crystals.
Further bimesogenic compounds are known in general from prior art (cf. also Hori, K., Limuro, M., Nakao, A., Toriumi, H., J. Mol. Struc. 2004, 699, 23-29 or GB 2 356 629).
Symmetrical dimeric compounds showing liquid crystalline behaviour are further disclosed in Joo-Hoon Park et al. “Liquid Crystalline Properties of Dimers Having o-, m- and p-Positional Molecular structures”, Bill. Korean Chem. Soc., 2012, Vol. 33, No. 5, pp. 1647-1652.
Similar liquid crystal compositions with short cholesteric pitch for flexoelectric devices are known from EP 0 971 016, GB 2 356 629 and Coles, H. J., Musgrave, B., Coles, M. J., and Willmott, J., J. Mater. Chem., 11, p. 2709-2716 (2001). EP 0 971 016 reports on mesogenic estradiols, which, as such, have a high flexoelectric coefficient.
Typically, for light modulation elements utilizing the ULH mode the optical retardation d*Δn (effective) of the cholesteric liquid-crystalline medium should preferably be such that the equation (7)
sin 2(π·d·Δn/λ)=1 (7)
wherein
d is the cell gap and
λ is the wavelength of light
is satisfied. The allowance of deviation for the right hand side of equation is +1-3%.
The dielectric anisotropy (Δ∈) of a suitable cholesteric liquid-crystalline medium should be chosen in that way that unwinding of the helix upon application of the addressing voltage is prevented. Typically, Δ∈ of a suitable liquid crystalline medium is preferably higher than −5, and more preferably 0 or more, but preferably 10 or less, more preferably 5 or less and most preferably 3 or less.
The utilized cholesteric liquid-crystalline medium preferably have a clearing point of approximately 65° C. or more, more preferably approximately 70° C. or more, still more preferably 80° C. or more, particularly preferably approximately 85° C. or more and very particularly preferably approximately 90° C. or more.
The nematic phase of the utilized cholesteric liquid-crystalline medium according to the invention preferably extends at least from approximately 0° C. or less to approximately 65° C. or more, more preferably at least from approximately −20° C. or less to approximately 70° C. or more, very preferably at least from approximately −30° C. or less to approximately 70° C. or more and in particular at least from approximately −40° C. or less to approximately 90° C. or more. In individual preferred embodiments, it may be necessary for the nematic phase of the media according to the invention to extend to a temperature of approximately 100° C. or more and even to approximately 110° C. or more.
Typically, the cholesteric liquid-crystalline medium utilized in a light modulation element in accordance with the present invention comprises one or more bimesogenic compounds, which are preferably selected from the group of compounds of formulae A-I to A-III,
and wherein
Preferably used are compounds of formulae A-I to A-III wherein
Especially preferably used are compounds of formula A-III wherein
Preferably used are compounds of formula A-I in which
Preferably used are compounds of formula A-II in which
Most preferably used are compounds of formula A-III in which
Preferably, the compounds of formula A-III are asymmetric compounds, preferably having different mesogenic groups MG31 and MG32.
Generally preferred are compounds of formulae A-I to A-III in which the dipoles of the ester groups present in the mesogenic groups are all oriented in the same direction, i.e. all —CO—O— or all —O—CO—.
Especially preferred are compounds of formulae A-I and/or A-II and/or A-III wherein the respective pairs of mesogenic groups (MG11 and MG12) and (MG21 and MG22) and (MG31 and MG32) at each occurrence independently from each other comprise one, two or three six-atomic rings, preferably two or three six-atomic rings.
A smaller group of preferred mesogenic groups is listed below. For reasons of simplicity, Phe in these groups is 1,4-phenylene, PheL is a 1,4-phenylene group which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OH, NO2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, in particular F, Cl, CN, CH3, C2H5, OCH3, COCH3 and OCF3, most preferably F, Cl, CH3, OCH3 and COCH3 and Cyc is 1,4-cyclohexylene. This list comprises the sub-formulae shown below as well as their mirror images
-Phe-Z-Phe- II-1
-Phe-Z-Cyc- II-2
-Cyc-Z-Cyc- II-3
-PheL-Z-Phe- II-4
-PheL-Z-Cyc- II-5
-PheL-Z-PheL- II-6
-Phe-Z-Phe-Z-Phe- II-7
-Phe-Z-Phe-Z-Cyc- II-8
-Phe-Z-Cyc-Z-Phe- II-9
-Cyc-Z-Phe-Z-Cyc- II-10
-Phe-Z-Cyc-Z-Cyc- II-11
-Cyc-Z-Cyc-Z-Cyc- II-12
-Phe-Z-Phe-Z-PheL- II-13
-Phe-Z-PheL-Z-Phe- II-14
-PheL-Z-Phe-Z-Phe- II-15
-PheL-Z-Phe-Z-PheL- II-16
-PheL-Z-PheL-Z-Phe- II-17
-PheL-Z-PheL-Z-PheL- II-18
-Phe-Z-PheL-Z-Cyc- II-19
-Phe-Z-Cyc-Z-PheL- II-20
-Cyc-Z-Phe-Z-PheL- II-21
-PheL-Z-Cyc-Z-PheL- II-22
-PheL-Z-PheL-Z-Cyc- II-23
-PheL-Z-Cyc-Z-Cyc- II-24
-Cyc-Z-PheL-Z-Cyc- II-25
Particularly preferred are the sub formulae II-1, II-4, II-6, II-7, II-13, II-14, II-15, II-16, II-17 and II-18.
In these preferred groups, Z in each case independently has one of the meanings of Z1 as given above for MG21 and MG22. Preferably Z is —COO—, —OCO—, —CH2CH2—, —C≡C— or a single bond, especially preferred is a single bond.
Very preferably the mesogenic groups MG11 and MG12, MG21 and MG22 and MG31 and MG32 are each and independently selected from the following formulae and their mirror images
Very preferably, at least one of the respective pairs of mesogenic groups MG11 and MG12, MG21 and MG22 and MG31 and MG32 is, and preferably, both of them are each and independently, selected from the following formulae IIa to IIn (the two reference Nos. “II i” and “II l” being deliberately omitted to avoid any confusion) and their mirror images
wherein
L is in each occurrence independently of each other F or Cl, preferably F and
r is in each occurrence independently of each other 0, 1, 2 or 3, preferably 0, 1 or 2.
The group
in these preferred formulae is very preferably denoting
furthermore
Particularly preferred are the sub formulae IIa, IId, IIg, IIh, IIi, IIk and IIo, in particular the sub formulae IIa and IIg.
In case of compounds with a non-polar group, R11, R12, R21, R22, R31, and R32 are preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.
If R11 and R12, R21 and R22 and R31 and R32 are an alkyl or alkoxy radical, i.e. where the terminal CH2 group is replaced by —O—, this may be straight chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. where one CH2 group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, for example.
In case of a compounds with a terminal polar group, R11 and R12, R21 and R22 and R31 and R32 are selected from CN, NO2, halogen, OCH3, OCN, SCN, CORx, COORx or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms. Rx is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms. Halogen is preferably F or Cl.
Especially preferably R11 and R12, R21 and R22 and R31 and R32 in formulae A-I, A-II, respectively A-III are selected of H, F, Cl, CN, NO2, OCH3, COCH3, COC2H5, COOCH3, COOC2H5, CF3, C2F5, OCF3, OCHF2, and OC2F5, in particular of H, F, Cl, CN, OCH3 and OCF3, especially of H, F, CN and OCF3.
In addition, compounds of formulae A-I, A-II, respectively A-III containing an achiral branched group R11 and/or R21 and/or R31 may occasionally be of importance, for example, due to a reduction in the tendency towards crystallization. Branched groups of this type generally do not contain more than one chain branch. Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.
The spacer groups Sp1, Sp2 and Sp3 are preferably a linear or branched alkylene group having 5 to 40 C atoms, in particular 5 to 25 C atoms, very preferably 5 to 15 C atoms, in which, in addition, one or more non-adjacent and non-terminal CH2 groups may be replaced by —O—, —S—, —NH—, —N(CH3)—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—.
“Terminal” CH2 groups are those directly bonded to the mesogenic groups. Accordingly, “non-terminal” CH2 groups are not directly bonded to the mesogenic groups R11 and R12, R21 and R22 and R31 and R32.
Typical spacer groups are for example —(CH2)o—, —(CH2CH2O)p—CH2CH2—, with o being an integer from 5 to 40, in particular from 5 to 25, very preferably from 5 to 15, and p being an integer from 1 to 8, in particular 1, 2, 3 or 4.
Preferred spacer groups are pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, diethyleneoxyethylene, dimethyleneoxybutylene, pentenylene, heptenylene, nonenylene and undecenylene, for example.
Especially preferred are compounds of formulae A-I, A-II and A-III wherein Sp1, Sp2, respectively Sp3 are alkylene with 5 to 15 C atoms. Straight-chain alkylene groups are especially preferred.
Preferred are spacer groups with even numbers of a straight-chain alkylene having 6, 8, 10, 12 and 14 C atoms.
In another embodiment of the present invention are the spacer groups preferably with odd numbers of a straight-chain alkylene having 5, 7, 9, 11, 13 and 15 C atoms. Very preferred are straight-chain alkylene spacers having 5, 7, or 9 C atoms.
Especially preferred are compounds of formulae A-I, A-II and A-III wherein Sp1, Sp2, respectively Sp3 are completely deuterated alkylene with 5 to 15 C atoms. Very preferred are deuterated straight-chain alkylene groups. Most preferred are partially deuterated straight-chain alkylene groups.
Preferred are compounds of formula A-I wherein the mesogenic groups R11-MG11- and R12-MG1- are different. Especially preferred are compounds of formula A-I wherein R11-MG11- and R12-MG12- in formula A-I are identical.
Preferred compounds of formula A-I are selected from the group of compounds of formulae A-I-1 to A-I-3
wherein the parameter n has the meaning given above and preferably is 3, 5, 7 or 9, more preferably 5, 7 or 9.
Preferred compounds of formula A-II are selected from the group of compounds of formulae A-II-1 to A-II-4
wherein the parameter n has the meaning given above and preferably is 3, 5, 7 or 9, more preferably 5, 7 or 9.
Preferred compounds of formula A-III are selected from the group of compounds of formulae A-III-1 to A-II-11
wherein the parameter n has the meaning given above and preferably is 3, 5, 7 or 9, more preferably 5, 7 or 9.
Particularly preferred exemplary compounds of formulae A-I are the following compounds:
symmetrical ones:
and non-symmetrical ones:
Particularly preferred exemplary compounds of formulae A-II are the following compounds:
symmetrical ones:
and non-symmetrical ones:
Particularly preferred exemplary compounds of formulae A-III are the following compounds:
symmetrical ones:
and non-symmetrical ones:
The bimesogenic compounds of formula A-I to A-III are particularly useful in flexoelectric liquid crystal light modulation elements as they can easily be aligned into macroscopically uniform orientation, and lead to high values of the elastic constant k11 and a high flexoelectric coefficient e in the applied liquid crystalline media.
The compounds of formulae A-I to A-III can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
In a preferred embodiment, the cholesteric liquid crystalline medium optionally comprise one or more nematogenic compounds, which are preferably selected from the group of compounds of formulae B-I to B-III
wherein
are in each occurrence independently
alternatively one or more of
and
Further preferred are cholesteric liquid-crystalline media comprising one or more nematogens of formula B-I selected from the from the group of formulae B-I-1 to B-I-, preferably of formula B-I-2 and/or B-I-4, most preferably B-I-4
wherein the parameters have the meanings given above and preferably
Further preferred are cholesteric liquid-crystalline media comprising one or more nematogens of formula B-II selected from the from the group of formulae B-II-1 and B-II-2, preferably of formula B-II-2 and/or B-II-4, most preferably of formula B-II-1
wherein the parameters have the meanings given above and preferably
Further preferred are cholesteric liquid-crystalline media comprising one or more nematogens of formula B-III, preferably selected from the group compounds of formulae B-III-1 to B-III-3
wherein the parameters have the meanings given above and preferably
The compounds of formulae B-I to B-III are either known to the expert and can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart.
The cholesteric liquid-crystalline media comprise one or more chiral compounds with a suitable helical twisting power (HTP), in particular those disclosed in WO 98/00428.
Preferably, the chiral compounds are selected from the group of compounds of formulae C-I to C-III,
the latter ones including the respective (S,S) enantiomers,
wherein E and F are each independently 1,4-phenylene or trans-1,4-cyclo-hexylene, v is 0 or 1, Z0 is —COO—, —OCO—, —CH2CH2— or a single bond, and R is alkyl, alkoxy or alkanoyl with 1 to 12 C atoms.
Particularly preferred cholesteric liquid-crystalline media comprise one or more chiral compounds, which themselves do not necessarily have to show a liquid crystalline phase and give good uniform alignment themselves.
The compounds of formula C-II and their synthesis are described in WO 98/00428. Especially preferred is the compound CD-1, as shown in table D below. The compounds of formula C-III and their synthesis are described in GB 2 328 207.
Further, typically used chiral compounds are e.g. the commercially available R/S-5011, CD-1, R/S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).
The above mentioned chiral compounds R/S-5011 and CD-1 and the (other) compounds of formulae C-I, C-II and C-III exhibit a very high helical twisting power (HTP), and are therefore particularly useful for the purpose of the present invention.
The cholesteric liquid-crystalline medium preferably comprises preferably 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral compounds, preferably selected from the above formula C-III, in particular CD-1, and/or formula C-III and/or R-5011 or S-5011, very preferably, the chiral compound is R-5011, S-5011 or CD-1.
The amount of chiral compounds in the cholesteric liquid-crystalline medium is preferably from 0.5 to 20%, more preferably from 1 to 15%, even more preferably 1 to 10%, and most preferably 1 to 5%, by weight of the total mixture.
The cholesteric liquid-crystalline medium preferably comprises, one more polymerisable compounds, which are added to the above described liquid-crystalline medium. After introduction of the cholesteric liquid-crystalline medium into the light modulation element, the polymerisable compounds of the cholesteric liquid-crystalline medium are polymerised or cross-linked in situ, usually by UV photopolymerisation. The addition of polymerisable mesogenic or liquid-crystalline compounds, also known as “reactive mesogens” (RMs), to the LC mixture has been proven particularly suitable in order further to stabilise the ULH texture (e.g. Lagerwall et al., Liquid Crystals 1998, 24, 329-334.).
Preferably, the polymerisable liquid-crystalline compounds are selected from the group of compounds of formula D,
P-Sp-MG-R0 D
wherein
Further preferred polymerisable mono-, di-, or multireactive liquid crystalline compounds are disclosed for example in WO 93/22397, EP 0 261 712, DE 195 04 224, WO 95/22586, WO 97/00600, U.S. Pat. No. 5,518,652, U.S. Pat. No. 5,750,051, U.S. Pat. No. 5,770,107 and U.S. Pat. No. 6,514,578.
Preferred polymerisable groups are selected from the group consisting of CH2═CW1—COO—, CH2═CW—CO—,
CH2═CW2—(O)k3—, CW1═CH—CO—(O)k3—, CW1═CH—CO—NH—, CH2═CW1—CO—NH—, CH3—CH═CH—O—, (CH2═CH)2CH—OCO—, (CH2═CH—CH2)2CH—OCO—, (CH2═CH)2CH—O—, (CH2═CH—CH2)2N—, (CH2═CH—CH2)2N—CO—, HO—CW2W3—, HS—CW2W3—, HW2N—, HO—CW2W3—NH—, CH2═CW1—CO—NH—, CH2═CH—(COO)k1-Phe-(O)k2—, CH2═CH—(CO)k1-Phe-(O)k2—, Phe-CH═CH—, HOOC—, OCN— and W4W5W6Si—, in which W1 denotes H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 C atoms, in particular H, F, Cl or CH3, W2 and W3 each, independently of one another, denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, W4, W5 and W6 each, independently of one another, denote Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W7 and W8 each, independently of one another, denote H, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1,4-phenylene, which is optionally substituted by one or more radicals L as being defined above but being different from P-Sp, and k1, k2 and k3 each, independently of one another, denote 0 or 1, k3 preferably denotes 1, and k4 is an integer from 1 to 10.
Particularly preferred groups P are CH2═CH—COO—, CH2═C(CH3)—COO—, CH2═CF—COO—, CH2═CH—, CH2═CH—O—, (CH2═CH)2CH—OCO—, (CH2═CH)2CH—O—,
in particular vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.
In a further preferred embodiment of the invention, the polymerisable compounds of the formulae I* and II* and sub-formulae thereof contain, instead of one or more radicals P-Sp-, one or more branched radicals containing two or more polymerisable groups P (multifunctional polymerisable radicals). Suitable radicals of this type, and polymerisable compounds containing them, are described, for example, in U.S. Pat. No. 7,060,200 B1 or US 2006/0172090 A1. Particular preference is given to multifunctional polymerisable radicals selected from the following formulae:
—X-alkyl-CHP1—CH2—CH2P2 I*a
—X-alkyl-C(CH2P1)(CH2P2)—CH2P3 I*b
—X-alkyl-CHP1CHP2—CH2P3 I*c
—X-alkyl-C(CH2P1)(CH2P2)—CaaH2aa+1 I*d
—X-alkyl-CHP1—CH2P2 I*e
—X-alkyl-CHP1P2 I*f
—X-alkyl-CP1P2—CaaH2aa+1 I*g
—X-alkyl-C(CH2P1)(CH2P2)—CH2OCH2—C(CH2P3)(CH2P4)CH2P5 I*h
—X-alkyl-CH((CH2)aaP1)((CH2)bbP2) I*i
—X-alkyl-CH P1CHP2—CaaH2aa+1 l*k
in which
Preferred spacer groups Sp are selected from the formula Sp′-X′, so that the radical “P-Sp-” conforms to the formula “P-Sp′-X′-”, where
Typical spacer groups Sp′ are, for example, —(CH2)p1—, —(CH2CH2O)q1—CH2CH2—, —CH2CH2—S—CH2CH2—, —CH2CH2—NH—CH2CH2— or —(SiRxRxx—O)p1—, in which p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and Rx and Rxx have the above-mentioned meanings.
Particularly preferred groups —X′-Sp′- are —(CH2)p1—, —O—(CH2)p1—, —OCO—(CH2)p1—, —OCOO—(CH2)p1—.
Particularly preferred groups Sp′ are, for example, in each case straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethyl-ene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.
More preferred polymerisable mono-, di-, or multireactive liquid crystalline compounds are shown in the following list:
wherein
In particular the polymerisable mono-, di-, or multireactive liquid crystalline are preferably selected from compounds of the following formulae,
wherein
The total concentration of these polymerisable compounds is in the range of 0.1% to 25%, preferably 0.1% to 15%, more preferably 0.1% to 10% based on the total mixture. The concentrations of the individual polymerisable compounds used each are preferably in the range of 0.1% to 25%.
The polymerisable compounds are polymerised or cross-linked (if a compound contains two or more polymerisable groups) by in-situ polymerisation in the cholesteric liquid crystal medium between the substrates of the LC light modulation element. Suitable and preferred polymerisation methods are, for example, thermal or photopolymerisation, preferably photopolymerisation, in particular UV photopolymerisation.
If necessary, one or more initiators may also be added here. Suitable conditions for the polymerisation, and suitable types and amounts of initiators, if present, are known to the person skilled in the art and are described in the literature.
If utilized, the radical photoinitiators are preferably selected from the commercially available Irgacure® or Darocure® (Ciba AG) series, such as, for example, Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 817, Irgacure 907, Irgacure 1300, Irgacure, Irgacure 2022, Irgacure 2100, Irgacure 2959, or Darocure TPO.
The above-mentioned polymerisable compounds are also suitable for polymerisation without initiator, which is associated with considerable advantages, such as, for example, lower material costs and in particular less contamination of the cholesteric liquid crystal medium by possible residual amounts of the initiator or degradation products thereof.
If an initiator is employed, its proportion in the mixture as a whole is preferably 0.001 to 5% by weight, particularly preferably 0.005 to 0.5% by weight. However, the polymerisation can also take place without addition of an initiator. In a further preferred embodiment, the cholesteric liquid crystal medium does not comprise a polymerisation initiator.
The polymerisable component or the cholesteric liquid-crystalline medium may also comprise one or more stabilisers in order to prevent undesired spontaneous polymerisation of the RMs, for example during storage or transport. Suitable types and amounts of stabilisers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilisers of the Irganox® series (Ciba AG). If stabilisers are employed, their proportion, based on the total amount of RMs or polymerisable compounds, is preferably 10-500000 ppm, particularly preferably 50-50000 ppm.
The polymerisable compounds can be added individually to the cholesteric liquid-crystalline medium, but it is also possible to use mixtures comprising two or more polymerisable compounds. On polymerisation of mixtures of this type, copolymers are formed.
The cholesteric liquid-crystalline medium which can be used in accordance with the invention is prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned compounds with one or more polymerisable compounds as defined above and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing.
The liquid crystal media may contain further additives like for example further stabilizers, inhibitors, chain-transfer agents, co-reacting monomers, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments or nanoparticles in usual concentrations.
If present, the total concentration of these further constituents is in the range of 0.1% to 20%, preferably 0.1% to 8%, based on the total mixture. The concentrations of the individual compounds used each are preferably in the range of 0.1% to 20%. The concentration of these and of similar additives is not taken into consideration for the values and ranges of the concentrations of the liquid crystal components and compounds of the liquid crystal media in this application. This also holds for the concentration of the dichroic dyes used in the mixtures, which are not counted when the concentrations of the compounds respectively the components of the host medium are specified. The concentration of the respective additives is always given relative to the final doped mixture.
In general, the total concentration of all compounds in the media according to this application is 100%.
It goes without saying to the person skilled in the art that the LC media may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
A typical process of preparing a liquid crystal light modulation element comprises at least the steps of
a) cutting and cleaning of the substrates, providing the driving electrode structure and common electrode structure on each of the substrates, coating of a dielectric layer on the driving electrode structure, providing the alignment electrode structure on the dielectric layer, providing an alignment layer on the alignment electrode structure and/or common electrode structure, assembling the cell using an adhesive (UV or heat curable) with spacer, filling the cell with the cholesteric liquid-crystalline medium,
b) heating the cholesteric liquid crystal medium to its isotropic phase,
c) cooling the cholesteric liquid crystal medium below the clearing point while applying an AC field between the electrodes, which is sufficient to switch the liquid crystal medium between switched states,
d) exposing said layer of the cholesteric liquid crystal medium to photo radiation that induces photopolymerisation of the polymerisable compounds, while applying an AC field between the electrodes,
e) cooling the cholesteric liquid crystal medium to room temperature with or without applying an electric field or thermal controlling.
f) exposing said layer of the cholesteric liquid crystal medium to photo radiation that induces photopolymerisation of any remaining polymerisable compounds that were not polymerised in step d), optionally while applying an AC field between said electrodes.
In the first step (step a) the cholesteric liquid crystal medium, as described above and below, is provided as a layer between two substrates forming a cell. Typically the cholesteric liquid crystal medium is filled into the cell. Conventional filling methods can be used which are known to the skilled person, like for example the so-called “one-drop filling” (ODF). Likewise also other commonly known methods can be utilized, such as, for example, vacuum injection method or inkjet printing method (IJP)
The construction of the light modulation elements according to the invention corresponds to the usual geometry for ULH displays, as described in the prior art cited at the outset.
In the second step (step b) the cholesteric liquid crystal medium is heated above the clearing point of the mixture into its isotropic phase. Preferably, the cholesteric liquid crystal medium is heated 1° C. or more above the clearing point, more preferably 5° C. or more above the clearing point and even more preferably 10° C. or more above the clearing point of the utilized cholesteric liquid crystal medium.
In the third step (step c) the cholesteric liquid crystal medium is cooled below the clearing point of the mixture. Preferably, the cholesteric liquid crystal medium is cooled 1° C. or more below the clearing point, more preferably 5° C. or more below the clearing point and even more preferably 10° C. or more below the clearing point of the utilized cholesteric liquid crystal medium.
The cooling rate is preferably −20° C./min or less, more preferably −10° C./min or less, in particular −5° C./min or less.
Whilst cooling down a voltage, preferably an AC voltage, is applied to the electrodes of the light modulation element, which is sufficient to switch the liquid crystal medium between switched states. The applied voltage is thereby depending on which LC mode is used and can be easily adjusted by the person skilled in the art. Suitable and preferred voltages are in the range from 5 to 60 V, more preferably 10 to 50 V. In a preferred embodiment, the applied voltage stays constant during the following irradiation step. It is likewise preferred, that the applied voltage is increased or decreased.
In the irradiation step (step d), the light modulation element is exposed to photo radiation that causes photopolymerisation of the polymerisable functional groups of the polymerisable compounds contained in the cholesteric liquid crystal medium. As a result these compounds are substantially polymerised or crosslinked (in case of compounds with two or more polymerisable groups) in situ within the cholesteric liquid crystal medium between the substrates forming the light modulation element. The polymerisation is induced for example by exposure to UV radiation.
The wavelength of the photo radiation should not be too low, in order to avoid damage to the LC molecules of the medium, and should preferably be different from, very preferably higher than, the UV absorption maximum of the LC host mixture (component B). On the other hand, the wavelength of the photo radiation should not be too high, so as to allow quick and complete UV photopolymerisation of the RMs, and should be not higher than, preferably the same as or lower than the UV absorption maximum of the polymerisable component (component A).
Suitable wavelengths are preferably selected from 300 to 400 nm, for example 305 nm or more, 320 nm or more, 340 nm or more, or even 376 nm or more.
The irradiation or exposure time should be selected such that polymerisation is as complete as possible, but still not be too high to allow a smooth production process. Also, the radiation intensity should be high enough to allow quick and complete polymerisation as possible, but should not be too high to avoid damage to the cholesteric liquid crystal medium. Since the polymerisation speed also depends on the reactivity of the RMs, the irradiation time and the radiation intensity should be selected in accordance with the type and amount of RMs present in the cholesteric liquid crystal medium.
Suitable and preferred exposure times are in the range from 10 seconds to 20 minutes, preferably from 30 seconds to 15 minutes.
Suitable and preferred radiation intensities are in the range from 1 to 50 mW/cm2, preferably from 2 to 10 mW/cm2, more preferably from 3 to 5 mW/cm2.
During polymerisation a voltage, preferably an AC voltage, is applied to the electrodes of the light modulation element. Suitable and preferred voltages are in the range from 1 to 30 V, preferably from 5 to 20 V. Preferably, the AC frequencies are in the range from 200 Hz to 20 k Hz.
In the step e) the cholesteric liquid crystal medium is cooled down to room temperature. If actively cooling is applied, the cooling rate in step e) is preferably −2° C./min or more, more preferably −5° C./min or more, in particular −10° C./min or more It is likewise preferred to perform the active cooling stepwise while applying a first cooling rate which differs from the following cooling rates, for example, applying a first cooling rate of −2° C./min or more and then −10° C./min or more. Whilst cooling down optionally also a voltage, preferably an AC voltage, can be applied to the electrodes of the light modulation element, which is sufficient to switch the liquid crystal medium between switched states. Suitable and preferred voltages are in the range from 5 to 30 V, preferably from 10 to 20 V. Preferably, the AC frequencies are in the range from 200 Hz to 20 k Hz.
In the end curing step (step f) said layer of a liquid crystal medium is exposed to photo radiation, which wavelength is preferably selected from a longer wavelength than the selected wavelength utilized in step d) and which is capable to induce photopolymerisation of any remaining polymerisable compounds that were not polymerised in step d).
Suitable ranges of the second wavelength are preferably from 300 to 450 nm, for example 305 nm or more, 320 nm or more, 340 nm or more, 376 nm more, 400 nm or more, or even 435 nm or more. More preferably, the utilized wavelength is mandatorily longer than in the first curing step d.
Suitable and preferred exposure times are in the range from 30 minutes to 150 minutes, preferably from 60 minutes to 130 minutes.
Suitable and preferred radiation intensities are in the range from 0.1 to 30 mW/cm2, preferably from 0.1 to 20 mW/cm2, more preferably from 0.1 to 10 mW/cm2.
During polymerisation optionally a voltage, preferably an AC voltage, is applied to the electrodes of the light modulation element, more preferably no voltage is applied. If a voltage is applied the preferred voltages are in the range from 1 to 30 V, preferably from 5 to 20 V. Preferably, the AC frequencies are in the range from 200 Hz to 20 kHz.
The functional principle of the device according to the invention will be explained in detail below. It is noted that no restriction of the scope of the claimed invention, which is not present in the claims, is to be derived from the comments on the assumed way of functioning.
Starting from the ULH texture, the cholesteric liquid-crystalline medium can be subjected to flexoelectric switching by application of an electric field between the driving electrode structures and common electrode structure, which are directly provided on the substrates. This causes rotation of the optic axis of the material in the plane of the cell substrates, which leads to a change in transmission when placing the material between crossed polarizers. The flexoelectric switching of inventive materials is further described in detail in the introduction above and in the examples.
The homeotropic “off state” of the light modulation element in accordance with the present invention provides excellent optical extinction and therefore a favourable contrast.
The required applied electric field strength is mainly dependent on two parameters. One is the electric field strength across the common electrode structure and driving electrode structure, the other is the Ac of the host mixture. The applied electric field strengths are typically lower than approximately 10 V/μm−1, preferably lower than approximately 8 V/μm−1 and more preferably lower than approximately 6 V/μm−1. Correspondingly, the applied driving voltage of the light modulation element according to the present invention is preferably lower than approximately 30 V, more preferably lower than approximately 24 V, and even more preferably lower than approximately 18 V.
The light modulation element according to the present invention can be operated with a conventional driving waveform as commonly known by the expert.
The light modulation element of the present invention can be used in various types of optical and electro-optical devices.
Said optical and electro optical devices include, without limitation electro-optical displays, liquid crystal displays (LCDs), non-linear optic (NLO) devices, and optical information storage devices.
Preferably the optical or electro-optical device comprises at least one electric circuit, which is capable of driving the driving electrode in combination with the common electrode of the light modulation element in order to drive the light modulation element.
More preferably, the optical or electro-optical device comprises an additional electric circuit, which is capable of driving the alignment electrode in combination with the driving electrode of the light modulation in order to align the cholesteric liquid crystalline medium in the ULH texture.
In particular, the optical or electro-optical device comprises at least one electric circuit, which is capable of driving the light modulation element with the alignment electrode in combination with the common electrode and which is additionally capable of driving the light modulation element with the driving electrode in combination with the common electrode.
The functional principle of the optical or electro-optical device including the alignment procedure and the driving procedure will be explained in detail below and with respect to
In accordance with the present invention the common electrode structure and the “FFS-type” structured substrate array of the light modulation element, which includes the alignment and driving electrode structure, which are each connected to a switching element, such as a thin film transistor (TFT) or thin film diode (TFD).
Preferably, the driving electrode structure is electrically connected to the drain of a first TFT (TFT1) and the alignment electrode structure is electrically connected to the drain of a second TFT (TFT2), as it is depicted in
Preferably, the source of the first TFT (TFT1) is electrically connected to a data line, and the source of the second TFT (TFT2) is electrically connected to a so called common electrode, as it is depicted in
In order to align the cholesteric liquid crystalline medium of the light modulation element of the present invention in the ULH texture, a high voltage (Vgh: 10V to 100V) is applied to the gate line in the electric circuit to turn on both TFT1 and TFT2. Consequently, the voltage of the driving electrode (Vp: 0V to 70V) is equal to the voltage of the data line (Vd) and the voltage of the alignment electrode (Va) is equal to that of the common electrode (Vc: 0V to 40V). Because of the voltage differences between the driving electrode and alignment electrode the electric field aligns the cholesteric liquid crystalline medium of the light modulation element of the present invention in the ULH texture as described before.
In order to drive the light modulation element according to the present invention, a high voltage (Vgh: 10V to 100V) is applied to the gate line in the electric circuit in a very short time to turn on both TFT1 and TFT2 for charging the respective capacitances CLC, CST and CC. The change to low voltage (Vgl: −20V to 10V) turns both TFT1 and TFT2 off. Consequently, the voltage of the driving electrode (Vp) is almost the same as the voltage of the data line (Vd) because the capacitors are fully charged. The voltage of the alignment electrode (Va) is defined as:
Va=(Vp−Vc)*CC/(CLC+CST)
With large Cc, the voltage of the alignment electrode (Va) is very close to voltage of the driving electrode (Vp). So the driving electrode and alignment electrode both can drive the light modulation element according to the present invention.
According to
In order to align the cholesteric liquid crystalline medium of the light modulation element of the present invention in the ULH texture, the voltage of the alignment electrode (Va: 0V to 70V) and the common electrode (Vc: 0V to 40V) are applied separately. Because of the voltage differences between the common electrode and alignment electrode, the electric field aligns the cholesteric liquid crystalline medium of the light modulation element of the present invention in the ULH texture as described before.
In order to drive the light modulation element according to the present invention, a high voltage (Vgh: 10V to 100V) is applied to the gate line in the electric circuit in a very short time to turn on TFT charging the respective capacitances CLC, CST. The change to low voltage (Vgl: −20V to 10V) turns both TFT1 and TFT2 off. Consequently, the voltage of the driving electrode (Vp) is almost the same as the voltage of the data line (Vd) because the capacitors are fully charged. The voltage of the alignment electrode (Va) is electrically connect with common electrode (Vc)
Va=Vc
So the driving electrode can drive the light modulation element according to the present invention.
Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.
The parameter ranges indicated in this application all include the limit values including the maximum permissible errors as known by the expert. The different upper and lower limit values indicated for various ranges of properties in combination with one another give rise to additional preferred ranges.
Throughout this application, the following conditions and definitions apply, unless expressly stated otherwise. All concentrations are quoted in percent by weight and relate to the respective mixture as a whole, all temperatures are quoted in degrees Celsius and all temperature differences are quoted in differential degrees. All physical properties are determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany, and are quoted for a temperature of 20° C., unless expressly stated otherwise. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δ∈) is determined at a frequency of 1 kHz or if explicitly stated at a frequency 19 GHz. The threshold voltages, as well as all other electro-optical properties, are determined using test cells produced at Merck KGaA, Germany. The test cells for the determination of Δ∈ have a cell thickness of approximately 20 μm. The electrode is a circular ITO electrode having an area of 1.13 cm2 and a guard ring. The orientation layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic orientation (∈∥) and polyimide AL-1054 from Japan Synthetic Rubber, Japan, for homogeneous orientation (∈⊥). The capacitances are determined using a Solatron 1260 frequency response analyser using a sine wave with a voltage of 0.3 Vrms. The light used in the electro-optical measurements is white light. A set-up using a commercially available DMS instrument from Autronic-Melchers, Germany, is used here.
Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and are not intended to (and do not) exclude other components. On the other hand, the word “comprise” also encompasses the term “consisting of” but is not limited to it.
It will be appreciated that many of the features described above, particularly of the preferred embodiments, are inventive in their own right and not just as part of an embodiment of the present invention. Independent protection may be sought for these features in addition to, or alternative to any invention presently claimed.
Throughout the present application it is to be understood that the angles of the bonds at a C atom being bound to three adjacent atoms, e.g. in a C═C or C═O double bond or e.g. in a benzene ring, are 120° and that the angles of the bonds at a C atom being bound to two adjacent atoms, e.g. in a C≡C or in a C≡N triple bond or in an allylic position C═C═C are 180°, unless these angles are otherwise restricted, e.g. like being part of small rings, like 3-, 5- or 5-atomic rings, notwithstanding that in some instances in some structural formulae these angles are not represented exactly.
It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention. Alternative features serving the same, equivalent or similar purpose may replace each feature disclosed in this specification, unless stated otherwise. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
For the present invention,
denote trans-1,4-cyclohexylene, and
denote 1,4-phenylene.
The following abbreviations are used to illustrate the liquid crystalline phase behavior of the compounds: K=crystalline; N=nematic; N2=second nematic; S=smectic; Ch=cholesteric; I=isotropic; Tg=glass transition. The numbers between the symbols indicate the phase transition temperatures in ° C.
In the present application and especially in the following examples, the structures of the liquid crystal compounds are represented by abbreviations, which are also called “acronyms”. The transformation of the abbreviations into the corresponding structures is straightforward according to the following three tables A to C.
All groups CnH2n+1, CmH2m+1, and ClH2l+1 are preferably straight chain alkyl groups with n, m and l C-atoms, respectively, all groups CnH2n, CmH2m and ClH2l are preferably (CH2)n, (CH2)m and (CH2)l, respectively and —CH═CH— preferably is trans- respectively E vinylene.
Table A lists the symbols used for the ring elements, table B those for the linking groups and table C those for the symbols for the left hand and the right hand end groups of the molecules.
Table D lists exemplary molecular structures together with their respective codes.
wherein n and m each are integers and three points “ . . . ” indicate a space for other symbols of this table.
Preferably, the liquid crystalline media according to the present invention comprise one or more compounds selected from the group of compounds of the formulae of the following table.
The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight and particularly preferably 1 ppm to 3% by weight, of stabilisers. The LC media preferably comprise one or more stabilisers selected from the group consisting of compounds from Table E.
The LC media in accordance with the present invention preferably comprise one or more reactive mesogens selected from the group consisting of compounds from Table F.
The following liquid crystalline host mixture (M1) is prepared.
The clearing point of mixture M1 is 97° C.
The following liquid crystalline host mixture (M2) is prepared.
The clearing point of mixture M2 is 73° C.
The following reactive mesogenic compounds are utilized for the working examples of the present application:
A fully ITO coated substrate (40 nm ITO electrode, 600 nm SiNx dielectric layer) a polyimide solution (AL-3046, JSR Corporation) is spin coated and then dried for 90 min in an oven at 180° C. The approx. 50 nm thick orientation layer is rubbed with a rayon cloth. A fully ITO coated substrate is also coated with AL-3046 (2nd substrate array), the surface of the PI is rubbed and the two substrate arrays are assembled by using a UV curable adhesive (loaded with 3 μm spacer) to align both rubbing directions in anti-parallel condition. From the assembled substrate array pair, the single cells are cut out by scribing the glass surface with a glass scribing wheel. The resulting test cell is then filled with the corresponding mixture by capillary action.
When no electric field is applied, the cholesteric liquid crystalline medium exhibits Grandjean texture due to planar anchoring conditions imposed by the anti-parallel rubbed polyimide alignment layers.
99.7% w/w host M-1 and 0.3% w/w of RM-33 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (105° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 95° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 600 s while an applying electrode field (14V, 600 Hz square waveform). The cell is cooled down from 95° C. (cooling rate 3° C./min) to 80° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 80° C. (cooling rate 20° C./min) to 35° C. while an applying electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 2).
99.2% w/w host M-1 and 0.8% w/w of RM-33 are mixed and the resulting mixture is introduced into a test cell as described above and then treated as given in Example 1.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 2).
98.0% w/w host M-1 and 2.0% w/w of RM-33 are mixed and the resulting mixture is introduced into a test cell as described above and then treated as given in Example 1.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 2).
98.0% w/w host M-1 and 2.0% w/w of RM-33 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (105° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 95° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 7800 s while applying an electrode field (14V, 600 Hz square waveform). The cell is cooled down from 95° C. (cooling rate 3° C./min) to 80° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 80° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage).
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 2).
Heating the sample up to 105° C.—keeping the temperature for 1 min.—cooling down to 35° C. without electric field, (cooling rate: 20° C./min.)
Heating the sample up to 105° C.—keeping the temperature for 1 min.—cooling down to 35° C. while applying an electric field.
99.7% w/w host M-1 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above and then treated as given in Example 1.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 3).
99.4% w/w host M-1 and 0.6% w/w of RM-41 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (105° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 95° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 2 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). The cell is cooled down from 95° C. (cooling rate 3° C./min) to 80° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 80° C. (cooling rate 20° C./min) to 35° C. with an applied electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 3).
99.7% w/w host M-1 and 0.3% w/w of RM-39 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (105° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 95° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 0.5 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 95° C. (cooling rate 3° C./min) to 80° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 80° C. (cooling rate 20° C./min) to 35° C. with an applied electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 3).
Heating the sample up to 105° C.—keeping the temperature for 1 min.—cooling down to 35° C. without electric field, (cooling rate: 20° C./min.)
Heating the sample up to 105° C.—keeping the temperature for 1 min.—cooling down to 35° C. (while applying an electric field.
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 4).
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 15 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 60° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 4).
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 40 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s. The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 4).
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 48 mW/cm2 for 50 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp)) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 4).
Heating the sample up to 85° C.—keeping the temperature for 1 min.—cooling down to 35° C. without electric field, (cooling rate: 20° C./min.)
Heating the sample up to 85° C.—keeping the temperature for 1 min.—cooling down to 35° C. (while applying an electric field.
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 5).
99.7% w/w host M-2 and 0.3% w/w of RM-1 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 7800 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage).
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 5).
99.7% w/w host M-2 and 2.0% w/w of RM-33 are mixed and the resulting mixture is introduced into a test cell as described above.
The cell is heated to the isotropic phase of the cholesteric liquid crystal medium (85° C.) and kept at that temperature for 1 min. While applying an electrode field (14 V, 600 Hz square wave driving) the cholesteric liquid crystal medium is cooled down from isotropic phase to 65° C. (cooling rate 3° C./min) to give a ULH Alignment. The cell is then exposed to UV light (Dymax 41014; Bluewave 200 ver. 3.0 (Mercuric UV lamp) with 320 nm filter) with 4 mW/cm2 for 600 s while applying an electrode field (14V, 600 Hz square waveform). Then the cell is cooled down from 65° C. (cooling rate 3° C./min) to 60° C. while applying an electrode field (12V, 600 Hz square wave driving). Again, the cell is cooled down from 60° C. (cooling rate 20° C./min) to 35° C. while applying an electrode field (keep waveform is saturated by adjusting frequency and voltage). The cell is then exposed to UV light (Toshiba, C type, Green UV; (fluorescent lamp) with 4 mW/cm2 for 7200 s.
The resulting PS-ULH texture is then tested in view of its stability after a thermal treatment and a driving treatment (cf. Table 5).
Heating the sample up to 85° C.—keeping the temperature for 1 min.—cooling down to 35° C. without electric field, (cooling rate: 20° C./min.)
Heating the sample up to 85° C.—keeping the temperature for 1 min.—cooling down to 35° C. while applying an electric field.
Each cell is driven by a square wave electric field of 80 Hz and 10 Volt.
The optical response follows the polarity of the field and shows ULH flexoelectric-optic switching through crossed polarizers.
The mixture M-2 shows a typical waveform for the optical response, while having a response time (Ton) of 2.4 ms.
The typical waveform for the optical response is also observed for the mixture M-2 comprising RM-1 (example 8) after curing. However, the response time (Ton) is 2.2 ms.
When the PS-ULH texture is stabilized by 2.0% RM-33, the optical response curve shows a significant waveform distortion and exhibits also a significant longer response time (Ton) (9.3 ms).
| Number | Date | Country | Kind |
|---|---|---|---|
| 15000198.0 | Jan 2015 | EP | regional |
| 15001978.4 | Jul 2015 | EP | regional |
| 15001979.2 | Jul 2015 | EP | regional |
| 15001980.0 | Jul 2015 | EP | regional |
| 15001981.8 | Jul 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/000006 | 1/5/2016 | WO | 00 |
