Patent Application
20180237696
This invention provides a material combination consisting of a biphasic system comprising a liquid crystal material in combination with a second immiscible fluid, optical elements containing said material combination, able to be transformed into components useful in various optical applications including lenses where the focal length can be controlled using an electric field. Furthermore, the invention relates to the use of such lenses for display devices operable in a 2D mode or a 3D mode, optical shutters, beamsteerers, diffraction gratings, or electronic paper displays.
Adaptive optical components such as e.g. variable focus lenses are commonly used in optical systems. Here, the focal length is adjusted by mechanical actuation of lens sets using motors or piezoelectric actuators. Mechanical tuning suffers from higher power consumption and miniaturization difficulties when it is used for portable applications that require small dimensions. To overcome the problems associated with mechanical focus systems alternative variable lenses were developed such as gradient-index-changed lenses [cf. T. Nose, S. Masuda and S. Sato, “A liquid crystal microlens with hole-patterned electrodes on both substrates,” Jpn. J. Appl. Phys. 31, 1643 (1992); Y. Choi, J.-H. Park, J.-H Kim. and S.-D. Lee, “Fabrication of a focal length variable microlens array based on a nematic liquid crystal,” Optical Mater. 21, 643 (2003); H Ren, Y H Fan and S T Wu, “Liquid-crystal microlens arrays using patterned polymer networks,” Opt. Lett. 29, 1608 (2004)]. The gradient-index-changed lens adjusts its focal length by electrically redistributing individual liquid crystal molecules within the lens where the liquid crystal molecules are sealed in between two Indium Tin Oxide (ITO) glasses.
Tunable optofluidic devices, as opposed to solid state photonic devices, are based on optical interfaces made of liquids. Because of the properties of the liquid phase, devices based on this technology have the advantage of e.g. fast adaptable optical output and robustness and many technical applications of this technology have been developed such as adaptive-focus lenses, beam steerers, gratings, irises, optical switches and displays. An example are shape-changed lenses [e.g. B. Berge and J. Peseux, “Variable focal lens controlled by an external voltage: An application of electrowetting,” Eur. Phys. J. E 3, 159 (2000); S. Kwon and L. P. Lee, “Focal length control by microfabricated planar electrodes-based liquid lens (PELL),” Transducers Eurosensors, Germany, 10-14 June, (2001); N. Chronis, G. L. Liu, K-H Jeong and L. P. Lee, “Tunable liquid-filled microlens array integrated with microfluidic network,” Opt. Express 11, 2370 (2003); M. Agarwal, R. A. Gunasekaran, P. Coane and K. Varahramyan, “Polymer-based variable focal length microlens system,” J. Micromech. Microeng. 14, 1665 (2004)].
In order to be able to manipulate the optical interface, various techniques have been applied, e.g. electrowetting or dielectrophoresis.
The shape-changed lens, also known as liquid lens, adjusts its focal length by electrically transforming the surface profile of a liquid droplet. The surface profile that depends on the contact angle of the droplet can be changed by the electrowetting effect. Salt is commonly added to water in order to increase water conductivity for the electrowetting mechanism and to widen operation temperature of water. Electrolysis, Joule heating, microbubbles and evaporation were also found to hinder optical performance and operation conditions of the water-based liquid lens. [F. Mugele and J-C Baret, “Electrowetting: from basics to applications,” J. Phys.: Condens. Matter 17, R705 (2005)]. The electrolysis of the salty water could be minimized based on the “electrowetting on dielectric technique” that places an insulating layer on the electrodes. The insulating layer reduces the Joule heating effect and the microbubbles; however, it leads to higher operation voltages [E. Seyrat and R. A. Hayes, “Amorphous fluoropolymers as insulators for reversible low-voltage electrowetting”, J. Appl. Phys. 90, 1383 (2001)]. Further, high saturated vapor pressure of the salty water (i.e. 5 torr) requires expensive hermetic packaging (i.e. typically metal-glass package) to seal the water inside the lens for long term operation. The use of the electrowetting effect to form a microlens array using water has been described in e.g. “High speed adaptive liquid microlens array”, C. U. Murade, D. van der Ende, and F. Mugele; Optics Express, Vol. 20, No. 16, 18180, (2012). G. McHale, C. V. Brown, M. I. Newton, G. G. Wells, and N. Sampara; Phys. Rev. Lett. 107, 186101 (2011) described that liquid dielectrophoresis induced by non-uniform electric fields can be used to enhance and control the wetting of dielectric liquids on substrates containing in-plane electrodes. This enables the modification of size and shape of the surface of a liquid without the above mentioned disadvantages of electrowetting. The term dielectrowetting is utilized when the underlying wetting effect is driven by dielectrophoresis. This can occur when non-uniform electric fields and electrically insulating fluids are used.
A particular class of materials that have been demonstrated to be suitable for dielectrophoresis is nematic liquid crystals. Liquid crystals can be considered as insulating dielectric fluids when the molecules have non-zero dielectric anisotropy. C.-C. Cheng, C. A. Chang and J. A. Yeh, Opt. Exp. 14(9), 4101 (2006), describe the use of liquid crystals to make active lenses that exploit the dielectrophoresis effect by altering the shape of a droplet of a LC mixture on a substrate containing a concentric ITO electrode pattern. However, the commercially available materials used here have permittivities comparable to common solvents.
The spreading of liquids using this dielectrowetting effect has also been described in e.g. C. V. Brown, G. G. Wells, M. I. Newton and G. McHale, Nature Photonics 3(7), 403 (2009). This paper further describes the case where thin films can be induced to wrinkle (when further dielectrowetting is not possible). This effect is known as “forced wrinkling” and the peak of the wrinkle is between the electrodes and the trough is coincident with the electrode.
Similar approaches of making active lenses have been disclosed in e.g. WO 2006/046185 and U.S. Pat. No. 7,483,218. However in both cases, the effect is based on electrophoresis rather than dielectrophoresis.
In C. V. Brown, G. G. Wells, M. I. Newton and G. McHale, Nature Photonics 3(7) 403 (2009), forced wrinkling was applied to an oil air interface to give cylindrical lenses. Such liquid based devices are restricted in their orientation of operation by gravity. However, it is possible that the surface wrinkle could be produced at the interface between two immiscible liquids, e.g. oil-water, in an encapsulated device, as described in GB 2422680. This type of approach is used in the Varioptic variable focus liquid lens to produce devices which can be used in any orientation and which are robust to shock and mechanical vibrations [Berge, B. & Peseux, J. Variable focal lens controlled by an external voltage: An application of electrowetting. Eur. Phys. J. E3, 159-163 (2000)].
The disadvantage of this approach is that there is a smaller difference between the refractive indices of oil and water relative to the large difference between the refractive indices of oil and air. Therefore, to produce the maximum diffraction efficiency (e.g. to reach the minimum in the transmission of the zero order undeviated beam) the wrinkle amplitude at the interface between two fluids would need to be several times larger than the amplitude that would be required at the oil-air interface. To compensate for the loss of difference in refractive index by replacing air with a fluid medium, new material combinations are required being susceptible to low operating voltage and at the same time having high dielectric constant, low surface tension, low viscosity, suitable refractive indices and also good thermal and chemical stability especially when exposed to irradiation, in order to enable robust devices with good optical performance and high mechanical stability.
Liquid crystal mixtures with high permittivity are known to the person skilled in the art for liquid crystal displays utilising polymer stabilised blue phase liquid crystals. In WO 2012/163470 and WO 2013/156113 such blue phase liquid crystal mixtures are disclose comprising a basic host material with high permittivity to be used in combination with a chiral dopant with high helical twisting power, necessary to achieve the blue phase, and polymerisable compounds to stabilise the blue phase. For the basic host material itself without additives, no application is described so far.
Perfluorinated hydrocarbons, (poly)ethers and amines are known to be immiscible with common organic chemicals and various applications are described, such as fluorous phase chemistry in chemical synthesis using perfluorinated hydrocarbons (I. T. Horvat (Ed.), Topics Curr. Chem. Vol. 308, Springer Verlag Berlin, Heidelberg, 2012), for medical purposes, e.g. burn treatment (WO 81/00002) or synthetic blood (U.S. Pat. No. 405,798). Further, e.g. fluorosilicone oils are used for example as antifoam (U.S. Pat. No. 5,454,979) and fluorinated polyethers are an important class of lubricating oils (e.g. EP 1 681 339 A2).
Surprisingly it was found that a liquid crystal medium with high permittivity in combination with a second perfluorinated fluid that is immiscible with said liquid crystal medium is suitable to meet the above mentioned requirements for the production of optical components for the use as adaptable lenses. Such LC-medium exhibits a high permittivity, low viscosity, a good thermal and light stability. Suitable second media exhibit low viscosities, low miscibility with the LC-media and sufficiently different refractive indices from said LC-media.
The present invention relates to a material combination containing
The present invention further relates to an optical component for generating spatially varying interfacial refraction of waves of light by means of dielectrophoresis, comprising:
As used herein, “fluid” refers to a continuous, amorphous substance whose molecules move freely past one another. A fluid may be a gas, liquefied gas, liquid or liquid under pressure or flowable particulate matter.
As used herein, “fluid enclosure” may refer to a device for physically storing a fluid.
In a preferred embodiment, the second fluid comprises one or more substantially fluorinated or perfluorinated compounds. Preferably, the second fluid entirely consists of substantially fluorinated or perfluorinated compounds, particularly preferably it consists entirely of perfluorinated compounds.
Perfluorinated means that substantially all the hydrogen atoms of the carbon materials have been replaced by fluorine atoms. While the perfluorinated materials are preferred, carbon materials which are substantially fluorinated can also be used in this invention. “Substantially fluorinated” indicates that most of the hydrogen atoms have been replaced by fluorine atoms, and that further replacement does not substantially decrease the miscibility with non-fluorinated materials or partially fluorinated materials. It is believed that this level is reached when about 50% of the hydrogen atoms have been replaced by fluorine atoms. Also certain of the fluorine atoms of foregoing materials may be substituted by other halogen atoms such as chlorine.
As indicated, perfluorinated means that substantially all the hydrogen atoms of the carbon material have been replaced by fluoride atoms. It is conceivable in the manufacture of such compounds that minor amounts of substantially fluorinated derivatives may be mixed with completely fluorinated compounds. This is permissible provided that the lack of complete replacement of all hydrogens does not affect the essential characteristics of the liquid perfluorocarbons of this invention. It is preferred that at least 95% of the hydrogen atoms have—been replaced, more preferably at least 98% and even more preferably 100%.
Among the perfluorocarbon compounds that may be employed are perfluorodecalin (PP5), perfluoro-1-methyldecaline, perfluoro-n-undecane, perfluorododecane, perfluoro-n-octylcyclohexane, perfluoro-p-diisopropylcyclohexane, perfluoroisopropylcyclohexane, perfluoro-n-butylcyclohexane perfluoro-m-diisopropylcyclohexane, perfluoro-1,2-dimethylcyclohexane, perfluorotrimethylcyclohexane, perfluorotetramethylcyclohexane, perfluoro-1-methyl-4-isopropylcyclohexane, perfluoro-1-methyl-4-t-butylcyclohexane, perfluoropentadecane, perfluoro(methylcyclopentane), perfluorohexane, perfluoroheptane, perfluorokerosene, perfluorotetradecahydrophenanthrene, perfluorododecahydrofluorene, perfluorobicyclo[4.3.0]nonane, perfluoro-endo-tetrahydrodicyclopentadiene, perfluoroadamantane, perfluoro-ethyladamantane, perfluoro-methyladamantane, perfluoro-ethylmethyladamantane, perfluoro-ethyldimethyladamantane, perfluoro-triethyladamantane, perfluoro-trimethyldiadamantane, perfluoro-methyldiadamantane, perfluoro-1,3,5,7-tetramethyladamantane, perfluoro-1,3-dimethyladamantane, perfluoro-tetrahydrodicyclopentadiene, perfluoro-methylbicyclo[2.2.2]octane, perfluoro-dimethylbicyclo[2.2.2]octane, perfluoro-pinane, perfluoro-camphane, perfluoro-1,4,6,9-dimethanodecaline, perfluoro-bicyclo[4.3.2]undecane, perfluoro-bicyclo[5.3.0]decane, perfluoro-exo-tetrahydrodicyclopentadiene, perfluorobicyclo[5.3.0]decane, perfluorodimethylbicyclo[3.3.1.]nonane, perfluoro-2,6-dimethylbicyclo[3.3.1]nonane, perfluoro-3-methylbicyclo[3.3.1]nonane, perfluorodecahydroacenaphthene, perfluorotrimethyl-bicyclo[3.3.1.]nonane, perfluoro-7-methyl bicyclo[4.3.0.]nonane, perfluor-n-octylbromid, perfluorotributylamine (FC47), perfluoro-N,N-dialkylcyclohexylamine, perfluoroalkylmorpholine, perfluoroalkylpiperidine, perfluorotetrahydrofuran (FC80), perfluoro-2-butyltetrahydrofuran, perfluoroether (PID) [(CF3)2CFOCF2(CF2)2CF2OCF(CF3)2], perfluoroether (PIID) [(CF3)2CFOCF2(CF2)6CF2OCF(CF3)2], perfluoropolymer (E3) [CF3CHF(OCF2C(CF3)F)2OCF2CF2CF3], perfluoropolymer (E4) [CF3CHF(OCF2C(CF3)F)3OCF2CF2CF3], perfluoroetherpolymer (Fomblin Y), fluorosilicone oil
(CH3)3SiO—Si(CH3)(CH2CH2Rf)nOSi(CH3)3
where Rf is CnF2n+1, n being an integer from 1 to 4, p is an integer such that the average viscosity at room temperature ranges from 50 to 10000cS, preferably from 50 to 100, marketed by Dow Corning as FS® 1265 when Rf is CF3.
The perfluorocarbons and any derivatives thereof may be generally termed as “liquids”. The term “liquids”, as used herein, is a comprehensive designation incorporating compounds that are in a state neither solid nor gaseous such as liquids, emulsions and gels. The term “perfluorocarbon” means a “cyclic” or “acyclic” compound of carbon. Whereas the term “substituted derivatives thereof” characterizes substituted perfluorocarbons with chemical elements within their structures such as oxygen, nitrogen, chlorine and bromine
It is to be understood that perfluorocarbon liquids of this invention may be formed of “neat” perfluorocarbon liquids, emulsions, suspensions or solutions of perfluorocarbons in mixture with themselves or other solvents. While some of the foregoing compounds are solid at ambient temperature they are soluble in ones which are liquid at ambient temperature and such a mixture could be used. For instance, perfluoro-1,3-dimethyl adamantane is normally a solid but in mixture with perfluorotrimethyl-bicyclo[3.3.1.]nonane a liquid is formed, i.e., DAWN.
The useful substantially fluorinated or perfluorinated materials are those which are generally liquids at temperatures and pressures, including ambient temperatures and pressures. Perfluorinated C8 or lower materials and up to C18 or higher materials can be used in this invention. Mixtures of various different perfluorinated materials can also be used.
The above perfluorocarbons can be synthesized by well known chemical or electrochemical processes. The preferred perfluorinated materials are either commercially available or can be prepared following methods described in the following U.S. Pat. Nos. 4,105,798; 3,911,138 and 3,962,439 or Houben-Weyl, Methods in Organic Chemistry, Volume E10—Organo-Fluorine Compounds, Volumes 1-5 (4th Edition).
In a preferred embodiment of the present invention the first fluid comprises a liquid crystal medium comprising one or more mesogenic compounds of formula I,
In a preferred embodiment of the present invention the LC medium comprises one more compounds of formula I-1,
wherein
A12, L11 to L15, R11 X11 and and Z11 have one of the meanings as indicated above in formula I.
Compounds I-1 are preferably selected from the group of compounds of its sub-formulae I-1-1 and I-1-2, preferably of formula I-1-2,
wherein R11 has the meaning given under formula I above and preferably is n-alkyl, most preferably ethyl, n-propyl, n-butyl, n-pentyl, or n-hexyl.
In a preferred embodiment of the present invention, the LC medium comprises one or more compounds of formula I-2
wherein
A11, L11 to L14, R11, X11 and Z11 have the meaning as indicated above in formula I.
In a preferred embodiment of the present invention, the LC medium comprises one more compounds of formula I-2 selected from the group of compounds of formulae I-2-1 to I-2-5
wherein the parameters have one of the meanings as indicated under formula I.
In a preferred embodiment of the present invention the compounds of formula I-2-1 to I-2-5 are preferably selected from the group of compounds of the sub-formulae I-2-1a to I-2-1c, I-2-2a to I-2-2f, I-2-3a to I-2-3c, I-2-4a to I-2-4f and I-2-5a to I-2-5f, more preferably from the group of compounds of formula I-2-2c, I-2-3c or I-2-2f,
wherein R11 has one of the meanings as indicated above in formula II and preferably is n-alkyl, most preferably ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl.
In a preferred embodiment of the present invention, the LC medium comprises one or more compounds of formula I-3,
wherein A11, L11 to L16, R11, X11 and Z11 have the meanings as defined in formula I above.
The compounds of formula I-3 are preferably selected from
wherein L11 to L14, R11 and X11 have one of the meanings indicated in formula I above.
In a further preferred embodiment of the present invention the compounds of formulae I-3-1, I-3-2 and I-3-3 are selected from the sub-formulae I-3-1a to I-3-1f, I-3-2a to I-3-2c and I-3-3a to I-3-3f
In a preferred embodiment of the present invention, the LC medium comprises one or more compounds of formula I-4,
wherein
In a further preferred embodiment the compounds of formula I-4 are preferably selected from compounds of formulae I-4-1 or I-4-2 or a combination thereof.
wherein the parameters R11, L11 to L13 and X11 have one of corresponding meanings given above in formula I.
Compounds of formula I-4-1 and I-4-2 are preferably selected from the group of compounds of the following sub-formulae
wherein R11 has the meaning given under formula I above and preferably is n-alkyl, most preferably ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl.
In a preferred embodiment of the present invention the LC-medium comprises one more compounds of formula II
In a preferred embodiment of the present invention the mesogenic media comprise one more compounds of formula II-1 or II-2 or a combination thereof.
Compounds of formula II-1 are preferably selected from the group of compounds of its sub-formulae II-1-1a and II-1-1b.
wherein R21 has the meaning defined above in formula I and is preferably n-butyl or n-pentyl.
Compounds of formula II-2 are preferably selected from the group of compounds of its sub-formulae II-2-1 to II-2-8, preferably of formula II-2-1 to II-2-4, most preferably of formula II-2-3,
wherein R21 has the meaning given under formula II above and preferably is n-butyl or n-pentyl.
An alkyl or an alkoxy radical, i.e. an alkyl where the terminal CH2 group is replaced by —O—, in this application may be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. an alkyl group in which one non-terminal CH2 group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxy-methyl), 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.
An alkenyl group, i.e. an alkyl group wherein one or more CH2 groups are replaced by —CH═CH—, may be straight-chain or branched. It is preferably straight-chain, has 2 to 10 C atoms and accordingly is preferably vinyl, prop-1-, or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.
Especially preferred alkenyl groups are C2-C7-1 E-alkenyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-1 E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples for particularly preferred alkenyl groups are vinyl, 1 E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 C-atoms are generally preferred.
In an alkyl group, wherein one CH2 group is replaced by —O— and one by —CO—, these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group —CO—O— or an oxycarbonyl group —O—CO—. Preferably such an alkyl group is straight-chain and has 2 to 6 C atoms.
It is accordingly preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxy-ethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxy-carbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy-carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)-butyl.
An alkyl group wherein two or more CH2 groups are replaced by —O— and/or —COO—, it can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis-(ethoxycarbonyl)-hexyl.
A alkyl or alkenyl group that is monosubstituted by CN or CF3 is preferably straight-chain. The substitution by CN or CF3 can be in any desired position.
An alkyl or alkenyl group that is at least monosubstituted by halogen, it is preferably straight-chain. Halogen is preferably F or Cl, in case of multiple substitution preferably F. The resulting groups include also perfluorinated groups. In case of monosubstitution the F or Cl substituent can be in any desired position, but is preferably in w-position. Examples for especially preferred straight-chain groups with a terminal F substituent are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. Other positions of F are, however, not excluded.
Halogen means F, Cl, Br and I and is preferably F or Cl, most preferably F.
The compounds of formula I and II are accessible by the usual methods known to the expert. Starting materials are either commercially available or accessible by published methods.
Preferably the first fluid according to the instant invention comprises one or more compounds selected from the group of compounds of formulae I and II.
The concentration of the individual compounds in the first fluid according to the present invention are preferably in the range from 0.5% or more to 70% or less, more preferably in the range from 1% or more to 60% or less and most preferably in the range from 5% or more to 50% or less.
The first fluid comprises a mixture of one or more compounds selected from the group of compounds of formulae I and II, preferably in a total concentration in the range from 70% or more to 100.0% or less, preferably from 80% or more to 100.0% or less and most preferably from 90% or more to 100.0% or less.
In particular, the first fluid preferably comprises one or more compounds of formula I in a total concentration in the range from 40% or more to 100.0% or less, preferably from 60% or more to 90% or less and most preferably from 80% or more to 90% or less.
In case the first fluid comprises one or more compounds formula II, the total concentration of these compounds preferably is in the range from 1% or more to 30% or less, preferably from 5% or more to 25% or less and most preferably from 10% or more to 20% or less.
Preferred embodiments are indicated below:
The compounds of the formulae I and II are colourless, stable and readily miscible with one another and with other liquid-crystalline materials. The optimum mixing ratio of the compounds of the formulae I and II depends substantially on the desired properties, on the choice of the components of the formulae I or II, and on the choice of any other components that may be present. Suitable mixing ratios within the range given above can easily be determined from case to case.
The total amount of compounds of the formulae I and II in the first fluid is in many cases not crucial. The mixtures can therefore comprise one or more further mesogenic compounds for the purposes of optimisation of various properties. Such compounds are known to the person skilled in the art. However, the observed effect on the operating voltage and the operating temperature range is generally greater, the higher the total concentration of compounds of the formulae I and II.
In a particularly preferred embodiment, the media according to the invention comprise one or more compounds each of the formulae I and II. A favourable synergistic effect with the compounds of the formula I results in particularly advantageous properties. In particular, mixtures comprising compounds of formula I and of formula II are distinguished by their low operating voltages.
The individual compounds of the formulae I and II, which can be used in the media according to the invention, are either known or can be prepared analogously to the known compounds.
In another preferred embodiment the first fluid comprises one or more compounds selected from the group of compounds of formula I and/or II, and additionally non-mesogenic compounds.
Said non mesogenic compounds are used to adapt the properties of the first fluid according to the needs of the optical component and are preferably high boiling organic liquids, preferably selected from 3-phenoxytoluene, butoxybenzene, benzyl methyl ether, benzyl ethyl ether, benzyl propyl ether, benzyl butyl ether, 1,4-benzodioxane, dipropoxybenzene, 2,5-dimethoxytoluene, 4-ethylphenetole, 1,2,4-trimethoxybenzene, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, dibenzyl ether, 4-tert.-butylanisole, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,2-dimethyl-1,3-bonzodioxole, 1,8-cineole, 2,3-dihydro-2-methylbenzofuran, 2,3-dihydrobenzofuran, 3,5-dimethylanisole, 2,5-dimethylanisole, 4-ethylanisole, 1,2-methylenedioxybenzene.
Liquid means that the substance has a melting point below room temperature.
High boiling according to the present invention means that the boiling point of the liquid at normal pressure is above 150° C., preferably above 180° C., most preferably above 200° C.
In a preferred embodiment of the present invention the first fluid is a nematic liquid crystal.
In another preferred embodiment the first fluid is isotropic at room temperature.
Further it is preferred that the dielectric constant of the first fluid is 100 to 1000 or above, more preferably 200 to 500 or above.
The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more compounds of the formula I with one or more compounds of the formulae II or 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 invention furthermore relates to the process for the preparation of the LC media according to the invention.
In the present invention and especially in the following examples, the structures of the mesogenic compounds are indicated by means of abbreviations, also called acronyms. In these acronyms, the chemical formulae are abbreviated as follows using Tables A to C below. All groups CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n-1, CmH2m-1 and ClH2l-1 denote straight-chain alkyl or alkenyl, preferably 1 E-alkenyl, each having n, m and I C atoms respectively. Table A lists the codes used for the ring elements of the core structures of the compounds, while Table B shows the linking groups. Table C gives the meanings of the codes for the left-hand or right-hand end groups. The acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right-hand end group. Table D shows illustrative structures of compounds together with their respective abbreviations.
in which n and m each denote integers, and the three dots “ . . . ” are place-holders for other abbreviations from this table.
The following table shows illustrative structures together with their respective abbreviations. These are shown in order to illustrate the meaning of the rules for the abbreviations. They furthermore represent compounds which are preferably used.
GGP-n-F
GGP-n-CL
PGIGI-n-F
PGIGI-n-CL
GGP-n-T
PGU-n-T
GGU-n-T
DPGU-n-F
PPGU-n-F
DPGU-n-T
PPGU-n-T
PUQU-n-N
GUQU-n-N
GUQU-n-F
PUQGU-n-F
GUQGU-n-F
PUQGU-n-T
GUQGU-n-T
MGQU-n-F
MGQU-n-T
MGQU-n-N
MUQU-n-F
MUQU-n-T
MUQU-n-N
NGQU-n-F
NGQU-n-T
NGQU-n-N
NUQU-n-F
NUQU-n-T
NUQU-n-N
PZG-n-N
PZU-n-N
CPZG-n-N
DGUQU-n-F
DUUQU-n-F
DGUQU-n-T
DUUQU-n-T
DGUQU-n-N
DUUQU-n-N
DUQGU-n-F
DUQGU-n-T
DUQGU-n-N
in which n preferably, independently of one another, denotes an integer from 1 to 7, preferably from 2 to 6.
The following table, Table E, shows illustrative compounds which can be used as stabiliser in the mesogenic media according to the present invention.
In a preferred embodiment of the present invention, the mesogenic media comprise one or more compounds selected from the group of the compounds from Table E.
The following table, Table F, shows illustrative compounds which can preferably be used as chiral dopants in the mesogenic media according to the present invention.
C 15
CB 15
CM 21
CM 44
CM 45
CM 47
CC
CN
R/S-811
R/S-1011
R/S-2011
R/S-3011
R/S-4011
R/S-5011
In a preferred embodiment of the present invention, the liquid-crystal media comprise one or more compounds selected from the group of the compounds from Table F.
The mesogenic media according to the present application preferably comprise two or more, preferably four or more, compounds selected from the group consisting of the compounds from the above tables.
The liquid-crystal media according to the present invention preferably comprise
The substrates may be made from any suitable material which allows confinement of the fluid and is preferably an optically isotropic material (i.e. one which has no birefringence), such as glass.
The thickness of the substrate is preferably 0.1 mm-3 mm, more preferably 0.5 mm-2 mm and most preferably 1.0 mm-1.5 mm. The substrate is preferably transparent in the region of visible light.
The fluid enclosure has an internal volume to receive first and second fluids, preferably in the form of immiscible liquids arranged relative to each other in separate layers. The first fluid is a liquid crystal material, and the second fluid is a non-conductive liquid, preferably a substantially fluorinated liquid. In preferred embodiments, both the liquid crystal and second fluid are substantially transparent to light and each has a different refractive index being different from the other fluid when the liquid crystal is in the isotropic state and when the liquid crystal is birefringent at least one of the uniaxial refractive indices of the liquid crystal is different from the refractive index of the second fluid.
The first and second electrodes are preferably interdigitated electrodes which comprise at least one pair of comb-shaped electrodes being arranged so as to oppose each other with their teeth interleaved. The width of the electrodes is preferably 5-240 μm, more preferably 10-150 μm, most preferably 25-100 μm and can be the same for each electrode or different, preferably the same. The interelectrode gap is preferably 1-100 μm, more preferably 5-75 μm, most preferably 10-50 μm and can be the same for each gap or different, preferably the same.
Preferably, the interelectrode gap is smaller than the electrode linewidth by a factor in the range of 0.9 to 0.1, more preferably 0.25 to 0.75 and most preferably 0.4 to 0.6. The electrodes are preferably transparent and may be made from any suitable transparent conductive material, preferably indium tin oxide (ITO), indium zinc oxide (IZO), antimony tin oxide (ATO), RuO2 or PEDOT, most preferably ITO. The electrodes preferably have a resistance per square below 100 Ω/□.
In a preferred refinement of the present invention the electrodes are covered with a polymer layer (30) having high transparency, preferably a polyimide or Teflon®, to guard against charge injection from the electrodes (20, 21), or to promote wetting of the liquid crystal. Further, it can be preferred that said polymer layer is a liquid crystal orientation layer (rubbed polyimide) to promote preferred alignment of the liquid crystal.
Preferably the upper substrate (11) is untreated.
Further it can be preferred that the upper substrate is covered with a polymer layer (31) having high transparency, preferably a polyimide or Teflon®.
References herein to “transparent” are to be taken as meaning that the material or substance permits most, if not all, of the light incident on the material or substance to pass therethrough without significant attenuation. Moreover, all references to “light”, “incident light” and associated terms, are to be understood as referring to in particular, visible light, but may also include other radiations from other regions of the electromagnetic spectrum, e.g. ultra-violet and infra-red.
In all embodiments of the present invention the voltage applied can be either d.c. or a.c., preferably a.c.
As a result of the applied voltage, the interface between first fluid (40) and the second fluid (41) now has taken the shape of a periodic wave, thus forming a sequence of cylindrical lenses. Since the height of the wrinkles depends on the voltage the focal length of these cylindrical lenses can be controllably adjusted as a result of varying the voltage applied to the electrodes.
When the applied voltage between the first and second electrodes (20, 21) is lowered or reduced to zero the system reverts to the initial state shown in
The following abbreviations and symbols are used:
Unless explicitly noted otherwise, all concentrations in the present application are indicated in percent by weight and relate to the corresponding mixture as a whole without solvents.
Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are indicated in degrees Celsius (° C.). M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures.
All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Darmstadt, Germany, and apply to a temperature of 20° C., and Δn is determined at 589 nm and Δε at 1 kHz, unless explicitly indicated otherwise in each case.
The liquid-crystalline properties of the individual compounds are, unless indicated otherwise, determined in the nematic host mixture ZLI-4792 (commercially available from Merck KGaA, Darmstadt) at a concentration of 10%.
“Room temperature” means 20° C., unless indicated otherwise.
The examples below illustrate the present invention without limiting it in any way.
A liquid crystalline mixture M-1 is prepared as follows.
A liquid crystalline mixture M-2 is prepared as follows.
Table 1 summarises the properties of M-1 and M-2 in comparison with isotropic liquid TTE and commercially available liquid crystal E7.
From the materials shown in table 1, cylindrical lens elements were fabricated and characterised in the following manner.
Single fluid experiments were first performed to demonstrate the effect and to characterise the lens elements using a first fluid (40) without application of a second fluid (41). Single fluid experiments were performed with a borosilicate glass slide substrate. The substrate had been pre-coated with an approximately 25 nm thick layer of indium tin oxide of resistivity approximately 100 Ohm/square. This coating was provided commercially by Prazisions Glas and Optik GmbH, Iserlohn, Germany. Standard photolithographic procedures were used to etch and pattern the indium tin oxide layer to produce an array of co-planar interdigital stripe electrodes, (corresponding to 20, 21 in
From
Correspondingly, when using M-1 or M-2, the focal length can be shortened at relatively lower voltages, as shown in
The data shown in
An approx. 20 μm thick film of LC-mixture M-1 (Electrodes: linewidth 80 μm, gaps 40 μm) as the first fluid was covered with a layer of perfluorodecalin as the second fluid.
As can be seen from
| Number | Date | Country | Kind |
|---|---|---|---|
| 15002386.9 | Aug 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/001226 | 7/14/2016 | WO | 00 |
