Patent Grant
8277684
The invention relates to a liquid-crystalline medium of negative dielectric anisotropy based on a mixture of polar compounds, which comprises at least one compound selected from the group of the compounds of the formulae IA, IB and IC
in which
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and, if L=F, R2C may also denote halogen, preferably F or Cl,
Media of this type can be used, in particular, for electro-optical displays having active-matrix addressing based on the ECB effect and for IPS (in-plane switching) displays and FFS (fringe field switching) displays. The medium according to the invention preferably has negative dielectric anisotropy.
The principle of electrically controlled birefringence, the ECB effect or also DAP (deformation of aligned phases) effect, was described for the first time in 1971 (M. F. Schieckel and K. Fahrenschon, “Deformation of nematic liquid crystals with vertical orientation in electrical fields”, Appl. Phys. Lett. 19 (1971), 3912). This was followed by papers by J. F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).
The papers by J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3) and H. Schad (SID 82 Digest Techn. Papers (1982), 244) showed that liquid-crystalline phases must have high values for the ratio of the elastic constants K3/K1, high values for the optical anisotropy Δn and values for the dielectric anisotropy of Δ∈≦−0.5 in order to be suitable for use in high-information display elements based on the ECB effect. Electro-optical display elements based on the ECB effect have a homeotropic edge alignment (VA technology=vertically aligned). Dielectrically negative liquid-crystal media can also be used in displays which use the so-called IPS or FFS effect.
Displays which use the ECB effect, as so-called VAN (vertically aligned nematic) displays, for example in the MVA (multi-domain vertical alignment, for example: Yoshide, H. et al., paper 3.1: “MVA LCD for Notebook or Mobile PCs . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6 to 9, and Liu, C. T. et al., paper 15.1: “A 46-inch TFT-LCD HDTV Technology . . . ”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 750 to 753), PVA (patterned vertical alignment, for example: Kim, Sang Soo, paper 15.4: “Super PVA Sets New State-of-the-Art for LCD-TV”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 760 to 763), ASV (advanced super view, for example: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, paper 15.2: “Development of High Quality LCDTV”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757) modes, have established themselves as one of the three more recent types of liquid-crystal display that are currently the most important, in particular for television applications, besides IPS (inplane switching) displays (for example: Yeo, S. D., paper 15.3: “An LC Display for the TV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 & 759) and the long-known TN (twisted nematic) displays. The technologies are compared in general form, for example, in Souk, Jun, SID Seminar 2004, Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6/1 to M-6/26, and Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7/1 to M-7/32. Although the response times of modern ECB displays have already been significantly improved by addressing methods with overdrive, for example: Kim, Hyeon Kyeong et al., paper 9.1: “A 57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 106 to 109, the achievement of video-compatible response times, in particular on switching of grey shades, is still a problem which has not yet been satisfactorily solved.
Industrial application of this effect in electro-optical display elements requires LC phases, which have to satisfy a multiplicity of requirements. Particularly important here are chemical resistance to moisture, air and physical influences, such as heat, infrared, visible and ultraviolet radiation and direct and alternating electric fields.
Furthermore, industrially usable LC phases are required to have a liquid-crystalline mesophase in a suitable temperature range and low viscosity.
None of the hitherto-disclosed series of compounds having a liquid-crystalline mesophase includes a single compound which meets all these requirements. Mixtures of two to 25, preferably three to 18, compounds are therefore generally prepared in order to obtain substances which can be used as LC phases. However, it has not been possible to prepare optimum phases easily in this way since no liquid-crystal materials having significantly negative dielectric anisotropy and adequate long-term stability were hitherto available.
Matrix liquid-crystal displays (MLC displays) are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:
In the case of type 1, the electro-optical effect used is usually dynamic scattering or the guest-host effect. The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joints.
In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect.
A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on intensively worldwide.
The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.
The TFT displays disclosed hitherto usually operate as TN cells with crossed polarisers in transmission and are back-lit.
The term MLC displays here covers any matrix display with integrated non-linear elements, i.e. besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).
MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORI-MACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff., Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff., Paris]. With decreasing resistance, the contrast of an MLC display deteriorates. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the inside surfaces of the display, a high (initial) resistance is very important for displays that have to have acceptable resistance values over a long operating period.
The disadvantages of the MLC-TN displays disclosed hitherto are their comparatively low contrast, the relatively high viewing-angle dependence and the difficulty of producing grey shades in these displays.
There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times and a low threshold voltage with the aid of which various grey shades can be produced.
For television applications in particular, it is a very important to achieve short response times. In order to achieve this, the dielectrically neutral compounds used in ECB applications are, in particular, compounds of the formulae
In LCD television applications, reliability problems frequently occurs, such as, for example, image sticking, i.e. apparent “burning-in” of the image if the display has been addressed over an extended time.
This problem frequently only occurs after extended running times of the television sets. The cause is frequently regarded as being the long exposure time to the backlight at the same time as increased operating temperatures, which can result in still unexplained processes in the display, for example an interaction between alignment layer and a liquid-crystal mixture. On the part of the liquid-crystal mixture, the cause of the occurrence of image sticking is regarded as being the neutral alkenyl compounds frequently used.
The invention is based on the object of providing liquid-crystal mixtures, in particular for monitor and TV applications, which are based on the ECB effect or on the IPS or FFS effect, which do not have the above-mentioned disadvantages or only do so to a reduced extent. In particular, it must be ensured for monitors and televisions that they also operate at extremely high and extremely low temperatures and at the same time have short response times and at the same time have improved reliability behaviour, in particular have no or significantly reduced image sticking after long operating times.
Surprisingly, it has now been found that this object can be achieved if nematic liquid-crystal mixtures which comprise at least one compound from the group of the compounds of the formulae IA, IB and IC are used in these display elements.
The compounds of the formulae IA, IB and IC are distinguished by the fact that the double bond in the alkenyl side chain is not terminal.
Compounds of the formula IA are known, for example, from EP 0 168 683 B1 and EP 0 122 389 B1. The compounds of the formula IB are known, for example, from EP 0 969 071 B1. The compounds of the formula IC are known, for example, from EP 0 969 071 B1.
The invention thus relates to a liquid-crystalline medium based on a mixture of polar compounds which comprises at least one compound selected from the group of the compounds of the formulae IA, IB, IC.
The mixtures according to the invention preferably exhibit very broad nematic phase ranges with clearing points ≧60° C., preferably ≧65° C., in particular ≧70° C., very favourable values for the capacitive threshold, relatively high values for the holding ratio and at the same time very good low-temperature stabilities at −30° C. and −40° C. as well as very low rotational viscosities and short response times. The mixtures according to the invention are furthermore distinguished by the fact that, in addition to the improvement in the rotational viscosity γ1, an increase in the elastic constant K33 for improving the response times can be observed, and exhibit improved reliability behaviour.
Some preferred embodiments of the mixtures according to the invention are given below:
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
and/or
and/or
The compounds of the formula In and of the sub-formulae In-1 to In-16 are preferably employed in concentrations ≧5% by weight, in particular 5-30% by weight and very particularly preferably 5-25% by weight, in the mixtures according to the invention.
The invention furthermore relates to an electro-optical display having active-matrix addressing based on the ECB, IPS or FFS effect, characterised in that it contains, as dielectric, a liquid-crystalline medium according to one or more of Claims 1 to 9.
The liquid-crystalline medium according to the invention preferably has a nematic phase from ≦−20° C. to ≧70° C., particularly preferably from ≦−30° C. to ≧80° C., very particularly preferably from ≦−40° C. to ≧90° C.
The expression “have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that clearing still does not occur on heating from the nematic phase. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the electro-optical use for at least 100 hours. If the storage stability at a temperature of −20° C. in a corresponding test cell is 1000 h or more, the medium is referred to as stable at this temperature. At temperatures of −30° C. and −40° C., the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured by conventional methods in capillaries.
The liquid-crystal mixture preferably has a nematic phase range of at least 60 K and a flow viscosity ν20 of that most 30 mm2·s−1 at 20° C.
The values of the birefringence Δn in the liquid-crystal mixture are generally between 0.07 and 0.16, preferably between 0.08 and 0.12.
The liquid-crystal mixture according to the invention has a Δ∈ of about −0.5 to −8.0, in particular of −3.0 to −6.0, where Δ∈ denotes the dielectric anisotropy. The rotational viscosity γ1 at 20° C. is preferably <165 mPa·s, in particular <140 mPa·s.
The liquid-crystal media according to the invention have relatively low values for the threshold voltage (V0). They are preferably in the range from 1.7 V to 3.0 V, particularly preferably ≦2.75 V and very particularly preferably ≦2.4 V.
For the present invention, the term “threshold voltage” relates to the capacitive threshold (V0), also known as the Freedericksz threshold, unless explicitly indicated otherwise.
In addition, the liquid-crystal media according to the invention have high values for the voltage holding ratio, in particular after exposure to display backlights, in liquid-crystal cells.
In general, liquid-crystal media having a low addressing voltage or threshold voltage exhibit a lower voltage holding ratio than those having a greater addressing voltage or threshold voltage and vice versa.
For the present invention, the term “dielectrically positive compounds” denotes compounds having a Δ∈>1.5, the term “dielectrically neutral compounds” denotes those having −1.5≦Δ∈≦1.5 and the term “dielectrically negative compounds” denotes those having Δ∈<−1.5. The dielectric anisotropy of the compounds is determined here by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture in at least one test cell in each case having a layer thickness of 20 μm with homeotropic and with homogeneous surface alignment at 1 kHz. The measurement voltage is typically 0.5 V to 1.0 V, but is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
The host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792 and the host mixture used for dielectrically negative compounds is ZLI-2857, both from Merck KGaA, Germany. The values for the respective compounds to be investigated are obtained from the change in the dielectric constants of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed. 10% of the compound to be investigated are dissolved in the host mixture. If the solubility of the substance is too low for this, the concentration is halved in steps until the investigation can be carried out at the desired temperature.
All temperature values indicated for the present invention are in ° C.
The voltage holding ratio is determined in test cells produced at Merck KGaA. The measurement cells have soda-lime glass substrates and are provided with polyimide alignment layers (polyimide AL 60702 from JSR). The layer thickness is uniformly 6.0 μm. The area of the transparent ITO electrodes is 1 cm2.
The mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, VAN, MVA, (S)—PVA and ASV. They are furthermore suitable for IPS (in-plane switching), FFS (fringe field switching) and PALC applications of negative Δ∈.
The nematic liquid-crystal mixtures in the displays according to the invention generally comprise two components A and B, which themselves consist of one or more individual compounds.
Component A has significantly negative dielectric anisotropy and gives the nematic phase a dielectric anisotropy of ≦−0.5. Besides one or more compounds of the formulae IA, IB and/or IC, it preferably comprises the compounds of the formulae IIA and/or IIB, furthermore compounds of the formula III.
The proportion of component A is preferably between 45 and 100%, in particular between 60 and 100%.
For component A, one (or more) individual compound(s) which has (have) a value of Δ∈≦−0.8 is (are) preferably selected. This value must be more negative, the smaller the proportion A in the mixture as a whole.
Component B has pronounced nematogeneity and a flow viscosity of not greater than 30 mm2·s−1, preferably not greater than 25 mm2·s−1, at 20° C.
Particularly preferred individual compounds in component B are extremely low-viscosity nematic liquid crystals having a flow viscosity of not greater than 18 mm2·s−1, preferably not greater than 12 mm2·s−1, at 20° C.
Component B is monotropically or enantiotropically nematic, has no smectic phases and is able to prevent the occurrence of smectic phases down to very low temperatures in liquid-crystal mixtures. For example, if various materials of high nematogeneity are added to a smectic liquid-crystal mixture, the nematogeneity of these materials can be compared through the degree of suppression of smectic phases that is achieved.
A multiplicity of suitable materials is known to the person skilled in the art from the literature. Particular preference is given to compounds of the formula III.
In addition, these liquid-crystal phases may also comprise more than 18 components, preferably 18 to 25 components.
The phases preferably comprise 4 to 15, in particular 5 to 12, and particularly preferably <10, compounds of the formulae IA, IB and/or IC and compounds of the formulae IIA and/or IIB and optionally III.
Besides compounds of the formulae IA, IB, IC, and the compounds of the formulae IIA and/or IIB and optionally III, other constituents may also be present, for example in an amount of up to 45% of the mixture as a whole, but preferably up to 35%, in particular up to 10%.
The other constituents are preferably selected from nematic or nematogenic substances, in particular known substances, from the classes of the azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclo hexanecarboxylates, phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzyl phenyl ethers, tolans and substituted cinnamic acid esters.
The most important compounds which are suitable as constituents of liquid-crystal phases of this type can be characterised by the formula IV
R9-L-G-E-R10 IV
in which L and E each denote a carbo- or heterocyclic ring system from the group formed by 1,4-disubstituted benzene and cyclohexane rings, 4,4′-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline,
In most of these compounds, R9 and R19 are different from one another, one of these radicals usually being an alkyl or alkoxy group. Other variants of the proposed substituents are also common. Many such substances or also mixtures thereof are commercially available. All these substances can be prepared by methods known from the literature.
It goes without saying for the person skilled in the art that the VA, IPS, FFS or PALC mixture according to the invention may also comprise compounds in which, for example, H, N, O, Cl and F have been replaced by the corresponding isotopes.
Polymerisable compounds, so-called reactive mesogens (RMs), for example as disclosed in U.S. Pat. No. 6,861,107, may furthermore be added to the mixtures according to the invention in concentrations of preferably 0.12-5% by weight, particularly preferably 0.2-2%, based on the mixture. Mixtures of this type can be used for so-called polymer-stabilised VA modes, in which polymerisation of the reactive mesogens is intended to take place in the liquid-crystalline mixture. The prerequisite for this is that the liquid-crystal mixture does not itself comprise any polymerisable components.
The construction of the liquid-crystal displays according to the invention corresponds to the usual geometry, as described, for example, in EP-A 0 240 379.
The following examples are intended to explain the invention without limiting it. Above and below, percent data denote percent by weight; all temperatures are indicated in degrees Celsius.
Besides the compounds of the formulae IIA and/or IIB and one or more compounds from the group of the compounds of the formulae IB, IC and ID, the mixtures according to the invention preferably comprise one or more of the compounds indicated below.
The following abbreviations are used:
The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner which is conventional per se. 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.
By means of suitable additives, the liquid-crystal phases according to the invention can be modified in such a way that they can be employed in any type of, for example, ECB, VAN, IPS, GH or ASM-VA LCD display that has been disclosed to date.
The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example, UV absorbers, antioxidants, nanoparticles and free-radical scavengers. For example, 0-15% of pleochroic dyes, stabilisers or chiral dopants may be added.
For example, 0-15% of pleochroic dyes may be added, furthermore conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973)), may be added in order to improve the conductivity or substances may be added in order to modify the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.
Table A shows possible dopants which can be added to the mixtures according to the invention. If the mixtures comprise a dopant, it is employed in amounts of 0.01-4% by weight, preferably 0.1-1.0% by weight.
C 15
CB 15
CM 21
R/S-811
CM 44
CM 45
CM 47
CN
R/S-1011
R/S-2011
R/S-3011
R/S-4011
R/S-5011
Stabilisers which can be added, for example, to the mixtures according to the invention in amounts of up to 10% by weight, based on the total amount of the mixture, preferably 0.01 to 6% by weight, in particular 0.1 to 3% by weight, are shown below in Table B.
The following examples are intended to explain the invention without limiting it. Above and below,
The display used for measurement of the threshold voltage has two plane-parallel outer plates at a separation of 20 μm and electrode layers with overlying alignment layers of SE-1211 (Nissan Chemicals) on the insides of the outer plates, which effect a homeotropic alignment of the liquid crystals.
All concentrations in this application relate to the corresponding mixture or mixture component, unless explicitly indicated otherwise. All physical properties are determined as described in “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, status November 1997, Merck KGaA, Germany, and apply for a temperature of 20° C., unless explicitly indicated otherwise.
In each case, 20% of one of the individual substances mentioned under V18 a-i are incorporated into the host indicated above, and the VHR (100) [%] after exposure to a backlight is measured:
The table shows that the compounds of the formulae IA, IB and IC exhibit a higher voltage holding ratio in the host after backlight exposure than the reference substances.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2007 038 684 | Aug 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2008/006500 | 8/7/2008 | WO | 00 | 2/12/2010 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2009/021671 | 2/19/2009 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4676604 | Petrzilka | Jun 1987 | A |
| 5013478 | Petrzilka | May 1991 | A |
| 5976407 | Tarumi et al. | Nov 1999 | A |
| 6126857 | Reiffenrath et al. | Oct 2000 | A |
| 6174572 | Hirschmann et al. | Jan 2001 | B1 |
| 6419999 | Tarumi et al. | Jul 2002 | B1 |
| 6692657 | Kato et al. | Feb 2004 | B1 |
| 6764723 | Lee et al. | Jul 2004 | B2 |
| 20030136945 | Hirschmann et al. | Jul 2003 | A1 |
| Number | Date | Country |
|---|---|---|
| 44 26 799 | Feb 1995 | DE |
| 44 14 647 | Nov 1995 | DE |
| 197 07 807 | Sep 1998 | DE |
| 198 32 789 | May 1999 | DE |
| 199 43 649 | Jun 2000 | DE |
| 10 2005 05854 | Jun 2007 | DE |
| 0 122 389 | Oct 1984 | EP |
| 0 168 683 | Jan 1986 | EP |
| 0 834 49 | Apr 1998 | EP |
| 0 969 071 | Jan 2000 | EP |
| Number | Date | Country | |
|---|---|---|---|
| 20110193020 A1 | Aug 2011 | US |
