Patent Grant
11932797
The invention includes a liquid-crystalline medium which comprises at least one compound selected from the group of the compounds of the formulae IA to IH,
in which
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 or FFS (fringe field switching) displays.
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 Δε≤−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 (in-plane 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 term MLC displays here encompasses 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., SORIMACHI, 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 along operating period.
There is still 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 generated.
The disadvantage of the MLC-TN displays frequently used is due to their comparatively low contrast, the relatively high viewing-angle dependence and the difficulty of generating grey shades in these displays.
VA displays have significantly better viewing-angle dependencies and are therefore principally used for televisions and monitors. However, there continues to be a need to improve the response times here. However, properties such as, for example, the low-temperature stability and the reliability must not be impaired at the same time.
The invention is based on an object, for example, of providing liquid-crystal mixtures, in particular for monitor and TV applications, based on the ECB effect or on the IPS or FFS effect, which do not have the disadvantages indicated above, or only do so to a reduced extent. In particular, it must be ensured for monitors and televisions that they also work at extremely high and extremely low temperatures and at the same time have short response times and at the same time have an improved reliability behaviour, in particular exhibit no or significantly reduced image sticking after long operating times. Other objectives are described or are apparent from the description herein.
Neutral bicyclic compounds having a terminal double bond, such as, for example, the compound of the formula
are frequently employed if liquid-crystalline mixtures having fast response times are required. However, compounds of this type have the disadvantage that, in some applications, they lead to an impairment of the display properties, such as, for example, increased occurrence of image sticking.
Compounds of the Formula
in which n and m each, independently of one another, denote 1, 2, 3, 4, 5 or 6, have the disadvantage that they are generally not soluble in high concentrations in liquid-crystal mixtures, which in turn has an adverse effect on the response time.
An object of the present invention is therefore to find liquid-crystal mixtures which on the one hand have fast response times and on the other hand have good reliability due to the use of neutral compounds which have good solubility in liquid-crystal mixtures.
Surprisingly, it is possible to improve the rotational viscosity values and thus the response times if one or more, preferably at least one or two, compounds of the general formulae IA to IH are used in liquid-crystal mixtures, in particular in LC mixtures having negative dielectric anisotropy Δε, preferably for VA, IPS and FFS displays. With the aid of the compounds of the formulae IA to IH, which contain a non-terminal double bond, it is possible to prepare liquid-crystal mixtures, preferably VA, PS-VA, PSA, IPS and FFS mixtures, which have short response times, at the same time good phase properties and good low-temperature behaviour.
The liquid-crystalline mixtures according to the invention are distinguished, for example, by a very good ratio of the rotational viscosities and the elastic constants, preferably K3. In particular, the reliability is improved. This includes, in particular, ODF mura and also interactions with peripheral materials, such as, for example, the adhesive frame, which is frequently also called “corner mura”. Furthermore, image sticking is minimised.
The invention thus relates to a liquid-crystalline medium which comprises at least one compound of the formula IA, IB, IC, ID, IE, IF, IG and/or IH.
The mixtures according to the invention preferably exhibit very broad nematic phase ranges with clearing points ≥65° C., preferably ≥70° C., in particular ≥75° C., very favourable values of the capacitive threshold, relatively high values of the holding ratio and at the same time very good low-temperature stabilities at −20° C. and −30° C., as well as very low rotational viscosity values 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 71, relatively high values of the elastic constants K3 for improving the response times can be observed. The compounds of the formulae IA to IH are suitable, in particular, for the preparation of liquid-crystalline mixtures having a negative Δε.
Some preferred embodiments of the mixtures according to the invention are indicated below.
In the compounds of the formulae IA to IH, Z1, independently of one another, preferably denotes a single bond.
Preferred compounds of the formulae IA to IH are shown below:
The compounds of the formulae IA to IH are preferably prepared as follows:
R′═C3H, C4H9, cyclopropyl, cyclobutyl or cyclopentyl
Particularly preferred compounds are prepared as follows:
The media according to the invention preferably comprise one or two compounds from the group of the compounds of the formulae IA to IH.
The compounds of the formulae IA to IH are preferably employed in the liquid-crystalline medium in amounts of 1-50% by weight, preferably 5 50% by weight and very particularly preferably 10-50% by weight.
Preferred embodiments of the liquid-crystalline medium according to the invention are indicated below:
in which
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —OCO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring,
In the compounds of the formulae IIA and IIB, Z2 may have identical or different meanings. In the compounds of the formula IIB, Z2 and Z2′ may have identical or different meanings.
In the compounds of the formulae IIA, IIB and IIC, R2A, R2B and R2C each preferably denote alkyl having 1-6 C atoms, in particular CH3, C2H5, n-C3H, n-C4H9, n-C5H11, furthermore alkenyl, in particular CH2═CH, CH3CH═CH, C2H5CH═CH, C3H7CH═CH
In the compounds of the formulae IIA and IIB, L1, L2, L3 and L4 preferably denote L1=L2=F and L3=L4=F, furthermore L1=F and L2=Cl, L1=Cl and L2=F, L3=F and L4=Cl, L3=Cl and L4=F. Z2 and Z2′ in the formulae IIA and IIB preferably each, independently of one another, denote a single bond, furthermore a —C2H4— bridge.
If in the formula IIB Z2═—C2H4— or —CH2O—, Z2′ is preferably a single bond or, if Z2═—C2H4— or —CH2O—, Z2 is preferably a single bond. In the compounds of the formulae IIA and IIB, (O)CvH2v+1 preferably denotes OCvH2v+1, furthermore CvH2v+1. In the compounds of the formula IIC, (O)CvH2v+1 preferably denotes CvH2v+1.
In the compounds of the formula IIC, L3 and L4 preferably each denote F.
In the compounds of the formulae IIA and IIB, L5 denotes H or CH3, preferably H.
Preferred compounds of the formulae IIA, IIB and IIC are indicated below:
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring, and
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring, and alkyl denotes an alkyl radical having 1-6 C atoms.
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring. R1 and R2 preferably each, independently of one another, denote straight-chain alkyl or alkenyl, where the compounds of the formula O-17 are not identical with the compounds of the formulae IA and IB.
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring, preferably denote straight-chain alkyl, straight-chain alkoxy or straight-chain alkenyl, and
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring. c is 0, 1 or 2 and d is 1 or 2. R1 and R2 preferably, independently of one another, denote alkyl, alkoxy, alkenyl or alkenyloxy having 1 or 2 to 6 C atoms respectively.
—C≡C—, —CF2O—, —OCF2—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, a cyclopropyl ring, cyclobutyl ring or cyclopentyl ring, and alkyl denotes an alkyl radical having 1-6 C atoms. s denotes 1 or 2.
Particularly preferred mixture concepts are indicated below: (the acronyms used are explained in Table A). n and m here each, independently of one another, denote 1-15, preferably 1-6.
The mixtures according to the invention preferably comprise
Preference is furthermore given to mixtures according to the invention which comprise the following mixture concepts:
(n and m each, independently of one another, denote 1-6.)
Preferred mixture concepts according to the invention comprise one of the following combinations of liquid-crystalline compounds (n, m=1, 2, 3, 4, 5 or 6, unless defined otherwise):
The medium according to the invention preferably comprises more than one compound of the formula CC-n-Vm, where n=2-6 and m=1-6. The compounds of the formula CC-n-Vm include, in particular, compounds of the formulae CC-4-V1, CC-3-V1 and CC-3-V2. The total concentration of compounds of the formula CC-n-Vm in the mixture according to the invention is preferably 5-45% by weight, in particular 15-35%.
In a preferred embodiment, the medium according to the invention, besides one or more compounds of the formulae IA to IH, comprises at least one compound selected from the group of the compounds of the formulae T-20, T-21, IIA-26, IIA-28, IIIA-33, IIA-39, IIA-50, IIA-51, IIB-16, BF-1, BF-2, V-10, O-6a, L-4 and CC-3-V.
The invention furthermore relates to an electro-optical display having active-matrix addressing based on the ECB, VA, PS-VA, PA-VA, IPS, PS-IPS, SA-VA, UB-FFS, FFS or PS-FFS effect, characterised in that it contains, as dielectric, a liquid-crystalline medium as described above.
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 at 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 0.13.
The liquid-crystal mixture according to the invention has a Δε of −0.5 to −8.0, in particular −2.5 to −6.0, where Δε denotes the dielectric anisotropy. The rotational viscosity γ1 at 20° C. is preferably ≤150 mPa-s, in particular ≤120 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 ≤2.5 V and very particularly preferably ≤2.3 V.
For the present invention, the term “threshold voltage” relates to the capacitive threshold (V0), also known as the Freedericks threshold, unless explicitly indicated otherwise.
In addition, the liquid-crystal media according to the invention have high values for the voltage holding ratio 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 higher addressing voltage or threshold voltage and vice versa.
For the present invention, the term “dielectrically positive compounds” denotes compounds having a Δε≥1.5, the term “dielectrically neutral compounds” denotes those having −1.5≤Δε≤1.5 and the term “dielectrically negative compounds” denotes those having Δε<−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.
All temperature values indicated for the present invention are in ° C.
The mixtures according to the invention are suitable for all VA-TFT applications, such as, for example, VAN, MVA, (S)-PVA, ASV, PSA (polymer sustained VA) and PS-VA (polymer stabilized VA), SA-VA (surface alignment VA), SS-VA (surface stabilised VA). They are furthermore suitable for IPS (in-plane switching) and FFS (fringe field switching) applications having negative Δε.
The nematic liquid-crystal mixtures in the displays according to the invention may 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 to IH, it preferably comprises the compounds of the formulae IIA, IIB and/or IIC, furthermore one or more compounds of the formula O-17.
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 Δε≤−0.8 is (are) preferably selected. This value would 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.
A multiplicity of suitable materials is known to the person skilled in the art from the literature for this purpose. Particular preference is given to compounds of the formula O-17.
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.
The mixture may optionally also comprise a component C, comprising compounds having a dielectric anisotropy of Δε≥1.5. These so-called positive compounds are generally present in a mixture of negative dielectric anisotropy in amounts of ≤20% by weight, based on the mixture as a whole.
If the mixture according to the invention comprises one or more compounds having a dielectric anisotropy of Δε≥1.5. these are preferably one or more compounds selected from the group of the compounds of the formulae P-1 to P-5,
in which
The compounds of the formulae P-1 to P-5 are preferably employed in the mixtures according to the invention in concentrations of 1-15%, in particular 2-10%.
Particular preference is given to the compound of the formula
which is preferably employed in the mixtures according to the invention in amounts of 2-15%.
In addition, these liquid-crystal phases may also comprise more than 18 components, preferably 18 to 25 components.
Besides one or more compounds of the formulae IA to IH, the phases preferably comprise 4 to 15, in particular 5 to 12, and particularly preferably <10, compounds of the formulae IIA, IIB and/or IIC and optionally one or more compounds of the formula O-17.
Besides compounds of the formulae IA to IH and the compounds of the formulae IIA, IIB and/or IIC and optionally O-17, 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 cyclohexanecarboxylates, 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
R20-L-G-E-R21 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,
or a C—C single bond, Q denotes halogen, preferably chlorine, or —CN, and R20 and R21 each denote alkyl, alkenyl, alkoxy, alkoxyalkyl or alkoxycarbonyloxy having up to 18, preferably up to 8, carbon atoms, or one of these radicals alternatively denotes CN, NC, NO2, NCS, CF3, SF5, OCF3, F, Cl or Br.
In most of these compounds, R20 and R21 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 or FFS 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 0.01-5% by weight, particularly preferably 0.2-2% by weight, based on the mixture. These mixtures may optionally also comprise an initiator, as described, for example, in U.S. Pat. No. 6,781,665. The initiator, for example Irganox-1076 from BASF, is preferably added to the mixture comprising polymerisable compounds in amounts of 0-1%. Mixtures of this type can be used for so-called polymer-stabilised VA modes (PS-VA) or PSA (polymer sustained VA), 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 itself does not comprise any polymerisable components.
In a preferred embodiment of the invention, the polymerisable compounds are selected from the compounds of the formula M
RMa-AM1-(ZM1-AM2)m1-RMb M
in which the individual radicals have the following meaning:
Particularly preferred compounds of the formula M are those in which
Very particular preference is given to compounds of the formula M in which one of RMa and RMb or both denote P or P-Sp-.
Suitable and preferred RMs or monomers or comonomers for use in liquid-crystalline media and PS-VA displays or PSA displays according to the invention are selected, for example from the following formulae:
in which the individual radicals have the following meanings:
r denotes 0, 1, 2, 3 or 4,
s denotes 0, 1, 2 or 3,
t denotes 0, 1 or 2,
x denotes 0 or 1.
In the compounds of the formulae M1 to M36,
preferably denotes
in which L, identically or differently on each occurrence, has one of the above meanings and preferably denotes F, C, CN, NO2, CH3, C2H5, C(CH3)3, CH(CH3)2, CH2CH(CH3)C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5 or P-Sp-, particularly preferably F, Cl, CN, CH3, C2H5, OCH3, COCH3, OCF3 or P-Sp-, very particularly preferably F, Cl, CH3, OCH3, COCH3 or OCF3, in particular F or CH3.
Suitable polymerisable compounds are listed, for example, in Table D.
The liquid-crystalline media in accordance with the present application preferably comprise in total 0.1 to 10%, preferably 0.2 to 4.0%, particularly preferably 0.2 to 2.0%, of polymerisable compounds.
Particular preference is given to the polymerisable compounds of the formula M and the formulae RM-1 to RM-102.
The mixtures according to the invention may furthermore comprise conventional additives, such as, for example, stabilisers, antioxidants, UV absorbers, nanoparticles, microparticles, etc.
The structure 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.
Throughout the patent application, 1,4-cyclohexylene rings and 1,4-phenylene rings are depicted as follows:
The cyclohexylene rings are trans-14-cyclohexylene rings.
Throughout the patent application and in the working examples, the structures of the liquid-crystal compounds are indicated by means of acronyms. Unless indicated otherwise, the transformation into chemical formulae is carried out in accordance with Tables 1-3. All radicals CnH2n+1, CmH2m+1 and Cm′H2m′+1 or CnH2n n and CmH2m are straight-chain alkyl radicals or alkylene radicals respectively, in each case having n, m, m′ or z C atoms respectively. n, m, m′, z each denote, independently of one another, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 1, 2, 3, 4, 5 or 6. In Table 1 the ring elements of the respective compound are coded, in Table 2 the bridging members are listed and in Table 3 the meanings of the symbols for the left-hand or right-hand side chains of the compounds are indicated.
Besides one or more compounds of the formulae IA to IH, the mixtures according to the invention preferably comprise one or more compounds of the compounds from Table A mentioned below.
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, such as, for example, phenols, HALS (hindered amine light stabilisers), for example Tinuvin 770 (=bis(2,2,6,6-tetramethyl-4-piperidyl) sebacinate), or chiral dopants may be added. Suitable stabilisers for the mixtures according to the invention are, in particular, those listed in Table B.
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 B shows possible dopants which can be added to the mixtures according to the invention. If the mixtures comprise a dopant, it is added in amounts of 0.01-4% by weight, preferably 0.01-3% by weight.
Stabilisers which can be added, for example, to the mixtures according to the invention in amounts of O-10% by weight, preferably 0.001-5% by weight, in particular 0.001-1% by weight, are shown below.
Table D shows example compounds which can preferably be used as reactive mesogenic compounds in the LC media in accordance with the present invention. If the mixtures according to the invention comprise one or more reactive compounds, they are preferably employed in amounts of 0.01-5% by weight. It may also be necessary to add an initiator or a mixture of two or more initiators for the polymerisation. The initiator or initiator mixture is preferably added in amounts of 0.001-2% by weight, based on the mixture. A suitable initiator is, for example, Irgacure (BASF) or Irganox (BASF).
In a preferred embodiment, the mixtures according to the invention comprise one or more polymerisable compounds, preferably selected from the polymerisable compounds of the formulae RM-1 to RM-102. Media of this type are suitable, in particular, for PS-VA, PS-FFS and PS-IPS applications. Of the reactive mesogens shown in Table D, compounds RM-1, RM-2, RM-3, RM-4, RM-5, RM-11, RM-15, RM-17, RM-35, RM-41, RM-44, RM-64, RM-83, RM-95, RM-98 and RM-100 are particularly preferred.
If the medium comprises more than one mesogenic compound, it is preferred to employ two mesogenic compounds. The following mesogenic compounds are preferably employed together:
The following examples are intended to explain the invention without limiting it. In the examples, m.p. denotes the melting point and C denotes the clearing point of a liquid-crystalline substance in degrees Celsius; boiling temperatures are denoted by m.p. Furthermore:
C denotes crystalline solid state, S denotes smectic phase (the index denotes the phase type), N denotes nematic state, Ch denotes cholesteric phase, I denotes isotropic phase, Tg denotes glass-transition temperature. The number between two symbols indicates the conversion temperature in degrees Celsius an.
The host mixture used for determination of the optical anisotropy Δn of the compounds of the formulae IA to IH is the commercial mixture ZLI-4792 (Merck KGaA). The dielectric anisotropy Δε is determined using commercial mixture ZLI-2857. The physical data of the compound 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. In general, 10% of the compound to be investigated are dissolved in the host mixture, depending on the solubility.
Unless indicated otherwise, parts or percent data denote parts by weight or percent by weight.
Above and below:
Unless explicitly noted otherwise, all values indicated in the present application for temperatures, 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, Tg=glass state, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The numbers between these symbols represent the transition temperatures.
The term “threshold voltage” for the present invention relates to the capacitive threshold (V0), also called the Freedericksz threshold, unless explicitly indicated otherwise. In the examples, as is generally usual, the optical threshold can also be indicated for 10% relative contrast (V10).
The display used for measurement of the capacitive threshold voltage consists of two plane-parallel glass outer plates at a separation of 20 μm, which each have on the insides an electrode layer and an unrubbed polyimide alignment layer on top, which cause a homeotropic edge alignment of the liquid-crystal molecules.
The display or test cell used for measurement of the tilt angle consists of two plane-parallel glass outer plates at a separation of 4 μm, which each have on the insides an electrode layer and a polyimide alignment layer on top, where the two polyimide layers are rubbed antiparallel to one another and cause a homeotropic edge alignment of the liquid-crystal molecules.
The polymerisable compounds are polymerised in the display or test cell by irradiation with UVA light (usually 365 nm) of a defined intensity for a pre-specified time, with a voltage simultaneously being applied to the display (usually 10 V to 30 V alternating current, 1 kHz). In the examples, unless indicated otherwise, a 50 mW/cm2 mercury vapour lamp is used, and the intensity is measured using a standard UV meter (make Ushio UNI meter) fitted with a 365 nm band-pass filter.
The tilt angle is determined by a rotational crystal experiment (Autronic-Melchers TBA-105). A low value (i.e. a large deviation from the 90° angle) corresponds to a large tilt here.
The VHR value is measured as follows: 0.3% of a polymerisable monomeric compound are added to the LC host mixture, and the resultant mixture is introduced into TN-VHR test cells (rubbed at 90°, alignment layer TN polyimide, layer thickness d≈6 μm). The HR value is determined after 5 min at 100° C. before and after UV exposure for 2 h (sun test) at 1 V, 60 Hz, 64 μs pulse (measuring instrument: Autronic-Melchers VHRM-105).
In order to investigate the low-temperature stability, also known as “LTS”, i.e. the stability of the LC mixture to spontaneous crystallisation-out of individual components at low temperatures, bottles containing 1 g of LC/RM mixture are stored at −10° C., and it is regularly checked whether the mixtures have crystallised out.
The so-called “HTP” denotes the helical twisting power of an optically active or chiral substance in an LC medium (in μm). Unless indicated otherwise, the HTP is measured in the commercially available nematic LC host mixture MLD-6260 (Merck KGaA) at a temperature of 20° C.
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, comprising all solid or liquid-crystalline components, without solvents. All physical properties are determined in accordance with “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.
The following mixture examples having negative dielectric anisotropy are suitable, in particular, for liquid-crystal displays which have at least one planar alignment layer, such as, for example, IPS and FFS displays, in particular UB-FFS (=ultra-bright FFS), and for VA displays.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M145 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M1 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M2 is mixed with 0.2% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M5 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M11 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M17 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M18 is mixed with 0.2% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M19 is mixed with 0.2% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M20 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M21 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M21 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M22 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M22 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M22 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M23 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M25 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M30 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M31 is mixed with 0.2% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M32 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M36 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M37 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M37 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M40 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M41 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M44 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M44 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M52 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M55 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M58 is mixed with 0.2% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M89 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M90 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M91 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M92 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M92 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M95 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M96 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M97 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M98 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M99 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M99 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M100 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M100 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M101 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M102 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M103 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M104 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M105 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M105 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M106 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M107 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M108 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M109 is mixed with 0.25% of the polymerisable compound of the formula
Examples M1-M202 may additionally also comprise one of the two stabilisers selected from Table C.
The PS-VA mixtures according to the invention comprising a polymerisable compound (reactive mesogen) exhibit higher polymerisation rates, a stable tilt angle and very short response times.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M221 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M221 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M221 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M221 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M226 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M226 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M226 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M226 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M234 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M234 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M238 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M240 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M255 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M255 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M255 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M269 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M269 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M269 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M273 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M273 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M299 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M299 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M305 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M305 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M312 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M312 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M333 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M336 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M339 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M339 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M339 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M344 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M344 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M362 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
Zur Herstellung einer SA-VA (self-alignment-VA)-Mischung, the mixture according to Example M362 is mixed with 0.3% of the polymerisable compound of the formula
0.001% of Irganox 1076 and
0.6% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M365 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M365 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M368 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M370 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M372 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M372 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M362 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M242 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M361 is mixed with 0.3% of the polymerisable compound of the formula
The mixture according to Example M379 is stabilised with 0.04% of the compound of the formula
The mixture according to Example M379 is stabilised with 0.04% of the compound of the formula
and
0.03% of the compound of the formula
The mixture according to Example M379 is stabilised with 0.04% of the compound of the formula
and
0.03% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M384 is mixed with 0.25% of the polymerisable compound of the formula
and 0.01% of the compound of the formula
The mixture according to Example M384 is stabilised with 0.01% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M389 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M389 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M389 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M393 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M395 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M395 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M395 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M399 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M399 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M399 is mixed with 0.25% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M399 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M399 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M406 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M406 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M406 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M406 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M406 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M412 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M412 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M412 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M412 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M412 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M231 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of an SA-VA mixture, the mixture according to Example M418 is mixed with 0.4% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M232 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M421 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M237 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M237 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M233 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M240 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M427 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M427 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M427 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M427 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M427 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M433 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M433 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M421 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M437 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M437 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M437 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M437 is mixed with 0.35% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M437 is mixed with 0.3% of the polymerisable compound of the formula
The following stabilisers are added to the mixture according to Example M437:
The following stabilisers are added to the mixture according to Example M382:
The following stabiliser is added to the mixture according to Example M382:
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M14 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M14 is mixed with 0.3% of the polymerisable compound of the formula
and 0.001% of Irganox 1076.
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M14 is mixed with 0.3% of the polymerisable compound of the formula
The following stabiliser is added to the mixture according to Example M14:
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M450 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M451 is mixed with 0.6% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M453 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M454 is mixed with 0.6% of the compound of the formula
The following stabiliser is added to the mixture according to Example M456:
The following stabiliser is added to the mixture according to Example M456:
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M456 is mixed with 0.3% of the polymerisable compound of the formula
and
0.015%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M460 is mixed with 0.3% of the polymerisable compound of the formula
and
0.02%
The following stabiliser is added to the mixture according to Example M460:
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M389 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.6% of the compound of the formula
The following stabiliser is added to the mixture according to Example M464:
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M389 is mixed with
0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.6% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M464 is mixed with 0.3% of the polymerisable compound of the formula
and
0.02%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M468 is mixed with 0.35% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.01%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M468 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.01%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M468 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.01%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M472 is mixed with 0.3% of the polymerisable compound of the formula
and
0.02%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M474 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M476 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M477 is mixed with 0.6% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M479 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M479 is mixed with 0.3% of the polymerisable compound of the formula
0.001% Irganox 1076 and
0.015%
For the preparation of an SA-VA (self-alignment VA) mixture, the mixture according to Example M480 is mixed with 0.6% of the compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M483 is mixed with 0.3% of the polymerisable compound of the formula
For the preparation of a PS (polymer stabilised) mixture, for example for PS-VA, PS-IPS or PS-FFS displays, the mixture according to Example M483 is mixed with 0.3% of the polymerisable compound of the formula
| Number | Date | Country | Kind |
|---|---|---|---|
| 102017010883.8 | Nov 2017 | DE | national |
| 18197753 | Sep 2018 | EP | regional |
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|---|---|---|---|
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| 20150076405 | Han et al. | Mar 2015 | A1 |
| 20160002532 | Saito et al. | Jan 2016 | A1 |
| 20160264865 | Hirschmann | Sep 2016 | A1 |
| 20170233651 | Han et al. | Aug 2017 | A1 |
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|---|---|---|
| 1147829 | Apr 1997 | CN |
| 101790574 | Jul 2010 | CN |
| 101796162 | Aug 2010 | CN |
| 104650928 | May 2015 | CN |
| 104837955 | Aug 2015 | CN |
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| 105969402 | Sep 2016 | CN |
| 102008036808 | Feb 2009 | DE |
| 102008035718 | Mar 2009 | DE |
| 2930223 | May 2017 | EP |
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| Entry |
|---|
| Search report in corresponding EP18207798.2 dated Apr. 9, 2019 (pp. 1-13). |
| Search report in corresponding ROC (Taiwan) Patent Application No. 107141923 dated May 5, 2022 (pp. 1-13). |
| Notice of Reasons for Rejection in corresponding JP Patent Application No. 2018-218822 dated Oct. 4, 2022 (pp. 1-6). |
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| Number | Date | Country | |
|---|---|---|---|
| 20220325180 A1 | Oct 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16196488 | Nov 2018 | US |
| Child | 17161964 | US |
