Electro-optical display, and liquid-crystal medium contained therein

[0001] The present invention relates to active matrix-addressed liquid-crystal displays (AMDs or AM LCDs), in particular those which use an active matrix of thin-film transistors (TFTs) or of varistors. In addition, the present application relates to liquid-crystal media for use in such displays. Such AMDs can use various active electronic switching elements. Most widespread are displays using three-pole switching elements. These are also preferred in the present invention. Examples of such three-pole switching elements are MOS (metal oxide silicon) transistors or the abovementioned TFTs or varistors. In the case of TFTs, various semiconductor materials, predominantly silicon or cadmium selenide, are used. In particular, polycrystalline silicon or amorphous silicon is used. In contrast to the three-pole electronic switching elements, matrices of 2-pole switching elements, such as, for example, MIM (metal insulator metal) diodes, ring diodes or back-to-back diodes, can be employed in AMDs. Although these are also provided by the present application, they are, as explained in greater detail below, not preferred owing to the inferior electro-optical properties achieved by the AMDs.

[0002] In liquid-crystal displays of this type, the liquid crystals are used as dielectrics whose optical properties change reversibly on application of an electric voltage. Electro-optical displays which use liquid crystals as media are known to the person skilled in the art. These liquid-crystal displays use various electro-optical effects. The most common conventional displays use the TN effect (twisted nematic, having a nematic structure which is twisted by about 90°), the STN effect (supertwisted nematic) or the SBE effect (supertwisted birefringence effect). In these and similar electro-optical effects, liquid-crystalline media of positive dielectric anisotropy (Δε) are used.

[0003] Besides the abovementioned electro-optical effects which require liquid-crystal media of positive dielectric anisotropy, there are other electro-optical effects which use liquid-crystal media of negative dielectric anisotropy, such as, for example, the ECB effect (electrically controlled birefringence) and its subforms DAP (deformation of aligned phases), VAN (vertically aligned nematics) and CSH (colour super homeotropics).

[0004] The IPS effect (in-plane switching), which has been increasingly used recently, can use both dielectrically positive and dielectrically negative liquid-crystal media, similarly to guest/host displays, which, depending on the display mode used, can use dyes either in dielectrically positive or in dielectrically negative media.

[0005] An electro-optical effect which has been described recently (Kim, K. H., Park, S. B., Shim, J.-U., Chen, J. and Souk, J. H., International Display Workshop '97, p. 175 ff. (1997), Lee, S. H., Kim, Y. H., Jung, T. K., Park, I. C., Lee, Y. H., Rho, B. G., Park, J. S. and Park, H. S., International Display Workshop '97, p. 9 ff. (1997) and Liu, W., Kelly, J. and Chen, J., SID 98 Digest, p. 318-322 (1998)) combines the advantages of good brightness, viewing-angle dependence and response time of the VAN displays with the advantage of the IPS displays, the use of electrodes on only one substrate, also called interdigital electrodes. This effect uses dielectrically positive liquid-crystal media which are initially homeotropically aligned. The electrodes are on the same side as the liquid-crystal layer, resulting in the formation of a horizontal electrical field (HEF) which is substantially parallel to the liquid-crystal layer.

[0006] These displays use, like the abovementioned VAN displays, an optically negative compensation layer whose optical retardation is adapted to the optical retardation of the liquid-crystal layer and is usually identical to the latter.

[0007] The liquid-crystal media employed in the abovementioned liquid-crystal displays and all liquid-crystal displays utilizing similar effects generally consist predominantly and usually even almost exclusively of liquid-crystal compounds having the corresponding dielectric anisotropy, i.e. compounds of positive dielectric anisotropy in the case of dielectrically positive media and compounds of negative dielectric anisotropy in the case of dielectrically negative media. The reason for this is that the operating voltage should be as low as possible in displays in general, including in displays using these effects. Use is therefore made of liquid-crystal media of very large dielectric anisotropy which are generally composed predominantly of dielectrically positive liquid-crystal compounds and contain at most relatively small proportions of dielectrically neutral compounds.

[0008] In the respective types of media (dielectrically positive or dielectrically negative), use is typically made of at best significant amounts of dielectrically neutral liquid-crystal compounds, since in general the liquid-crystal displays must have the lowest possible addressing voltages. For this reason, liquid-crystal compounds having a dielectric anisotropy which is opposite in sign to the dielectric anisotropy of the medium are generally employed extremely sparingly or not at all.

[0009] An exception is formed here by liquid-crystalline media for MIM displays (metal insulator metal) [J. G. Simmons, Phys. Rev. Vol. 155 No. 3, pp. 657-660; K. Niwa et al., SID 84 Digest, pp. 304-307, June 1984], in which the liquid-crystal media are addressed on an active matrix of thin film transistors (TFD, thin film diodes). In this type of addressing, which utilizes the non-linear characteristic line of diode switching, a storage capacitor cannot be charged together with the electrodes of the liquid-crystal display elements (pixels), in contrast to TFT displays. Thus, in order to minimize the effect of the voltage drop during the addressing cycle, the highest possible base value of the dielectric constant is necessary. In dielectrically positive media, as employed, for example, in MIM-TN displays, the dielectric constant perpendicular to the molecular axis (ε⊥) must thus be as large as possible, since it determines the base capacity of the pixel. To this end, as in WO 93/01253, EP 0 663 502 and DE 195 21 483, compounds of negative dielectric anisotropy are used in the dielectrically positive liquid-crystal media, besides dielectrically positive compounds.

[0010] EP 0 394 419 proposes dielectrically positive liquid-crystal media for active matrix displays based on dielectrically neutral and dielectrically positive liquid-crystal compounds, which may optionally contain dielectrically negative compounds.

[0011] The liquid-crystal media of the prior art have relatively poor low-temperature stabilities. Thus, the nematic phases frequently extend only down to −20° C. and in some cases even only down to 0° C.

[0012] In addition, the threshold voltage (V10) is simultaneously relatively high, often greater than 1.0 V and usually even greater than 1.3 V.

[0013] In particular when they have low threshold voltages, the majority of the liquid-crystal media of the prior art have relatively large values for Δn, frequently greater than 0.11, sometimes even significantly greater than 0.12 and predominantly greater than 0.10.

[0014] However, such large Δn values are not particularly advantageous for VA HEF displays having a typical optical retardation d·Δn of approximately 0.32 μm. Such large Δn values require very small layer thicknesses to be achieved, which are favourable for the response times observed, but result in low production yields.

[0015] It has hitherto been a problem to achieve the relatively small Δn values required at the same time as a very high polarity, i.e. high Δε.

[0016] There thus was and is a great demand for liquid-crystal media which do not have the disadvantages of the media of the prior art, or at least do so to a significantly reduced extent, and which simultaneously are suitable for use in conjunction with homeotropic edge alignment.

[0017] This is achieved by using the liquid-crystal media according to the invention.

[0018] The electro-optical displays according to the invention comprise liquid-crystal media which comprise

[0019] a) one or more strongly dielectrically positive compound(s) selected from the group of the compounds of the formulae I to III

[0020] in which

[0021] R1, R2 and R3 are each, independently of one another, alkyl or alkoxy having 1 to 7 carbon atoms, preferably n-alkyl or n-alkoxy, particularly preferably having 1 to 5 carbon atoms, or alkenyl, alkoxyalkyl or alkenyloxy having 2 to 7 carbon atoms, preferably 1E-alkenyl, unbranched alkoxylalkyl or alkenyloxy, particularly preferably having 2 to 4 carbon atoms,

[0022] n1 is 0 or 1,

[0023] n3 is 1 or 2, and

[0024] X2 is F, Cl, OCF2H or OCF3, and

[0025] L21 and L22 are H or F;

[0026] and optionally

[0027] b) one or more dielectrically positive compound(s) of the formula IV

[0028] in which

[0029] R4 is as defined above for R1 under the formula I, and

[0030] Z41 is —CH2—CH2—, —CF2—O—, —O—CF2— or a single bond, preferably —CH2—CH2— or a single bond, preferably a single bond,

[0031] Z42 is —COO—, —CH2—CH2—, —CF2—O—, —O—CF2— or a single bond, preferably —COO—, —CH2—CH2— or a single bond, preferably —COO— or a single bond,

[0032] X4 is F, Cl, OCF2H or OCF3, preferably F, OCF2H or OCF3, and

[0033] Y41 and Y42 are each, independently of one another, H or F,

[0034] where, in the case where X4=F, preferably at least one of Y41 and Y42 is F, and preferably both Y41 and Y42 are F,

[0035] and optionally

[0036] c) one or more dielectrically positive compound(s) of the formula V

[0037] in which

[0038] R5 is as defined above for R1 under the formula I, and

[0039] Z51 and Z52 are each, independently of one another, —CH2CH2— or a single bond, preferably a single bond,

[0040] X5 is F, Cl, OCF2H or OCF3, preferably F, OCF2H or OCF3, and

[0041] n52 is 0 or 1,

[0042] n51 is 1 and, in the case where n52=1, is also 2;

[0043] and optionally

[0044] d) one or more dielectrically positive compound(s) of the formula VI

[0045] in which

[0046] R6 is as defined above for R1 under the formula I, and

[0047] Z61 and Z62 are each, independently of one another, —CH2CH2—, —COO— or a single bond, preferably —CH2CH2— or a single bond, particularly preferably a single bond,

[0048] are each, independently of one another,

[0049] n6 is 0 or 1, preferably 0;

[0050] and optionally

[0051] e) one or more dielectrically neutral compound(s) of the formula VII

[0052] in which

[0053] R71 and R72 are each, independently of one another, as defined above for R1 under the formula I, and

[0054] Z71 and Z72 are each, independently of one another, —COO—, —CH2CH2— or a single bond, preferably —COO— or a single bond, particularly preferably at most one of the two being —COO—,

[0055] are each, independently of one another,

[0056] particularly preferably, if present, at least one being

[0057] n71 and n72 are each, independently of one another, 0 or 1;

[0058] and optionally

[0059] f) one or more dielectrically neutral compound(s) of the formula VIII

[0060] in which

[0061] R81 and R82 are each, independently of one another, as defined above for R1 under the formula I, and

[0062] Z81 and Z82 are each, independently of one another, —COO—, —CH2CH2— or a single bond, preferably —COO— or a single bond, particularly preferably a single bond,

[0063] are each, independently of one another,

[0064] and

[0065] n81 and n82 are each, independently of one another, 0 or 1,

[0066] the compounds of the formula VII being excluded from inclusion in the compounds of formula VIII.

[0067] The liquid-crystal media preferably comprise in each case one or more compound(s) of at least one formula, preferably two or more different formulae, selected from the group consisting of the compounds of the formulae Ia, Ib, II1 to II3, IIIa and IIIb

[0068] in which the parameters are as defined above under the respective formulae (I to III).

[0069] The compounds of the formula II1 are preferably selected from the group consisting of the compounds II1a to II1d:

[0070] in which R2 is as defined above under formula II1. Particular preference is given to compounds of the formula II1a and/or II1c.

[0071] Preference is given to the compounds of the formula II2 selected from the group consisting of the compounds II2a to II2h

[0072] in which R2 is as defined above under formula II2. Particular preference is given to compounds of the formula II2d.

[0073] Preference is given to the compounds of the formula II3 selected from the group consisting of the compounds of the formulae II3a to II3c

[0074] in which R3 is as defined above under formula II3. Particular preference is given to compounds of the formula II3a.

[0075] Preference is given to the compounds of the formula IV selected from the group consisting of the compounds of the formulae IV1 to IV4

[0076] in which the parameters are as defined above under formula IV. Particular preference is given to compounds of the formula IV1 and/or IV4.

[0077] Preference is given to the compounds of the formula IV1 selected from the group consisting of the compounds of the formulae IV1a to IV1f

[0078] in which R4 is as defined above under formula IV1. Particular preference is given to compounds of the formula IV1a in which R4 is preferably alkenyl, of the formulae IV1b, IV1c and/or IV1f.

[0079] Preference is given to the compounds of the formula IV2 selected from the group consisting of the compounds of the formulae IV2a to IV2e

[0080] in which R4 is as defined above under formula IV2. Particular preference is given to compounds of the formula IV2a, IV2b and/or IV2d.

[0081] Preference is given to the compounds of the formula IV3 selected from the group consisting of the compounds of the formulae IV3a to IV3e

[0082] in which R4 is as defined above under formula IV3. Particular preference is given to compounds of the formula IV3a and/or IV3b.

[0083] Preference is given to the compounds of the formula IV4 selected from the group consisting of the compounds of the formulae IV4a to IV4e

[0084] in which R4 is as defined above under formula IV4. Particular preference is given to compounds of the formula IV4c.

[0085] Preference is given to the compounds of the formula V selected from the group consisting of the compounds of the formulae V1 to V3

[0086] in which the parameters are as defined above under formula V.

[0087] Preference is given to the compounds of the formula V1 selected from the group consisting of the compounds of the formulae V1a to V1f

[0088] in which R5 is as defined above under formula V1. Particular preference is given to compounds of the formula V1a, V1d and/or V1e and very particularly preferably of the formula V1a.

[0089] Preference is given to the compounds of the formula V2 selected from the group consisting of the compounds of the formulae V2a to V2d

[0090] in which R5 is as defined above under formula V2. Particular preference is given to compounds of the formula V2b.

[0091] Preference is given to the compounds of the formula V3 selected from the group consisting of the compounds of the formulae V3a to V3f

[0092] in which R5 is as defined above under formula V3. Particular preference is given to compounds of the formula V3b.

[0093] Preference is given to the compounds of the formula VI selected from the group consisting of the compounds of the formulae VI1 and VI2

[0094] in which the parameters are as defined above under formula VI. Particular preference is given to compounds of the formula VI1.

[0095] Preference is given to the compounds of the formula VI1 selected from the group consisting of the compounds of the formulae VI1a to VI1d

[0096] in which R6 is as defined above under formula VI. Particular preference is given to compounds of the formula VI1a, VI1b and/or VI1d and very particularly preferably of the formula VI1a and/or VI1d.

[0097] Preference is given to the compounds of the formula VI2 selected from the group consisting of the compounds of the formulae VI2a and VI2b

[0098] in which R6 is as defined above under formula VI. Particular preference is given to compounds of the formula VI2a.

[0099] Preference is given to the compounds of the formula VII selected from the group consisting of the compounds of the formulae VII1 to VII3

[0100] in which the parameters are as defined above under formula VII.

[0101] Preference is given to the compounds of the formula VII1 selected from the group consisting of the compounds of the formulae VII1a to VII1d

[0102] in which, in each case independently of one another,

[0103] n and m are each an integer from 1 to 7, preferably from 1 to 5,

[0104] l is 0 or 1, preferably 0, and

[0105] p and q are each an integer from 0 to 3, preferably 0 or 1.

[0106] Preference is given to the compounds of the formula VII2 selected from the group consisting of the compounds of the formulae VII2a to VII2d

[0107] in which R71 and R72 are as defined above under formula VII2.

[0108] Preference is given to the compounds of the formula VII3 selected from the group consisting of the compounds of the formulae VII3a to VII3c

[0109] in which R71 and R72 are as defined above under formula VII3.

[0110] Preference is given to the compounds of the formula VIII selected from the group consisting of the compounds of the formulae VIII1 to VIII3

[0111] in which R81 and R82 are as defined above under formula VIII.

[0112] Preference is given to the compounds of the formula VIII1 selected from the group consisting of the compounds of the formulae VIII1a to VIII1d

[0113] in which, in each case independently of one another,

[0114] n and m are each an integer from 1 to 7, preferably from 1 to 5,

[0115] l is 0 or 1, preferably 0, and

[0116] p and q are each an integer from 0 to 3, preferably 0 or 1.

[0117] Preference is given to the compounds of the formula VIII2 selected from the group consisting of the compounds of the formulae VIII2a and VIII2b

[0118] in which R81 and R82 are as defined above under formula VIII2.

[0119] Preference is given to the compounds of the formula VIII3 selected from the group consisting of the compounds of the formulae VIII3a and VIII3b

[0120] in which R81 and R82 are as defined above under formula VIII3.

[0121] In a first preferred embodiment, the liquid-crystal medium comprises

[0122] a1) one or more strongly dielectrically positive compound(s) selected from the group consisting of the compounds of the formulae I and II

[0123] in which the parameters are as defined above under the respective formulae, and

[0124] Z2 is preferably —COO—, and

[0125] b1) one or more compound(s) selected from the group consisting of the dielectrically positive compounds of the formulae IV to VI and the dielectrically neutral compounds of the formulae VII and VIII

[0126] in which the parameters are as defined above under the respective formulae (IV to VIII).

[0127] In a first preferred sub-embodiment of this embodiment, the liquid-crystal medium comprises

[0128] a11) one or more strongly dielectrically positive compound(s) of the formula I

[0129] in which the parameters are as defined above under formula I,

[0130] preferably selected from the group consisting of the compounds of the formulae Ia and Ib, and particularly preferably in each case one or more compound(s) both of the formula Ia and of the formula Ib

[0131] in which the parameters are as defined above under the respective formulae (Ia and Ib), and

[0132] b11) one or more dielectrically neutral compound(s) of the formula VII

[0133] in which the parameters are as defined above under formula VII,

[0134] preferably selected from the group consisting of the compounds of the formulae VII1 to VII3

[0135] in which the parameters are as defined above under formula VII.

[0136] In this preferred sub-embodiment, the liquid-crystal medium preferably comprises

[0137] one or more compound(s) selected from the group consisting of the compounds of the formulae Ia and Ib, preferably in a total concentration of from 20% to 60% and particularly preferably from 30% to 50%, and/or

[0138] one or more, preferably two to five, compound(s) of the formula Ia in a total concentration of preferably from 10% to 45%, particularly preferably from 15% to 35%, and very particularly preferably from 17% to 26%, and/or

[0139] one or more, preferably two to four, compound(s) of the formula Ib in a total concentration of preferably from 5% to 30%, particularly preferably from 8% to 22%, and very particularly preferably from 10% to 20%, and/or

[0140] one or more, preferably four to ten, compound(s) of the formula VII, preferably in a total concentration of from 40% to 80% and particularly preferably from 50% to 70%, and/or

[0141] one or more, preferably two to six, compound(s) of the formula VII1, preferably in a total concentration of from 30% to 70% and particularly preferably from 40% to 60%, and/or

[0142] one or more, preferably two to five, compound(s) of the formula VII2, preferably in a total concentration of from 4% to 30% and particularly preferably from 8% to 20%, and/or

[0143] optionally one or more, preferably two to five, compound(s) of the formula VII3, preferably in a total concentration of from 3% to 20% and particularly preferably from 5% to 15%.

[0144] In this preferred sub-embodiment, the liquid-crystal medium comprises, in total, preferably at most 20%, particularly preferably less than 15%, very particularly preferably less than 10% and most preferably less than 5% of compounds which are not covered by the formulae I and VII.

[0145] In a second preferred sub-embodiment, the liquid-crystal medium comprises

[0146] a12) one or more strongly dielectrically positive compound(s) of the formula II

[0147] in which the parameters are as defined above under formula II,

[0148] preferably selected from the group consisting of the compounds of the formulae II1 to II3, particularly preferably of the formula II1

[0149] in which the parameters are as defined above under the respective formulae (II1 to II3),

[0150] and particularly preferably one or more compound(s) selected from the group consisting of the compounds of the formulae II1a to II1d, II2a to II2e and II3a to II3c, very particularly preferably selected from the group consisting of the compounds of the formula II1a and/or II1c, optionally additionally II2d and/or II3a

[0151] in which the parameters are as defined above under the respective formulae,

[0152] b12) optionally one or more strongly dielectrically positive compound(s) selected from the group consisting of the compounds of the formulae I and III

[0153] in which the parameters are as defined above under the respective formulae (I and III),

[0154] preferably selected from the group consisting of the compounds of the formulae Ia, Ib, IIIa and IIIc, particularly preferably selected from the group consisting of the compounds of the formulae Ia and IIIa,

[0155] in which the parameters are as defined above under the respective formulae (Ia, Ib, IIIa and IIIb),

[0156] c12) optionally one or more dielectrically positive compound(s) selected from the group consisting of the compounds of the formulae IV and V

[0157] in which the parameters are as defined above under the respective formulae (IV and V), preferably one or more compounds of at least one of the formulae IV and V, particularly preferably in each case at least one compound of the formula IV and of the formula V, and

[0158] d12) optionally one or more dielectrically positive compound(s) of the formula VI

[0159] in which the parameters are as defined above under formula VI,

[0160] e12) optionally one or more dielectrically neutral compound(s) selected from the group consisting of the compounds of the formulae VII and VIII, preferably of the formula VII,

[0161] in which the parameters are as defined above under the respective formulae (VII and VIII).

[0162] In this second preferred sub-embodiment, the liquid-crystal medium preferably comprises

[0163] one or more compound(s) of the formula II, preferably selected from the group consisting of the compounds of the formulae IIa, IIc, II2d and II3a, preferably in a total concentration of from 10% to 70%, particularly preferably from 20% to 60%, and very particularly preferably from 25% to 55%, and/or

[0164] optionally one or more, preferably one to four, compound(s) of the formula I, preferably of the formula Ia, in a total concentration of preferably from 0% to 25%, particularly preferably from 2% to 20%, and very particularly preferably from 4% to 15%, and/or

[0165] optionally one or more, preferably one to three, compound(s) of the formula III, preferably of the formula IIIa, in a total concentration of preferably from 0% to 30%, particularly preferably from 5% to 25%, and very particularly preferably from 10% to 20%, and/or

[0166] optionally one or more, preferably two to five, compound(s) selected from the group consisting of the compounds of the formulae IV and V, preferably obligatorily of at least one of the formulae IV or V and particularly preferably obligatorily both of the formula IV and of the formula V, in a total concentration of preferably from 0% to 80%, particularly preferably from 10% to 75%, and very particularly preferably from 15% to 70%, and/or

[0167] optionally one or more, preferably one to four, compound(s) of the formula VI, preferably selected from the group consisting of the compounds of the formulae VI1a and VI1d, in a total concentration of preferably from 0% to 49%, particularly preferably from 10% to 45%, and very particularly preferably from 31% to 39%, and/or optionally one or more, preferably four to ten, compound(s) selected from the group consisting of the compounds of the formulae VII and VIII, preferably of the formula VII, preferably in a total concentration of from 0% to 40%, particularly preferably from 3% to 30%, and very particularly preferably from 4% to 21%.

[0168] In this preferred sub-embodiment, the liquid-crystal medium comprises, in total, preferably at most 20%, particularly preferably less than 15%, very particularly preferably less than 10% and most preferably less than 5% of compounds which are not covered by the formulae I to VIII.

[0169] According to this preferred sub-embodiment, the liquid-crystal medium preferably comprises

[0170] one or more compound(s) of the formula II, preferably selected from the group consisting of the compounds of the formulae IIa, IIc, II2d and II3a, particularly preferably of the formula II1a, preferably in a total concentration of from 10% to 50%, particularly preferably from 20% to 40%, and very particularly preferably from 25% to 35%, and

[0171] optionally, preferably obligatorily, one or more, preferably one to three, compound(s) of the formula I, preferably of the formula Ia, in a total concentration of preferably from 1% to 15%, particularly preferably from 2% to 12%, and very particularly preferably from 4% to 9%, and

[0172] optionally, preferably obligatorily, one or more compounds of the formula III, preferably of the formula IIIa, in a total concentration of preferably from 5% to 25%, particularly preferably from 8% to 19%, and very particularly preferably from 11% to 18%, namely

[0173] one or more compounds selected from the group consisting of the compounds of formulae I and III, preferably both of the formula I and III, and

[0174] optionally, preferably obligatorily, one or more compounds of the formula III, preferably of the formula IIIa, in a total concentration of preferably from 5% to 25%, particularly preferably from 8% to 19%, and very particularly preferably from 11% to 18%, and

[0175] optionally one or more compounds of the formula V, preferably of the formula Va and/or the formula Vd, in a total concentration of preferably from 0% to 40%, particularly preferably from 20% to 35%, and very particularly preferably from 23% to 33%, and

[0176] optionally, preferably obligatorily, one or more compounds of the formula VII, preferably selected from the group consisting of the compounds of the formulae III1 to III3, in a total concentration of preferably from 0% to 30%, particularly preferably from 3% to 26%, and very particularly preferably from 5% to 9%,

[0177] or

[0178] one or more compound(s) of the formula II, preferably selected from the group consisting of the compounds of the formulae IIa and IIc, particularly preferably either of the formula II1a or of the formula II1c, preferably in a total concentration of from 10% to 50%, particularly preferably from 20% to 40%, and very particularly preferably from 25% to 35%, and

[0179] optionally one or more compound(s) of the formula IId, preferably in a total concentration of from 0% to 30%, particularly preferably from 6% to 24%, and very particularly preferably from 9% to 14%, and

[0180] one or more compound(s) selected from the group consisting of the compounds of the formulae IV and V, preferably both of the formula IV and of the formula V, preferably in a total concentration of from 40% to 80%, particularly preferably from 45% to 75%, and very particularly preferably from 60% to 73%, and

[0181] optionally one or more compound(s) selected from the group consisting of the compounds of the formulae VII and VIII, preferably of the formula VII, preferably in a total concentration of from 0% to 15%, particularly preferably from 1% to 10%, and very particularly preferably from 3% to 9%.

[0182] If the liquid-crystal media according to the invention comprise compounds of the formula IV1a, R4 is in these compounds preferably ethyl, n-propyl, n-butyl, n-pentyl, vinyl or 1E-propenyl, particularly preferably vinyl or 1E-propenyl.

[0183] Owing to their Δn which is relatively high for application purposes, the compounds of the formula V, in particular those of the group consisting of the formulae V1 to V3, are usually used at most in relatively small amounts. An exception among these compounds is formed by compounds of the formula V3, in particular of the formula V3b, which can be used in relatively large amounts and are preferably used owing to their high Δε and their comparatively small Δn.

[0184] The compounds of the formula VIII also have relatively high birefringence values and are preferably used at most in relatively small amounts of typically up to 10%, preferably up to 5%.

[0185] Furthermore, the liquid-crystal media according to all preferred embodiments preferably comprise one or more compounds selected from the group consisting of the compounds of the formulae VII1a to VII1d, VII2a to VII2e and VII3a and VII3b:

[0186] in which n and m are each, independently of one another, from 1 to 5, and o and p are each, both independently thereof and independently of one another, from 0 to 3,

[0187] in which R71 and R72 are each as defined above under the formula VII1, and the phenyl rings may optionally be fluorinated. R71 is preferably n-alkyl having 1 to 5 carbon atoms, particularly preferably having 1 to 3 carbon atoms, and R72 is preferably n-alkyl or n-alkoxy having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms. Of these, particular preference is given to compounds selected from the group consisting of the compounds of the formulae VII1a to VII1d, VII2a and VII3b. The liquid-crystal media optionally comprise one or more compounds selected from the group consisting of the compounds of the formulae VIIIa to VIIIc:

[0188] in which R81 and R82 are each as defined above under the formula VIII, and the phenyl rings may optionally be fluorinated. R81 is preferably n-alkyl having 1 to 5 carbon atoms, particularly preferably having 1 to 3 carbon atoms, and R82 is preferably n-alkyl or n-alkoxy having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms. Of these, particular preference is given to compounds selected from the group consisting of the compounds of the formulae VIIIa and VIIIc.

[0189] The liquid-crystal media according to the invention preferably have nematic phases of in each case at least from −20° C. to 65° C., preferably from −30° C. to 70° C., very particularly preferably from −40° C. to 80° C. The term “having a nematic phase” here means firstly that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature, and secondly that no clearing occurs during heating from the nematic phase. Testing at low temperatures is carried out in a flow viscometer at the corresponding temperature, and checked by storage in test cells having an appropriate layer thickness for electro-optical use, for at least 100 hours. At high temperatures, the clearing point is measured by conventional methods in capillaries.

[0190] The liquid-crystal media according to the invention are furthermore characterized by relatively low optical anisotropy values. The birefringence values are preferably in the range from 0.050 to 0.120, particularly preferably in the range from 0.065 to 0.100 and very particularly preferably in the range from 0.075 to 0.090:

[0191] In addition, the liquid-crystal media according to the invention have small threshold voltage values of less than or equal to 1.5 V, preferably less than or equal to 1.0 V, particularly preferably less than or equal to 0.9 V, very particularly preferably less than or equal to 0.8 V.

[0192] These preferred values for the individual physical properties are also maintained when in each case combined with one another. Thus, media according to the invention have, in particular, the following property combinations:

1NematicNematiclower limitupper limitof Phaseof PhaseThresholdT/° C.T/° C.Δnvoltage/VAccording to≦−20≧65≦0.095≦1.0the inventionPreferred≦−30≧70≦0.090≦0.9Particularly≦−40≧80≦0.088≦0.8preferred

[0193] where, as throughout the application, “≦” means less than or equal to and “≧” means greater than or equal to.

[0194] Particularly preferably, the abovementioned preferred concentration ranges also apply to this preferred combination of compounds.

[0195] The individual compounds are usually employed in concentrations of from 1% to 25%, preferably from 2% to 23%, particularly preferably from 3% to 19%.

[0196] Independently of the abovementioned limits for the total amount of the compounds of the formula I, compounds of the formula Ia are employed in these liquid-crystal media in a concentration of from 1% to 15%, preferably from 2% to 14%, particularly preferably from 2% to 8%. The compounds having relatively short alkyl chains, in particular ethyl and propyl, are preferably used in a lower concentration than the compounds having relatively long alkyl chains, in particular butyl, pentyl and heptyl.

[0197] In the present application, the term “compounds” means both one and a plurality of compounds, which is generally specially emphasized by using the notation “compound(s)”.

[0198] In the present application, the term “dielectrically positive compounds” is taken to mean compounds having a Δεof >1.5, the term “dielectrically neutral compounds” is taken to mean compounds in which −1.5≦Δε≦1.5, and “dielectrically negative compounds” is taken to mean compounds in which Δε is <−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 this mixture at 1 kHz in at least one test cell each with a thickness of 10 μm and a homeotropic and homogeneous surface alignment. The measurement voltage is typically from 0.5 V to 1.0 V, but is always less than the capacitive threshold of the respective liquid-crystal mixture.

[0199] The host mixture used for dielectrically positive compounds is ZLI-4792 and that used for dielectrically neutral and dielectrically negative compounds is ZLI-3086, both from Merck KGaA, Germany. The values for the respective compounds to be investigated are obtained from the change in dielectric constants of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound employed.

[0200] The term “threshold voltage” in the present application relates to the optical threshold for 10% relative contrast (V10), unless explicitly stated otherwise.

[0201] However, in relation to the liquid-crystal mixtures of negative dielectric anisotropy, the term “threshold voltage” is used in the present application for the capacitive threshold voltage (V0), also known as the Freedericksz threshold, unless explicitly stated otherwise.

[0202] All concentrations in this application, unless explicitly stated otherwise, are given in percent by weight and relate to the corresponding mixture as a whole. All physical properties are and have been determined as described in “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany, and apply to a temperature of 20° C., unless explicitly stated otherwise. Δn is determined at 589 nm and Δε at 1 kHz. The threshold voltages and the other electro-optical properties were determined in test cells produced at Merck KGaA, Germany, using white light in a commercial measuring instrument from Otsuka, Japan. To this end, cells were used, depending on Δn of the liquid crystals, with a thickness corresponding to the 1st Gooch and Tarry transmission minimum. The optical retardation d·Δn of the cells was thus about 0.32 μm. The cells were operated in so-called “normally white mode” with a polarizer transmission direction perpendicular to the respective adjacent rubbing directions. The characteristic voltages were all determined with perpendicular observation. The threshold voltage was given as V10 for 10% relative contrast, the central limit voltage V50 for 50% relative contrast and the saturation voltage V90 for 90% relative contrast.

[0203] For the liquid-crystal media having negative dielectric anisotropy, the threshold voltage was determined as the capacitive threshold voltage V0 (also known as the Freedericksz threshold) in cells containing liquids which had been homeotropically aligned by lecithin.

[0204] The liquid-crystal media according to the invention may, if necessary, also comprise further additives and chiral dopants in conventional amounts. The amount of these additives employed is in total from 0% to 10%, based on the total amount of mixture, preferably from 0.1% to 6%. The concentrations of the individual compounds employed are preferably from 0.1 to 3%. The concentration of these and similar additives is not taken into account when giving the concentrations and the concentration ranges of the liquid-crystal compounds in the liquid-crystal media.

[0205] The compositions consist of a plurality of compounds, preferably from 3 to 30, particularly preferably from 6 to 20, very particularly preferably from 10 to 16 compounds, which are mixed in a conventional manner. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, expediently at elevated temperature. If the temperature selected is above the clearing point of the principal constituent, completion of the dissolution operation is particularly easily observed. However, it is also possible to prepare the liquid-crystal mixtures in other conventional ways, for example by using premixtures or from a so-called “multibottle system”.

[0206] 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 TN-AMD that has been disclosed hitherto.

[0207] The entire disclosure of all applications, patents and publications, cited above, and of corresponding German Application No. DE 10020814.2, filed Apr. 28, 2000, is hereby incorporated by reference.

[0208] The examples below illustrate the invention without limiting it. In the examples, 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) of a liquid-crystal substance are given in degrees Celsius. Percentages are by weight.

[0209] Unless stated otherwise, all percentages above and below are percent by weight, and the physical properties are the values at 20° C., unless explicitly stated otherwise.

[0210] All temperature values given in this application are ° C. and all temperature differences are correspondingly difference degrees, unless explicitly stated otherwise.

[0211] In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals CnH2n+1 and CmH2m+1 are straight-chain alkyl radicals having n and m carbon atoms respectively. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is given. In individual cases, the acronym for the parent structure is followed, separated by a hyphen, by a code for the substituents R1, R2, L1 and L2:

2Code for R1,R2, L1, L2R1R2L1L2nmCnH2n+1CmH2m+1HHnOmCnH2n+1OCmH2m+1HHnO.mOCnH2n+1CmH2m+1HHnCnH2n+1CNHHnN.FCnH2n+1CNHFnFCnH2n+1FHHnOFOCnH2n+1FHHnClCnH2n+1ClHHnF.FCnH2n+1FHFnF.F.FCnH2n+1FFFnmFCnH2n+1CmH2m+1HFnCF3CnH2n+1CF3HHnOCF3CnH2n+1OCF3HHnOCF3.FCnH2n+1OCF3HFnOCF3F.FCnH2n+1OCF3FFnOCF2CnH2n+1OCHF2HHnOCF2.FCnH2n+1OCHF2HFnOCF2.F.FCnH2n+1OCHF2FFnSCnH2n+1NCSHHnVsNCrH2r+1-CH═CH-C5H2sCNHHnsNCrH2r+1-O-CsH2sCNHHnAmCnH2n+1COOCmH2m+1HHnCl.FCnH2n+1ClHF

[0212]

3

TABLE A

PYP

PYRP

BCH

CBC

CCH

CCP

CPTP

CEPTP

ECCP

CECP

EPCH

PCH

PDX

PTP

BECH

EBCH

CPC

EHP

BEP

[0213]

4

TABLE B

CCZU-n-X

CDU-n-X

T15

K3n

M3n

CGP-n-X

Inm

CGU-n-X

CCGU-n-X

CGZU-n-X

CUZU-n-X

C-nm

C15

CB15

CBC-nm

CBC-nmF

CCN-nm

100

G3n

101

CCEPC-nm

102

CCPC-nm

103

CH-nm

104

HD-nm

105

HH-nm

106

NCB-nm

107

OS-nm

108

CHE

109

CBC-nmF

110

ECBC-nm

111

ECCH-nm

112

CCH-n1Em

113

T-nFN

114

B-nO.FN

115

CVCC-n-m

116

CVCP-n-m

117

CVCVC-n-m

118

CP-V-N

119

CC-n-V

120

CCG-V-F

121

CPP-nV2-m

122

CCP-V-m

123

CCP-V2-m

124

CPP-V-m

125

CPP-nV-m

126

CPP-V2-m

127

CC-V-V

128

CC-nV-V

129

CC-nV-Vm

130

CC-Vn-V

131

CC-Vn-mV

132

PCH-n(O)mFF

133

CCP-n(O)mFF

EXAMPLES

[0214] The examples below are intended to illustrate the invention without representing a limitation. Above and below, percentages are percent by weight. All temperatures are given in degrees Celsius. Δn is the optical anisotropy (589 nm, 20° C.), Δε the dielectric anisotropy (1 kHz, 20° C.), H.R. the voltage holding ratio (at 100° C., after 5 minutes in an oven, 1 V), and V10, V50 and V90 the threshold voltage, mid-grey voltage and saturation voltage respectively were determined at 20° C.

Example 1

[0215]

5

Compound/
Concentration/

abbreviation
% by mass
Properties

ME2N.F
4.0
Clearing point: T(N,I) = 66.0° C.

ME3N.F
5.0
Transition: T(S,N) <−30° C.

ME5N.F
12.0
ne (20° C., 589 nm) = 1.5670

HP-3N.F
7.0
Δn (20° C., 589 nm) = 0.0873

HP-4N.F
8.0
ε∥ (20° C., 1kHz) = 20.8

CCH-301
11.0
Δε (20° C., 1kHz) = 15.0

CCH-303
16.0
ν (20° C.,) = 26 cSt

CCH-501
13.0
ν (0° C.,) = 90 cSt

CCH-502
12.0
ν (−20° C.,) = 530 cSt

CH-33
4.0
ν (−30° C.,) = 2200 cSt

CH-35
4.0
V10 (20° C.,) = 0.95 V

CH-45
4.0
V50 (20° C.,) = 1.21 V

Σ
100.0
V90 (20° C.,) = 1.55 V

[0216] The liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display had good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 2

[0217]

6

Compound/
Concentration/

abbreviation
% by mass
Properties

CCP-2F.F.F
12.0
Clearing point: T(N,I) = 75.0° C.

CCP-3F.F.F
12.0
Transition: T(S,N) <−20° C.

CCP-5F.F.F
8.0
ne (20° C., 589 nm) = 1.5652

CCP-2OCF3
8.0
Δn (20° C., 589 nm) = 0.0878

CCP-3OCF3
8.0
ε∥ (20° C., 1kHz) = 20.1

CCP-5OCF3
7.0
Δε (20° C., 1kHz) = 15.3

CGU-2-F
8.0

CGZU-2-F
8.0

CGZU-3-F
12.0
V10 (20° C.,) = 0.93 V

CGZU-5-F
10.0
V50 (20° C.,) = 1.18 V

CCH-35
5.0
V90 (20° C.,) = 1.51 V

PCH-7F
2.0

Σ
100.0

[0218] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 3

[0219]

7

Compound/
Concentration/

abbreviation
% by mass
Properties

CCP-2F.F.F
12.0
Clearing point: (N,I) = 70.0° C.

CCP-3F.F.F
12.0
Transition: (S,N) <−20° C.

CCP-5F.F.F
8.0
ne (20° C., 589 nm) = 1.5652

CCP-2OCF2.F.F
4.0
Δn (20° C., 589 nm) = 0.0888

CCP-2OCF3
8.0
ε∥ (20° C., 1kHz) = 20.5

CCP-3OCF3
8.0
Δε (20° C., 1kHz) = 15.4

CCP-50CF3
8.0

CUZU-2-F
10.0
V10 (20° C.,) = 0.91 V

CUZU-3-F
10.0
V50 (20° C.,) = 1.15 V

CUZU-5-F
10.0
V90 (20° C.,) = 1.48 V

CGU-3-F
10.0

Σ
100.0

[0220] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 4

[0221]

8

Compound/
Concentration/

abbreviation
% by mass
Properties

ME2N.F
2.0
Clearing point: (N,I) = 65.0° C.

ME3N.F
2.0
Transition: (S,N) <−30° C.

CCZU-2-F
7.0
ne (20° C., 589 nm) = 1.5653

CCZU-3-F
15.0
Δn (20° C., 589 nm) = 0.0880

CCZU-5-F
7.0
ε∥ (20° C., 1kHz) = 23.7

PCH-3N.F.F
13.0
Δε (20° C., 1kHz) = 16.5

CCH-3
5.0

PDX-3
14.0
V10 (20° C.,) = 0.84 V

PDX-5
12.0
V50 (20° C.,) = 1.03 V

CCP-3OCF3
8.0
V90 (20° C.,) = 1.34 V

CCP-5OCF3
7.0

CCH-33
5.0

CCPC-35
3.0

Σ
100.0

[0222] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 5

[0223]

9

Compound/
Concentration/

abbreviation
% by mass
Properties

PCH-3N.F.F
14.0
Clearing point: (N,I) = 68.0° C.

CCZU-2-F
5.0
Transition: (S,N) <−20° C.

CCZU-3-F
19.0
ne (20° C., 589 nm) = 1.5727

CCZU-5-F
5.0
Δn (20° C., 589 nm) = 0.0894

CGU-2-F
8.0
ε∥ (20° C., 1kHz) = 24.1

CGU-3-F
10.0
Δε (20° C., 1kHz) = 17.5

CGU-5-F
5.0

CCPC-33
4.0
V10 (20° C.,) = 0.90 V

CCPC-34
3.0
V50 (20° C.,) = 1.11 V

CCP-2F.F.F
5.0
V90 (20° C.,) = 1.41 V

CCP-3F.F.F
12.0

CCP-5F.F.F
5.0

ME2N.F
2.0

ME3N.F
3.0

Σ
100.0

[0224] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 6

[0225]

10

Compound/
Concentration/

abbreviation
% by mass
Properties

PCH-3N.F.F
14.0
Clearing point: (N,I) = 65.0° C.

CCZU-2-F
5.0
Transition: (S,N) <−20° C.

CCZU-3-F
19.0
ne (20° C., 589 nm) = 1.5710

CCZU-5-F
5.0
Δn (20° C., 589 nm) = 0.0877

CGU-2-F
8.0
ε∥ (20° C., 1kHz) = 24.0

CGU-3-F
10.0
Δε (20° C., 1kHz) = 17.3

CGU-5-F
3.0

CCPC-33
4.0
V10 (20° C.,) = 0.92 V

CCPC-34
2.0
V50 (20° C.,) = 1.12 V

CCP-2F.F.F
8.0
V90 (20° C.,) = 1.42 V

CCP-3F.F.F
11.0

CCP-5F.F.F
4.0

ME2N.F
2.0

ME3N.F
3.0

CCGU-3-F
2.0

Σ
100.0

[0226] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 7

[0227]

11

Compound/
Concentration/

abbreviation
% by mass
Properties

PCH-3N.F.F
16.0
Clearing point: (N,I) = 67.0° C.

CCZU-2-F
5.0
Transition: (S,N) <−20° C.

CCZU-3-F
19.0
ne (20° C., 589 nm) = 1.5669

CCZU-5-F
5.0
Δn (20° C., 589 nm) = 0.0856

CGU-2-F
4.0
ε∥ (20° C., 1kHz) = 23.6

CGU-3-F
7.0
Δε (20° C., 1kHz) = 16.6

CGU-5-F
2.0

CCPC-33
4.0
V10 (20° C.,) = 0.94 V

CCPC-34
2.0
V50 (20° C.,) = 1.15 V

BCH-3F.F.F
7.0
V90 (20° C.,) = 1.46 V

CCGU-3-F
6.0

CDU-2-F
7.0

CDU-3-F
10.0

CDU-5-F
6.0

Σ
100.0

[0228] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 8

[0229]

12

Compound/
Concentration/

abbreviation
% by mass
Properties

CCZU-2-F
5.0
Clearing point: (N,I) = 67.0° C.

CCZU-3-F
19.0
Transition: (S,N) <−20° C.

CCZU-5-F
5.0
ne (20° C., 589 nm) = 1.5751

CCPU-V-1
3.0
Δn (20° C., 589 nm) = 0.0892

CC-5-V
18.0
ε∥ (20° C., 1kHz) = 27.1

CDU-2-F
10.0
Δε (20° C., 1kHz) = 20.4

CDU-5-F
7.0

CP-3OCF3
4.0
V10 (20° C.,) = 0.75 V

ME2N.F
6.0
V50 (20° C.,) = 0.94 V

ME3N.F
6.0
V90 (20° C.,) = 1.24 V

ME4N.F
11.0

CCG-V-F
6.0

Σ
100.0

[0230] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Example 9

[0231]

13

Compound/
Concentration/

abbreviation
% by mass
Properties

CCP-2F.F.F
11.0
Clearing point (N, I) = 70.5° C.

CCP-3F.F.F
11.0
Transition (S, N) < −40° C.

CCP-20CF3.F
5.0
ne (20° C., 589 nm) = 1.5680

CGU-2-F
11.0
Δn (20° C., 589 nm) = 0.0896

CGU-3-F
11.0
ε∥ (20° C., 1 kHz) = 19.1

CGU-5-F
4.0
Δε (20° C., 1 kHz) = 14.2

CCZU-2-F
6.0

CCZU-3-F
15.0
V10 (20° C.) = 1.00 V

CCZU-5-F
6.0
V50 (20° C.) = 1.22 V

CPZG-2-0T
6.0
V90 (20° C.) = 1.56 V

CPZG-3-0T
7.0

CC-3-V1
7.0

Σ
100.0

[0232] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display has good contrast with low viewing-angle dependence and was virtually free from cross-talk between adjacent on and off pixels.

Comparative Example 1

[0233]

14

Compound/
Concentration/

abbreviation
% by mass
Properties

ME2N.F
3.0
Clearing point: T (N, T) = 70.0° C.

ME3N.F
4.0
Transition: T (S, N) < −40° C.

PDX-3
11.0
ne (20° C., 589 nm) = 1.5692

PDX-4
10.0
Δn (20° C., 589 nm) = 0.0880

HP-3N.F
2.0
ε∥ (20° C., 1 kHz) = 15.6

HP-5N.F
5.0
Δε (20° C., 1 kHz) = 9.9

PYP-5F
10.0
ν (20° C.) = 23 cSt

CCH-301
10.0
ν (0° C.) = 72 cSt

CCH-303
12.0
ν (−20° C.) = 400 cSt

CCH-502
11.0
ν (−30° C.) = 1400 cSt

CH-33
4.0
ν (−30° C.) = 6500 cSt

CH-35
4.0

CH-43
4.0
V10 (20° C.) = 1.24 V

CH-53
4.0
V50 (20° C.) = 1.50 V

CCPC-33
4.0
V90 (20° C.) = 1.87 V

CCPC-35
4.0

Σ
100.0

[0234] As in Example 1, the liquid-crystal medium was introduced into a VA HEF display with TFT addressing. This display does not have a good contrast since Δε was too small. It is already evident from a comparison of the saturation voltages V90 of the present mixture with those of the other Examples that the driving voltage required to reach the saturation value of the contrast was too high for most applications.

Electro-optical display, and liquid-crystal medium contained therein

Information

Publication Number

Date Filed

Date Published

Inventors

CPC

US Classifications

International Classifications

Abstract

Description

Claims

Priority Claims (1)