WO2001064814A1

WO2001064814A1 - Supertwisted nematic liquid crystal displays, liquid crystal compositions and compounds

Info

Publication number: WO2001064814A1
Application number: PCT/EP2000/012732
Authority: WO
Inventors: Doina Ionescu; Matthew Francis; David Coates
Original assignee: Merck Patent Gmbh
Priority date: 2000-02-28
Filing date: 2000-12-14
Publication date: 2001-09-07
Also published as: CN1248033C; EP1261679A1; CN1437647A; JP5236140B2; JP2003525474A; AU2001223656A1

Abstract

The invention relates to supertwist liquid-crystal displays (STN-LCDs) having short switching times and good steepnesses and angle dependencies, and to the novel nematic liquid-crystal mixtures used therein, which comprise compounds of formula (A) together with compounds of formula (IB), wherein R?3, R4, L1, L2, m, Y1, Y2¿ and W have the meanings given in the text and to compounds of formula (IA).

Description

Supertwisted Nematic Liquid Crystal Displays, Liquid Crystal Compositions and Compounds

The invention relates to supertwist nematic liquid-crystal displays (STN- LCDs) having short switching times and good steepnesses and angle dependencies, and to the novel nematic liquid-crystal mixtures used therein.

STN-LCDs as in the heading are known, for example from EP 0,131 ,216 B1 ; DE 3,423,993 A1 ; EP 0,098,070 A2; M. Schadt and F. Leenhouts, 17th Freiburg conference on liquid crystals (8-10.04.87); K. Kawasaki et al., SID 87 Digest 391 (20.6); M. Schadt and F. Leenhouts, SID 87 Digest 372 (20.1); K. Katoh et al., Japanese Journal of Applied Physics, Vol. 26, No. 11 , L 1784-L1786 (1987)rF. Leenhouts et al., Appl. Phys. Lett. 50 (21), 1468 (1987); H.A. van Sprang and H.G. Koopman, J. Appl. Phys. 62 (5), 1734 (1987); T.J. Scheffer and J. Nehring, Appl. Phys. Lett. 45 (10), 1021 (1984), M. Schadt and F. Leenhouts, Appl. Phys. Lett. 50 (5), 236 (1987) and E.P. Raynes, Mol. Cryst. Liq. Cryst. Letters, Vol. 4 (1), pp. 1-8 (1986). The term STN-LCD here includes any relatively highly twisted display element having a twist angle with a value between 160 ° and 720 °, such as, for example, the display elements of Waters et al. (CM. Waters et al., Proc. Soc. Inf. Disp. (New York) (1985) (3rd Intern. Display Conference, Kobe, Japan), the STN-LCDs (DE OS 3,503,259), SBE-LCDs (T.J. Scheffer and J. Nehring, Appl. Phys. Lett. 45 (1984) 1021), OMI- LCDs (M. Schadt andF. Leenhouts, Appl. Phys. Lett. 50 (1987), 236, DST- LCDs (EP OS 0,246,842) or BW-STN-LCDs (K. Kawasaki et al., SID 87 Digest 391 (20.6)).

Compared with standard TN displays, STN-LCDs of this type are distinguished by significantly better steepnesses of the electrooptical characteristic curve (in the following simply called 'steepness') and, associated therewith, better contrast values, and by a significantly lower angle dependence of the contrast. Of particular interest are STN-LCDs with extremely short switching times, in particular also at relatively low temperatures. In order to achieve short switching times, the rotational viscosities, in particular of the liquid crystal mixtures have hitherto been optimized using usually optimized combinations of liquid crystal components and optionally also monotropic additives of relatively high vapour pressure.

However, the switching times achieved were not adequate for all applications.

Shorter switching times can also be achieved by reducing the thickness of LC layer of the STN-LCD and using liquid-crystal mixtures with a higher birefringence Δn.

All these approaches to shorter switching times, however, still end up with mixtures which were not adequate for every use.

Further demands for STN-LCD are a higher multiplexability (resulting in a smaller number of driving IC's), lower threshold voltages and a high steepness.

To achieve a high steepness in STN-LCDs, the liquid crystal mixtures should exhibit comparatively high values of the ratio of the elastic constants K₃₃/K-π and comparatively low values of Δε/ε_±, wherein Δε is the dielectric anisotropy and ε_x is the dielectric constant in vertical direction to the long molecular axis.

Apart of the optimization of the contrast and the switching times such liquid crystal mixtures should fulfill further important requirements such as:

1. A broad d/p window of cell gap d and pitch p, which is defined as the range between the lower and upper limit of the d/p values.

2. A high chemical stability. 3. A high electrical resistance.

4. A low dependence of the threshold voltage on temperature and frequency.

Optimal parameters, however, cannot be achieved simultaneously for all the properties mentioned above because of opposite influence of different material parameters such as dielectric and elastic properties. Thus, the parameter combinations achieved so far are still not sufficient, especially for high multiplex STN-LCDs (with a multiplex rate in the range of 1/400), but also for middle and low multiplex STN-LCD (multiplex rate in the range of 1/64 and 1/16, respectively).

Therefore, there continues to be a great demand for improved STN-LCDs having short switching times and, at the same time, a broad service- temperature range, a high steepness (i.e. low steepness values), good angle dependency of the contrast and low threshold voltage, which meet the abovementioned requirements.

The invention has the object of providing STN-LCDs which only have the above mentioned disadvantages to a small extent, or not at all, and at the same time have very useful overall properties, especially short switching times at low temperatures, a high steepness and an improved temperature dependence of the operating voltage.

It has now been found that this object can be achieved if nematic liquid- crystal mixtures are used which comprise compounds of formula IA

together with compounds of formula IB

wherein

R^J is an alkenyl group with 2 to 7 C atoms, R⁴ is an optionally fluorinated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or COO- in such a manner that O atoms are not directly adjacent to one another, or, in case m = 1 , R⁴ can also be Q-Y,

Q is CF₂, OCF₂, CFH, OCFH or a single bond,

Y is F or CI,

L¹ and L² are each independently H or F,

m is 0 or 1 , -

Y¹ and Y² are each independently H or F,

R⁵ is alkenyl or alkynyl having 2 to 10 C atoms,

R⁶ is alkyl or alkoxy having 1 to 10 C atoms, alkenyl, aikenyloxy, alkynyl or alkynyloxy having 2 to 10 C atoms and

R⁷ is alkynyl or alkynyloxy having 2 to 10 C atoms.

In case

preferably at least one of Y¹ and Y² is F, most preferably both are F.

Also generally, preferably at least one of Y¹ and Y² is F and most preferably both are F,

The use of compounds of formula IA together with compounds of formula IB in the liquid crystal mixtures for STN-LCDs according to the invention especially leads to

• a high steepness

• a low threshold voltage with a low temperature dependence, and

• short switching times especially at low temperatures.

Furthermore, the liquid crystal mixtures according to the present invention show the following advantageous properties

- a low viscosity,

- a low temperature dependence of the threshold voltage and the operating voltage, - improved stability of the mixture in the display at low temperatures.

The invention thus relates to an STN-LCD having two plane-parallel outer plates which, together with a frame, form a cell, a nematic liquid-crystal mixture of positive dielectric anisotropy which is present in the cell, electrode layers with superposed alignment layers on the insides of the outer plates, a pre-tilt angle between the longitudinal axis of the molecules at the surface of the outer plates and the outer plates of from about 1 degree to 30 degrees, and a twist angle of the liquid-crystal mixture in the cell from alignment layer to alignment layer with a value of between 22.5 and 600°,

wherein the nematic liquid-crystal mixture essentially consists of

a) 30-90 % by weight of a liquid-crystalline component A, comprising one or more compounds having a dielectric anisotropy of more than +1.5;

b) 10-55 % by weight of a liquid-crystalline component B, comprising one or more compounds having a dielectric anisotropy from -1.5 to +1.5;

c) 0-10 % by weight of a liquid-crystalline component D, comprising one or more compounds having a dielectric anisotropy of less than -1.5 and

d) optionally an optically active component C in such an amount that the ratio between the layer thickness (separation of the plane-parallel outer plates) and the natural pitch of the chiral nematic liquid-crystal mixture is from about 0.2 to 1.3,

characterized in that the liquid crystal mixture comprises at least one compound of formula IA

wherein

R is an alkenyl group with 2 to 7 C atoms, R⁴ is an optionally fluorinated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or COO- in such a manner that O atoms are not directly adjacent to one another, or, in case m = 1 , R⁴ can also be Q-Y,

Q is CF₂, OCF₂, CFH, OCFH or a single bond,

Y is F or CI,

L¹ and L² are each independently H or F,

m is 0 or 1 —

and at least one compound of Component A, having the formula

wherein

Y¹ and Y² are each independently H or F, preferably at least one is F, most preferably both are F,

R⁵ is alkenyl or alkynyl having 2 to 10 C atoms,

R⁷ is alkynyl or alkynyloxy having 2 to 10 C atoms.

Another object of the invention are inventive liquid crystal mixtures as described above and below for use in STN-LCDs.

The formula IA comprises the following subformulae

wherein R³, L¹, L², Q and Y have the meanings of formula IA and

R⁴ is an optionally fluohnated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or -COO- in such a manner that O atoms are not directly adjacent to one another.

In the formulae IA-1 , IA-2 and IA-3, R³ is especially preferably 1 E-alkenyl oder 3 E-alkenyl with 2 to 7 C-atoms. Especially preferred compounds of formula IA-1 are those wherein R⁴ is alkenyl with 2 to 7 C atoms, in particular those of the following formulae

wherein R^3a and R^4a are each independently H, CH₃, C₂H₅ or n-C₃H and alkyl is an alkyl group with 1 to 7 C atoms.

Particularly preferred are STN-LCDs according to the present invention, wherein the liquid crystal mixture comprises at least one compound selected of formulae IA-1 a and IA-1 c, wherein R^3a and R^4a respectively have the same meaning.

Of the compounds of formula IA-2 especially preferred are those wherein L¹ and L² are denoting H.

Further preferred compounds of formula IA-2 are those wherein R⁴ is alkyl with 1 to 8, in particular 1 , 2 or 3 C-atoms, and R³ is 1 E-alkenyl or 3E- alkenyl with 2 to 7, in particular 2, 3 or 4 C-atoms.

Of the compounds of formula IA-3 especially preferred are those wherein one or both of L¹ and L² are denoting F and Q-Y is F or OCF₃. Further preferred compounds of formula IA-3 are those wherein R³ is 1 E- alkenyl or 3E-alkenyl with 2 to 7, in particular 2, 3 or 4 C-atoms.

The compounds of formulae IA-1 and IA-2 having a dielectric anisotropy from - 1.5 to + 1.5 belong to component B as defined above, whereas polar compounds of formula IA-2 and in particular of formula IA-3 having a dielectric anisotropy of more than + 1.5 belong to component A as defined above.

The combination of compounds of formulae IA and IB leads to inventive mixtures with particularly low values of the rotational viscosity and to STN- LCD's with a high steepness of the electrooptical curve and fast switching times especially at low temperaiures.

The formula IB comprises the following preferred subformulae:

wherein R^a is alkenyl having 2 to 5 C atoms, preferably vinyl or 3-butenyl, R^b is alkyl having 1 to 7 C atoms or alkenyl having 2 to 7 C atoms, preferably n-alkyl having 1 to 5 C atoms and R^c is alkynyl having 2 to 7 C atoms, preferably 1-pentynyl, 1-butynyl or 1-propynyl.

Especially preferred are the compounds of formulae IB1 , IB3, IB6 and IB7.

Further compounds of component A are preferably selected of formula II

wherein R is an optionally fluohnated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or -COO- in such a manner that O atoms are not directly adjacent to one another*

are each independently ~ ^H

L⁵ and L⁶ are each independently H or F,

Z¹ and Z² are independently of each other -COO-, -CH₂CH₂-, -CH=CH- C≡C- or a single bond, and

n is 0, 1 or 2.

Especially preferred compounds of formula II are those of the following formulae

R

wherein R is as defined in formula II. R in these formulae is particularly preferably alkyl or alkoxy with 1 to 8 C atoms.

Especially preferred are compounds of formula lla, lib, He, lid and lie, in particular compounds of formula lla and lib.

Preferably component A further comprises one or more compounds of formula

wherein R⁸ is alkyl or alkoxy having 1 to 7 C atoms, Z² and n have each independently one of the meanings given for formula II,

and _

L¹, L², L⁵ and L⁶ are each independently H or F.

The compounds of formula III are preferably selected from the following formulae

lllc

L¹

R° ( HH >-CH _₀₂CWH. .,J — < O ^■CN Hie

wherein R, L¹ and L² have each independently one of the meanings of formula III.

Especially preferred are compounds of formula lllb, lllc and lllf, in particular compounds of the following subformulae

R^e H > — ( O >-COO- O >— CN Illf1

wherein R⁸ is as defined above.

Further preferred are compounds of formula lllh, wherein L² is H and L¹ is H or F, in particular F.

Preferably the liquid crystal mixtures according to the present invention comprise one or more compounds of formula V

wherein R has one of the meanings of formula II and Y²is F or Cl, in particular wherein R is alkyl or alkoxy with 1 to 8 C-atoms and/or Y² is F.

In addition to compounds of formula II, the component A can also comprise one or more compounds with terminal fluoro or fluohnated groups selected of formula II^*

wherein R, A, B, Z¹, Z² and n have each independently one of the meanings of formula II,

L³ and L⁴ are each independently H or F,

Y¹ is F or Cl, and

Q¹ is CF₂, OCF₂, CFH, OCFH or a single bond,

with the provisos that L³, L⁴ and Q¹-Y¹ are not at the same time F, and that in case n is 1 , A and B are both 1 ,4-cyclohexylene and Z¹ and Z² are single bonds, then R is not an alkenyl group with 2 to 7 C atoms.

Especially preferred compounds of formula II^* are those of the following formulae

wherein R is as defined in formula II, and L³ and L⁴ are each independently H or F. R in these formulae is particularly preferably alkyl or n c alkoxy with 1 to 8 C atoms.

The individual compounds of the formulae IA, IB, II, IT, III, V and also other compounds which can be used in the STN-LCDs according to the invention, are either known or can be prepared analogously to the known o compounds and procedures, e.g. as described in WO 9623851 ,

WO 9105780, DE 4327749, EP 390329, JP 2807357 or EP 679707. Preferred compounds of formula IB can be prepared according to the following scheme:

DCC: Dicyclohexylcarbodiim.de DMAP: 4-N,N-Dimethylaminopyhdine BuLi: n-Butyllithium 5 In particular the compounds of the formulae IA have low viscosities, in particular low rotational viscosities, low values of the ratio of the elastic constants (K₃/K₁) and lead therefore to short switching times, whereas the compounds of formula II with a high dielectric anisotropy, especially when being present in high amounts like in the inventive displays, lead to a reduced threshold voltage.

Preferred liquid-crystal mixtures which can be used according to the invention contain one or more compounds from component A preferably in a proportion of 30 % to 90 %, preferably 45 % to 75 %. These compounds or this compound have a dielectric anisotropy of more than +3 (preferably of more than +8, in particular more than +12).

Further preferred mixtures comprise • one or more, in particular two to five compounds of formula IA,

• one or more, in particular two to five compounds of formula IB,

• one or more, in particular two to six compounds of formula II,

• one or more, in particular two to six compounds of formula III, and

• one or more, in particular one, two or three compounds of formula V.

Preferred liquid-crystal mixtures contain one or more compounds from group B, preferably in a proportion of 10 to 45 %. These compounds or this compound from group B have in particular low values of the rotational viscosity y_..

Preferably component B comprises one or more compounds selected from the group comprising IV1 to IV9 with two rings

and/or one or more compounds selected from the group comprising IV10 to IV24 with three rings

in which R¹ and R² have each independently one of the meanings given for R in formula II, and the 1 ,4-phenyl groups in IV10 to IV19 and IV23 to IV31 can also independently of each other be mono- or polysubstituted by F.

Compounds of formula IV24, wherein R² is alkenyl having 2 to 5 C atoms are preferred. Of the compounds of formulae IV 25 to IV 31 especially preferred are those, wherein R¹ is alkyl and R² is alkyl or alkoxy, each having 1 to 7 C- atoms. Further preferred are compounds of formulae IV 25 and IV 31 , wherein L is F.

R¹ and R² in the compounds of formulae IV1 to IV30 is particularly preferably straight chain alkyl or alkoxy with 1 to 12 C-atoms.

The LC mixtures optionally also comprise an optically active component C, in an amount such that the ratio between the layer thickness (separation of the plane-parallel carrier plates) and the natural pitch of the chiral nematic liquid crystal mixture is.more than 0.2 suitable to the desired twist angle. Suitable dopants can be selected from a wide variety of known chiral materials and commercially available dopants such as cholesteryl nonanoate, S 811 (Merck KGaA, Darmstadt, FRG) and CB 15 (Merck Ltd., former, BDH, Poole, UK). The choice thereof is not crucial per se.

The amount of compounds of component C is preferably 0 to 10 %, in particular 0 to 5 %, very preferably 0 to 3 %.

In a further preferred embodiment the LC mixtures comprise 2 to 65 %, preferably 5 to 35 % by weight of liquid crystalline tolane compounds. Thereby it is possible to reduce the cell thickness and the switching times of the STN-LCDs. The tolane compounds are preferably selected from group T comprising T1 a, T1 b and T2a to T2h

wherein R¹ has one of the meanings of R in formula II, L¹ to L⁶ are each independently H or F, and Q and Y have one of the meanings given in formula I.

Particularly preferred compounds of formula T2e are those wherein one, two or three of the groups L¹ to L⁶ are F and the others are H, with both of L¹ and L², L³ and L⁴, L⁵ and L⁶ not being at the same time F.

The proportion of component(s) from group T is preferably 2 % to 65 %, in particular 5 % to 35 %.

The liquid crystal mixtures may~also comprise 0 to 10 % of one or more compounds having a dielectric anisotropy of -2 or less (component D).

The component D preferably comprises one or more compounds containing the structural element 2,3-difluoro-1 ,4-phenylene, such as described e.g. in DE-OS 38 07 801 , 38 07 861 , 38 07 863, -38 07 864 and 38 07 908. Especially preferred are tolane compounds with this structural element according to the PCT/DE 88/00133, in particular those of formulae T2f and T2g.

Further known compounds of component D are e.g. 2,3-Dicyano- hydroquinone or cyclohexane derivatives containing the structural element

as in DE-OS 32 31 707 or DE-OS 34 07 013.

The proportion of compounds of the component D comprising one or more compounds having a dielectric anisotropy < -1.5 is preferably about 0 % to 10 %, in particular about 0 % to 5 %. Those skilled in the art can easily adjust this proportion to produce the threshold voltage desired, it being possible to use, in principle, all customary liquid-crystal compounds where Δε < -1.5.

Especially preferably the inventive displays contain no compounds of component D. The term alkenyl in the meanings of R and R¹ to R⁴ is comprising straight chain and branched alkenyl groups, in case of R with 2 to 7 C atoms, in case of R, R², R³ and R⁴ with 2 to 12 C atoms. Straight chain alkenyl groups are preferred. Further preferred alkenyl groups are C₂-C₄-1 E-alkenyl, C₄-C₇-3E- alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-

C₇-1 E-alkenyl, C₄-C₇-3E-alkenyl and C₅-C₇-4-alkenyl.

Examples for preferred alkenyl groups are vinyl, 1 E-propenyl, 1 E-butenyl, 1 E-pentenyl, 1 E-hexenyl, 1 E-heptenyl, 3-buteπyl, 3E-pehtenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl and 6-heptenyl. Alkenyl groups with up to 5 C atoms are particularly preferred. Very particularly preferred are vinyl, 1 E-propenyl, 1 E-butenyl, 3E- butenyl and 3E-pentenyl, in particular vinyl and 3E-butenyl.

In further particularly preferred embodiments, the liquid crystal mixtures according to the present invention contain

at least one compound of each formula IA-1 a, IA-2a and IA-3a

alkenyl alkenyl^* IA-1 a

alkenyl

alkenyl F ,_A._3a

wherein alkenyl and alkenyl* are each independently an alkenyl group with 2 to 7 C atoms, and alkyl^* is an alkyl group with 1 , 2 or 3 C atoms,

one or more, preferably two to six, compounds of formulae IB1 , IB3, IB4 and IB5:

wherein R^a and R^b have the meaning given above.

11 to 55 %, preferably 15 to 42 % by weight of one or more, in particular two to four, alkenyl compounds of formula IA,

12 to 24 % by weight of one or more, in particular one or two, polar alkenyl compounds of formula IA-3,

5 to 25 %, preferably 7 to 20 % by weight of one or more, in particular two to four, compounds selected of formula IB,

12 to 48 %, preferably 18 to 36 % by weight of one or more, in particular two to six, compounds of formula III having a terminal cyano group, which are especially preferably selected of formulae lllb and lllc, 2 to 16 %, preferably 3 to 9 % by weight of one or more, in particular one or two, pyrimidine compounds of formula V,

2 to 35 %, preferably 5 to 20 % by weight of one or more, in particular two to four, tolane compounds of group T, which are especially preferably selected from formulae T2a and T2b,

Further preferred embodiments relate to liquid crystal mixtures that

contain a total of 3 to 8 compounds of formulae IA and IB, with the amount of these compounds being 15 to 45 %, preferably 20 to 40 % by weight of the total mixture,

- contain more than 58 % by weight of compounds having a positive dielectric anisotropy, in particular having a dielectric anisotropy of more than + 12,

contain no compounds of component B of formulae IV-1 to IV-31 and/or no compounds of component D,

essentially consist of compounds of formulae IA, IB, II, III, V and compounds of group T,

The inventive mixtures are characterized, especially when used in STN- LCDs with large cell gaps, by their low total switching times (t_tot = t_oπ + t_off). Low switching times are an especially important requirement for STN- LCDs e.g. when used in laptops, to allow better displaying of the cursor movements. Especially preferred are displays having switching times of 300 msec or less, in particular 250 msec or less.

The inventive STN-LCDs are characterized by a low threshold voltage. Preferably the threshold voltage is 1.3 V or less, in particular 1.25 V or less. The liquid crystal mixtures in the inventive STN-LCDs are dielectrically positive with Δε > 1.5. Particularly preferred are mixtures with Δε 3, very particularly preferred mixtures with Δε > 5.

The inventive liquid crystal mixtures exhibit advantageous values of the threshold voltage V₁₀ o_/2o and of the rotational viscosity γ-|. If the value for the optical path difference d ^■ Δn is fixed, the value for the cell gap d is determined by the optical anisotropy Δn. In particular in case of high values of d • Δn, the use of liquid crystal mixtures according to the present invention with a higher value of Δn is preferred, since in this case the value for d can be chosen to be comparatively small, leading to improved values of the switching time. However, inventive liquid crystal displays comprising inventive liquid crystal mixtures_with smaller values of Δn, too, are characterized by advantageous values of the switching times.

The liquid crystal mixtures according to the present invention are further characterized by their advantageous values of the steepness, and, in particular at temperatures above 20 °C, can be driven at high multiplex rates. Furthermore, the mixtures exhibit a high stability, a high electrical resistance and a low frequency dependency of the threshold voltage. The liquid crystal displays according to the present invention show a broad working temperature range and a good viewing angle dependency of the contrast.

The construction of the liquid-crystal display elements according to the present invention from polarizers, electrode base plates and electrodes having a surface treatment such that the preferential orientation (director) of the liquid-crystal molecules in each case adjacent thereto is usually mutually twisted from one electrode to the other by a value of 160 ° to 720 °, corresponds to the customary construction for display elements of this type. The term customary construction here is used in broad terms and also includes all derivatives and modifications of supertwist cells, in particular also matrix display elements. The surface tilt angle at the two support plates may be identical or different. Identical tilt angles are preferred. In TN-displays according to the invention the tilt angle between the long axes of the molecules at the surface of the base plates and the base plate is preferably in the range from 0° to 7°, in particular from 0,01 ° to 5°, very preferably from 0,1 to 2°. In STN-displays according to the invention the tilt angle is preferably in the range from 1 ° to 30°, in particular from 1° to 12°, very preferably from 3° to 10°.

The twist angle of the liquid crystal mixture between the alignment layers on the two base plates of the cell is in case of inventive TN-displays in the range from 22,5° to 170°, in particular from 45° to 130°, very preferably from 80° to 115°. In case of STN-displays the twist angle is in the range from 100° to 600°, in particular from 170° to 300°, very preferably from 180° to 270°.

An essential difference between the display elements accordding to the invention and the display elements customary hitherto based on the twisted nematic cell is, however, the choice of liquid-crystal components in the liquid-crystal layer.

The liquid-crystal mixtures which can be used according to the invention are prepared in a manner customary per se. In general, the desired amount of the components used in a relatively small amount is dissolved in the components making up the principal constituent, expediently 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, after mixing, for example by distillation.

The dielectrics may also contain further additives known to those skilled in the art and described in the literature. For example, 0-15 % of pleochroic dyes may be added.

The examples below are intended to illustrate the invention, without representing a limitation.

The abbreviations have the following meanings: Δn birefringence at 589 nm and 20 °C

T_ave average switching time = 0.5 (T_on + T_off)

T_on time from switching on until 90 % of the maximum contrast is reached,

T_0ff time from switching off until 10 % of the maximum contrast is reached,

V₁₀ threshold voltage (volt)

V₉₀ saturation voltage

go/V-io steepness

γ_rot rotational viscosity (mPa-s)

In the foregoing and the following, unless indicated otherwise, all temperatures are in degree Celsius and percentages are % by weight. The values for switching times and viscosities are related to 20 °C. The switching time is the average value t_ave as defined above.

The STN-LCD is addressed in multiplex operation (multiplex ratio 1 :240, bias 1 :15).

In the present patent application and in the following examples all chemical structures of LC compounds are given by acronyms the transformation of which into chemical formulae is done as shown in the following. All residues C_nH_2n+ι and C_mH_2m+1 are straight-chained alkyl groups with n resp. m carbon atoms. The code of Table B is self- explanatory. In Table A only the acronym for the core structure is given. In a concrete compound this acronym is followed by a dash and a code for the substituents R , R2, Li and L2 as follows:

The compounds given in Tabies A and B are particularly preferred components of the present invention. II

Table A:

(L¹,L², L³;HorF)

BCH CBC

CCH CCP

CPTP PTP

ECCP EPCH

CP ME

HP PCH i¹-/ H HVCOO-ZO HV-F

CCPC PYP-n-F

Table B:

CC-V-m CC-n-V

CCP-V-n

j- ^cn^H _2n ^ -^ ^~(^ ^C-^H^I

CCP-Vn-m

CCP-nV-m CCG-V-F

UZU-nA-N DU-n-N

Thio-A

Thio-B

CVCP-nV-Om Example 1

A STN display contains a liquid crystalline medium with the following properties:

Clearing point + 91 °C

Δn 0.1398 10 1.09 V

consisting of

ME2N.F - 8.00 %

ME3N.F 9.00 % ME4N.F 11.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 6.00 %

CCG-V-F 16.00 %

CCPC-33 5.00 % CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 5.00 %

CBC-53F 5.00 %

CBC-55F 2.00 % PPTUI-3-2 5.00 %

YZU-4-N 8.00 %

Example 2

Clearing point + 90 °C

Δn 0.1391

V₁₀ 1.10 V

V₉₀Λ/₁₀ 1.055

consisting of

ME2N.F — 8.00 %

ME3N.F 9.00 % ME4N.F 12.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 3.00 %

CCG-V-F 15.00 %

CCP-V-1 6.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 4.00 %

CBC-53F 4.00 % PPTUI-3-2 6.00 %

DU-5-N 8.00 %

Example 3

Clearing point + 91 °C

Δn 0.1478

V₉₀/V₁₀ 1.064

consisting of

ME2N.F - 8.00 %

ME3N.F 9.00 % ME4N.F 12.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 3.00 %

CCG-V-F 14.00 %

CCP-V-1 6.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 4.50 %

CBC-53F 4.50 % PPTUI-3-2 6.00 %

DU-3-N 8.00 %

Example 4

Clearing point + 89

Δn 0.1418

v₉₀/v₁₀ 1.067

consisting of

ME2N.F - 8.00 %

ME3N.F 8.00 % ME4N.F 9.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 10.00 %

CCG-V-F 14.00 % ^■

CCP-V-1 7.00 % CCPC-33 4.00 %

CCPC-34 4.00 %

CCPC-35 4.00 %

CBC-33F 4.00 %

CBC-53F 4.00 % PPTUI-3-2 6.00 %

UZU-3A-N 8.00 %

The melting point of the compound UZU-3A-N is 69 °C. Example 5

Clearing point + 90 °C

Δn 0.1400

consisting of

ME2N.F - 8.00 %

ME3N.F 9.00 % ME4N.F 10.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 6.00 %

CCG-V-F 17.00 % ^'

CCP-V-1 8.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 3.00 %

PPTUI-3-2 6.00 % PZU-V2-N 8.00 %

The melting point of the compound PZU-V2-N is 37 °C and the monotropic clearing point 8.2 °C. Example 6

Clearing point + 91 °C

Δn 0.1381

V₁₀ 1.06 V

V₉₀Λ/₁₀ 1.094

consisting of

ME2N.F — 8.00 %

ME3N.F 9.00 % ME4N.F 10.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 3.00 %

CCG-V-F 16.00 %

CCP-V-1 8.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 3.00 %

CBC-53F 3.00 % CBC-55F 3.00 %

PPTUI-3-2 4.00 %

Thio-A 8.00 %

Example 7

Clearing point + 90

Δn 0.1315

VgoΛ o 1.084

consisting of

ME2N.F 8.00 %

ME3N.F 9.00 % ME4N.F 12.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 5.00 %

CCG-V- F 17.00 %

CCP-V-1 6.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 3.00 %

CBC-53F 4.00 % PPTUI-3-2 3.00 %

PYP-3N.F.F 8.00 %

The melting point of the compound PYP-3N.F.F is 69 X. Example 8

Clearing point + 91 X

Δn 0.1341

V₁₀ 1.07 V

V₉₀/V₁₀ 1.028

consisting of

ME2N.F 8.00 %

ME3N.F 9.00 % ME4N.F 10.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 5.00 %

CCG-V-F 18.00 %

CCP-V-1 8.00 % CCPC-33 5.00 %

CCPC-34 5.00 %

CCPC-35 5.00 %

CBC-33F 3.00 %

CBC-53F 3.00 % PPTUI-3-2 3.00 %

PYP-4N.F.F 8.00 %

The melting point of the compound PYP-4N.F.F is 78 X. Example 9

Clearing point + 90

Δn 0.1385

V10 1.12 V

V₉₀/V₁₀ 1.098

consisting of

ME2N.F 8.00 %

ME3N.F 8.00 % ME4N.F 11.00 %

PCH-3N.F.F 10.00 %

CC-3-V1 10.00 %

CCG-V-F 17.00 %

CCP-V-1 8.00 % CCPC-33 4.00 %

CCPC-34 4.00 %

CCPC-35 5.00 %

PPTUI-3-2 7.00 %

Thio-B 8.00 %

Example 10

Clearing point + 97 X

Δn 0.1613

V₁₀ 1.23 V

V₉₀/V₁₀ 1.069 Tave 163 msec

consisting of

ME2N.F 4.00 % ME3N.F 4.00 %

PCH-3N.F.F 15.00 %

PZU-V2-N 14.00 %

CC-3-V1 8.00 %

CCP-V-1 13.00 % CVCP-V-O1 4.50 %

CVCP-1V-O1 4.50 %

PPTUI-3-2 16.00 %

CBC-33F 4.00 %

CBC-53F 4.00 % CCZU-3-F 9.00 %

Claims

Patent claims

1. Supertwist nematic liquid-crystal display containing two plane-parallel outer plates which, together with a frame, form a cell, a nematic liquid-crystal mixture of positive dielectric anisotropy which is present in the cell, electrode layers with superposed alignment layers on the insides of the outer plates which address each pixel by orthogonal row wave forms, pre-tilt angle between the longitudinal axis of the molecules at the surface of the outer plates and the outer plates of from about 1 degree to 30 degrees, and a twist angle of the liquid-crystal mixture in the cell from alignment layer to alignment layer with a value of between 22.5 and 600°, wherein the nematic liquid-crystal mixture essentially consists of

b) 10-55 % by weight of a liquid-crystalline component B. comprising one or more compounds having a dielectric anisotropy from -1.5 to +1.5;

c) 0-10 % by weight of a liquid-crystalline component D, comprising one or more compounds having a dielectric anisotropy of less than -1.

5, and

d) an optically active component C in such an amount that the ratio between the layer thickness (separation of the plane-parallel outer plates) and the natural pitch of the chiral nematic liquid- crystal mixture is from about 0.2 to 1.3, characterized in that the liquid crystal mixture comprises at least one compound of formula IA

wherein

R is an alkenyl group with 2 to 7 C atoms,

R is an optionally fluohnated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -0-, -CH=CH-, -CO-, -OCO- or COO- in such a manner that O atoms are not directly adjacent to one another, or , in case m = 1 , R⁴ can also be Q-Y,

Q is CF₂, OCF₂, CFH, OCFH or a single bond,

Y is F or CI,

L¹ and L are each independently H or F,

m is 0 or 1

and at least one compound of component A, having the formula IB

wherein Y¹ and Y² are each independently H or F,

R⁵ is alkenyl or alkynyl -having 2 to 10 C atoms,

R⁷ is alkynyl or alkynyloxy having 2 to 10 C atoms.

Display according to claim 1 , characterized in that the compounds of formula IA are selected from the following formulae IA-1 , IA-2, IA-3:

R^' H H R^< IA-1

wherein R³, L¹, L², Q and Y have the meanings given for formula IA in claim 1 and

R⁴ is an optionally fluohnated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent

CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or - COO- in such a manner that O atoms are not directly adjacent to one another.

Display according to claim 1 or 2, characterized in that the compounds of formula IB are selected from the following formulae IB1 to IB7:

wherein R^a is alkenyl having 2 to 5 C atoms, R^b is alkyl having 1 to 7

C atoms or alkenyl having 2 to 7 C atoms, and R^c is alkynyl having 2 to 7 C atoms.

Display according to one of the preceding claims, characterized in that component A further comprises one or more compounds of formula II

wherein

R is an optionally fluohnated alkyl, alkoxy, alkenyl or aikenyloxy group with 1 to 12 C atoms, wherein one or two non-adjacent CH₂ groups can be replaced by -O-, -CH=CH-, -CO-, -OCO- or COO- in such a manner that O atoms are not directly adjacent to one another, A — and

L⁵ and L⁶ are each independently H or F,

Z¹ and Z² are independently of each other -COO-, -CH₂CH₂- -CH=CH-, -C≡C- or a single bond, and

is O, 1 or 2.

Display according to claim 4, characterized in that the compounds of formula II are selected from the follwing formulae

R

R

wherein R is as defined for formula II in claim 4.

6. Display according to at least one of the preceding claims, characterized in that component A further comprises one or more compounds of formula III

wherein R⁸ is alkyl or alkoxy having 1 to 7 C atoms, Z² and n have each independently one of the meanings given for formula II in claim 4,

and _

L , L², L⁵ and L⁶ are each independently H or F.

7. Display according to claim 6, characterized in that the compounds of formula III are selected from the following formulae

wherein R is as defined for formula III in claim 6.

8. Display according to at least one of claims 1 to 7, characterized in that the liquid crystal mixture further comprises one or more compounds of formula V

wherein R has one of the meanings given for formula II in claim 4 and

Y² is F or Cl.

9. Display according to at least one of claims 1 to 8, characterized in that the liquid crystal mixture contains a total of 3 to 8 compounds of formulae IA and IB, with the amount of these compounds being 15 to

45 % by weight of the total mixture.

10. Display according to at least one of claims 1 to 9, characterized in that the liquid crystal mixture comprises more than 58 % by weight of one or more compounds having a positive dielectric anisotropy of more than + 12.

11. Display according to at least one of claims 1 to 10, characterized in that it has a threshold voltage of 1.3 V or less.

12. Liquid crystal mixture or composition as defined in at least one of claims 1 to 11.

13. Compoun d of formula

wherein

Y¹ and Y² are each independently H or F,

R⁵ is alkenyl or alkynyl having 2 to 10 C atoms,

R⁷ is alkynyl or alkynyloxy having 2 to 10 C atoms.