DE112018006358T5 - Liquid crystalline medium - Google Patents

Abstract

The invention relates to a liquid-crystalline medium which contains at least one compound of the formula X and one or more compounds selected from the group of the compounds of the formulas IIA, IIB and IIC, in which the groups and parameters which occur have the meanings given in claim 1 and its use for an active matrix display, in particular based on the VA-, PSA-, PA-VA-, SS-VA-, SA-VA-, PS-VA-, PALC-, IPS-, PS-IPS-, UB- FFS, U-IPS, FFS or PS-FFS effect.

Description

worin

• R^X1 und R^X2 jeweils unabhängig voneinander H, einen Alkyl- oder Alkoxyrest mit 1 bis 15 C-Atomen bedeuten, wobei in diesen Resten zusätzlich eine oder mehrere CH₂-Gruppen jeweils unabhängig voneinander so durch -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-,
  
  
  -O-, -CO-O-, -O-CO- ersetzt sein können, dass O-Atome nicht direkt miteinander verknüpft sind, und worin zusätzlich ein oder mehrere H-Atome durch Halogen ersetzt sein können,
• n 0 oder 1 bedeutet und
• Z^X1 bei jedem Auftreten unabhängig voneinander -CO-O-, -O-CO-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -CH₂-, -CH₂CH₂-, -(CH₂)₄-, -CH=CH-CH₂O-, -C₂F₄-, -CH₂CF₂-, -CF₂CH₂-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C=C- oder eine Einfachbindung bedeutet, und

gegebenenfalls, vorzugsweise zwingend, eine oder mehrere Verbindungen der Formel I

worin

• R¹¹ und R¹² jeweils unabhängig voneinander H, einen Alkyl- oder Alkoxyrest mit 1 bis 15 C-Atomen bedeuten, wobei in diesen Resten zusätzlich eine oder mehrere CH₂-Gruppen jeweils unabhängig voneinander so durch -C≡C-, -CF₂O-, -OCF₂-, -CH=CH-,
  
  
  -O-, -CO-O-, -O-CO- ersetzt sein können, dass O-Atome nicht direkt miteinander verknüpft sind, und worin zusätzlich ein oder mehrere H-Atome durch Halogen ersetzt sein können,
• 
  bei jedem Auftreten unabhängig voneinander
  1. a) einen 1,4-Cyclohexenylen- oder 1,4-Cyclohexylenrest, worin eine oder zwei nicht benachbarte CH₂-Gruppen durch -O- oder -S- ersetzt sein können,
  2. b) einen 1,4-Phenylenrest, worin eine oder zwei CH-Gruppen durch N ersetzt sein können,
  3. c) einen Rest aus der Gruppe Piperidin-1,4-diyl, 1,4-Bicyclo-[2.2.2]octylen, Naphthalin-2,6-diyl, Decahydronaphthalin-2,6-diyl, 1,2,3,4-Tetrahydronaphthalin-2,6-diyl, Phenanthren-2,7-diyl und Fluoren-2,7-diyl
  bedeutet, wobei die Reste a), b) und c) ein- oder mehrfach durch Halogenatome substituiert sein können,
• a 0, 1 oder 2, vorzugsweise 0 oder 1 ist,
• Z¹ bei jedem Auftreten unabhängig voneinander -CO-O-, -O-CO-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -CH₂-, -CH₂CH₂-, -(CH₂)₄-, -CH=CH-CH₂O-, -C₂F₄-,
• L¹¹ und L¹² -CH₂CF₂-, -CF₂CH₂-, -CF=CF-, -CH=CF-, -CF=CH-, -CH=CH-, -C≡C- oder eine Einfachbindung bedeutet und jeweils unabhängig voneinander F, Cl, CF₃ oder CHF₂, vorzugsweise H oder F, am stärksten bevorzugt F bedeuten,

und eine oder mehrere Verbindungen, die ausgewählt sind aus der Gruppe der Verbindungen der Formeln IIA, IIB und IIC

worin

• R^2A, R^2B und R^2C jeweils unabhängig voneinander H, einen Alkyloder Alkenylrest mit bis zu 15 C-Atomen bedeuten, der unsubstituiert, einfach durch CN oder CF₃ substituiert oder mindestens einfach durch Halogen substituiert ist, wobei in diesen Resten zusätzlich eine oder mehrere CH₂-Gruppen so durch -O-, -S-,
  
  -C≡C-, -CF₂O-, -OCF₂-, -OC-O- oder -O -CO- ersetzt sein können, dass O-Atome nicht direkt miteinander verknüpft sind,
• L¹ bis L⁴ jeweils unabhängig voneinander F, Cl, CF₃ oder CHF₂ bedeuten,
• Z² und Z^2' jeweils unabhängig voneinander eine Einfachbindung, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CH=CHCH₂O- bedeuten,
• p 0, 1 oder 2 bedeutet,
• q 0 oder 1 bedeutet und
• v 1 bis 6 bedeutet,

enthält.The invention relates to a liquid-crystalline medium which contains one or more compounds of the formula X

wherein

• R ^X1 and R ^X2 each, independently of one another, denote H, an alkyl or alkoxy radical having 1 to 15 carbon atoms, with one or more CH ₂ groups in these radicals additionally each independently of one another as represented by -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH = CH-,
  
  
  -O-, -CO-O-, -O-CO- can be replaced so that O atoms are not directly linked to one another, and in which one or more H atoms can also be replaced by halogen,
• n means 0 or 1 and
• Z ^X1 on each occurrence independently of one another -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₄ -, -CH = CH-CH ₂ O-, -C ₂ F ₄ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-, -C = C- or a single bond, and

optionally, preferably mandatory, one or more compounds of the formula I

wherein

• R ¹¹ and R ¹² each independently of one another denote H, an alkyl or alkoxy radical having 1 to 15 carbon atoms, with one or more CH ₂ groups in these radicals additionally each independently of one another as represented by -C soC-, -CF ₂ O-, -OCF ₂ -, -CH = CH-,
  
  
  -O-, -CO-O-, -O-CO- can be replaced so that O atoms are not directly linked to one another, and in which one or more H atoms can also be replaced by halogen,
• 
  at each occurrence independently of one another
  1. a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH ₂ groups can be replaced by -O- or -S-,
  2. b) a 1,4-phenylene radical, in which one or two CH groups can be replaced by N,
  3. c) a radical from the group piperidin-1,4-diyl, 1,4-bicyclo- [2.2.2] octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl
  means, where the radicals a), b) and c) can be substituted one or more times by halogen atoms,
• a is 0, 1 or 2, preferably 0 or 1,
• Z ¹ on each occurrence independently of one another -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₄ -, -CH = CH-CH ₂ O-, -C ₂ F ₄ -,
• L ¹¹ and L ¹² -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-, -C≡C- or a Denotes single bond and each independently denotes F, Cl, CF ₃ or CHF ₂ , preferably H or F, most preferably F,

and one or more compounds which are selected from the group of compounds of the formulas IIA, IIB and IIC

wherein

• R ^2A , R ^2B and R ^2C each, independently of one another, denote H, an alkyl or alkenyl radical with up to 15 carbon atoms, which is unsubstituted, monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, with one or more of these radicals several CH ₂ groups by -O-, -S-,
  
  -C≡C-, -CF ₂ O-, -OCF ₂ -, -OC-O- or -O -CO- can be replaced so that O atoms are not directly linked,
• L ¹ to L ⁴ each independently represent F, Cl, CF ₃ or CHF ₂ ,
• Z ² and Z ^{2 'are} each independently a single bond, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- , -OCO-, -C ₂ F ₄ -, -CF = CF-, -CH = CHCH ₂ O-,
• p means 0, 1 or 2,
• q means 0 or 1 and
• v means 1 to 6

contains.

Such media can be used in particular for electro-optical displays with active matrix addressing based on the ECB effect and for IPS displays (in-plane switching) or FFS displays (fringe field switching).

The principle of electrically controlled birefringence, the ECB (electrically controlled birefringence) effect or also DAP (deformation of erect phases) effect, was first described in 1971 ( MF Schieckel and K. Fahrenschon, “Deformation of nematic liquid crystals with vertical orientation in electrical fields”, Appl. Phys. Lett. 19 (1971), 3912) . Work by JF Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869) .

The work of 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) have shown that liquid-crystalline phases must have high values for the ratio of the elastic constants K ₃ / K ₁ , high values for the optical anisotropy Δn and values for the dielectric anisotropy of Δε ≤ -0.5 in order for high-information display elements based on the ECB effect can be used. Electro-optical display elements based on the ECB effect have a homeotropic edge orientation (VA technology = Vertically Aligned). Dielectric negative liquid crystal media can also be used for displays that use the so-called IPS or FFS effect.

Displays that use the ECB effect have proven to be so-called VAN (vertically aligned nematic) displays, for example in the MVA (multi-domain vertical alignment) designs, e.g. Yoshide, H. et al., Lecture 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, CT et al., Lecture 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, e.g.: Kim, Sang Soo, Lecture 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, e.g. Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Lecture 15.2: "Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757 ), next to IPS (In-Plane Switching) displays (e.g. Yeo, SD, Lecture 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, established as one of the three most important newer types of liquid crystal displays, especially for television applications. The technologies are described in general terms, 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, lan, SID Seminar 2004, Seminar M-7: "LCD Television", Seminar Lecture Notes, M-7/1 to M-7/32, compared. Although the switching times of modern ECB displays have already been significantly improved through control methods with override, e.g. Kim, Hyeon Kyeong et al., Lecture 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 Achieving video-compatible switching times, especially when switching gray levels, is still a problem that has not yet been satisfactorily solved.

For the technical application of this effect in electro-optical display elements, LC phases are required which must meet a large number of requirements. The chemical resistance to moisture, air and physical influences such as heat, radiation in the infrared, visible and ultraviolet range and electrical constant and alternating fields are particularly important here.

Furthermore, industrially usable LC phases are required to have a liquid-crystalline mesophase in a suitable temperature range and a low viscosity.

In none of the previously disclosed series of compounds with a liquid-crystalline mesophase is there an individual compound which meets all of 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, optimal phases could not easily be produced in this way, since no liquid-crystal materials with clearly negative dielectric anisotropy and adequate long-term stability were available up to now.

1. 1. MOS(Metal Oxide Semiconductor)-Transistoren auf Silicium-Wafer als Substrat
2. 2. Dünnschicht-Transistoren (TFTs) auf einer Glasplatte als Substrat.

Matrix liquid crystal displays (MLC displays) are known. Active elements (ie transistors), for example, can be used as non-linear elements for the individual switching of the individual pixels. One then speaks of an "active matrix", whereby two types can be distinguished:

1. 1. MOS (Metal Oxide Semiconductor) transistors on silicon wafer as substrate
2. 2. Thin film transistors (TFTs) on a glass plate as a substrate.

In type 1, dynamic scattering or the guest-host effect is usually used as the electro-optical effect. The use of monocrystalline silicon as substrate material limits the size of the display, since the modular composition of various partial displays also leads to problems at the joints.

With the more promising type 2, which is preferred, the TN effect is usually used as the electro-optical effect.

A distinction is made between two technologies: TFTs with compound semiconductors such as CdSe or TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on with great intensity worldwide.

The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counter-electrode on its inside. Compared to the size of the pixel electrode, the TFT is very small and practically does not disturb the image. This technology can also be expanded for fully color-compatible displays in which a mosaic of red, green and blue filters is arranged in such a way that one filter element is located opposite a switchable pixel.

The term MLC displays here includes any matrix display with integrated non-linear elements, i.e. In addition to the active matrix, 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. In addition to problems with regard to the angle dependency of the contrast and the switching times, MLC displays also have difficulties due to an 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, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, Sept. 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff, Paris ]. As the resistance decreases, the contrast of an MLC display deteriorates. Since the specific resistance of the liquid crystal mixture generally decreases over the life of an MLC display due to interaction with the inner surfaces of the display, a high (initial) resistance is very important for displays that have to have acceptable resistance values over a long operating period.

There is therefore still a great need for MLC displays with a very high specific resistance and, at the same time, a large working temperature range, short switching times and low threshold voltage, with the aid of which different gray levels can be generated.

The disadvantage of the frequently used MLC-TN displays is based on their comparatively low contrast, the relatively high dependence on the viewing angle and the difficulty in producing gray levels in these displays.

The market for VA, PS-VA, IPS, FFS and UB-FFS applications calls for fiberglass mixtures with fast switching times and very high reliability. One approach to achieving fast switching times is the identification of highly polar LC materials with low rotational viscosities, the use of which in LC mixtures enables the desired effect. However, the use of such highly polar LC materials has a negative influence on the reliability parameters, especially after exposure to light.

The invention is based on the object of providing liquid crystal mixtures, in particular for monitor and TV applications, which are based on the ECB, UB-FFS, IPS or FFS effect, which do not or only to a lesser extent the disadvantages indicated above exhibit. 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 very short switching times and at the same time have improved reliability behavior, in particular no or significantly reduced burn-in after long operating times.

werden als Bestandteile flüssigkristalliner Medien in der europäischen Patentanmeldung Nr. EP 17161352.4 erwähnt. Dort werden auch die Formeln

und

offenbart. In den Medien dieses Dokuments wird jedoch nur die eine einzige Verbindung

verwendet, bei der n 2 ist und m 5 ist.Compounds of the general formula

are used as components of liquid crystalline media in European patent application no. EP 17161352.4 mentioned. There are also the formulas

and

disclosed. In the media of this document, however, there is only one connection

where n is 2 and m is 5.

The invention thus relates to a liquid-crystalline medium which contains at least one compound of the formula X and one or more compounds selected from the group of the compounds of the formulas IIA, IIB and IIC. These media are particularly suitable for producing liquid crystal displays that have a fast switching time and good voltage holding capacity as well as excellent storage stability at low temperatures, sufficient for many applications.

The mixtures according to the invention preferably show very broad nematic phase ranges with clearing points ≥ 70 ° C., preferably ≥ 75 ° C., in particular ≥ 80 ° C., very favorable values for the capacitive threshold, relatively high values for the holding capacity and at the same time very good low temperature stabilities at -20 ° C and -30 ° C as well as very low rotational viscosities and short switching times. The mixtures according to the invention are furthermore distinguished by the fact that, in addition to improving the rotational viscosity γ ₁ , relatively high values of the elastic constant K ₃₃ can be observed to improve the switching times. The use of the compounds of the formula X in LC mixtures, preferably with negative dielectric anisotropy, reduces the ratio of rotational viscosity γ ₁ and elastic constants K _i .

Some preferred embodiments of the mixtures according to the invention are given below.

In the compounds of the formula X, R ^X1 and R ^{X2 are} each, independently of one another, preferably straight-chain alkyl, in particular CH ₃ , nC ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , nC ₅ H ₁₁ , nC ₆ H ₁₃ - or nC ₇ H ₁₅ , straight-chain alkoxy, in particular CH ₃ —O, nC ₂ H ₅ —O, nC ₃ H ₇ —O, nC ₄ H ₉ —O, nC ₅ H ₁₁ —O or nC ₆ H ₁₃ —O, furthermore alkenyl , in particular CH ₃ = CH, CH ₃ CH = CH, CH ₃ CH = CHCH ₂ or CH ₃ CH ₂ CH = CH, branched alkoxy, in particular (CH ₃ ) ₂ CH (CH ₂ ) ₃ O, and alkenyloxy, in particular CH ₂ = CHO, CH ₂ = CH ₂ CHO, CH ₃ CH ₂ = CHCHO or O CH ₂ CH ₂ CH = CHCH ₂ O.

R ^X1 particularly preferably denotes straight-chain alkyl with 1 to 7 carbon atoms and R ^X2 particularly preferably denotes straight-chain alkoxy with 1 to 6 carbon atoms, in particular methoxy, ethoxy, propoxy, butoxy, pentoxy or hexoxy.

bei denen die Parameter die jeweiligen vorstehend gegebenen Bedeutungen besitzen und

R^X1

vorzugsweise Alkyl oder Alkoxy ist und

R^X2

vorzugsweise Alkoxy ist.

Preferred compounds of the formula X which are present in the media are the compounds of the formulas X-1 and X-2

in which the parameters have the respective meanings given above and

R ^X1

is preferably alkyl or alkoxy and

R ^X2

is preferably alkoxy.

Preferred compounds of formula X-1 that are present in the media are the compounds of formulas X-1-1 and X-1-3

Preferred compounds of formula X-2 that are present in the media are the compounds of formulas X-2-1 and X-2-3

In the compounds of the formula I, R ¹¹ and R ^{12 are} each, independently of one another, preferably straight-chain alkyl, in particular CH ₃ , nC ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , nC ₅ H ₁₁ , nC ₆ H ₁₃ - or nC ₇ H ₁₅ , straight-chain alkoxy, in particular CH ₃ —O, nC ₂ H ₅ —O, nC ₃ H ₇ —O, nC ₄ H ₉ —O, nC ₅ H ₁₁ —O or nC ₆ H ₁₃ —O, furthermore alkenyl , in particular CH ₃ = CH, CH ₃ CH = CH, CH ₃ CH = CHCH ₂ or CH ₃ CH ₂ CH = CH, branched alkoxy, in particular (CH ₃ ) ₂ CH (CH ₂ ) ₃ O, and alkenyloxy, in particular CH ₂ = CHO, CH ₂ = CH ₂ CHO, CH ₃ CH ₂ = CHCHO or O CH ₂ CH ₂ CH = CHCH ₂ O.

R ¹¹ particularly preferably denotes straight-chain alkyl having 1 to 7 carbon atoms and R ¹² particularly preferably denotes straight-chain alkoxy having 1 to 6 carbon atoms, in particular methoxy, ethoxy, propoxy, butoxy, pentoxy or hexoxy.

L ¹¹ and L ¹² in formula I preferably both denote F.

worin
die Parameter die vorstehend gegebenen Bedeutungen besitzen, R¹¹ geradkettiges Alkyl bedeutet und R¹² vorzugsweise Alkoxy bedeutet und L¹¹ und L¹² vorzugsweise beide F bedeuten.Preferred compounds of the formula I which are present in the media are the compounds of the formulas I-1 to I-3, preferably of the formula I-2

wherein
the parameters have the meanings given above, R ^{11 is} straight-chain alkyl and R ^{12 is} preferably alkoxy and L ¹¹ and L ^{12 are} preferably both F.

worin die Parameter die vorstehend gegebenen Bedeutungen besitzen.In a preferred embodiment, the media contain one or more compounds of the formula I which are selected from the group of compounds of the formulas IO-1 to IO-3, preferably of the formula IO-2,

wherein the parameters have the meanings given above.

worin die Parameter die vorstehend gegebenen Bedeutungen besitzen.In another preferred embodiment, the media contain one or more compounds of the formula I which are selected from the group of compounds of the formulas IS-1 to IS-3, preferably of the formula IS-2,

wherein the parameters have the meanings given above.

worin die Parameter die vorstehend gegebenen Bedeutungen besitzen und vorzugsweise einer von R¹¹ und R¹² Alkoxy ist und stärker bevorzugt beide von ihnen Alkoxy sind.Further preferred compounds of the formula I which are present in the media are the compounds of the formulas I-4

wherein the parameters have the meanings given above, and preferably one of R ¹¹ and R ^{12 is} alkoxy, and more preferably both of them are alkoxy.

worin die Parameter die vorstehend gegebenen Bedeutungen besitzen und vorzugsweise einer von R¹¹ und R¹² Alkoxy ist und stärker bevorzugt beide von ihnen Alkoxy sind.Further preferred compounds of the formula I which are present in the media are the compounds of the formulas IO-4

wherein the parameters have the meanings given above, and preferably one of R ¹¹ and R ^{12 is} alkoxy, and more preferably both of them are alkoxy.

worin die Parameter die vorstehend gegebenen Bedeutungen besitzen und vorzugsweise einer von R¹¹ und R¹² Alkoxy ist und stärker bevorzugt beide von ihnen Alkoxy sind.Further preferred compounds of the formula I which are present in the media are the compounds of the formula IS-4

wherein the parameters have the meanings given above, and preferably one of R ¹¹ and R ^{12 is} alkoxy, and more preferably both of them are alkoxy.

In a preferred embodiment of the present invention, the media contain one or more compounds selected from the group of compounds of the formulas IO-1 to IO-3, and one or more compounds selected from the group of compounds of the formulas IS-1 through IS-3 are selected.

The compounds of the formula I can be prepared as is familiar to the person skilled in the art.

The compounds of formula I can, for example, as in US 2005/0258399 or WO 02/055463 A1 described.

The media according to the invention preferably contain one, two, three, four or more, preferably one, two or three compounds of the formula I.

The compounds of the formula X are preferably used in the liquid-crystalline medium in amounts of 1% by weight, preferably 3% by weight, based on the mixture as a whole. Liquid-crystalline media which contain 1 to 40% by weight, very particularly preferably 2 to 30% by weight, of one or more compounds of the formula I are particularly preferred.

The compounds of the formula I are preferably used in the liquid-crystalline medium in amounts of 1% by weight, preferably 3% by weight, based on the total mixture. Liquid-crystalline media which contain 1 to 40% by weight, very particularly preferably 2 to 30% by weight, of one or more compounds of the formula I are particularly preferred.

Preferred embodiments of the liquid-crystalline medium according to the invention are given below:

• In den Verbindungen der Formeln IIA und IIB kann Z² gleiche oder verschiedene Bedeutungen besitzen. In den Verbindungen der Formel IIB können Z² und Z^2' gleiche oder verschiedene Bedeutungen besitzen.
• In den Verbindungen der Formeln IIA, IIB und IIC bedeuten R^2A, R^2B und R^2C vorzugsweise jeweils Alkyl mit 1 bis 6 C-Atomen, insbesondere CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅H₁₁.
• In den Verbindungen der Formeln IIA und IIB bedeuten L¹, L², L³ und L⁴ vorzugsweise L¹ = L² = F und L³ = L⁴ = F, ferner L¹ = F und L² = Cl, L¹ = Cl und L² = F, L³ = F und L⁴ = Cl, L³ = Cl und L⁴ = F. Z² und Z^2' in den Formeln IIA und IIB bedeuten vorzugsweise jeweils unabhängig voneinander eine Einfachbindung, ferner eine -C₂H₄-Brücke.

a) Liquid-crystalline medium which additionally contains one or more compounds selected from the group of compounds of the formulas IIA, IIB and IIC,

• In the compounds of the formulas IIA and IIB, Z ^{2 can have} identical or different meanings. In the compounds of the formula IIB, Z ² and Z ^{2 'can have the} same or different meanings.
• In the compounds of the formulas IIA, IIB and IIC, R ^2A , R ^2B and R ^{2C are} preferably each alkyl having 1 to 6 carbon atoms, in particular CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , nC ₅ H ₁₁ .
• In the compounds of the formulas IIA and IIB, L ¹ , L ² , L ³ and L ^{4 are} preferably L ¹ = L ² = F and L ³ = L ⁴ = F, and L ¹ = F and L ² = Cl, L ¹ = Cl and L ² = F, L ³ = F and L ⁴ = Cl, L ³ = Cl and L ⁴ = F. Z ² and Z ^{2 '} in the formulas IIA and IIB preferably each independently represent a single bond, furthermore one -C ₂ H ₄ bridge.

If in formula IIB Z ² = -C ₂ H ₄ - or -CH ₂ O-, then Z ^{2 'is} preferably a single bond, or, if Z ^2' = -C ₂ H ₄ - or -CH ₂ O-, so Z ^{2 is} preferably a single bond. In the compounds of the formulas IIA and IIB, (O) C _v H _{2v + 1 is} preferably OC _v H _{2v + 1} , furthermore C _v H _{2v + 1} . In the compounds of the formula IIC, (O) C _v H _{2v + 1 is} preferably C _v H _2v + ₁ . In the compounds of the formula IIC, L ³ and L ^{4 are} preferably each F.

worin

alkyl und alkyl*

jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1 bis 6 C-Atomen bedeuten und

alkenyl und alkenyl*

jeweils unabhängig voneinander einen geradkettigen Alkenylrest mit 2 bis 6 C-Atomen bedeuten.

Preferred compounds of the formulas IIA, IIB and IIC are given below:

wherein

alkyl and alkyl *

each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms and

alkenyl and alkenyl *

each independently represent a straight-chain alkenyl radical having 2 to 6 carbon atoms.

Particularly preferred mixtures according to the invention contain one or more compounds of the formulas IIA-2, IIA-8, IIA-14, IIA-26, II-28, IIA-33, IIA-39, IIA-45, IIA-46, IIA-47 , IIA-50, IIB-2, IIB-11, IIB-16 and IIC-1.

The proportion of the compounds of the formulas IIA and / or IIB in the total mixture is preferably at least 20% by weight.

worin alkyl und alkyl* die vorstehend angegebenen Bedeutungen besitzen, vorzugsweise in Mengen von > 3 Gew.-%, insbesondere > 5 Gew.-% und besonders bevorzugt 5 bis 25 Gew.-%.Particularly preferred media according to the invention contain at least one compound of the formula IIC-1

where alkyl and alkyl * have the meanings given above, preferably in amounts of> 3% by weight, in particular> 5% by weight and particularly preferably 5 to 25% by weight.

enthält, worin

• _R ³¹ und _R ³² jeweils unabhängig voneinander einen geradkettigen Alkyl-, Alkoxy-, Alkenyl-, Alkoxyalkyl- oder Alkoxyrest mit bis zu 12 C-Atomen bedeuten und
• 
  
  
  oder
  
  bedeutet,
• _Z ³ eine Einfachbindung, -CH₂CH₂-, -CH=CH-, -CF₂O-, -OCF₂-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -C₄H₈-, -CF=CF- bedeutet.

b) Liquid-crystalline medium which additionally contains one or more compounds of the formula III

contains where

• _R ³¹ and _R ³² each independently represent a straight-chain alkyl, alkoxy, alkenyl, alkoxyalkyl or alkoxy radical with up to 12 carbon atoms and
• 
  
  
  or
  
  means
• _Z ^{3 is} a single bond, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C _{2 means} F ₄ -, -C ₄ H ₈ -, -CF = CF-.

worin

alkyl und alkyl*

jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1 bis 6 C-Atomen bedeuten.

Preferred compounds of the formula III are given below:

wherein

alkyl and alkyl *

each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms.

The medium according to the invention preferably contains at least one compound of the formula IIIa and / or formula IIIb.

The proportion of the compounds of the formula III in the total mixture is preferably at least 5% by weight.

und / oder

und / oder

vorzugsweise in Gesamtmengen von ≥ 5 Gew.-%, insbesondere ≥ 10 Gew.-%.c) Liquid-crystalline medium, additionally containing a compound of the formula

and or

and or

preferably in total amounts of 5% by weight, in particular 10% by weight.

vorzugsweise in Mengen von 2 bis 15 Gew.-%.Mixtures according to the invention containing the compound (acronym: CC-3-V1) are also preferred

preferably in amounts of 2 to 15% by weight.

Preferred mixtures contain 5 to 60% by weight, preferably 10 to 55% by weight, in particular 20 to 50% by weight of the compound of the formula (acronym: CC-3-V)

und eine Verbindung der Formel (Akronym: CC-3-V1)

enthalten, vorzugsweise in Mengen von 10 bis 60 Gew.-%.Mixtures that contain a compound of the formula (acronym: CC-3-V)

and a compound of the formula (acronym: CC-3-V1)

contained, preferably in amounts of 10 to 60 wt .-%.

enthält, worin

R^7-10

jeweils unabhängig voneinander eine der für R^2A in Anspruch 5 angegebenen Bedeutungen besitzen und

w und x

jeweils unabhängig voneinander 1 bis 6 bedeuten.

d) Liquid-crystalline medium which additionally contains one or more tetracyclic compounds of the formulas

contains where

R ^7-10

each independently have one of the meanings given for R ^2A in claim 5 and

w and x

each independently represent 1 to 6.

Mixtures which contain at least one compound of the formula V-9 are particularly preferred.

enthält, worin R¹⁴-R¹⁹ jeweils unabhängig voneinander einen Alkyl- oder Alkoxyrest mit 1 bis 6 C-Atomen bedeuten; z und m jeweils unabhängig voneinander 1 bis 6 bedeuten; x 0, 1, 2 oder 3 bedeutet.e) Liquid-crystalline medium which additionally contains one or more compounds of the formulas Y-1 to Y-6

contains in which R ¹⁴ -R ¹⁹ each independently represent an alkyl or alkoxy radical having 1 to 6 carbon atoms; z and m each independently represent 1 to 6; x is 0, 1, 2 or 3.

The medium according to the invention particularly preferably contains one or more compounds of the formulas Y-1 to Y-6, preferably in amounts of 5% by weight.

worinf) Liquid-crystalline medium, additionally containing one or more fluorinated terphenyls of the formulas T-1 to T-21

wherein

R denotes a straight-chain alkyl or alkoxy radical with 1 to 6 carbon atoms and m = 0, 1, 2, 3, 4, 5 or 6 and n denotes 0, 1, 2, 3 or 4.

R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy.

The medium according to the invention preferably contains the terphenyls of the formulas T-1 to T-21 in amounts of 2 to 30% by weight, in particular 5 to 20% by weight.

Compounds of the formulas T-1, T-2, T-4, T-20 and T-21 are particularly preferred. In these compounds, R is preferably alkyl, furthermore alkoxy, each having 1 to 5 carbon atoms. In the compounds of the formula T-20, R preferably denotes alkyl or alkenyl, in particular alkyl. In the compound of the formula T-21, R is preferably alkyl.

The terphenyls are preferably used in the mixtures according to the invention if the Δn value of the mixture is to be 0.1. Preferred mixtures contain 2 to 20% by weight of one or more terphenyl compounds selected from the group of compounds T-1 to T-21.

worin

alkyl und alkyl*

jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1 bis 6 C-Atomen bedeuten und

alkenyl und alkenyl*

jeweils unabhängig voneinander einen geradkettigen Alkenylrest mit 2 bis 6 C-Atomen bedeuten.

g) Liquid-crystalline medium, additionally containing one or more biphenyls of the formulas B-1 to B-3

wherein

alkyl and alkyl *

each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms and

alkenyl and alkenyl *

each independently represent a straight-chain alkenyl radical having 2 to 6 carbon atoms.

The proportion of the biphenyls of the formulas B-1 to B-3 in the total mixture is preferably at least 3% by weight, in particular 5% by weight.

Of the compounds of the formulas B-1 to B-3, the compounds of the formula B-2 are particularly preferred.

worin alkyl* einen Alkylrest mit 1 bis 6 C-Atomen bedeutet. Das erfindungsgemäße Medium enthält besonders bevorzugt eine oder mehrere Verbindungen der Formeln B-1a und/oder B-2c.Particularly preferred biphenyls are

wherein alkyl * denotes an alkyl radical having 1 to 6 carbon atoms. The medium according to the invention particularly preferably contains one or more compounds of the formulas B-1a and / or B-2c.

h) Liquid-crystalline medium containing at least one compound of the formulas Z-1 to Z-7

worin R und alkyl die vorstehend angegebenen Bedeutungen besitzen.

wherein R and alkyl have the meanings given above.

worin R¹ und R² die für R^2A angegebenen Bedeutungen besitzen. R¹ und R² bedeuten vorzugsweise jeweils unabhängig voneinander geradkettiges Alkyl oder Alkenyl.i) Liquid-crystalline medium, additionally containing at least one compound of the formulas 0-1 to 0-18

wherein R ¹ and R ^{2 have} the meanings given for R ^2A . R ¹ and R ^{2 are} preferably each, independently of one another, straight-chain alkyl or alkenyl.

Preferred media contain one or more compounds of the formulas O-1, O-3, O-4, O-6, O-7, O-10, O-11, O-12, O-14, O-15, O -16 and / or O-17.

Particularly preferred compounds contain one or more compounds selected from the group of compounds of the formula 0-17.

Mixtures according to the invention very particularly preferably contain the compounds of the formula O-10, O-12, O-16 and / or O-17, in particular in amounts of 5 to 30%.

Preferred compounds of the formulas O-10 and O-17 are given below:

The medium according to the invention particularly preferably contains the tricyclic compounds of the formula O-10a and / or of the formula O-10b in combination with one or more bicyclic compounds of the formulas 0-17a to O-17d. The total proportion of the compounds of the formulas O-10a and / or O-10b in combination with one or more compounds selected from the bicyclic compounds of the formulas O-17a to O-17d is 5 to 40%, very particularly preferably 15 to 35%.

Very particularly preferred mixtures contain the compounds O-10a and O-17a:

The compounds O-10a and 0-17a are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25% and particularly preferably 18 to 22%, based on the total mixture.

Very particularly preferred mixtures contain the compounds O-10b and O-17a:

The compounds O-10b and O-17a are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25% and particularly preferably 18 to 22%, based on the total mixture.

Very particularly preferred mixtures contain the following three compounds:

The compounds O-10a, O-10b and O-17a are preferably present in the mixture in a concentration of 15 to 35%, particularly preferably 15 to 25% and particularly preferably 18 to 22%, based on the total mixture.

worin R¹ und R² die vorstehend angegebenen Bedeutungen besitzen. Vorzugsweise bedeutet in den Verbindungen O-6, O-7 und 0-17 R¹ Alkyl oder Alkenyl mit 1 bis 6 bzw. 2 bis 6 C-Atomen und R² bedeutet Alkenyl mit 2 bis 6 C-Atomen.Preferred mixtures contain at least one compound selected from the group of compounds

wherein R ¹ and R ^{2 have} the meanings given above. In the compounds O-6, O-7 and 0-17, R ^{1 is} preferably alkyl or alkenyl having 1 to 6 or 2 to 6 carbon atoms and R ² is alkenyl having 2 to 6 carbon atoms.

worin alkyl einen Alkylrest mit 1 bis 6 C-Atomen bedeutet.Preferred mixtures contain at least one compound of the formulas O-6a, O-6b, O-7a, O-7b, O-17e, O-17f, O-17g and O-17h:

wherein alkyl denotes an alkyl radical having 1 to 6 carbon atoms.

The compounds of the formulas O-6, O-7 and 0-17e-h are preferably present in the mixtures according to the invention in amounts of 1 to 40% by weight, preferably 2 to 35% by weight and very particularly preferably 2 to 30% by weight .-% in front.

worin R^1N und R^2N jeweils unabhängig voneinander die für R^2A angegebenen Bedeutungen besitzen, vorzugsweise geradkettiges Alkyl, geradkettiges Alkoxy oder geradkettiges Alkenyl bedeuten, und

Z¹ und Z²

jeweils unabhängig voneinander -C₂H₄-, -CH=CH-, -(CH₂)₄-, -(CH₂)₃O-, -O(CH₂)₃-, -CH=CHCH₂CH₂-, -CH₂CH₂CH=CH-, -CH₂O-, -OCH₂-, -COO-, -OCO-, -C₂F₄-, -CF=CF-, -CF=CH-, -CH=CF-, -CF₂O-, -OCF₂-, -CH₂- oder eine Einfachbindung bedeuten.

j) Preferred liquid-crystalline media according to the invention contain one or more substances which contain a tetrahydronaphthyl or naphthyl unit, such as, for example, the compounds of the formulas N-1 to N-5

wherein R ^1N and R ^2N each independently have the meanings given for R ^2A , preferably straight-chain alkyl, straight-chain alkoxy or straight-chain alkenyl, and

Z ¹ and Z ²

each independently of one another -C ₂ H ₄ -, -CH = CH-, - (CH ₂ ) ₄ -, - (CH ₂ ) ₃ O-, -O (CH ₂ ) ₃ -, -CH = CHCH ₂ CH ₂ - , -CH ₂ CH ₂ CH = CH-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF-, -CF = CH-, - CH = CF-, -CF ₂ O-, -OCF ₂ -, -CH ₂ - or a single bond.

worin R^B1, R^B2, R^CR1, R^CR2, R^1, R² jeweils unabhängig voneinander die Bedeutung von R^2A besitzen. c ist 0,1 oder 2 und d bedeutet 1 oder 2. R¹ und R² bedeuten vorzugsweise unabhängig voneinander Alkyl oder Alkoxy mit 1 bis 6 C-Atomen. Die Verbindungen der Formeln BF-1 und BF-2 sollten nicht mit einer oder mehreren Verbindungen der Formel I identisch sein.k) Preferred mixtures contain one or more compounds selected from the group of difluorodibenzochroman compounds of the formula BC, chromanes of the formula CR, fluorinated phenanthrenes of the formulas PH-1 and PH-2, fluorinated dibenzofurans of the formula BF-1 and BF -2

wherein R ^B1, R ^B2, R ^CR1, R ^CR2, R ^1, R ² each independently have the meaning of R ^2A . c is 0, 1 or 2 and d is 1 or 2. R ¹ and R ^{2 are} preferably, independently of one another, alkyl or alkoxy having 1 to 6 carbon atoms. The compounds of the formulas BF-1 and BF-2 should not be identical to one or more compounds of the formula I.

The mixtures according to the invention contain the compounds of the formulas BC, CR, PH-1, PH-2 and / or BF, preferably in amounts of 3 to 20% by weight, in particular in amounts of 3 to 15% by weight.

worin

alkyl und alkyl*

jeweils unabhängig voneinander einen geradkettigen Alkylrest mit 1 bis 6 C-Atomen bedeuten und

alkenyl und alkenyl*

jeweils unabhängig voneinander einen geradkettigen Alkenylrest mit 2 bis 6 C-Atomen bedeuten.

Particularly preferred compounds of the formulas BC and CR are the compounds BC-1 to BC-7 and CR-1 to CR-5

wherein

alkyl and alkyl *

each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms and

alkenyl and alkenyl *

each independently represent a straight-chain alkenyl radical having 2 to 6 carbon atoms.

Mixtures which contain one, two or three compounds of the formula BC-2, BF-1 and / or BF-2 are very particularly preferred.

worin

R¹¹, R¹², R¹³

jeweils unabhängig voneinander einen geradkettigen Alkyl-, Alkoxy-, Alkoxyalkyl- oder Alkenylrest mit 1 bis 6 C-Atomen bedeuten,

R¹² und R¹³

zusätzlich Halogen, vorzugsweise F bedeuten,

i

0,1 oder 2 bedeutet.

I) Preferred mixtures contain one or more indane compounds of the formula In

wherein

R ¹¹ , R ¹² , R ¹³

each independently represent a straight-chain alkyl, alkoxy, alkoxyalkyl or alkenyl radical having 1 to 6 carbon atoms,

R ¹² and R ¹³

in addition halogen, preferably F,

i

Means 0,1 or 2.

Preferred compounds of the formula In are the compounds of the formulas In-1 to In-16 given below:

The compounds of the formulas In-1, In-2, In-3 and In-4 are particularly preferred.

The compounds of the formula In and the sub-formulas In-1 to In-16 are used in the mixtures according to the invention preferably in concentrations ≥ 5% by weight, in particular 5 to 30% by weight and very particularly preferably 5 to 25% by weight .

worinm) Preferred mixtures additionally contain one or more compounds of the formulas L-1 to L-11

wherein

R, R ¹ and R ² each independently have the meanings given for R ^2A in claim 5 and alkyl is an alkyl radical having 1 to 6 carbon atoms. s means 1 or 2.

The compounds of the formulas L-1 and L-4, in particular L-4, are particularly preferred.

The compounds of the formulas L-1 to L-11 are preferably used in concentrations of 5 to 50% by weight, in particular 5 to 40% by weight and very particularly preferably 10 to 40% by weight.

• (Die verwendeten Akronyme sind in Tabelle A erklärt. n und m bedeuten hier jeweils unabhängig voneinander 1 bis 15, vorzugsweise 1 bis 6).

Particularly preferred mixing concepts are given below:

• (The acronyms used are explained in Table A. Here, n and m each independently mean 1 to 15, preferably 1 to 6).

• - eine oder mehrere Verbindungen der Formel X, worin n = 0, R^X1= Alkyl und R^X2 = Alkoxy; und/oder
• - eine oder mehrere Verbindungen der Formel X, worin n = 1, R^X1= Alkyl und R^X2 = Alkoxy; und/oder
• - eine oder mehrere Verbindungen der Formel I, worin L¹¹ = L¹² = F, R¹ = Alkyl und R^1* = Alkoxy; und/oder
• - CPY-n-Om, insbesondere CPY-2-O2, CPY-3-O2 und/oder CPY-5-O2, vorzugsweise in Konzentrationen > 5 %, insbesondere 10 bis 30 %, bezogen auf die gesamte Mischung, und/oder
• - CY-n-Om, vorzugsweise CY-3-O2, CY-3-O4, CY-5-O2 und/oder CY-5-O4, vorzugsweise in Konzentrationen > 5 %, insbesondere 15 bis 50 %, bezogen auf die gesamte Mischung, und/oder
• - CCY-n-Om, vorzugsweise CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-O1 und/oder CCY-5-O2, vorzugsweise in Konzentrationen > 5 %, insbesondere 10 bis 30 %, bezogen auf die gesamte Mischung, und/oder
• - CLY-n-Om, vorzugsweise CLY-2-O4, CLY-3-O2 und/oder CLY-3-O3, vorzugsweise in Konzentrationen > 5 %, insbesondere 10 bis 30 %, bezogen auf die gesamte Mischung.

The mixtures according to the invention preferably contain

• - One or more compounds of the formula X, in which n = 0, R ^X1 = alkyl and R ^X2 = alkoxy; and or
• - One or more compounds of the formula X, in which n = 1, R ^X1 = alkyl and R ^X2 = alkoxy; and or
• - One or more compounds of the formula I in which L ¹¹ = L ¹² = F, R ¹ = alkyl and R ^{1 *} = alkoxy; and or
• - CPY-n-Om, in particular CPY-2-O2, CPY-3-O2 and / or CPY-5-O2, preferably in concentrations> 5%, in particular 10 to 30%, based on the total mixture, and / or
• - CY-n-Om, preferably CY-3-O2, CY-3-O4, CY-5-O2 and / or CY-5-O4, preferably in concentrations> 5%, in particular 15 to 50%, based on the entire mixture, and / or
• - CCY-n-Om, preferably CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-O1 and / or CCY-5-O2, preferably in concentrations> 5%, in particular 10 to 30%, based on the total mixture, and / or
• - CLY-n-Om, preferably CLY-2-O4, CLY-3-O2 and / or CLY-3-O3, preferably in concentrations> 5%, in particular 10 to 30%, based on the total mixture.

• - die Verbindungen der Formel X, vorzugsweise der Formeln X-1 und X-2, vorzugsweise der Formeln XOY-n-m, XOY-n-Om, CXOY-n-m und CXOY-n-Om insbesondere ausgewählt aus der Gruppe der Formeln XOY-3-2, XOY-3-O2 und XOY-3-O4, CXOY-3-1, CXOY-3-O2 und CXOY-3-O4 in einer Konzentration im Bereich von 1 bis 30 Gew.-%, stärker bevorzugt von 2 bis 25 Gew- %, besonders bevorzugt von 3 bis 20 Gew.-% und ganz besonders bevorzugt von 4 bis 15 Gew-%
• - die Verbindungen der Formel I, wenn vorhanden, vorzugsweise der Formeln I-1 bis I-3, d.h. der Formeln 1-0-1 bis I-O-3 und/oder I-S-1 bis I-S-3, speziell LB-3-O4 und/oder LB(S)-4-O3 in einer Konzentration im Bereich von 1 bis 20 Gew.-%, stärker bevorzugt von 2 bis 15 Gew.-%, besonders bevorzugt von 3 bis 12 Gew.-% und ganz besonders bevorzugt von 4 bis 11 Gew-%
• - CPY-n-Om und CY-n-Om, vorzugsweise in Konzentrationen von 10 bis 80 %, bezogen auf die gesamte Mischung, und/oder
• - CPY-n-Om und CK-n-F, vorzugsweise in Konzentrationen von 10 bis 70 %, bezogen auf die gesamte Mischung, und/oder
• - CPY-n-Om und PY-n-Om, vorzugsweise CPY-2-O2 und/oder CPY-3-O2 und PY-3-O2, vorzugsweise in Konzentrationen von 10 bis 45 %, bezogen auf die gesamte Mischung, und/oder
• - CPY-n-Om und CLY-n-Om, vorzugsweise in Konzentrationen von 10 bis 80 %, bezogen auf die gesamte Mischung, und/oder
• - CCVC-n-V, vorzugsweise CCVC-3-V, vorzugsweise in Konzentrationen von 2 bis 10 %, bezogen auf die gesamte Mischung, und/oder
• - CCC-n-V, vorzugsweise CCC-2-V und/oder CCC-3-V, vorzugsweise in Konzentrationen von 2 bis 10 %, bezogen auf die gesamte Mischung, und/oder
• - CC-V-V, vorzugsweise in Konzentrationen von 5 bis 50 %, bezogen auf die gesamte Mischung.

Mixtures according to the invention which contain: (n and m each independently mean 1 to 6) are also preferred.

• the compounds of the formula X, preferably of the formulas X-1 and X-2, preferably of the formulas XOY-nm, XOY-n-Om, CXOY-nm and CXOY-n-Om, in particular selected from the group of the formulas XOY-3 -2, XOY-3-O2 and XOY-3-O4, CXOY-3-1, CXOY-3-O2 and CXOY-3-O4 in a concentration in the range from 1 to 30% by weight, more preferably from 2 to 25% by weight, particularly preferably from 3 to 20% by weight and very particularly preferably from 4 to 15% by weight
• - the compounds of the formula I, if present, preferably of the formulas I-1 to I-3, ie of the formulas 1-0-1 to IO-3 and / or IS-1 to IS-3, especially LB-3-O4 and / or LB (S) -4-O3 in a concentration in the range from 1 to 20% by weight, more preferably from 2 to 15% by weight, particularly preferably from 3 to 12% by weight and very particularly preferably from 4 to 11 wt%
• - CPY-n-Om and CY-n-Om, preferably in concentrations of 10 to 80%, based on the total mixture, and / or
• - CPY-n-Om and CK-nF, preferably in concentrations of 10 to 70%, based on the total mixture, and / or
• - CPY-n-Om and PY-n-Om, preferably CPY-2-O2 and / or CPY-3-O2 and PY-3-O2, preferably in concentrations of 10 to 45%, based on the total mixture, and /or
• - CPY-n-Om and CLY-n-Om, preferably in concentrations of 10 to 80%, based on the total mixture, and / or
• - CCVC-nV, preferably CCVC-3-V, preferably in concentrations of 2 to 10%, based on the total mixture, and / or
• - CCC-nV, preferably CCC-2-V and / or CCC-3-V, preferably in concentrations of 2 to 10%, based on the total mixture, and / or
• - CC-VV, preferably in concentrations of 5 to 50%, based on the total mixture.

In a particularly preferred embodiment of the present invention, the medium contains one or more compounds selected from the group of the compounds of the formulas XOY-n-Om and CXOY-n-Om, in a concentration in the range from 2 to 15% and the Compound CC-3-V in a concentration in the range from 25 to 40% and the compound CC-3-V1 in a concentration in the range from 5 to 12%.

In a particularly preferred embodiment of the present invention, the medium contains the compound B-2O-O5 and / or B-2O-O5 and / or B-50-O5 in a concentration in the range from 2 to 8% and the compound CC-3 -V in a concentration in the range from 25 to 40% and the compound CC-3-V1 in a concentration in the range from 5 to 12%.

In a particularly preferred embodiment of the present invention, the medium contains the compound B (S) -2O-O4 and / or B (S) -2O-O5 and / or B (S) -2O-O6 in a concentration in the range of 2 up to 8% and the compound CC-3-V in a concentration in the range from 25 to 40% and the compound CC-3-V1 in a concentration in the range from 5 to 12%.

The invention also relates to an electro-optical display with active matrix addressing based on the ECB, VA, PS-VA, PA-VA, IPS, PS-IPS, FFS or PS-FFS effect, characterized in that that it contains a liquid-crystalline medium according to one or more of claims 1 to 11 as dielectric.

The liquid-crystalline medium according to the invention preferably has a nematic phase of -20 ° C to 70 ° C, particularly preferably -30 ° C to 80 ° C, very particularly preferably -40 ° C to 90 ° C .

Here, the expression “have a nematic phase” means on the one hand that no smectic phase and no crystallization are observed at low temperatures at the corresponding temperature, and on the other hand that no clearing occurs when the nematic phase is heated up. The investigation at low temperatures is carried out in a flow viscometer at the corresponding temperature and checked by storage in test cells with a layer thickness corresponding to the electro-optical application for at least 100 hours. If the storage stability at a temperature of -20 ° C. in a corresponding test cell is 1000 hours or more, the medium is said to be 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 in capillaries using customary methods.

The liquid-crystal mixture preferably has a nematic phase range of at least 60 K and a flow viscosity ν ₂₀ of at most 30 mm ² · 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, wherein Δε denotes the dielectric anisotropy. The rotational viscosity γ ₁ at 20 ° C. is preferably 150 mPa · s, in particular 120 mPa · s.

The liquid-crystal media according to the invention have relatively small values for the threshold voltage (Vo). 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.

The term “threshold voltage” relates for the present invention to the capacitive threshold (Vo), also called Freedericksz threshold, unless expressly stated otherwise.

In addition, the liquid-crystal media according to the invention have high values for the voltage holding capacity in liquid-crystal cells.

As a rule, liquid-crystal media with a low control voltage or threshold voltage have a lower voltage holding capacity than those with a higher control voltage or threshold voltage and vice versa.

For the present invention, the term “dielectrically positive connections” means connections with a Δε> 1.5, the term “dielectrically neutral connections” means those with −1.5 Δε 1.5 and the term “dielectrically negative connections” those with Δε <-1.5. The dielectric anisotropy of the compounds is determined by dissolving 10% of the compounds in a liquid crystalline host and determining the capacitance of the resulting mixture in at least one test cell each with a 20 µm layer thickness with homeotropic and homogeneous surface orientation at 1 kHz. The measurement voltage is typically 0.5 V to 1.0 V, but it is always lower than the capacitive threshold of the liquid crystal mixture being examined.

All values given for temperatures for the present invention are in ° C.

The mixtures according to the invention are suitable for all VA-TFT applications, e.g. VAN, MVA, (S) -PVA, ASV, PSA (polymer sustained VA) and PS-VA (polymer stabilized VA). They are also suitable for IPS (In-Plane Switching) and FFS (Fringe Field Switching) applications with negative Δε.

The nematic liquid crystal mixtures in the displays according to the invention generally contain two components A and B, which in turn consist of one or more individual compounds.

Component A has a clearly negative dielectric anisotropy and gives the nematic phase a dielectric anisotropy of -0.5. In addition to one or more compounds of the formula X, it preferably contains the compounds of the formulas IIA, IIB and / or IIC, and also one or more compounds of the formula 0-17.

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) is (are) preferably selected which has a value of Δε -0.8. This value must be all the more negative, the smaller the proportion A in the total mixture.

Component B has pronounced nematogenicity and a flow viscosity of not more than 30 mm ² · s ^-1 , preferably not more than 25 mm ² · s ^-1 , at 20 ° C.

A large number of suitable materials are known to the person skilled in the art from the literature. Compounds of the formulas 0-17 are particularly preferred.

Particularly preferred individual compounds in component B are extremely low-viscosity nematic liquid crystals with a flow viscosity of not more than 18 mm ² · s ^-1 , preferably not more than 12 mm ² · s ^-1 , at 20.degree.

Component B is monotropic or enantiotropically nematic, has no smectic phases and can prevent the occurrence of smectic phases down to very low temperatures in liquid-crystal mixtures. If, for example, a smectic liquid-crystal mixture is mixed with different materials with high nematogenicity, the nematogenicity of these materials can be compared through the degree of suppression of smectic phases achieved.

The mixture can optionally also contain a component C which contains compounds with a dielectric anisotropy of Δε 1.5. These so-called positive compounds are generally present in a mixture with negative dielectric anisotropy in amounts of 20% by weight, based on the total mixture.

The phases preferably contain, in addition to one or more compounds of the formula X, 4 to 15, in particular 5 to 12 and particularly preferably <10 compounds of the formulas IIA, IIB and / or IIC and optionally one or more compounds of the formula 0-17.

In addition to compounds of the formula X and the compounds of the formulas IIA, IIB and / or IIC and optionally 0-17, other constituents can also be present, e.g. in an amount of up to 45% of the total mixture, 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 azoxybenzenes, benzylidene anilines, biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl or cyclohexyl cyclohexanecarboxylates, phenylcyclohexanes, cyclohexylbaphthalenes, cyclohexylbaphthalenes, , 1,4-bis-cyclohexylbiphenyls or cyclohexylpyrimidines, phenyl- or cyclohexyldioxanes, optionally halogenated stilbenes, benzylphenyl ethers, tolanes and substituted cinnamic acid esters.

The most important compounds that can be considered as constituents of such liquid-crystal phases can be characterized by the formula IV R ²⁰ -LGER ²¹ IV wherein L and E each have a carbo- or heterocyclic ring system from the 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 mean, G -CH = CH- -N (O) = N- -CH = CQ- -CH = N (O) - -C≡C- -CH ₂ -CH ₂ - -CO-O- -CH ₂ -O- -CO-S- -CH ₂ -S- -CH = N- -COO-Phe-COO- -CF ₂ O- -CF = CF- -OCF ₂ - -OCH ₂ - - (CH ₂ ) ₄ - - (CH ₂ ) ₃ O- or a CC single bond, Q is halogen, preferably chlorine, or -CN and R ²⁰ and R ^{21 are} each alkyl, alkenyl, alkoxy, alkoxyalkyl or alkoxycarbonyloxy with up to 18, preferably up to 8 carbon atoms or one of these radicals is alternatively CN , NC, NO ₂ , NCS, CF ₃ , SF ₅ , OCF ₃ , F, Cl or Br means.

In most of these compounds, R ²⁰ and R ²¹ are different from one another, one of these radicals usually being an alkyl or alkoxy group. Other variants of the intended substituents are also possible common. Many such substances or mixtures thereof are commercially available. All these substances can be produced 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 can also contain compounds in which, for example, H, N, O, Cl and F are replaced by the corresponding isotopes.

The mixtures according to the invention can also contain polymerizable compounds, so-called reactive mesogens (RMs), for example as in FIG U.S. 6,861,107 disclosed, in concentrations of preferably 0.01 to 5 wt .-%, particularly preferably 0.2 to 2 wt .-%, based on the mixture, added. Optionally, these mixtures can also contain an initiator, such as in the U.S. 6,781,665 described. The initiator, for example Irganox-1076 from BASF, is added to the mixture containing polymerizable compounds, preferably in amounts of 0 to 1%. Mixtures of this kind can be used for so-called Polymer Stabilized VA modes (PS-VA) or PSA (Polymer Sustained VA), in which the reactive mesogens are to be polymerized in the liquid-crystalline mixture. The prerequisite for this is that the liquid-crystalline compounds of the LC host do not react under the polymerization conditions of the reactive mesogens, ie generally under the action of UV in the wavelength range from 320 to 360 nm. Liquid-crystalline compounds with an alkenyl side chain, such as CC-3-V, show no reaction for the RMs under the polymerization conditions (UV polymerization).

The mixtures according to the invention can furthermore contain customary additives, such as e.g. Stabilizers, antioxidants, UV absorbers, nanoparticles, microparticles, etc.

The structure of the liquid-crystal displays according to the invention corresponds to the customary geometry, for example as in EP-A 0 240 379 is described.

The following examples are intended to illustrate the invention without limiting it. Above and below, percentages mean percentages by weight; all temperatures are given in degrees Celsius.

oder

oder

Throughout the patent application, 1,4-cyclohexylene rings and 1,4-phenylene rings are represented as follows:

or

or

The cyclohexylene rings are trans-1,4-cyclohexylene rings, unless expressly stated otherwise.

In the entire patent application and in the exemplary embodiments, the structures of the liquid crystal compounds are indicated by acronyms. Unless otherwise stated, the transformation into chemical formulas takes place according to Tables 1 to 3. All radicals C _n H _{2n + 1} , C _m H _{2m + 1} and C _{m '} H _{2m' + 1} or C _n H _2n and C _m H _2m are straight-chain alkyl radicals or alkylene radicals each with n, m, m 'and z carbon atoms. n, m, m ', z are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 1, 2, 3, 4, 5 or 6. In The ring elements of the respective compound are coded in Table 1, the bridge members are listed in Table 2 and the meanings of the symbols for the left and right side chains of the compounds are given in Table 3.

Table 2: pontics E. -CH ₂ CH ₂ - V -CH = CH- T -C = C- W. -CF ₂ CF ₂ - Z -COO- ZI -OCO- O -CH ₂ O- OI -OCH ₂ - Q -CF ₂ O- QI -OCF ₂ - Table 3: side chains Left side chain Right side chain n- C _n H2 _{n + 1} - -n -C _n H _{2n + 1} nO- C _n H _{2n + 1-} O- -On -OC _n H _{2n + 1} V- CH ₂ = CH- -V -CH = CH ₂ nV- C _n H2 _{n + 1} -CH = CH- -nV -C _n H _2n -CH = CH ₂ Vn- CH ₂ = CH- C _n H _2n - -Vn -CH = CH-C _n H _{2n + 1} nVm- C _n H _{2n + 1} -CH = CH-C _m H _2m - -nVm -C _n H ₂ n -CH = CH-C _m H _{2m + 1} N- N≡C- -N -C≡N F- F- -F -F Cl- Cl- -Cl -Cl M- CFH ₂ - -M -CFH ₂ D- CF ₂ H- -D -CF ₂ H T- CF ₃ - -T -CF ₃ MO- CFH ₂ O- -OM -OCFH ₂ DO- CF ₂ HO- -OD -OCF ₂ H TO- CF ₃ O- -OT -OCF ₃ T- CF ₃ - -T -CF ₃ A- HC = C- -A -C = CH

In addition to one or more compounds of the formula X, the mixtures according to the invention preferably contain one or more compounds of the compounds mentioned below from Table A.

The liquid-crystal mixtures which can be used according to the invention are produced in a manner which is customary per se. In general, the desired amount of the components used in a smaller amount is dissolved in the components which form the main constituent, advantageously at an 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 thorough mixing, for example by distillation.

By means of suitable additives, the liquid crystal phases according to the invention can be modified in such a way that they can be used in any previously disclosed type of e.g. ECB, VAN, IPS, GH or ASM VA LCD displays can be used.

The dielectrics can also contain further additives known to the person skilled in the art and described in the literature, such as UV absorbers, antioxidants, nanoparticles and radical scavengers. For example, 0 to 15% of pleochroic dyes, stabilizers, such as phenols, HALS (h indered a mine l ight s tabilisers), or chiral dopants can be added. Suitable stabilizers for the mixtures according to the invention are, in particular, those listed in Table C.

Die erfindungsgemäßen Mischungen enthalten mindestens einen Stabilisator aus der nachfolgend genannten Tabelle C.For example, 0 to 15% of pleochroic dyes can be added, as well as conductive salts, preferably ethyl dimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf. Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973) ) to improve the conductivity, or substances can be added to modify the dielectric anisotropy, the viscosity and / or the orientation of the nematic phases. Such substances are for example in the DE-A 22 09 127 , 22 40 864 , 23 21 632 , 23 38 281 , 24 50 088 , 26 37 430 and 28 53 728 described.

The mixtures according to the invention contain at least one stabilizer from Table C.

Embodiments:

The following examples are intended to illustrate the invention without limiting it. In the examples, mp denotes the melting point and K denotes the clearing point of a liquid-crystalline substance in degrees Celsius; Boiling temperatures are indicated by m.p. It also denotes: K: crystalline solid state, S: smectic phase (the index denotes the phase type), N: nematic state, Ch: cholesteric phase, I: isotropic phase, T _g : glass transition temperature. The number between two symbols indicates the conversion temperature in degrees Celsius.

The sales mixture ZLI-4792 (Merck KGaA) is used as the host mixture for determining the optical anisotropy Δn of the compounds of the formula X. The sales mix ZLI-2857 is used to determine the dielectric anisotropy Δε. From the change in the dielectric constant of the host mixture after addition of the compound to be investigated and extrapolation to 100% of the compound used, the physical data of the compound to be investigated are obtained. The compound to be examined is usually 10% dissolved in the host mixture, depending on its solubility.

Unless otherwise stated, parts or percentages mean parts by weight or percentages by weight.

V_o

Schwellenspannung, kapazitiv [V] bei 20°C,

n_a

außerordentlicher Brechungsindex bei 20°C und 589 nm,

n_o

ordentlicher Brechungsindex bei 20°C und 589 nm,

Δn

optische Anisotropie bei 20°C und 589 nm,

ε⊥

dielektrische Permittivität senkrecht zum Direktor bei 20°C und 1 kHz,

ε∥

dielektrische Permittivität parallel zum Direktor bei 20°C und 1 kHz,

Δε

dielektrische Anisotropie bei 20°C und 1 kHz, Kl.p. & T(N,I)Klärpunkt [°C],

γ1

Rotationsviskosität gemessen bei 20°C [mPa·s], bestimmt nach dem Rotationsverfahren in einem magnetischen Feld,

K₁

elastische Konstante, „splay“-Deformation bei 20°C [pN],

K₂

elastische Konstante, „twist“-Deformation bei 20°C [pN],

K₃

elastische Konstante, „bend“-Deformation bei 20°C [pN] und

LTS

Tieftemperaturstabilität [Low temperature ­stability] (nematische Phase), bestimmt in Testzellen oder im Bulk, wie spezifiziert.

Above and below mean:

V _o

Threshold voltage, capacitive [V] at 20 ° C,

n _a

extraordinary refractive index at 20 ° C and 589 nm,

_no

decent index of refraction at 20 ° C and 589 nm,

Δn

optical anisotropy at 20 ° C and 589 nm,

ε⊥

dielectric permittivity perpendicular to the director at 20 ° C and 1 kHz,

ε∥

dielectric permittivity parallel to the director at 20 ° C and 1 kHz,

Δε

dielectric anisotropy at 20 ° C and 1 kHz, Kl.p. & T (N, I) clearing point [° C],

γ1

Rotational viscosity measured at 20 ° C [mPa · s], determined according to the rotation method in a magnetic field,

K ₁

elastic constant, "splay" deformation at 20 ° C [pN],

K ₂

elastic constant, "twist" deformation at 20 ° C [pN],

K ₃

elastic constant, "bend" deformation at 20 ° C [pN] and

LTS

Low temperature stability [L ow t emperature s tability] (nematic phase), determined in test cells, or in bulk, as specified.

Unless expressly stated otherwise, all values given in the present application are for temperatures, e.g. 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) or Kl.p., in degrees Celsius (° C ) specified. Melting point means melting point. Furthermore, Tg = glass state, K = 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” relates for the present invention to the capacitive threshold (Vo), also called Freedericksz threshold, unless expressly stated otherwise. In the examples, as is generally the case, the optical threshold for 10% relative contrast (V ₁₀ ) can also be specified.

The display used to measure the capacitive threshold voltage consists of two plane-parallel glass carrier plates at a distance of 20 µm, each of which has an electrode layer and an overlying, non-rubbed orientation layer made of polyimide, which cause the liquid crystal molecules to be homeotropically oriented.

The display or test cell used to measure the tilt angle consists of two plane-parallel glass carrier plates at a distance of 4 µm, each of which has an electrode layer and an overlying polyimide orientation layer on the inside, the two polyimide layers being rubbed antiparallel to each other and a homeotropic edge orientation of the liquid crystal molecules cause.

Unless otherwise stated, the VHR is determined at 20 ° C. (VHR ₂₀ ) and after 5 minutes in an oven at 100 ° C. (VHR ₁₀₀ ) in a commercially available instrument model 6254 from TOYO Corporation, Japan. The voltage used has a frequency in a range from 1 Hz to 60 Hz, unless specified more precisely.

The accuracy of the measured values of the VHR depends on the respective value of the VHR. The accuracy decreases with decreasing values. The deviations usually observed for values in the various ranges of magnitude are summarized in their magnitude in the following table. VHR area Deviation (relative) VHR values Δ _G VHR / VHR /% from to approx. 99.6% 100% +/- 0.1 99.0% 99.6% +/- 0.2 98% 99% +/- 0.3 95% 98% +/- 0.5 90% 95% +/- 1 80% 90% +/- 2 60% 80% +/- 4 40% 60% +/- 8 20% 40% +/- 10 10% 20% +/- 20

The stability against irradiation with UV is investigated in a “Suntest CPS”, a commercial device from Heraeus, Germany. The sealed test cells are irradiated for between 30 minutes and 2.0 hours, unless expressly stated, without additional heating. The irradiation power in the wavelength range from 300 nm to 800 nm is 765 W / m ² V. A UV “cut-off” filter with an edge wavelength of 310 nm is used to simulate the so-called window glass mode. In each test series, at least four test cells are examined for each condition and the respective results are given as mean values of the corresponding individual measurements. The decrease in the voltage holding capacity (ΔVHR) usually caused by exposure, e.g. by exposure to UV or by an LCD backlight, is determined using the following equation (1): $$\Delta VH\mathrm{R.}\left(t\right)=VH\mathrm{R.}\left(t\right)-VH\mathrm{R.}\left(t\right)-VH\mathrm{R.}\left(t=0\right)$$

To investigate the low temperature stability, also called "LTS", i.e. the stability of the LC mixture in bulk against spontaneous crystallization of individual components at low temperatures or the occurrence of smectic phases, several sealed bottles, each containing about 1 g of the material, at one or more given temperatures, typically -10 ° C, -20 ° C, -30 ° C and / or -40 ° C, and it is checked at regular intervals visually whether a phase transition can be observed or not. As soon as the first of the samples shows a change at a given temperature, the time is recorded. The time to the last check when no change was observed is noted as the respective LTS.

To measure the ion density, from which the specific resistance is calculated, the commercially available measuring system for LC material characteristics model 6254 from Toyo Corporation, Japan, is used with VHR test cells with AL16301 polyimide (JSR Corp., Japan) with a layer thickness 3.2 µm is used. The measurement is carried out after 5 minutes of storage in an oven at 60 ° C or 100 ° C.

The so-called “HTP” (“helical twisting power”) describes the helical twisting capacity of an optically active or chiral substance in an LC medium (in µm). Unless otherwise stated, the HTP is measured in the commercially available nematic FK host mixture MLD-6260 (Merck KGaA) at a temperature of 20 ° C.

Unless expressly stated otherwise, in the present application all concentrations are given in percent by weight and relate to the corresponding total mixture containing all solid or liquid-crystalline components, without solvents. All physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", as of November 1997, Merck KGaA, Germany, and apply to a temperature of 20 ° C, unless expressly stated otherwise.

The following mixture examples with negative dielectric anisotropy are particularly suitable for liquid crystal displays which have at least one planar orientation layer, e.g. IPS and FFS displays, especially UB-FFS (= ultra-bright FFS), as well as for VA displays.

Mixture examples and comparative examples

The comparison mixture C1 is prepared as follows: (MDA-16-1989) CY-3-O4 20.0% Clear point / ° C: 86.5 CCY-3-O2 8.0% Δn (589 nm, 20 ° C): 0.1089 CCY-3-O3 6.0% na (589 nm, 20 ° C): 1.5917 CCY-4-O2 8.0% Δε (1 kHz, 20 ° C): -4.3 CLY-3-O2 5.0% ε⊥ (1 kHz, 20 ° C]: 8.0 CLY-3-O3 5.0% K ₁ (pN, 20 ° C): 14.6 CLY-2-O42 6.0% K ₃ (pN, 20 ° C): 15.1 PYP-2-3 10.0% V ₀ (20 ° C) / V: 1.99 CC-3-V 26.0% γ1 (20 ° C) / mPas: 151 PGIY-2-O4 6.0% LTS _bulk (-20 ° C) / h: > 336 Σ 100.0% LTS _bulk (-30 ° C) / h: > 144

This mixture has the best possible switching times for the highest achievable VHR values, which leads to an average switching time, but very high VHR values.

The comparison mixture C2 is prepared as follows: CY-3-O2 12.0% Clear point / ° C: 85.2 CY-5-O2 10.5% Δn (589 nm, 20 ° C): 0.1120 CCY-3-O1 6.0% n _a (589 nm, 20 ° C): 1.5956 CCY-3-O2 6.0% Δε (1 kHz, 20 ° C): -4.2 CCY-5-O2 5.0% ε⊥ (1 kHz, 20 ° C]: 7.9 CPY-2-O2 12.0% K ₁ (pN, 20 ° C): 14.2 CPY-3-O2 12.0% K ₃ (pN, 20 ° C): 16.7 PYP-2-3 7.5% V ₀ (20 ° C) / V: 2.119 CC-3-V 26.4% γ ₁ (20 ° C) / mPas: 145 CC-3-V1 4.0% Σ 100.0%

This mixture has a balanced relationship between VHR and switching time.

The mixture M1 is made as follows: (MDA-17-372) CXOY-3-O4 11.0% Clear point / ° C: 87.1 CY-3-O4 13.0% Δn (589 nm, 20 ° C): 0.1042 CCY-3-O2 3.0% n _a (589 nm, 20 ° C): 1.5871 CCY-3-O3 3.0% Δε (1 kHz, 20 ° C): -4.2 CCY-4-O2 5.0% ε⊥ (1 kHz, 20 ° C]: 7.8 CLY-3-O2 5.0% K ₁ (pN, 20 ° C): 14.7 CLY-3-O3 5.0% K ₃ (pN, 20 ° C): 15.4 CLY-2-O4 7.0% V ₀ (20 ° C) / V: 2.02 PYP-2-3 10.0% γ ₁ (20 ° C) / mPas: 145 PGIY-2-04 6.0% CC-3-V 32.0% Σ 100.0%

The mixture M2 is made as follows: CXOY-3-O2 100% Clear point / ° C: 86.9 CY-3-O4 13.0% Δn (589 nm, 20 ° C): 0.1068 CCY-3-O2 3.0% n _a (589 nm, 20 ° C): 1.5899 CCY-3-O3 3.0% Δε (1 kHz, 20 ° C): -4.1 CCY-4-O2 5.0% ε⊥ (1 kHz, 20 ° C]: 7.8 CLY-3-O2 5.0% K ₁ (pN, 20 ° C): 14.8 CLY-3-O3 5.0% K ₃ (pN, 20 ° C): 15.6 CLY-2-O42 7.0% V ₀ (20 ° C) / V: 2.06 PYP-2-3 10.0% γ ₁ (20 ° C) / mPas: 139 PGIY-2-04 6.0% CC-3-V 31.0% Σ 100.0%

Mixture M3 is made as follows: XOY-3-O4 11.0% Clear point / ° C: 86.4 CCY-3-O3 7.0% Δn (589 nm, 20 ° C): 0.1119 CCY-4-O2 8.0% n _a (589 nm, 20 ° C): 1.5962 CLY-3-O2 6.0% Δε (1 kHz, 20 ° C): -4.2 CLY-3-O3 5.0% ε⊥ (1 kHz, 20 ° C]: 7.9 CLY-2-O4 5.0% K ₁ (pN, 20 ° C): 15.2 PYP-2-3 13.0% K ₃ (pN, 20 ° C): 15.4 PGIY-2-04 7.0% V ₀ (20 ° C) / V: 2.03 CC-3-V 27.0% γ ₁ (20 ° C) / mPas: 134 CC-3-V1 8.0% Σ 100.0%

The mixture M4 is made as follows: CXOY-3-O2 8.0% Clear point / ° C: 86.2 CY-3-O4 17.0% Δn (589 nm, 20 ° C): 0.1014 CCY-3-O3 5.0% n _a (589 nm, 20 ° C): 1.5836 CCY-4-O2 5.0% Δε (1 kHz, 20 ° C): -4.2 CLY-3-O2 7.0% ε⊥ (1 kHz, 20 ° C]: 7.8 CLY-3-O3 6.0% K ₁ (pN, 20 ° C): 14.7 CLY-4-O24 4.0% K ₃ (pN, 20 ° C): 15.5 CLY-2-O4 6.0% V ₀ (20 ° C) / V: 2.03 PYP-2-3 12.0% γ ₁ (20 ° C) / mPas: 139 CC-3-V 300% Σ 100.0%

The comparison mixture C3 is prepared as follows: B (S) -2O-O5 5.0% Clear point / ° C: 80.0 CY-3-O4 14.0% Δn (589 nm, 20 ° C): 0.1069 CY-5-04 1.5% n _a (589 nm, 20 ° C): 1.5913 CCY-3-O2 2.0% Δε (1 kHz, 20 ° C): -3.8 CLY-2-O42 5.0% ε⊥ (1 kHz, 20 ° C]: 7.40 CLY-3-O2 8.0% K ₁ (pN, 20 ° C): 14.1 CPY-2-O2 8.0% K ₃ (pN, 20 ° C): 14.6 CPY-3-O2 9.0% V ₀ (20 ° C) / V: 2.06 PYP-2-3 6.0% γ ₁ (20 ° C) / mPas: 108 CC-3-V 36.5% Σ 100.0%

Compared to that of Comparative Example 1, this mixture shows improved switching times, mainly due to its reduced γ ₁ , but a lower VHR.

Mixture M5 is made as follows: CXOY-3-O2 11.0% Clear point / ° C: 80.5 B (S) -2O-O5 5.0% Δn (589 nm, 20 ° C): 0.0952 CLY-2-O4 5.0% n _a (589 nm, 20 ° C): 1.5766 CLY-3-O2 8.0% Δε (1 kHz, 20 ° C): -3.8 CLY-3-O3 5.0% ε⊥ (1 kHz, 20 ° C]: 7.40 CY-3-O4 9.0% K ₁ (pN, 20 ° C): 14.3 CY-5-04 2.0% K ₃ (pN, 20 ° C): 15.5 CCY-3-O2 2.0% V ₀ (20 ° C) / V: 2.13 CPY-3-O2 4.0% γ ₁ (20 ° C) / mPas: 102 PYP-2-3 6.0% CC-3-V 43.0% Σ 100.0%

The mixture M6 is made as follows: CXOY-3-O2 7.5% Clear point / ° C: 106.5 Y-4O-O4 7.0% Δn (589 nm, 20 ° C): 0.1000 B (S) -2O-O4 4.0% n _a (589 nm, 20 ° C): 1.5820 B (S) -2O-O5 4.0% Δε (1 kHz, 20 ° C): -4.5 CCY-3-O2 9.0% ε⊥ (1 kHz, 20 ° C]: 7.9 CLY-3-O2 8.0% K ₁ (pN, 20 ° C): 20.0 CLY-3-O3 5.0% K ₃ (pN, 20 ° C): 20.8 CLY-4-O2 5.0% V ₀ (20 ° C) / V: 2.37 CLY-5-O2 5.0% γ ₁ (20 ° C) / mPas: 154 CPY-3-O2 5.5% PYP-2-3 13.0% CC-3-V 33.5% CC-3-V1 8.0% Σ 100.0%

The mixture M7 is made as follows: CXOY-3-O2 7.0% Clear point / ° C: 102.0 B (S) -2O-O4 4.0% Δn (589 nm, 20 ° C): 0.1024 B (S) -2O-O5 5.0% n _a (589 nm, 20 ° C): 1.5855 B (S) -2O-O6 3.0% Δε (1 kHz, 20 ° C): -4.5 CCY-3-O2 3.0% ε⊥ (1 kHz, 20 ° C]: 8.0 CLY-2-O4 3.0% K ₁ (pN, 20 ° C): 19.6 CLY-3-O2 8.0% K ₃ (pN, 20 ° C): 19.9 CLY-3-O3 5.0% V ₀ (20 ° C) / V: 2.23 CLY-4-O2 5.0% γ ₁ (20 ° C) / mPas: 138 CLY-5-O2 5.0% CPY-3-O2 4.0% CC-3-V 37.0% CC-3-V1 7.0% Σ 100.0%

The mixture M8 is made as follows: CXOY-3-O2 4.0% Clear point / ° C: 88.0 Y-4O-O4 1.5% Δn (589 nm, 20 ° C): 0.1032 B (S) -2O-O4 4.0% n _a (589 nm, 20 ° C): 1.5861 B (S) -2O-O5 5.0% Δε (1 kHz, 20 ° C): -3.7 B (S) -2O-O6 3.0% ε⊥ (1 kHz, 20 ° C]: 7.2 CLY-2-O4 2.0% K ₁ (pN, 20 ° C): 16.8 CLY-3-O2 5.0% K ₃ (pN, 20 ° C): 17.1 CLY-4-O2 5.0% V ₀ (20 ° C) / V: 2.28 CLY-5-O2 4.0% γ ₁ (20 ° C) / mPas: 97 CPY-3-O2 9.0% PGIY-2-04 4.0% CC-3-V 43.5% CC-3-V1 7.0% Σ 100.0%

The mixture M9 is made as follows: CXOY-3-O2 5.0% Clear point / ° C: 95.0 Y-4O-O4 1.0% Δn (589 nm, 20 ° C): 0.1018 B (S) -2O-O4 4.0% n _a (589 nm, 20 ° C): 1.5840 B (S) -2O-O5 5.0% Δε (1 kHz, 20 ° C): -3.9 B (S) -2O-O6 3.0% ε⊥ (1 kHz, 20 ° C]: 7.4 CLY-2-O4 2.0% K ₁ (pN, 20 ° C): 18.3 CLY-3-O2 8.0% K ₃ (pN, 20 ° C): 18.7 CLY-3-O3 1.0% V ₀ (20 ° C) / V: 2.30 CLY-4-O2 5.0% γ ₁ (20 ° C) / mPas: 113 CLY-5-O2 9.0% CPY-3-O2 9.0% CC-3-V 41.0% CC-3-V1 7.0% Σ 100.0%

Table 1: VHR values No. mixture γ ₁ (20 ° C) / mPas Yγ ₁ / K ₁ (20 ° C) / mPas / pN VHR * (60 ° C) /% 1 CM1 151 10.3 95.5 2 CM2 145 10.2 94.3 3 M1 145 9.9 94.9 4th M2 139 9.4 95.5 5 M3 134 8.8 93.0 6th M4 139 9.5 96.0 7th CM3 108 7.7 94.4 8th M5 102 94.9 (Note: * All VHR values measured at 1V, 1 Hz and at 60 ° C.)

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (15)

Liquid-crystalline medium, characterized in that it contains one or more compounds of the formula X

wherein R ^X1 and R ^{X2 are} each independently H, an alkyl or alkoxy radical having 1 to 15 carbon atoms, with one or more CH ₂ groups in these radicals additionally each independently of one another as represented by -C-C-, -CF ₂ O-, -OCF ₂ -, -CH = CH-,

-O-, -CO-O-, -O-CO- can be replaced so that O atoms are not directly linked to one another, and in which one or more H atoms can also be replaced by halogen, n is 0 or 1 and Z ^X1 on each occurrence independently of one another -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₄ -, -CH = CH-CH ₂ O-, -C ₂ F ₄ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-, -C = C- or a single bond, and optionally, preferably mandatory, one or more compounds of the formula I

wherein R ¹¹ and R ^{12 are} each independently H, an alkyl or alkoxy radical having 1 to 15 carbon atoms, with one or more CH ₂ groups in these radicals additionally each independently of one another as represented by -C≡C-, -CF ₂ O-, -OCF ₂ -, -CH = CH-,

-OO-, -CO-O-, -O-CO- can be replaced so that O atoms are not directly linked to one another, and in which one or more H atoms can also be replaced by halogen,

on each occurrence, independently of one another, a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH ₂ groups can be replaced by -O- or -S-, b) a 1,4- Phenylene radical, in which one or two CH groups can be replaced by N, c) a radical from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo [2.2.2] octylene, naphthalene-2,6-diyl, Decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, in which the radicals a), b) and c) can be substituted one or more times by halogen atoms, Z ¹¹ each occurrence independently of one another -CO-O-, -O-CO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, - OCH ₂ -, -CH ₂ CH ₂ -, - (CH ₂ ) ₄ -, -CH = CH-CH ₂ O-, -C ₂ F ₄ -, -CH ₂ CF ₂ -, -CF ₂ CH ₂ -, -CF = CF-, -CH = CF-, -CF = CH-, -CH = CH-, -C≡C- or a single bond and L ¹¹ and L ¹² each independently of one another F, Cl, CF ₃ or CHF ₂ , X ^{1 is} O or S and a is 1 or 2, preferably 1 utet, and one or more compounds selected from the group of compounds of the formulas IIA, IIB and IIC

wherein R ^2A , R ^2B and R ^{2C are} each independently H, an alkyl or alkenyl radical with up to 15 carbon atoms, which is unsubstituted, monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, in these radicals additionally one or more CH ₂ groups by -O-, -S-,

-C≡C-, -CF ₂ O-, -OCF ₂ -, -OC-O- or -O -CO- can be replaced so that O atoms are not linked directly to one another, L ¹ to L ⁴ each independently of one another F or Cl denote, Z ² and Z ^{2 '} each independently represent a single bond, -CH ₂ CH ₂ -, -CH = CH-, -CF ₂ O- -OCF ₂ -, -CH ₂ O- -OCH ₂ -, -COO-, -OCO- -C ₂ F ₄ -, -CF = CF-, -CH = CHCH ₂ O-, p is 0, 1 or 2, q is 0 or 1 and v is 1 to 6 . Liquid crystalline medium according to Claim 1 , characterized in that the medium contains one or more compounds selected from the group of compounds of the formulas I-1 to I-3

where the parameters in Claim 1 have given meanings. Liquid crystalline medium according to Claim 1 or 2 , characterized in that it contains one or more compounds selected from the group of compounds of the formulas IO-1 to IO-3

where the parameters in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 3 , characterized in that it contains one or more compounds selected from the group of compounds of the formulas IS-1 to I-SO-3

where the parameters in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 4th , characterized in that it contains one or more compounds of the formula IIA

contains, in which the parameters in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 5 , characterized in that it also contains one or more compounds of the formula IIB

contains, in which the parameters in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 6th , characterized in that the medium contains one or more compounds of the formula IIC

contains, in which the parameters in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 7th , characterized in that the medium additionally contains one or more compounds selected from the group of compounds of the formulas O-1 to O-18

wherein R ¹ and R ^{2 are} each independently of the other for R ^2A in Claim 1 have given meanings. Liquid-crystalline medium according to one or more of the Claims 1 to 8th , characterized in that the medium additionally contains one or more compounds selected from the group of compounds of the formulas T-1 to T-21

where R is a straight-chain alkyl or alkoxy radical having 1 to 6 carbon atoms and m = 0, 1, 2, 3, 4, 5 or 6 and n is 0, 1, 2, 3 or 4. Liquid-crystalline medium according to one or more of the Claims 1 to 9 , characterized in that the proportion of the compounds of the formula X in the total mixture is 1 to 40%. Liquid-crystalline medium according to one or more of the Claims 1 to 10 , characterized in that the proportion of the compounds of the formulas IIA to IC total medium is in the range from 10% to 70%. Process for producing a liquid-crystalline medium according to one or more of the Claims 1 to 11 , characterized in that one or more compounds of the formula X are mixed with one or more compounds selected from the group of compounds of the formulas IIA to IIC and one or more compounds of the formula. Use of the liquid-crystalline medium according to one or more of the Claims 1 to 11 in electro-optical displays. Electro-optical display with active matrix addressing, characterized in that it is a liquid-crystalline medium according to one or more of the dielectric Claims 1 to 11 contains. Electro-optical display after Claim 15 , which is a VA, PSA, PA-VA, SS-VA, SA-VA, PS-VA, PALC, IPS, PS-IPS, FFS, UB-FFS , U-IPS or PS-FFS display.