TW201510192A - Liquid-crystalline medium - Google Patents

Abstract

The invention relates to a liquid-crystalline medium which comprises at least one compound of the formula I, and at least one compound selected from the group of the compounds of the formulae IIA, IIB and IIC, in which R1, X1, ring A, ring B, Y1, Y2, Z1, Z1' a, b, R2A, R2B, R2C, L1, L2, Z2, Z2', p, q, and v have the meanings indicated in Claim 1, and to the use thereof for an active-matrix display, in particular based on the VA, PSA, PS-VA, PALC, FFS, PS-FFS, IPS or PS-IPS effect.

Description

Liquid crystal medium

The present invention relates to a liquid crystal medium comprising at least one compound of formula I,

And one or more compounds selected from the group of compounds of the formulae IIA, IIB and IIC,

Wherein: R ¹ represents an alkyl group or alkoxy group having 1 to 15 C atoms, wherein, in addition, one or more CH ₂ groups in the groups may be independent of each other in such a manner that the O atoms are not directly connected to each other. Ground-C≡C-, -CF ₂ O-, -CH=CH-, , -O-, -CO-O-, -O-CO-substitution, and wherein, in addition, one or more H atoms may be replaced by halogen, and X ¹ represents F, Cl, CN, OCN, SF ₅ , SCN, NCS a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkenyl group having 2 to 6 carbon atoms, a halogenated alkoxy group having 1 to 6 carbon atoms, a halogenated alkylalkane having 1 to 6 carbon atoms An oxy group, a halogenated alkenyloxy group having 2 to 6 carbon atoms, and Respectively independent of each other

However, at least one of the rings A and B is a dioxane or a piper ring, and Y ¹ and Y ² each independently represent H or F, and Z ¹ and Z ^{1 '} 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-, a represents 1 or 2 b represents 1 or 2 R ^2A , R ^2B and R ^2C each independently represent H, an alkyl group having up to 15 C atoms, which is unsubstituted Monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, wherein, in addition, one or more CH ₂ groups in such groups may be such that O atoms are not directly connected to each other via -O-, -S- , , -C≡C-, -CF ₂ O-, -OCF ₂ -, -OC-O- or -O-CO-, L ¹ and L ² each independently represent F, Cl, CF ₃ or CHF ₂ , 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-, (O)C _v H _2v+1 means OC _v H _2v+1 or C _v H _{2v +1} p means 1 or 2, q means 0 or 1, and v means 1 to 6.

Such media are particularly useful for electro-optical displays and IPS (coplanar switching) displays or FFS (Fringe Field Switching) displays with active matrix addressing based on the ECB effect. Further, the liquid crystal mixture of the present invention is suitable for a PS (Polymer Stabilized) or PSA (Polymer Continuous Alignment) type LC display.

The principle of the electrically controlled birefringence (ECB) effect or the deformation of aligned phase (DAP) effect was first described in 1971 (MFSchieckel and K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation". In electrical fields", Appl. Phys. Lett. 19 (1971), 3912). This is described in the paper by J. F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).

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) The paper shows that the liquid crystal phase must have a high value with respect to the ratio of the elastic constant K ₃ /K ₁ , a high value with respect to the optical anisotropy Δn, and about the dielectric anisotropy Δε A value of -0.5 for a high information display element based on the ECB effect. Electro-optic display elements based on the ECB effect have vertical edge alignment (VA technology = vertical alignment type). Dielectric negative liquid crystal media can also be used in displays that use the so-called IPS or FFS effect.

In addition to IPS (coplanar switching type) displays (eg: Yeo, S.D., document 15.3: "An LC Display for the TV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume II, 758 and 759 Page) Other than the well-known TN (twisted nematic) display, for example, MVA (multi-domain vertical alignment, for example: Yoshide, H. et al., document 3.1: "MVA LCD for Notebook or Mobile PCs...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume 1, pages 6 to 9, and Liu, CT et al., Document 15.1: "A 46-inch TFT-LCD HDTV Technology...", SID 2004 International Symposium , Digest of Technical Papers, XXXV, Volume II, pages 750-753), PVA (patterned vertical alignment, eg Kim, Sang Soo, document 15.4: "Super PVA Sets New State-of-the-Art for LCD -TV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume II, pages 760-763), ASV (Super Perspective, eg Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Document 15.2: "Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754-757) Modes using ECB-effect displays, such as the so-called VAN (Vertical Alignment Nematic) displays, have established themselves as The most important three Newer types of liquid crystal displays, one person (in particular for television applications). In general form, for example in Souk, Jun, SID Seminar 2004, seminar M-6: "Recent Advances in LCD Technology", Seminar Lecture Notes, M-6/1 to M-6/26, and Miller, Ian, SID Seminar 2004, seminar M-7: "LCD-Television", Seminar Lecture Notes, M-7/1 to M-7/32 compare these techniques. Although it has been proposed by means of overdrive, for example: Kim, Hyeon Kyeong et al., 9.1: "A 57-in. Wide UXGA TFT-LCD for HDTV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume I, pages 106-109 significantly improves the response time of modern ECB displays, but achieves a video-compatible reaction time, in particular with regard to gray-scale switching, which remains a problem that has not been satisfactorily solved.

This effect in industrial applications in electro-optical display elements requires that the LC phase must meet multiple requirements. Of particular importance here are the effects on moisture, air and the environment (such as heat, infrared, and See chemical resistance of ultraviolet radiation and DC and AC electric fields.

In addition, industrially available LC phases must have a liquid crystal mesophase at a suitable temperature range and at low viscosity.

None of the compounds disclosed herein having a liquid crystal mesophase includes a single compound that satisfies all of these requirements. Therefore, a mixture of 2 to 25 (preferably 3 to 18) compounds is usually prepared in order to obtain a substance usable as an LC phase. However, it is impossible to easily prepare an optimum phase in this manner because liquid crystal materials having significant negative dielectric anisotropy and sufficient long-term stability have not been obtained so far.

Matrix liquid crystal displays (MLC displays) are known. Non-linear elements that can be used for individual switching of individual pixels are, for example, active elements (i.e., transistors). Next, use the term "active matrix", where you can distinguish between two types:

1. MOS (Metal Oxide Semiconductor) transistor on a germanium wafer as a substrate

2. A thin film transistor (TFT) on a glass plate as a substrate.

In the case of Type 1, the electro-optical effect used is typically a dynamic scattering or a guest-subject effect. The use of single crystal germanium as the substrate material limits the size of the display because even a modular assembly of individual part-displays can cause problems at the joint.

In the preferred and more promising type 2, the electro-optic effect used is typically the TN effect.

A distinction is made between two technologies: a TFT containing a compound semiconductor such as CdSe or a TFT based on polycrystalline germanium or amorphous germanium. The latter technology is working intensively on a global scale.

The TFT matrix is applied to the inside of one glass plate of the display, and the other glass plate carries a transparent counter electrode therein. Compared to the size of the pixel electrode, the TFT is small and does not actually have an adverse effect on the image. This technique can also be extended to displays with full color capabilities in which the red, green and blue filter mosaics are configured in a manner that opposes the filter elements in relation to each switchable pixel.

The term MLC display herein encompasses any matrix display having integrated non-linear elements, ie, in addition to the active matrix, a display such as a varistor or a passive component of a diode (MIM=metal-insulator-metal).

This type of MLC display is particularly suitable for TV applications (such as pocket TV) or high information displays in automotive or aircraft construction. In addition to the problem of the angle dependence of contrast and response time, the difficulty in the specific resistance of the liquid crystal mixture is also high in the MLC display [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, page 141 and Following, Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, page 145 and below, Paris]. As the resistance decreases, the contrast of the MLC display deteriorates. Since the specific resistance of the liquid crystal mixture generally drops during the lifetime of the MLC display due to interaction with the internal surface of the display, high (initial) resistance is important for displays that must have acceptable resistance values over long periods of operation.

VA displays have significantly better viewing angle dependencies and are therefore primarily used in televisions and monitors. However, there is still a need to improve the response time here, especially for televisions that use frame rate (image change frequency/repetition rate) greater than 60 Hz. However, at the same time, properties such as low temperature stability must not be detracted.

The liquid crystal display (LC display) currently used is usually a TN (Twisted Nematic) type liquid crystal display. However, a disadvantage of such liquid crystal displays is that contrast has a strong dependence on viewing angle. In addition, a so-called VA (Vertical Alignment) display having a wide viewing angle is known. The LC cell of the VA display contains a layer of liquid crystal dielectric between the two transparent electrodes, wherein the liquid crystal medium typically has a negative dielectric (DC) anisotropy value. In the off state, the molecules of the LC layer are orthogonal (vertically) aligned or have a slanted vertical alignment. Apply voltage to the counter electrode Thereafter, realignment of LC molecules parallel to the electrode surface occurs. Furthermore, OCB (Optically Compensatory Bend) displays are known which are based on birefringence effects and have an LC layer with a so-called "bend" alignment and generally positive (DC) anisotropy. After the voltage is applied, realignment of the LC molecules orthogonal to the electrode surface occurs. Additionally, OCB displays typically contain one or more birefringent optical retardation films to prevent undesired light transmission of the unit in dark conditions. Compared to TN displays, OCB displays have a wider viewing angle and shorter response times. IPS (coplanar switching type) displays are also known which comprise an LC layer between two substrates, only one of which has an electrode layer typically having a comb structure. When a voltage is applied, the electric field thus generated has a significant component parallel to the LC layer. This results in realignment of the LC molecules in the plane of the layer. Furthermore, a so-called FFS (Fringe Field Switching Type) display has been proposed (see especially SHJung et al., Jpn. J. Appl. Phys., Vol. 43, No. 3, 2004, 1028), which is also on the same substrate. Two electrodes are included, but in contrast to an IPS display, only one of these electrodes is in the form of a structured (comb) electrode and the other electrode is unstructured. This produces a strong so-called "fringe field", that is, a strong electric field close to the edge of the electrode, and an electric field having both a strong vertical component and a strong horizontal component throughout the cell. Both the IPS display and the FFS display have a low viewing angle dependence.

In newer types of VA displays, the uniform orientation of the LC molecules is limited to a plurality of relatively small regions within the LC cell. Disclinations may exist between such domains that are also known as tilt domains. Contrast and grayscale of VA displays with tilted domains have greater viewing angle independence than conventional VA displays. In addition, displays of this type are easier to manufacture because, for example, additional processing of the electrode surface by rubbing to make the molecules uniformly aligned in the on state is no longer necessary. Conversely, the preferred direction of tilt or pretilt angle is controlled by the particular design of the electrodes. In so-called MVA (Multi-Zone Vertical Alignment) displays, this is typically achieved by electrodes having protrusions that cause local pre-tilt. Thus, after application of the voltage, the LC molecules are aligned parallel to the electrode surface in different directions in different defined regions of the cell. In turn, "controlled" switching is achieved, and the formation of disturbing disclination lines is prevented. Do This configuration improves the viewing angle of the display, but it reduces its transparency to light. Another development of MVA uses protrusions only on one electrode face, while the opposite electrode has slits that improve the transparency to light. The slit electrode creates a non-uniform electric field in the LC cell after application of the voltage, which means that controlled switching is still achieved. With regard to the further improvement of the transmittance, the interval between the slit and the protrusion can be increased, but this causes an increase in the response time. In the so-called PVA (Patternized VA), the two electrodes are constructed by means of slits on the opposite faces so that the protrusions are completely redundant, which leads to an increase in contrast and improved transmittance, but it is technically difficult and makes the display mechanically The impact (tap, etc.) is more sensitive. However, for many applications, such as monitors and especially TV screens, there is a need to reduce the response time of the display and improve contrast and brightness (transmission).

Another development is the so-called PS (Polymer Stabilized) display, which is also known by the term "PSA" (continuous alignment of polymers). In such displays, a smaller amount (eg, 0.3%, typically <1%) of the polymerizable compound is added to the liquid crystal medium and, after introduction into the LC cell, typically with or without voltage applied between the electrodes In situ polymerization or crosslinking by UV photopolymerization. It has been found to be particularly suitable to add a polymerizable liquid crystal primordium or liquid crystal compound (also referred to as "reactive liquid crystal precursor" (RM)) to the LC mixture. At the same time, the PSA principle is being used in a variety of classic LC displays. Thus, for example, PSA-VA, PSA-OCB, PS-IPS, PS-FFS, and PS-TN displays are known. Typically, a voltage is applied, for example, in the case of a PSA-VA display; in the case of a PSA-IPS display, a voltage is applied or not applied to carry out in-situ polymerization of the polymerizable compound. As shown in the test unit, the PSA method causes the unit to be pre-tilted. In the case of a PSA-OCB display, it is therefore possible to stabilize the curved structure so that the offset voltage is unnecessary or can be reduced. In the case of a PSA-VA display, this pre-tilt has a positive effect on the response time. For PSA-VA displays, standard MVA or PVA pixel and electrode layouts can be used. In addition, however, it is possible, for example, to use only one structured electrode face and no protrusions, which significantly simplifies production while producing excellent contrast while achieving excellent transparency to light. PSA-VA displays are described, for example, in JP 10-036847 A, EP 1 170 626 A2, EP 1 378 557 A1, EP 1 498 468 A1, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/0103804 A1 in. PSA-OCB displays are described, for example, in T.-J-Chen et al, Jpn. J. Appl. Phys. 45, 2006, 2702-2704 and SHKim, L.-C-Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647. PS-IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. 1999, 75(21), 3264. PS-TN displays are described, for example, in Optics Express 2004, 12(7), 1221.

In particular, for monitor applications and especially for TV applications, there is a continuing need to optimize the reaction time and contrast and brightness (and therefore transmission) of LC displays. The PSA approach provides a vital advantage here. In particular, in the case of PSA-VA, the reduction in response time associated with the pre-tilt that can be measured in the test unit can be achieved without significant adverse effects on other parameters.

However, it has been found that LC mixtures known from the prior art still have some disadvantages when used in VA, PS-VA, PSA, PALC, IPS, PS-IPS, FFS and PS-FFS displays due to image sticking problems.

Therefore, there is still a great need for a liquid crystal mixture for an MLC display that has little or no image residue, but has a very high specific resistance, a large operating temperature range, a short response time, and a low threshold voltage. Produces a variety of gray levels. In addition, it should be possible to use liquid crystal mixtures in VA, IPS and FFS, PALC and PS-VA, PSA, PS-IPS, PS-FFS displays, and it should not exhibit the disadvantages described above, or should only be To a lesser extent, and at the same time should have improved characteristics. In PS-VA and PSA displays, the liquid crystal medium comprising the polymerizable component should be capable of establishing sufficient pretilt in the MLC display and should have a relatively high voltage holding ratio (VHR or HR).

The present invention is based on the object of providing liquid crystal media that are particularly useful in IPS, FFS, VA, and PS-VA displays, and are particularly suitable for use in monitors and TV applications, such liquid crystal media. Do not have the disadvantages indicated above, or only to a lesser extent. In particular, monitors and televisions must be designed to work at very high and low temperatures, while having short response times and improved reliability characteristics, especially after long operating times. Significantly reduced image retention.

Surprisingly, if a polar compound of the formula I is used in a liquid crystal mixture, in particular an LC mixture having a negative dielectric anisotropy (preferably for a VA display), it is possible to significantly reduce image sticking while improving rotation. Viscosity values and thus improved response time. Furthermore, it has been surprisingly found that the use of the liquid crystal media of the present invention in PS-VA and PSA displays contributes to a particularly low pretilt angle and rapid establishment of the desired tilt angle. This has been demonstrated in the context of the medium of the invention by means of pretilt measurement. In particular, it has been possible to achieve pre-tilt without the addition of a photoinitiator. Additionally, as has been demonstrated by exposure time dependent measurements of pretilt angles, the media of the present invention exhibit a significantly faster pretilt angle than materials known from the prior art.

The invention accordingly relates to a liquid-crystalline medium according to claim 1 comprising at least one compound of the formula I and at least one compound selected from the group consisting of formula IIA, IIB or IIC. In a preferred embodiment, the liquid crystal medium of claim 1 is characterized by a negative dielectric anisotropy (Δε).

The compound of formula I in the liquid crystal medium has both a low rotational viscosity value and a high dielectric anisotropy absolute value. It is therefore possible to prepare a liquid crystal compound having a short response time while having good phase characteristics and good low temperature characteristics, preferably a mixture of VA, IPS, FFS, PS-VA, PS-IPS and PS-FFS.

The invention further relates to a liquid crystal medium comprising an LC mixture of the invention as described above and below and one or more polymerizable compounds preferably selected from the group consisting of reactive liquid crystal primaries.

The present invention further relates to a liquid crystal medium for PS-VA applications comprising the LC mixture of the present invention as described above and below, and which may be composed of one or more selected from the group consisting of reactive liquid crystal primaries A polymer obtained from a group of polymerizable compounds.

The invention further relates to a process for the preparation of a liquid crystal mixture according to the invention, wherein at least one compound of the formula I and other liquid crystal primor compounds and optionally one or more polymerizable compounds and/or one or more additives and/or Stabilizer mixing.

The invention further relates to a process for producing an LC display, wherein the LC mixture of the invention is mixed with one or more polymerizable compounds and optionally with other liquid crystal compounds and/or additives and/or stabilizers, in this way The obtained mixture is introduced into an LC cell having two substrates and two electrodes as described above and below, and the (or equivalent) polymerizable compound is preferably polymerized at the electrode with application of a voltage. The mixture of the present invention preferably exhibits a wide range of nematic phase ranges, clear points 70 ° C, preferably 75 ° C, especially 80 ° C; very favorable capacitance threshold, relatively high retention value and excellent low temperature stability at -20 ° C and -30 ° C, as well as very low rotational viscosity and short response time. Further, by the fact that in addition to the improvement of the rotational viscosity γ ₁ , the fact that the relatively high elastic constant K ₃₃ value for the response time is improved can be observed to distinguish the mixture of the present invention.

Some preferred embodiments of the mixtures of the invention are indicated below.

In the compound of formula I, R ¹ preferably denotes a straight-chain alkyl group, specifically C ₂ H ₅ , n-C ₃ H ₇ , n-C ₄ H ₉ , n-C ₅ H ₁₁ , n-C ₆ H ₁₃ , in addition Alkenyl or alkoxy, such as CH ₂ =CH, CH ₃ CH=CH, CH ₃ CH ₂ CH=CH, C ₃ H ₇ CH=CH, OC ₂ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ , OC ₅ H ₁₁ , OC ₆ H ₁₃ and alkenyloxy groups such as OCH ₂ CH=CH ₂ , OCH ₂ CH=CHCH ₃ , OCH ₂ CH=CHC ₂ H ₅ . More preferably, R ¹ represents C ₂ H ₅ , normal C ₃ H ₇ , normal C ₄ H ₉ , and positive C ₅ H ₁₁ .

In the compound of formula I, X ¹ preferably denotes F, Cl, CN, SF ₅ , NCS, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkenyl group having 2 to 6 carbon atoms, having 1 A fluorinated alkoxy group to 6 carbon atoms, a fluorinated alkyl alkoxy group having 1 to 6 carbon atoms or a fluorinated alkenyloxy group having 2 to 6 carbon atoms. X ^{1 is} particularly preferably F, Cl, CF ₃ , CHF ₂ , OCF ₃ , OCHF ₂ , OCHFCF ₃ , OCHFCHF ₂ , OCHFCH ₂ F, OCF ₂ CH ₃ , OCF ₂ CHF ₂ , OCF ₂ CH ₂ F, OCF ₂ CF ₂ CHF ₂ , OCF ₂ CF ₂ CH ₂ F, OCFHCF ₂ CF ₃ , OCFHCF ₂ CHF ₂ , OCF ₂ CHFCF ₃ , OCF ₂ CF ₂ CF ₃ , OCF ₂ CF ₂ CClF ₂ , OCClFCF ₂ CF ₃ , OCH=CF ₂ , OCF=CF ₂ , OCH=CHF, OCF=CH ₂ , CH=CF ₂ , CF=CF ₂ or CF=CHF. X ⁰ is particularly preferred for F, OCF ₃ or CF ₃ .

Preferred compounds of formula I are compounds of formulae I-1 to I-35,

Wherein R ¹ and X ¹ have the meanings mentioned above. In a preferred embodiment, R ¹ represents a linear alkyl group having 1 to 6 C atoms or an alkenyl group having 2 to 6 C atoms.

Among the specified subformulae I-1 to I-35, particularly preferred are compounds of the formulae I-2, I-4, I-18, I-28 and I-35. In a particularly preferred embodiment, X ^{1 of the} compounds of formula I and subformulae I-1 to I-35 represent F.

A compound of formula I wherein ring A or B represents a dioxane ring is preferred.

Preferably, the compound of the formula I and its subformula is employed in an amount of from 0.001 to 25% by weight, preferably from 0.01 to 10% by weight, based on the homologue and in a mixture. If a plurality of compounds of the formula I are employed in the mixtures according to the invention, the total concentration of all compounds of the formula I is from 0.001 to 25% by weight, preferably from 0.001 to 10% by weight, based on the mixture.

In the compounds of formula I and subformulae, Y ¹ and Y ² each independently represent F independently of one another. R ¹ preferably represents a linear alkyl group. X ^{1 is} preferably F, OCF ₃ or CF ₃ .

The medium of the present invention preferably comprises one, two, three, four or more, preferably a compound of formula I.

In the compounds of formula IIA and IIB, Z ² may have the same or different meanings. In the compound of the formula IIB, Z ² and Z ^{2 '} may have the same or different meanings.

In the compounds of formula IIA, formula IIB and formula IIC, R ^2A , R ^2B and R ^2C each preferably represent an alkyl group having from 1 to 6 C atoms, especially CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , positive C ₄ H ₉ , positive C ₅ H ₁₁ .

In the compounds of the formulae IIA and IIB, L ¹ , L ² , L ³ and L ⁴ preferably denote L ¹ = L ² = F and L ³ = L ⁴ = F, furthermore L ¹ = F and L ² = Cl or L ¹ = Cl and L ² = F. Z ² and Z ^{2 '} in the formulae IIA and IIB preferably each independently represent a single bond, and further represent a -C ₂ H ₄ - or -CH ₂ O-bridge.

If Z ² = -C ₂ H ₄ - in the formula IIB, Z ^{2 ' is} preferably a single bond, or if Z ^{2 '} = -C ₂ H ₄ -, Z ^{2 is} preferably a single bond. In the compounds of the formulae IIA and IIB, (O)C _v H _2v+1 preferably denotes OC _v H _2v+1 and further denotes C _V H _2v+1 . In the compound of the formula IIC, (O)C _v H _2v+1 preferably denotes C _v H _2v+1 . In the compound of the formula IIC, L ¹ and L ² each preferably represent F.

Preferred compounds of formula IIA, formula IIB and formula IIC are as follows: Wherein the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms.

A particularly preferred mixture of the invention comprises one or more of Formulas IIA-2, IIA-8, IIA-14, IIA-20, IIA-33, IIA-35, IIA-43, IIA-49, IIB-2, IIB-11 , compounds of IIB-16 and IIC-1.

The proportion of the compound of the formula IIA and/or IIB in the entire mixture is preferably at least 20% by weight.

A particularly preferred medium of the invention comprises at least one compound of the formula IIB-11 or IIC-1,

Wherein alkyl and alkyl* have the meaning indicated above, preferably in an amount of 1% by weight, especially >2% by weight and particularly preferably 2-25% by weight.

Preferred embodiments of the liquid crystal medium of the present invention are as follows: a) a liquid crystal medium additionally comprising one or more compounds of the formula III,

Wherein: R ³¹ and R ³² each independently represent a linear alkyl group, an alkoxyalkyl group, an alkenyl group or an alkoxy group having up to 12 C atoms, Express or Z ³ represents a single bond, -CH ₂ CH ₂ -, -CH=CH-, -(CH ₂ ) ₄ -, -CF ₂ CF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF=CF-, -CH=CHCH ₂ O-.

Preferred compounds of formula III are as follows:

Wherein: the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms.

The medium of the present invention preferably comprises at least one compound of formula IIIa and / or formula IIIb.

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

b) a liquid crystal medium additionally containing a compound of the formula: And/or And/or And/or

Better total 5 wt%, especially 10% by weight.

In a preferred embodiment, the LC mixture of the present invention additionally contains the compound CC-3-V

The better mixture contains the compounds CC-3-V and CC-3-V1

c) a liquid crystal medium additionally comprising one or more tetracyclic compounds of the formula:

Wherein: R ^7-10 each independently have one of the meanings specified by R ^2A as in the first aspect, (O) C _x H _2x+1 represents OC _x H _2x+1 or C _x H _2x+1 w and x each represent 1 to 6 independently of each other.

More preferably, it is a mixture comprising at least one compound of the formula V-9.

d) a liquid crystal medium additionally comprising one or more compounds of the formulae Y-1 to Y-6,

Wherein R ^{14 to} R ¹⁹ each independently represent an alkyl group or alkoxy group having 1 to 6 C atoms; z and m each independently represent 1-6; and x represents 0, 1, 2 or 3.

The medium of the present invention preferably further comprises one or more compounds of the formulae Y-1 to Y-6, preferably in an amount of 5 wt%.

e) a liquid crystal medium additionally comprising one or more fluorinated terphenyls of the formula T-1 to formula T-22,

Wherein: R represents a linear alkyl group or alkoxy group having 1 to 7 C atoms, and m = 0, 1, 2, 3, 4, 5 or 6 and n represents 0, 1, 2, 3 or 4.

R preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a pentyloxy group.

The medium of the invention preferably comprises from 3 to 30% by weight, in particular from 5 to 20% by weight, of terphenyl of the formula T-1 to the formula T-22.

Particularly preferred are compounds of the formulae T-1, T-2, T-4, T-20 and T-21. In these compounds, R preferably represents an alkyl group, and further represents an alkoxy group each having 1 to 5 C atoms. In the compound of the formula T-20, R preferably denotes an alkyl or alkenyl group, especially an alkyl group. In the compound of the formula T-21, R preferably represents an alkyl group.

If the mixture is △n value Preferably, diphenyl is used in the mixture of the invention. A preferred mixture comprises from 2 to 20% by weight of one or more biphenyl compounds selected from the group of compounds T-1 to T-22.

f) a liquid crystal medium additionally comprising one or more biphenyls of the formulae B-1 to B-4,

Wherein: the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkoxy group means a linear alkoxy group having 1 to 6 C atoms, an alkenyl group and an alkenyl group * Each of them independently represents a linear alkenyl group having 2 to 6 C atoms.

The proportion of biphenyl of the formulae B-1 to B-4 in the entire mixture is preferably at least 3% by weight, in particular 5 wt%.

Among the compounds of the formulae B-1 to B-4, the compound of the formula B-2 is particularly preferred.

Especially good biphenyl

Wherein alkyl* represents an alkyl group having 1 to 6 C atoms. Medium preferred package of the invention Containing one or more compounds of the formula B-1a and/or formula B-2c.

g) a liquid crystal medium additionally comprising at least one compound of the formulae Z-1 to Z-7,

Wherein R and alkyl have the meanings indicated above.

h) a liquid crystal medium additionally comprising at least one compound of the formulae O-1 to O-17,

Wherein R ¹ and R ² have the meanings indicated with respect to R ^2A . R ¹ and R ² each preferably independently represent a linear alkyl group.

Preferred media comprise one or more of formulas O-1, O-3, O-4, O-5, O-6, O-10, O-12, O-14, O-15, O-16 and/or Compound of O-17.

The mixture of the invention preferably comprises a compound of the formula O-10, the formula O-16 and/or the formula O-17, in particular in an amount of from 5% to 30%.

Preferred compounds of formula O-10 and O-17 are as follows:

The medium of the present invention preferably comprises a tricyclic compound of the formula O-10a and/or the formula O-10b and One or more bicyclic compounds of the formula O-17a to O-17g. The total proportion of the compound of the formula O-10a and/or O-10b and the compound of one or more bicyclic compounds selected from the formulae O-17a to O-17g is from 5% to 40%, particularly preferably in the form of a mixture. 15% - 35%.

A very good mixture contains the compounds O-16a and O-17a:

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

A very good mixture contains the compounds O-10b and O-17a:

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

A very good mixture consists of the following three compounds:

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

i) preferred liquid crystal media of the present invention comprise one or more materials containing tetrahydronaphthyl or naphthyl units, such as compounds of formula N-1 to formula N-5,

Wherein R ^1N and R ^2N each independently have the meaning indicated with respect to R ^2A , preferably represents a linear alkyl group, a linear alkoxy group or a linear alkenyl group, and Z ¹ and Z ² are each independently represented - 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.

j) a preferred mixture comprising one or more difluorodibenzos selected from the group consisting of BC Alkane compound, formula CR a compound of a fluorinated phenanthrene of the formulae PH-1 and PH-2, a fluorinated dibenzofuran of the formula BF-1 and BF-2,

Wherein: R ^B1 , R ^B2 , R ^CR1 , R ^CR2 , R ¹ , and R ² each independently have the meaning of R ^2A . c is 0, 1, or 2.

The mixture of the invention preferably comprises a compound of the formula BC, CR, PH-1, PH-2, BF-1 and/or BF-2 in an amount of from 3 to 20% by weight, especially from 3 to 15% by weight.

The compounds of the formula BC and the formula CR are compounds BC-1 to BC-7 and CR-1 to CR-5, Wherein: R ² has the meaning given above, and the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkenyl group and the alkenyl group are each independently represented by 2 a linear alkenyl group of up to 6 C atoms.

Particularly preferred are mixtures comprising one, two or three compounds of the formula BC-2, BC-3, BF-1a and BF-1b.

k) a preferred mixture comprising one or more indane compounds of the formula In, Wherein: R ¹¹ , R ¹² and R ¹³ each independently represent a linear alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 6 C atoms, and R ¹² and R ¹³ additionally represent a halogen, Better F, Express i means 0, 1, or 2.

A preferred compound of the formula In is a compound of the formula In-1 to Formula In-16 as shown below:

More preferably, it is a compound of the formula In-1, the formula In-2, the formula In-3 and the formula In-4.

The concentration of the compound of the formula In and the sub-forms In-1 to In-16 used in the mixture of the present invention is preferably 5 wt%, especially 5-30 wt% and very preferably 5-25 wt%.

l) a preferred mixture additionally comprising one or more compounds of the formula L-1 to formula L-11, Wherein: R, R ¹ and R ² each independently have the meanings assigned to R ^2A as in the first embodiment, and the alkyl group represents an alkyl group having 1 to 6 C atoms. s means 1 or 2.

It is especially preferred to be a compound of the formula L-1 and L-4, especially L-4.

The compound of the formula L-1 to the formula L-11 is preferably used in a concentration of 5 to 50% by weight, particularly 5 to 40% by weight and very preferably 10 to 40% by weight.

m) the medium additionally comprises one or more compounds of the formula EY,

Wherein R ¹ , R ^1* , L ¹ and L ² have the meanings specified in formula I and formula IIA. In the compound of the formula EY, R ¹ and R ^{1* are} preferably represented by having 2 alkoxy groups of C atoms, and L ¹ = L ² = F. Especially preferred is a compound of the formula

It is especially preferred to be a compound of the formula EY-1 to EY-12, especially EY-2, EY-9 and EY-10.

n) the medium additionally comprises one or more diphenylacetylene compounds of the formula To-1 to To-12, Wherein R ¹ and R ² each independently have the meaning of R ¹ as in the first embodiment, preferably a linear alkyl group, an alkoxy group or an alkenyl group, especially a linear alkane having 1 to 6 C atoms. base. Alkyl, alkoxy and alkenyl have the meanings as described above.

The alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms, the O-alkyl group represents a linear alkoxy group having 1 to 6 C atoms, and the alkenyl group has 2 to a linear alkenyl group of 6 C atoms.

Eugenbiphenylacetylene is a compound of the formulas To-1, To-2, To-4, To-9, To-10 and To-11.

o) The medium additionally comprises one or more biphenyl compounds of the formula V-1 to V-4

Wherein R ¹ has the meaning of R ¹ as in the first embodiment, and preferably represents a linear alkyl group, an alkoxy group or an alkenyl group, especially a linear alkyl group having 1 to 6 C atoms. X ¹ has the meaning of R ¹ as in the first embodiment, and preferably represents F, OCF ₃ or CF ₃ .

The compound of the formula V-1 to the formula V-4 is preferably used in a concentration of 0.001 to 15% by weight, particularly 0.01 to 10% by weight and very preferably 0.015 to 8% by weight.

The concept of a very good mixture is as follows: (The first word used is explained in Table A. Here n and m each represent 1 to 6 independently of each other).

Furthermore, it is preferred to comprise a mixture of the following mixture components: - CPY-n-Om, especially CPY-2-O2, CPY-3-O2 and/or CPY-5-O2, based on the total mixture, at a higher concentration More preferably 5%, especially 10%-30%, - CY-n-Om, preferably CY-3-O2, CY-3-O4, CY-5-O2 and/or CY-5-O4, The concentration of the entire mixture is preferably more than 5%, especially 15% to 50%, - CCY-n-Om, preferably CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY- 3-O1 and/or CCY-5-O2, preferably in a concentration of > 5%, especially 10% to 30%, based on the entire mixture, - CLY-n-Om, preferably CLY-2-O4, CLY -3-O2 and / or CLY-3-O3, off Preferably, the concentration of the mixture is > 5%, especially 10% to 30%, - CK-nF, preferably CK-3-F, CK-4-F and/or CK-5-F, for the entire Preferably, the mixture is > 5%, especially 5% to 25%.

Furthermore, it is preferred to comprise a mixture of the following mixture components: - CCH-nm + CY-n-Om and / or - CCH-nm, preferably CCH-23, CCH-34 and / or CCH-35, + CCY- n-Om and / or - CPY-n-Om + CY-n-Om, the concentration is preferably from 10% to 80% of the entire mixture, and / or - CCH-nm + CY-n-Om + CCY- n-Om+CPY-n-Om and / or - CPY-n-Om+CY-n-Om+CC-3-V and / or - CPY-n-Om+CY-n-Om+CCY-n- Om+CC-3-V and / or - CPY-n-Om+CCY-n-Om+PY-n-Om+CC-3-V and / or - CPY-n-Om+CLY-n-Om+ PY-n-Om+CC-3-V and / or - CPY-n-Om+CY-n-Om+CC-3-V1 and / or - CPY-n-Om+CLY-n-Om, concentration Preferably, it is 10%-80% of the entire mixture.

The invention further relates to a method based on ECB, VA, PS-VA, PALC, An active matrix addressed electro-optical display of IPS, PS-IPS, FFS or PS-FFS effect, characterized in that it contains a liquid crystal medium as one or more of the technical solutions 1 to 15 as a dielectric.

The liquid crystal medium of the present invention preferably has -20 ° C to 70 ° C, especially good for -30 ° C to 80 ° C, especially -40 ° C to Nematic phase at 90 °C.

The expression "having a nematic phase" herein means that on the one hand, the smectic phase and crystallization are not observed at a low temperature at the corresponding temperature, and on the other hand, no clarification occurs after the nematic phase is heated. The investigation at low temperatures was carried out in a flow viscometer at the corresponding temperature and was checked by storage in a test unit having a layer thickness corresponding to the electro-optical application for at least 100 hours. If the storage stability in the corresponding test unit at a temperature of -20 ° C is 1000 hours or more, the medium is said to be stable at this temperature. At -30 ° C and -40 ° C, the corresponding time is 500h and 250h. At elevated temperatures, clear spots are measured in the capillary by conventional methods.

The liquid crystal mixture preferably has a nematic phase range of at least 60K and a flow viscosity ν _{20 of} at most 30 mm ² s ^-1 at 20 °C.

The birefringence value Δn in the liquid crystal mixture is usually between 0.07 and 0.16, preferably between 0.08 and 0.12.

The liquid crystal mixture of the present invention preferably has a negative dielectric anisotropy Δ ε of especially -0.5 to -8.0. More preferably, it is a mixture of the invention having a Δε value of from -2.5 to -6.0. The preferred mixture has a value of ε _average = (ε _| + 2 ε _⊥ ) / 3 in the range of 5-10 at 20 °C.

Rotational viscosity γ _{1 at} 20 ° C is preferred 200mPa. s, especially for 180mPa. s.

The liquid crystal medium of the present invention has a relatively low threshold voltage value (V ₀ ). It is preferably in the range of 1.7V to 3.0V, preferably 3V and extremely good 2.5V.

For the present invention, the term "threshold voltage" system on a capacitive threshold (V _0), also known as Freedericks threshold, unless otherwise clear instructions.

Further, the liquid crystal medium according to the present invention has high voltage retention in the liquid crystal cell ratio.

In general, a liquid crystal medium having a low address voltage or a threshold voltage exhibits a lower voltage holding ratio than a liquid crystal medium having a higher address voltage or threshold voltage, and vice versa.

For the purposes of the present invention, the term "dielectrically positive compound" means a compound having Δ ε > 1.5, and the term "dielectric neutral compound" means that they have -1.5. △ε The compound of 1.5, and the term "dielectric negative compound" means that they have a compound having Δ ε < -1.5. The dielectric anisotropy of the compound is determined here by dissolving 10% of the compound in the liquid crystal host and measuring the capacitance of the resulting mixture in at least one test cell, in each case having a layer thickness of 20 μm and having a vertical at 1 kHz. And parallel surface alignment. The measurement voltage is typically from 0.5V to 1.0V, but is always below the capacitance threshold of the individual liquid crystal mixtures studied.

All temperature values described herein are in the form of °C.

The inventive mixtures are suitable for all VA-TFT applications such as VAN, MVA, (S)-PVA, ASV, PSA (Polymer Continuous VA) and PS-VA (Polymer Stabilized VA). It is also suitable for IPS (coplanar switching type) and FFS (fringe field switching type) applications with negative Δε.

The nematic liquid crystal mixture in the display of the present invention typically comprises two components A and B, which themselves are composed of one or more individual compounds.

Component A has significant negative dielectric anisotropy and is provided -1 nematic phase of dielectric anisotropy. In addition to one or more compounds of formula I having positive dielectric anisotropy, it preferably comprises one or more compounds of formula IIA, IIB and/or IIC having negative dielectric anisotropy, and furthermore at least one compound of formula III .

The proportion of component A is preferably between 45% and 100%, in particular between 60% and 100%.

For component A, the preferred option has One (or more) individual compounds of the value of Δε of -0.8. The smaller the ratio A in the entire mixture, the more negative this value must be.

Component B has significant nematogeneity and a flow viscosity at 20 ° C of no greater than 30 mm ² . s ^-1 , preferably no more than 25mm ² . s ^-1 .

A particularly preferred individual component of component B is a flow viscosity at 20 ° C of no greater than 18 mm ² . Very low viscosity nematic liquid crystal of s ^-1 (preferably not more than 12mm ² .s ^-1 ).

Component B is a unimorphic or tautomeric nematic, has no smectic phase and is capable of preventing the occurrence of low to very low temperatures of the smectic phase in the liquid crystal mixture. For example, if various high nematic base materials are added to the smectic liquid crystal mixture, the nematic basis of the materials can be compared by the degree of inhibition of the achieved smectic phase.

The mixture may also comprise component C, including A compound having a dielectric anisotropy Δ ε of 1.5. The amount of such so-called positive compounds present in the mixture of negative dielectric anisotropy is generally 20% by weight.

Those skilled in the art are aware of numerous suitable materials from the literature. It is especially preferred to be a compound of formula III.

Further, these liquid crystal phases may also contain 18 or more components, preferably 18 to 25 components.

In addition to one or more compounds of the formula I, the phases preferably comprise from 4 to 15, especially from 5 to 12 and particularly preferably less than 10 compounds of the formula IIA, IIB and/or IIC and, as the case may be, compounds of the formula III.

In addition to the compounds of the formula I and the compounds of the formulae IIA, IIB and/or IIC and optionally the compounds of the formula III, the other constituents may, for example, comprise up to 45%, but preferably up to 35%, especially up to 10%, of the total mixture. The quantity exists.

The other ingredients are preferably selected from nematic or nematic primordial substances (in particular, known substances) from the following classes: azobenzene, benzylidene aniline, biphenyl, terphenyl, phenyl benzoate or benzene Cyclohexyl formate, phenyl cyclohexanecarboxylate or cyclohexyl cyclohexanecarboxylate, phenylcyclohexane, cyclohexylbiphenyl, cyclohexylcyclohexane, cyclohexylnaphthalene, 1,4-dicyclohexylbiphenyl or Cyclohexylpyrimidine, phenyl- or cyclohexyldioxane, optionally ruthenium halide, benzyl phenyl ether, Diphenylacetylene and substituted cinnamate.

The most important compound suitable as a component of this type of liquid crystal phase has the following formula IV: R ²⁰ -LGER ²¹ IV

Wherein L and E each represent a system derived from 1,4-disubstituted benzene and cyclohexane, 4,4'-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane, 2,5- Carbocyclic or heterocyclic ring system formed by disubstituted pyrimidine and 1,3-dioxane ring, 2,6-disubstituted naphthalene, dihydronaphthalene and tetralin, quinazoline and tetrahydroquinazoline .

G represents -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 represents halogen (preferably chlorine) or -CN, and R ²⁰ and R ²¹ each represent an alkyl group, an alkenyl group, an alkoxy group, an alkene having up to 18, preferably up to 8 carbon atoms. An oxyalkyl or alkoxycarbonyloxy group, or one of such groups, either represents CN, NC, NO ₂ , NCS, CF ₃ , SF ₅ , OCF ₃ , F, Cl or Br.

In most of these compounds, R ²⁰ and R ²¹ are different from each other, and one of these groups is usually an alkyl group or an alkoxy group. Other variations of the proposed substituents are also common. Many of these materials or mixtures thereof are commercially available. All such materials can be prepared by methods known from the literature.

It will be apparent to those skilled in the art that the VA, IPS or FFS mixture of the present invention may also comprise, for example, compounds in which H, N, O, Cl and F have been replaced by the corresponding isotopes.

Prepared in a manner known per se, for example, by mixing one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above and optionally with other liquid crystal compounds and/or additives The LC medium used in the invention. In general, it is preferred to dissolve a desired amount of the component used in a smaller amount in a component constituting the main component at a high temperature. It is also possible to mix solutions of the components in an organic solvent such as acetone, chloroform or methanol, and remove the solvent again, for example, by distillation after thorough mixing. The invention further relates to a process for the preparation of the LC medium of the invention.

The mixture of the present invention may additionally contain conventional additives such as stabilizers, antioxidants, UV absorbers, nanoparticles, particles, and the like.

The structure of the liquid crystal display of the invention corresponds to a common geometry, as described, for example, in EP-A 0 240 379.

The structure of the LC display of the present invention corresponds to the common geometry of PSA displays as described in the prior art cited in the introduction. The geometry without protrusions is preferred, especially if the electrodes on the (additional) color filter side are unconstructed and only the electrodes on the TFT side have the geometry of the slits. Particularly suitable and preferred electrode structures for PS-VA displays are described, for example, in US 2006/0066793 A1.

The combination of the liquid crystal mixture of the present invention and the polymeric compound mentioned above and below achieves low threshold voltage, low rotational viscosity value and excellent low temperature stability in the LC medium of the present invention and maintains high definition and high definition The HR value and allows for a particularly low pretilt angle to be quickly established in the PSA display. In particular, in PSA displays, LC media exhibits significantly reduced response times, especially grayscale response times, compared to media from prior art.

Further, a polymerizable compound called a reactive liquid crystal precursor (RM) (for example, as disclosed in US Pat. No. 6,861,107) may be added to the present invention in a concentration of preferably from 0.12 to 5% by weight, particularly preferably from 0.2 to 2% by weight, based on the mixture. In the mixture. These mixtures may also comprise an initiator, as described, for example, in U.S. 6,781,665. Initiator (eg from Ciba Chemicals) Irganox-1076) is preferably added to the mixture comprising the polymerizable compound in an amount of from 0 to 1%. Such a mixture can be used in the so-called polymer stabilized VA mode (PS-VA) or PSA (polymer continuous type VA), wherein the polymerization of the reactive liquid crystal precursor is intended to occur in the liquid crystal mixture. A prerequisite for this is that the liquid crystal mixture itself does not contain any polymerizable components.

The IPS and PSA displays of the present invention have two electrodes, preferably in the form of transparent layers, applied to one or both of the substrates to form an LC cell. One electrode is applied to each of the two substrates in each case, as for example in the PSA-VA, PSA-OCB or PSA-TN display of the invention, or both electrodes are applied to only two substrates In one of the cases, the other substrate is electrodeless, as in, for example, the PSA-IPS or PSA-FFS display of the present invention.

The following meanings apply to the above and below.

Unless otherwise indicated, the term "PSA" is used to denote a PS display and a PSA display.

The terms "tilt" and "tilt angle" refer to the oblique alignment of the LC molecules of the liquid crystal medium relative to the surface of the cells in the LC display (preferably PS or PSA display herein). The tilt angle here represents the average angle (<90°) between the longitudinal molecular axis of the LC molecule (LC director) and the surface of the planar parallel outer plate forming the LC cell. Here, the low tilt angle value (i.e., the large deviation from the 90° angle) corresponds to a large tilt. A suitable method for measuring the tilt angle is given in the example. The tilt angle values disclosed above and below are related to this measurement method unless otherwise indicated.

The term "liquid crystal primordium group" is known to those skilled in the art and is described in the literature and represents an anisotropy due to the attraction and repulsive interaction of the group which substantially contributes to causing low molecular weight or a group of liquid crystal (LC) phases in the polymer matrix. The compound containing a liquid crystal primordium group (liquid crystal primordial compound) does not necessarily have to have an LC phase by itself. For liquid crystal primordial compounds, LC phase characteristics may also be exhibited only after mixing with other compounds and/or after polymerization. Typical liquid crystal primordial groups are, for example, rigid rod or dish shaped cells. In Pure Appl. Chem. 73 (5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, An overview of the terms and definitions used in connection with liquid crystal primordia or LC compounds is given in Angew. Chem. 2004, 116, 6340-6368.

The term "spacer" (also referred to hereinafter as "Sp") is known to those skilled in the art and is described in the literature, see, for example, Pure Appl. Chem. 73(5), 888 (2001). And C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. The terms "spacer" or "spacer" as used above and hereinafter, unless otherwise indicated, denotes a flexible group in which a liquid crystal priming group and a polymerizable group are bonded to each other in a polymerizable liquid crystal primordial compound.

The term "reactive mesogenic primordium" or "RM" denotes a compound containing a liquid crystal primordium group and one or more functional groups (also referred to as a polymerizable group or group P) suitable for polymerization.

The terms "low molecular weight compound" and "non-polymerizable compound" mean a compound which is usually a monomer which does not contain conditions suitable for polymerization under ordinary conditions known to those skilled in the art (specifically, for polymerization of RM) Lower) a functional group to be polymerized.

For the purposes of the present invention, the term "liquid crystal medium" is intended to mean a medium comprising an LC mixture and one or more polymerizable compounds, such as reactive liquid crystal primaries. The term "LC mixture" (or "host mixture") is intended to mean a composition consisting only of non-polymerizable, low molecular weight compounds, preferably two or more liquid crystal compounds and optionally other additives, such as palmitic doping. A liquid crystal mixture composed of a stabilizer or a stabilizer. "Non-polymerizable" means that the compound is stable or non-reactive with respect to the polymerization at least under the conditions for polymerizing the polymerizable compound.

More preferably, it is a liquid crystal mixture having a nematic phase, specifically a nematic phase at room temperature.

Preferred PS mixtures comprising at least one compound of the formula I are distinguished in particular as follows: The concentration of the polymerisable component is from 0.01 to 5% by weight, in particular from 0.01 to 1% by weight and particularly preferably from 0.01 to 0.5% by weight, based on the total mixture.

- The liquid crystal medium does not contain a compound containing a vinyloxy end group (-O-CH=CH ₂ ).

- a PS-VA or PSA display comprising the PS mixture of the invention preferably has 85°, especially good Pre-tilt angle of 80°.

In the VA type display of the present invention, molecules in the layer of the liquid crystal medium in the off state are aligned (vertically) perpendicular to the electrode surface or have an oblique vertical alignment. After a voltage is applied to the electrodes, realignment of the LC molecules with the longitudinal molecular axes parallel to the electrode surface occurs.

The LC mixture of the present invention used in a VA type display has a negative dielectric anisotropy Δ ε of preferably -0.5 to -10, especially -2.5 to -7.5 at 20 ° C and 1 kHz.

The birefringence Δn in the LC medium of the present invention used in a VA type display is preferably less than 0.16, particularly preferably between 0.06 and 0.14, especially between 0.07 and 0.12.

The LC medium of the present invention may also comprise other additives known to those skilled in the art and described in the literature, such as polymerization initiators, inhibitors, stabilizers, surface active materials or palmitic dopants. These may be polymerizable or non-polymerizable. The polymerizable additive is thus classified in the polymerizable component or component A). The non-polymerizable additives are therefore classified in the LC mixture (host mixture) or the non-polymerizable component or component B).

The LC mixture and LC medium can comprise, for example, one or more pairs of palmitic dopants, preferably selected from the group consisting of compounds from Table B below.

Furthermore, 0 to 15%, preferably 0 to 10%, of one or more of dielectric anisotropy, viscosity and/or alignment for modifying the nematic phase may be selected from the group consisting of polychromatic dyes, nanoparticles, and conductive salts. Additives to the group of complex salts and complex materials are added to the LC medium. Suitable and preferred conductive salts are, for example, the complex salts of ethyl dimethyldodecyl ammonium 4-hexaoxybenzoate, tetrabutylboron tetrabutylammonium or crown ethers (see, for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258, 1973). Substances of this type are described, for example, in DE-A-22 09 127, DE-A-22 40 864, DE-A-23 21 632, DE-A-23 38 281, DE-A-24 50 088, DE -A-26 37 430 and DE-A-28 53 728.

To produce a PSA display, polymerize or crosslink by in situ polymerization in a liquid crystal medium between substrates of an LC display with application of a voltage (if a compound contains two Or two or more polymerizable groups) polymerizable compounds. The polymerization can be carried out in one step. It is also possible to first carry out the polymerization in the first step under application of a voltage to produce a pretilt angle; and subsequently polymerize or crosslink the unreacted compound in the first step in the second polymerization step without application of a voltage (finally Cured).

Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, especially UV photopolymerization. One or more initiators may also be added here if necessary. Suitable polymerization conditions and suitable initiator types and amounts are known to those skilled in the art and are described in the literature. For example, commercially available photoinitiators Irgacure651 ^® , Irgacure 184 ^® , Irgacure 907 ^® , Irgacure 369 ^® or Darocure 1173 ^® (Ciba AG) are suitable for free radical polymerization. If an initiator is used, the proportion thereof is preferably from 0.001% to 5%, particularly preferably from 0.001% to 1%. However, it is also possible to carry out the polymerization without adding an initiator. In another preferred embodiment, the liquid crystal medium does not contain a polymerization initiator.

The polymerizable component A) or the LC medium may also contain one or more stabilizers to prevent improper spontaneous polymerization of the RM, for example during storage or transportation. Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature. For example, commercially available from stabilizer Irganox ^® series (BASF), the such as Irganox ^® 1076 is particularly suitable. If a stabilizer is used, its proportion in the total amount of RM or polymerizable component A) is preferably from 10 to 10,000 ppm, particularly preferably from 50 to 500 ppm.

Polymerizable compounds are also suitable for polymerization without an initiator, which is associated with considerable advantages, such as lower material costs and, in particular, less contamination of the liquid crystal medium by potentially residual amounts of initiator or degradation products thereof.

The LC medium of the present invention for use in a PSA display preferably comprises 5%, especially good 1%, very good 0.5% and better 0.01%, especially good 0.1% polymerizable compound, specifically a polymerizable compound having the formula given above and below.

It is especially preferred to be an LC medium comprising one, two or three polymerizable compounds.

Further, it is preferred that the non-pivotic polymerizable compound and its components A) and/or B) The composition is only selected from LC media consisting of a group of non-palphatic compounds.

Further, it is preferred that the polymerizable component or component A) comprises one or more polymerizable compounds containing one polymerizable group (single reaction) and two or more (preferably two) polymerizable groups. An LC medium of one or more polymerizable compounds of a group (two or more reactions).

Further, a PSA display and an LC medium in which the polymerizable component or component A) contains only a polymerizable compound containing two polymerizable groups (di-reactive) are preferred.

The polymerizable compound may be added individually to the LC medium, but it is also possible to use a mixture comprising two or more polymerizable compounds of the invention. The copolymer is formed by polymerizing the mixtures. The invention further relates to polymerizable mixtures as described above and below. The polymerizable compound can be a liquid crystal primordial or a non-liquid crystal primordial. More preferably, it is a polymerizable liquid crystal primordial compound, also known as a reactive liquid crystal primordial (RM).

Suitable and preferred RMs for use in the LC media and PSA displays of the present invention are as follows.

In a preferred embodiment of the invention, the polymerizable compound is selected from the group consisting of the compound of formula I* R ^a -A ¹ -(Z ¹ -A ² ) _m -R ^b I*

Wherein each group has the following meaning: R ^a and R ^b each independently represent P, P-Sp-, H, halogen, SF ₅ , NO ₂ , carbon or a hydrocarbon group, wherein the groups R ^a and R ^b At least one represents or contains a group P or P-Sp-, P represents the polymerizable group identically or differently at each occurrence, and Sp represents the same or different spacer or single bond at each occurrence, A ¹ And A ² each independently represent an aromatic, heteroaromatic, alicyclic or heterocyclic group, preferably having 4 to 25 ring atoms, which may also contain a fused ring, and which may also be mono- or poly-substituted by L Substituted, L represents P-Sp-, H, OH, CH ₂ OH, halogen, SF ₅ , NO ₂ , carbon or hydrocarbyl, and Z ¹ represents the same or different -O-, -S-, on each occurrence. -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _n1 -, -CH=CH -, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ⁰ R ⁰⁰ or a single bond, and R ⁰ and R ⁰⁰ each independently represent H or An alkyl group having 1 to 12 C atoms, and m represents 0, 1, 2, and 3 4, n1 represents a 2, 3 or 4.

The compound of the formula I* is a compound wherein R ^a and R ^b each independently represent P, P-Sp-, H, F, Cl, Br, I, -CN, -NO ₂ , -NCO, - NCS, -OCN, -SCN, SF ₅ or a linear or branched alkyl group having 1 to 25 C atoms, wherein additionally, one or more non-adjacent CH ₂ groups may cause O and/or S atoms to each other The modes that are not directly connected are each independently -C(R ⁰ )=C(R ⁰⁰ )-, -C≡C-, -N(R ⁰⁰ )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, and wherein, in addition, one or more H atoms may be replaced by F, Cl, Br, I, CN, P or P-Sp- Wherein at least one of the groups R ^a and R ^b represents or contains a group P or P-Sp-, and A ¹ and A ² each independently represent 1,4-phenylene, naphthalene-1,4-di Base, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, indole-2,7-diyl, indole-2,7-diyl, 2-sided oxy-2H-benzopyran -3,6-diyl, 2-sided oxy-2H-benzopyran-3,7-diyl, 4-sided oxy-4H-benzopyran-2,6-diyl, 4- Sideoxy-4H-benzopyran-3,6-diyl, 4-sided oxy-4H-benzopyran-3,7-diyl (common name coumarin or flavonoid), in addition, this One of the groups or One CH group may be N, cyclohexane-1,4-substitution, addition, one or more non-adjacent CH ₂ groups may be interrupted by O and / or S, 1,4- extending cyclohexene Base, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]hept-2,6-diyl, piperidine- 1,4-Diyl, decalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro- 4,7-A bridged indole-2,5-diyl substitution, wherein all such groups may be unsubstituted or monosubstituted or polysubstituted by L, and L represents P, P-Sp-, OH, CH ₂ OH , F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ^x ) ₂ , -C(=O)Y ¹ , -C(=O)R ^x , -N(R ^x ) ₂ , optionally substituted decyl, optionally substituted aryl having 6 to 20 C atoms, or linear having 1 to 25 C atoms Or a branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy group, in addition, one or more of the H atoms may be replaced by F, Cl or P-Sp- , P denotes a polymerizable group, Y ¹ represents halogen, R ^x represents P, P-Sp-, H, halogen, a straight-chain 1-25 C atoms, branched, or Alkyl group having, in addition, one or more non-adjacent CH ₂ groups may be such that O and / or S atoms as not directly connected to each other via the -O -, - S -, - CO -, - CO-O- , -O-CO-, -O-CO-O-substitution, and additionally, wherein one or more H atoms may be substituted by F, Cl, P or P-Sp-, as appropriate, from 6 to 40 C a aryl or aryloxy group of the atom, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms, the other preferred compound of formula I* being selected from one of the following subgroups or Many compounds: - m is 2 or 3, - m is 2, - R ^a and R ^b represent the same or different groups P-Sp-, - R ^a and R ^b represent the same or different groups P- Sp-, wherein one or more of the groups Sp represents a single bond, - m is 2 or 3, and R ^a and R ^b represent the same group P-Sp-, - such groups R ^a and R ^b One represents P-Sp- and the other represents a non-polymerizable group, preferably a linear or branched alkyl group having 1 to 25 C atoms, and further, one or more non-adjacent CH ₂ groups thereof O may be such, and / or S atoms are not connected to the way each independently of each other directly to one another by ^{-C (R 00) = C (} R 000) -, - C≡C -, - N (R 00) - -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution, and further, one or more of the H atoms may pass through F, Cl, Br , I or CN substitution, - one or more groups Sp represents a single bond, - one or more groups Sp represents -(CH ₂ ) _p1 -, -(CH ₂ ) _p1 -O-, -(CH ₂ ) _P1 -OCO- or -(CH ₂ ) _p1 -OCOO-, wherein p1 represents an integer from 1 to 12, and r1 represents an integer from 1 to 8, - L does not represent and/or contains a polymerizable group, -A ¹ and A ² independently of one another represents 1,4-phenylene or naphthalene-2,6-diyl, wherein additionally one or more CH groups of such groups may be replaced by N and, additionally, may be passed through a single Fluorinated or polyfluorinated, - Z ¹ is selected from the group consisting of -O-, -CO-O-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, - OCF ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- and a single bond, -L is a non-polymerizable group The group is preferably selected from the group consisting of F, Cl, -CN, a linear and branched alkyl group having 1 to 25 C atoms, wherein additionally, one or more non-adjacent CH ₂ groups may be made O and / or S atoms are not connected to the way each independently of each other directly to one another by ^{-C (R 00) = C (} R 000) - ^{-C≡C -, - N (R 00} ) -, - O -, - S -, - CO -, - CO-O -, - O-CO- or -O-CO-O- substituted, and further wherein One or more H atoms may be replaced by F, Cl, Br, I or CN.

The preferred I* compound is selected from the following subtypes:

Wherein: P ¹ and P ² have one of the meanings specified for P and preferably represent an acrylate group, a methacrylate group, a fluoroacrylate group, an oxetane, a vinyloxy group or an epoxy group. Sp ¹ and Sp ² each independently have one of the meanings assigned to Sp or represent a single bond, wherein one or more of the groups P ¹ -Sp ¹ - and P ² -Sp ² may also represent R ^aa Wherein at least one of the groups P ¹ -Sp ¹ - and P ² -Sp ² is different from R ^aa , and R ^aa represents F, Cl, -CN, a linear or branched alkane having 1 to 25 C atoms Further, wherein, in addition, one or more non-adjacent CH ₂ groups may be such that the O and/or S atoms are not directly connected to each other independently of each other by -C(R ⁰⁰ )=C(R ⁰⁰⁰ )-, C≡C-, -N(R ⁰⁰ )-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, and wherein, One or more H atoms may be replaced by F, Cl, Br, I or CN, R ⁰ , R ⁰⁰ have the meanings specified in formula I*, and Z ¹ represents -O-, -CO-, -C(R ^y R ^z )- or -CF ₂ CF ₂ -, Z ² and Z ³ each independently represent -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ - or - (CH _{2) n} -, wherein n 2, 3 or 4, L has the meaning indicated by the above formula I, L' and L" each independently represent H, F or Cl, r represents 0, 1, 2, 3 or 4, and s represents 0 1, 2 or 3, t represents 0, 1 or 2, x represents 0 or 1, and R ^y and R ^z each independently represent H, CH ₃ or CF ₃ .

Other preferred compounds of formula I* are selected from the following subtypes:

Each of the groups has the meanings indicated by the formulas M1 to M21.

In another preferred embodiment of the invention, the polymerizable compound is a palmitic or optically active compound selected from Formula II* (for palm RM): (R*-(A ¹ -Z ¹ ) _m ) _k -Q II* wherein A ¹ , Z ¹ and m have one of the meanings indicated in the formula I* identically or differently at each occurrence, R* having the same or different One of the meanings indicated by R ^a , where R* may be palmar or non-palpharital, and Q represents a k-valent palm-like group as defined in formula I*, as appropriate L is mono- or poly-substituted, k is 1, 2, 3, 4, 5 or 6, wherein the compounds contain at least one group R* or L which represents or contains a group P or P- as defined above Sp-.

The compound of formula II* has a monovalent group Q of formula III*,

Wherein L and r each have the same or different meanings as indicated above, and A* and B* each independently represent fused benzene, cyclohexane or cyclohexene, t being the same at each occurrence or 0, 1 or 2 are represented differently, and u represents 0, 1 or 2 identically or differently each time it occurs.

More preferably, it is a group of the formula III*, wherein u represents 1.

Other preferred compounds of formula II* contain a monovalent group Q of formula IV* or one or more groups R*,

Wherein: Q ¹ represents an alkyl or alkoxy group or a single bond having 1 to 9 C atoms, and Q ² represents an optionally fluorinated alkyl or alkoxy group having 1 to 10 C atoms, , wherein one or two non-adjacent CH ₂ groups may be such that O and/or S atoms are not directly connected to each other via -O-, -S-, -CH=CH-, -CO-, -OCO-, -COO-, -O-COO-, -S-CO-, -CO-S- or -C≡C-substitution; Q ³ represents F, Cl, CN or as defined for Q ² but different from Q ² Alkyl or alkoxy.

Preferred groups of formula IV* are, for example, 2-butyl (=1-methyl-propyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-B Hexyl group, 2-propyl-pentyl, especially 2-methyl Butyl, 2-methylbutoxy, 2-methyl-pentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-indenyl, 2-indenyl, 2 -dodecyl, 6-methoxyoctyloxy, 6-methyloctyloxy, 6-methyl-octyloxy, 5-methylheptyloxycarbonyl, 2-methylbutanoxy , 3-methyl-pentanyloxy, 4-methylhexyloxy, 2-chloropropoxy, 2-chloro-3-methylbutanoxy, 2-chloro-4-methyl Pentyloxy, 2-chloro-3-methyl-pentanyloxy, 2-methyl-3-oxa-pentyl, 2-methyl-3-oxahexyl, 1-methoxypropyl -2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy Base, 2-fluoro-decyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoro-methyl-octyloxy.

Other preferred compounds of formula II* contain a divalent group Q of formula V*,

Wherein L, r, t, A* and B* have the meaning indicated above.

Other preferred compounds of formula II* contain a divalent group Q selected from the group consisting of:

Wherein Phe represents a phenyl group which is optionally substituted or polysubstituted by L, and R ^x represents F or an optionally fluorinated alkyl group having 1 to 4 C atoms.

Suitable palms are described in, for example, GB 2 314 839 A, US 6,511,719, US 7,223,450, WO 02/34739 A1, US 7,041,345, US 7,060,331 or US 7,318,950. Suitable binaphthyl-containing RMs are described, for example, in US 6,818,261, US 6,916,940, US 7,318,950 and US 7,223,450.

The palmitic structural elements and the polymerizable and polymerized compounds containing the palmitic structural elements shown above and below may be optically active, ie, in pure enantiomer form or as two enantiomers. Any desired form of the mixture, or in the form of a racemic form. It is preferred to use a racemate. The use of racemates has several advantages over the use of pure enantiomers, such as significantly lower synthesis complexity and lower material costs.

The compound of formula II* is preferably present in the LC medium in the form of a racemate.

The preferred compound of formula II* is selected from the following subtypes:

Wherein L, P, Sp, m, r and t have the meaning indicated above, and Z and A each have the same or different meanings for Z ¹ and A ¹ respectively, and t1 is present at each occurrence. The time is 0 or 1 identically or differently.

The term "carbon-based" means a monovalent or polyvalent organic radical containing at least one carbon atom which is free of other atoms (such as, for example, -C≡C-) or optionally one or more other atoms, such as N, O, S, P, Si, Se, As, Te or Ge (e.g., carbonyl, etc.). the term "Hydrocarbyl" means a carbon group additionally containing one or more H atoms and optionally one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge.

"Halogen" means F, Cl, Br or I.

The carbyl or hydrocarbyl group can be a saturated or unsaturated group. The unsaturated group is, for example, an aryl group, an alkenyl group or an alkynyl group. The carbon group or hydrocarbon group having more than 3 C atoms may be straight chain, branched chain and/or cyclic and may also contain a spiro linkage or a fused ring.

The terms "alkyl", "aryl", "heteroaryl" and the like also include polyvalent groups such as alkyl, aryl, heteroaryl and the like.

The term "aryl" means an aromatic carbon group or a group derived therefrom. The term "heteroaryl" means an "aryl" group as defined above containing one or more heteroatoms.

Preferred carbon and hydrocarbyl groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkyl groups having from 1 to 40, preferably from 1 to 25, particularly preferably from 1 to 18, C atoms. a carbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group and an alkoxycarbonyloxy group; an optionally substituted aryl or aryloxy group having 6 to 40, preferably 6 to 25, C atoms; or having 6 to 40, preferably 6 to 25, C atoms, optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkoxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyl Oxyl and aryloxycarbonyloxy.

Other preferred carbon and hydrocarbyl groups are C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl, C ₄ -C ₄₀ alkyl diene a C ₄ -C ₄₀ polyalkenyl group, a C ₆ -C ₄₀ aryl group, a C ₆ -C ₄₀ alkylaryl group, a C ₆ -C ₄₀ arylalkyl group, a C ₆ -C ₄₀ alkylaryloxy group, C ₆ -C ₄₀ arylalkoxy, C ₂ -C ₄₀ heteroaryl, C ₄ -C ₄₀ cycloalkyl, C ₄ -C ₄₀ cycloalkenyl, and the like. More preferably, it is a C ₁ -C ₂₂ alkyl group, a C ₂ -C ₂₂ alkenyl group, a C ₂ -C ₂₂ alkynyl group, a C ₃ -C ₂₂ allyl group, a C ₄ -C ₂₂ alkyldienyl group, a C ₆ - C ₁₂ aryl, C ₆ -C ₂₀ arylalkyl and C ₂ -C ₂₀ heteroaryl.

Other preferred carbyl and hydrocarbyl groups are straight chain, branched or cyclic alkyl groups having from 1 to 40, preferably from 1 to 25, C atoms which are unsubstituted or substituted by F, Cl, Br, I or CN. Substituted or polysubstituted and wherein one or more of the non-adjacent CH ₂ groups may be such that each of the O and/or S atoms are not directly connected to each other via -C(R ^x )=C(R ^x )-, -C≡C-, -N(R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- substitution.

R ^x preferably denotes H, halogen, a linear, branched or cyclic alkyl chain having 1 to 25 C atoms, and additionally, one or more of the non-adjacent C atoms may pass through -O-, -S- , -CO-, -CO-O-, -O-CO-, -O-CO-O- and wherein one or more H atoms may be substituted by fluorine, optionally with 6 to 40 C atoms Aryl or aryloxy, or optionally substituted heteroaryl or heteroaryloxy having 2 to 40 C atoms.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, positive Dodecyloxy and the like.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, 2-methylbutyl, n-pentyl, Dipentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-decyl, n-decyl, n-undecyl, N-dodecyl, dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene Base.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, Third butoxy, 2-methylbutoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy, N-dodecyloxy and the like.

Preferred amine groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

The aryl and heteroaryl groups may be monocyclic or polycyclic, that is, they may contain a ring such as benzene Or two or more rings, which may also be fused (such as naphthyl) or covalently bonded (such as biphenyl), or contain a combination of a fused ring and a linking ring. The heteroaryl group contains one or more heteroatoms preferably selected from the group consisting of O, N, S and Se.

More preferably, it is a monocyclic, bicyclic or tricyclic aryl group having 6 to 25 C atoms and a monocyclic, bicyclic or tricyclic heteroaryl group having 2 to 25 C atoms, which optionally contains a fused ring and optionally Replaced. Further, it is preferably 5 members, 6 members or 7 members of an aryl group and a heteroaryl group, and further, one or more of the CH groups may be such that the O atoms and/or the S atoms are not directly connected to each other via N, S or O. Replacement.

Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, 1,1':3',1"-biphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, anthracene, dihydrogen Oh, , hydrazine, tetracene, pentacene, benzopyrene, anthracene, anthracene, anthracene, and snail.

Preferred heteroaryl groups are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, Isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3, 4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; 6-membered ring, Such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1 , 2,3,4-tetrazine, 1,2,3,5-tetrazine; or a condensing group such as anthracene, isoindole, pyridazine, oxazole, benzimidazole, benzotriazole, Anthraquinone, naphthyl imidazole, phenimidazole, pyridazole, pyrazinazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthraquinone, phenanthroxazole, isoxazole, benzothiazole, benzo Furan, isobenzofuran, dibenzofuran, quinoline, isoquinoline, acridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinaline Porphyrin, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzoxazine, benzopyrimidine, quinoxaline, phenazine, Pyridine, azacarbazole, benzoporphyrin, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene , benzothiadiazole thiophene or a combination of such groups. Heteroaryl groups can also be substituted with alkyl, alkoxy, sulfanyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

The (non-aromatic) alicyclic and heterocyclic groups encompass a saturated ring, that is, a ring containing only a single bond, and a partially unsaturated ring, that is, a ring having a complex bond. The heterocycle contains one or more heteroatoms preferably selected from the group consisting of Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may be monocyclic, that is, contain only one ring (such as cyclohexane), or multiple rings, that is, contain a plurality of rings (such as decalin or dicyclooctane). ). It is especially preferred to be a saturated group. Further, a monocyclic, bicyclic or tricyclic group having 3 to 25 C atoms is preferred, which optionally contains a fused ring and is optionally substituted. Further, preferably a 5, 6, 7 or 8 membered carbocyclic group, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more Non-adjacent CH ₂ groups may be replaced by -O- and/or -S-.

Preferred alicyclic and heterocyclic groups are, for example, a 5-membered group such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine; a 6-member group such as cyclohexane, decane, cyclohexene, tetrahydrogen Piperane, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; a 7-member group such as cycloheptane; and a condensed group such as tetrahydronaphthalene, Decalin, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6- Dibasic, octahydro-4,7-methyl bridge indole-2,5-diyl.

Preferred substituents are, for example, groups which promote dissolution (such as alkyl or alkoxy groups), electron withdrawing groups (such as fluorine, nitro or nitrile), or used to increase the glass transition temperature (Tg) of the polymer. Substituents, especially bulky groups, such as a tertiary butyl group or an optionally substituted aryl group.

Preferred substituents referred to above and below as "L" are, for example, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O _{^{) N (R x) 2,}} -C (= O) Y 1, -C (= O) R x, -N (R x) 2, where R ^x has the meaning indicated above, and Y ¹ represents halogen, Optionally substituted decyl or aryl group having 6 to 40, preferably 6 to 20 C atoms, and linear or branched alkyl group having 1 to 25 C atoms, alkoxy group, alkylcarbonyl group An alkoxycarbonyl group, an alkylcarbonyloxy group or an alkoxycarbonyloxy group, wherein one or more H atoms are optionally substituted by F or Cl.

"Substituted decyl or aryl" preferably means halogen, -CN, R ⁰ , -OR ⁰ , -CO-R ⁰ , -CO-OR ⁰ , -O-CO-R ⁰ or -O- CO-OR ⁰ substituted, wherein R ⁰ has the meaning indicated above.

Particularly preferred substituents L are, for example, F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , COCH ₃ , COC ₂ H ₅ , COOCH ₃ , COOC ₂ H ₅ , CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , and further phenyl.

Preferred Where L has one of the meanings indicated above.

The polymerizable group P is a group suitable for a polymerization reaction such as a radical or ionic chain polymerization, an addition polymerization reaction or a polycondensation reaction, or a polymer-like reaction such as addition or condensation on a polymer main chain. More preferably, it is a chain-polymerized group, especially a group containing a C=C double bond or a -C≡C-parallel bond, and a group suitable for ring-opening polymerization, such as an oxetane or an epoxy group.

Preferred group P is selected from the group consisting of CH ₂ =CW ¹ -COO-, CH ₂ =CW ¹ -CO-, , CH ₂ =CW ² -(O) _k3 -, CW ¹ =CH-CO-(O) _k3 -, CW ¹ =CH-CO-NH-, CH ₂ =CW ¹ -CO-NH-,CH ₃ - CH=CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH-CH ₂ ) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, (CH ₂ = CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, HO-CW ² W ³ -, HS-CW ² W ³ -, HW ² N-, HO-CW ² W ³ -NH-, CH ₂ =CW ¹ -CO-NH-,CH ₂ =CH-(COO) _k1 -Phe-(O) _k2 -,CH ₂ =CH-(CO) _k1 -Phe-(O) _k2 -, Phe-CH=CH-, HOOC-, OCN- and W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ represents H, F, Cl, CN, CF ₃ , phenyl having 1 to 5 C atoms or An alkyl group, especially H, F, Cl or CH ₃ , W ² and W ³ each independently represent H or an alkyl group having 1 to 5 C atoms, especially H, methyl, ethyl or n-propyl , W ⁴ , W ⁵ and W ⁶ each independently represent Cl, an oxaalkyl group having 1 to 5 C atoms or an oxacarbonylalkyl group, and W ⁷ and W ⁸ each independently represent H, Cl or have An alkyl group of 1 to 5 C atoms, Phe represents a 1,4-phenylene group, which is optionally substituted by one or more groups L different from P-Sp- as defined above, k ₁ , k ₂ And k ₃ each independently represent 0 or 1, and k _{3 is} preferably represented 1.

The preferred group P is CH ₂ =CW ¹ -COO-, especially CH ₂ =CH-COO-, CH ₂ =C(CH ₃ )-COO- and CH ₂ =CF-COO-, in addition to CH ₂ = CH-O-, (CH ₂ =CH) ₂ CH-OCO-, (CH ₂ =CH) ₂ CH-O-, and

Particularly preferred groups P are ethyleneoxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy, especially acrylate and methyl. Acrylate based.

Preferably, the spacer Sp is selected from the group of Sp'-X' such that the group P-Sp- corresponds to the formula P-Sp'-X'-, wherein: Sp' represents 1 to 20, preferably 1 to 12 a C atom of an alkyl group, which may be mono- or polysubstituted by F, Cl, Br, I or CN, and additionally, one or more non-adjacent CH ₂ groups may cause an O and/or S atom. The modes that are not directly connected to each other are independently -O-, -S-, -NH-, -NR ⁰ -, -SiR ⁰⁰ R ⁰⁰⁰ -, -CO-, -COO-, -OCO-, -OCO- O-, -S-CO-, -CO-S-, -NR ⁰⁰ -CO-O-, -O-CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-NR ⁰⁰ -, -CH=CH- or - C≡C-substitution, X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰⁰ -, -NR ⁰⁰ -CO-, -NR ⁰⁰ -CO-NR ⁰⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, - SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond, R ⁰⁰ and R ⁰⁰⁰ each independently represent 1 to 12 C atoms H or alkyl, and Y ² and Y ³ each independently represent H, F, Cl or CN.

X' is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ -CO -NR ⁰ - or single button.

Typical spacers Sp' are, for example, -(CH ₂ ) _p1 , -(CH ₂ CH ₂ O) _q1 -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, -CH ₂ CH ₂ -NH-CH ₂ CH ₂ - or -(SiR ⁰⁰ R ⁰⁰⁰ -O) _p1 -, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ⁰⁰ and R ⁰⁰⁰ have the above indicated meaning.

The preferred group -X'-Sp'- is -(CH ₂ ) _p1 -, -O-(CH ₂ ) _p1 -, -OCO-(CH ₂ ) _p1 -, -OCOO-(CH ₂ ) _p1 - .

In each case, the preferred group Sp' is, for example, a straight-chain ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a hydrazine group, and a hydrazine group. Base, undecydecyl, decyldecyl, octadecyl, ethylidene, ethyl, methyleneoxy, butyl, ethylthio, ethyl, N-N- Methyl imine group ethyl, 1-methylalkyl, vinyl, propylene and butenyl.

In another preferred embodiment of the invention, P-Sp- denotes a group (polyfunctional polymerizable group) containing two or more polymerizable groups. Suitable groups of this type and polymerizable compounds containing the same and their preparation are described, for example, in US 7,060,200 B1 or US 2006/0172090 A1. More preferably, it is a polyfunctional polymerizable group selected from the group consisting of P-Sp-:-X-alkyl-CHP ¹ -CH ₂ -CH ₂ P ² I*a

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ P ³ I*b

-X-alkyl-CHP ¹ CHP ² -CH ₂ P ³ I*c

-X-alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-C _aa H _2aa+1 I*d

-X-alkyl-CHP ¹ -CH ₂ P ² I*e

-X-alkyl-CHP ¹ P ² I*f

-X-alkyl-CP ¹ P ² -C _aa H _2aa+1 I*g

-X-Alkyl-C(CH ₂ P ¹ )(CH ₂ P ² )-CH ₂ OCH ₂ -C(CH ₂ P ³ )(CH ₂ P ⁴ )CH ₂ P ⁵ I*h

-X-alkyl-CH((CH ₂ ) _aa P ¹ )((CH ₂ ) _bb P ² ) I*i

-X-alkyl-CHP ¹ CHP ² -C _aa H _2aa+1 I*k

-X'-alkyl-C(CH ₃ )(CH ₂ P ¹ )(CH ₂ P ² ) I*m

Wherein: alkyl represents a single bond or a straight or branched alkyl group having from 1 to 12 C atoms, wherein one or more non-adjacent CH ₂ groups may cause the O and/or S atoms not to be directly connected to each other. The modes are each independently -C(R ⁰⁰ )=C(R ⁰⁰⁰ )-, -C≡C-, -N(R ⁰⁰ )-, -O-, -S-, -CO-, -CO-O -, -O-CO-, -O-CO-O-substitution, and additionally, wherein one or more H atoms may be replaced by F, Cl or CN, wherein R ⁰⁰ and R ⁰⁰⁰ have the meaning indicated above, aa And bb each independently represent 0, 1, 2, 3, 4, 5 or 6, and X has one of the meanings indicated with respect to X', and P ^1-5 each independently have an indication of P One of the meanings.

The polymerizable compound and RM can be prepared similarly to those known to those skilled in the art and described in organic chemical standard work such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart. . Other synthetic methods are given in the literature cited above and below. In the simplest case, for example by using a corresponding acid, acid derivative or halogenated compound containing a group P such as (meth)acryloyl chloride or (meth)acrylic acid, in a dehydrating reagent such as DCC (two The synthesis of these RMs is carried out by esterification or etherification of 2,6-dihydroxynaphthalene or 4,4'-dihydroxybiphenyl in the presence of cyclohexylcarbodiimide).

The LC mixtures and LC media of the present invention are generally suitable for use with any type of PS or PSA display, especially those based on LC media having negative dielectric anisotropy, particularly preferably for PSA-VA, PSA-IPS Or PS-FFS display. However, those skilled in the art can also perform the steps of the present invention in other PS or PSA type displays other than the above mentioned displays, for example via their basic structure or via the individual components used (such as The nature, arrangement or structure of the substrate, alignment layer, electrode, addressing element, backlight, polarizer, color filter, compensation film, etc., which is the case, is the use of the LC mixture and LC medium of the present invention.

The following examples illustrate the invention without limiting it. However, it is apparent to those skilled in the art that the preferred mixture concept and preferred compounds and their respective concentrations, as well as combinations thereof, are shown. In addition, the examples illustrate what properties and combinations of properties can be achieved.

The following examples are intended to illustrate the invention without limiting it. Above and below, the percentage data represents weight percent; all temperatures are indicated in degrees Celsius.

Throughout the patent application, the 1,4-cyclohexyl ring and the 1,4-phenylene ring are described as follows:

In addition to the compounds of formula IIA and/or IIB and/or IIC, one or more compounds of formula I, the mixtures of the invention preferably comprise one or more compounds from Table A as shown below.

Liquid crystal mixtures which can be used in accordance with the invention are prepared in a manner conventionally known. In general, it is preferred to dissolve the components in the required amounts in a relatively small amount in the components constituting the main component at a high temperature. It is also possible to mix solutions of the components in an organic solvent such as acetone, chloroform or methanol, and remove the solvent again, for example, by distillation after thorough mixing.

The liquid crystal phase of the present invention can be modified in a manner by means of suitable additives so that it can be used in any type of, for example, an ECB, VAN, IPS, GH or ASM-VA LCD display that has been disclosed to date.

The dielectric may also include other additives known to those skilled in the art and described in the literature, such as UV absorbers, antioxidants, nanoparticles, and free radical scavengers. For example, 0-15% pleochroic dye, stabilizer, or palmitic dopant can be added. Stabilizers suitable for use in the mixtures of the invention are especially the stabilizers listed in Table B.

For example, 0-15% of a multi-color dye may be added, and a conductive salt may be further added, preferably 4-dimethyloxybutyric acid ethyldimethyldodecyl ammonium, tetraphenylhydroboration tetrabutylate a double salt of ammonium or a crown ether (see, for example, Haller et al., Mol. Cryst. Liq. Cryst. Vol. 24, pp. 249-258 (1973)) to improve conductivity or addable substances to modify the nematic phase. Electrical anisotropy, viscosity and/or alignment. Substances of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

Table B shows possible dopants that can be added to the inventive mixtures. If the mixture contains The dopant is used in an amount of from 0.01 to 4% by weight, preferably from 0.1 to 1.0% by weight.

Stabilizers which can be added, for example, to the mixture of the invention in an amount of up to 10% by weight, preferably from 0.01 to 6% by weight, especially from 0.1 to 3% by weight, based on the total of the mixture, are shown in Table C below. Preferred stabilizers are especially BHT derivatives such as 2,6-di-tert-butyl-4-alkylphenol and Tinuvin 770 as well as Tunivin P and Tempol.

Preferred reaction liquid crystal priming groups (polymerizable compounds) for use in the PSA and PS-VA applications are shown in Table D below, preferably used in the mixtures of the present invention:

Working example:

The following examples are intended to illustrate the invention and not to limit it.

All temperature values indicated in this application (eg melting point T(C,N), smectic (S) phase to nematic (N) phase transition T(S,N) and clear point T unless otherwise expressly stated otherwise) (N, I)) are all indicated in degrees Celsius (°C). M.p. represents the melting point, cl.p. = clear point. Further, C = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The number between these symbols represents the transition temperature.

The bulk mixture used to determine the optical anisotropy Δn of the compound of formula I is the commercially available mixture ZLI-4792 (Merck KGaA). The dielectric anisotropy Δε was measured using a commercially available mixture ZLI-2857. The physical data of the compound to be studied is obtained from the change in the dielectric constant of the host mixture after addition of the compound to be studied and extrapolated to 100% of the compound used. Generally, depending on the solubility, 10% of the compound to be studied is dissolved in the host mixture.

Parts or percentages indicate parts by weight or percentage by weight unless otherwise indicated.

In the above and below, V ₀ represents the threshold voltage at 20 ° C, the capacitance [V] n _e represents the abnormal refractive index at 20 ° C and 589 nm, and n _o represents the general refractive index at 20 ° C and 589 nm. , △ n denotes optical anisotropy at 20 ℃ and ε _⊥ denotes the vertical under the 589nm at 20 ℃ 1kHz and directors in the dielectric susceptibility, ε _∥ denotes parallel deg.] C and at 20 is directed in 1kHz Dielectric sensitivity, ε _average (ε _∥ +2ε _⊥ ) / 3 △ ε represents dielectric anisotropy at 20 ° C and 1 kHz cl.p., T (N, I) represents a clear point [ ° C] γ ₁ represents the rotational viscosity measured at 20 ° C [mPa. s], which is determined by the rotation method in the magnetic field. K ₁ represents the elastic constant at 20 ° C, and the "tilt" deformation [pN] K ₃ represents the elastic constant at 20 ° C, and the "bending" deformation [pN] LTS represents The low temperature stability (nematic phase) measured in the test unit, HR ₂₀ represents the voltage holding ratio [%] at 20 ° C, and HR ₁₀₀ represents the voltage holding ratio [%] at 100 ° C.

The display for measuring the threshold voltage has two plane parallel outer plates spaced 20 μm apart and an electrode layer with a cover alignment layer of SE-1211 (Nissan Chemicals) on the inner side of the outer plate, which can realize the vertical of the liquid crystal Orientation.

All concentrations in this application are in the respective mixtures or mixture components unless otherwise specifically indicated. All physical properties are determined as described in "Merck Liquid Crystals, Physical Properties of Liquid Crystals", dated November 1997, Merck KGaA, Germany and applicable to temperatures of 20 ° C unless otherwise expressly indicated.

All concentrations and % values (except for HR, contrast, and transmittance values) in this application are expressed in weight percent and with respect to the entire corresponding mixture containing all solid or liquid crystal components but no solvent, unless explicitly stated otherwise.

Unless otherwise expressly indicated otherwise, for the present invention, the term "threshold voltage" on the capacitive threshold (V _0), also known as Feder Rex (Freedericks) threshold. In the example, the optical threshold (V ₁₀ ) of 10% relative contrast can also be indicated by conventional conventions.

The display for measuring the capacitive threshold voltage consists of two plane-parallel glass outer plates spaced 20 μm apart, each having an electrode layer inside and an unfriction polyimine alignment layer at the top, such a poly The amine alignment layer achieves vertical edge alignment of the liquid crystal molecules.

The display or test unit for measuring the tilt angle consists of two plane-parallel glass outer plates spaced 4 μm apart, each having an electrode layer inside and a polyimide layer on the top, wherein the two polyimides The layers are rubbed in anti-parallel to each other and achieve vertical edge alignment of the liquid crystal molecules.

The polymerizable compound is polymerized in a display or test unit by irradiation with UVA light for a predetermined period of time while applying a voltage to the display (typically 10V to 30V alternating current, 1 kHz). In the examples, unless otherwise indicated, the polymerization using a metal halide lamp and 100mW / cm ² of intensity, and using a standard meter UVA (UVA sensor having the high Hoenle UV meter) measured strength.

The tilt angle was determined by a rotary crystal experiment (Autronic-Melchers TBA-105). Here, the lower value (i.e., the larger deviation from the 90° angle) corresponds to a larger tilt.

The VHR value was measured as follows: 0.3% of the polymerizable monomer compound was added to the LC host mixture, and the resulting mixture was introduced into a VA-VHR test unit (unfriction, at 90°, VA-polyimine alignment layer, Layer thickness d 6 μm). The HR values were measured before and after 5 minutes at 100 ° C for UV exposure at 1 V, 60 Hz, 64 μs pulse (measuring instrument: Autronic-Melchers VHRM-105).

Example M1

Example M2

To prepare the PS-VA mixture, 0.3% RM1

It was added to the liquid crystal mixture according to Example M1.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

The reliability of the LC mixtures M1 and M2 can be further increased, for example by using the following additives:

Examples M1a) and M2a)

Will be less than 100ppm compound

Add to the LC mixture of Example M1 and the LC mixture of Example M2.

Examples M1b) and M2b)

Will be less than 100ppm compound

Add to the LC mixture of Example M1 and the LC mixture of Example M2.

Examples M1c) and M2c)

Will be less than 100ppm compound

Add to the LC mixture of Example M1 and the LC mixture of Example M2.

Example M1d) and M2d)

Will be less than 500ppm compound

Add to the LC mixture of Example M1 and the LC mixture of Example M2.

Example M1e) and M2e)

Will be less than 100ppm compound

Add to the LC mixture of Example M1 and the LC mixture of Example M2.

Example M3

To prepare a PS-VA or PS-FFS mixture, 0.25% RM74

It was added to the liquid crystal mixture according to Example M1.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M4

To prepare the PS-VA mixture, 0.25% RM35

It was added to the liquid crystal mixture according to Example M1.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M5

Example M6

To prepare the PS-VA mixture, 0.3% RM1

Add to the liquid crystal mixture according to Example M5.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M7

To prepare the PS-VA mixture, 0.2% RM41

Add to the liquid crystal mixture according to Example M5.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M8

Example M9

To prepare the PS-VA mixture, 0.3% RM1

Add to the liquid crystal mixture according to Example M8.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M10

To prepare the PS-VA mixture, 0.2% RM17

Add to the liquid crystal mixture according to Example M8.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M11

To prepare the PS-VA mixture, 0.2% RM61

Add to the liquid crystal mixture according to Example M8.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M12

To prepare the PS-VA mixture, 0.3% RM41

Add to the liquid crystal mixture according to Example M8.

The PS-VA mixture is introduced into a unit with a vertical alignment. After applying a voltage of 24 V, the unit was irradiated with UV light having a power of 100 mW/cm ² .

Example M13

To prepare the PS-VA mixture, 0.3% RM41

It was added to the liquid crystal mixture according to Example M1.

Example M14

Example M15

Example M16

Example M17

Example M18

Example M19

Example M20

Example M21

Example M22

Example M23

Example M24

Example M25

Example M26

Example M27

Example M28

Example M29

Example M30

Example M31

Example M32

Example M33

Example M34

Example M35

Example M36

Example M37

Example M38

Example M39

Example M40

To prepare a PS-VA or PS-FFS mixture, 0.3% RM1

Add to the liquid crystal mixture according to Example M39.

The reliability of the LC mixtures M39 and M40 can be further increased, for example by using the following additives:

Examples M39a) and M40a)

Will be less than 100ppm compound

Add to the LC mixture of Example M39 and the LC mixture of Example M40.

Examples M39b) and M40b)

Will be less than 100ppm compound

Add to the LC mixture of Example M39 and the LC mixture of Example M40.

Examples M39c) and M40c)

Will be less than 100ppm compound

Add to the LC mixture of Example M39 and the LC mixture of Example M40.

Examples M39d) and M40d)

Will be less than 500ppm compound

Add to the LC mixture of Example M39 and the LC mixture of Example M40.

Examples M39e) and M40e)

Will be less than 100ppm compound

Add to the LC mixture of Example M39 and the LC mixture of Example M40.

Example M41

To prepare a PS-VA or PS-FFS mixture, 0.25% RM74

Add to the liquid crystal mixture according to Example M39.

Example M42

To prepare a PS-VA or PS-FFS mixture, 0.25% RM35

Add to the liquid crystal mixture according to Example M39.

Example M43

To prepare a PS-VA or PS-FFS mixture, 0.3% RM83

Add to the liquid crystal mixture according to Example M39.

Example M44

To prepare a PS-VA or PS-FFS mixture, 0.3% RM83

Add to the liquid crystal mixture according to Example M34.

Example M45

To prepare a PS-VA or PS-FFS mixture, 0.3% RM83

Add to the liquid crystal mixture according to Example M36.

Example M46

Example M47

To prepare a PS-VA or PS-FFS mixture, 0.3% RM1

Add to the liquid crystal mixture according to Example M46.

The reliability of the LC mixtures M46 and M47 can be further increased, for example by using the following additives:

Examples M46a) and M47a)

Will be less than 100ppm compound

Add to the LC mixture of Example M46 and the LC mixture of Example M47.

Examples M46b) and M47b)

Will be less than 100ppm compound

Add to the LC mixture of Example M46 and the LC mixture of Example M47.

Examples M46c) and M47c)

Will be less than 100ppm compound

Add to the LC mixture of Example M46 and the LC mixture of Example M47.

Examples M46d) and M47d)

Will be less than 500ppm compound

Add to the LC mixture of Example M46 and the LC mixture of Example M47.

Examples M46e) and M47e)

Will be less than 100ppm compound

Add to the LC mixture of Example M47 and the LC mixture of Example M47.

Example M48

To prepare a PS-VA or PS-FFS mixture, 0.25% RM74

Add to the liquid crystal mixture according to Example M46.

Example M49

To prepare a PS-VA or PS-FFS mixture, 0.25% RM35

Add to the liquid crystal mixture according to Example M46.

Example M50

To prepare a PS-VA or PS-FFS mixture, 0.3% RM83

Add to the liquid crystal mixture according to Example M46.

Example M51

Example M52

To prepare a PS-VA or PS-FFS mixture, 0.3% RM74

Add to the liquid crystal mixture according to Example M51.

Example M53

To prepare the PS-VA mixture, 0.25% RM35

Add to the liquid crystal mixture according to Example M51.

Example M54

To prepare a PS-VA or PS-FFS mixture, 0.3% RM83

Add to the liquid crystal mixture according to Example M51.

Example M55

To prepare a PS-VA or PS-FFS mixture, 0.3% RM96

Add to the liquid crystal mixture according to Example M51.

Claims (28)

A liquid crystal medium characterized in that it comprises at least one compound of the formula I, And at least one compound selected from the group of compounds of the formulae IIA, IIB and IIC, Wherein: R ¹ represents an alkyl group or alkoxy group having 1 to 15 C atoms, wherein, in addition, one or more CH ₂ groups in the groups may be independent of each other in such a manner that the O atoms are not directly connected to each other. Ground-C≡C-, -CF ₂ O-, -CH=CH-, , -O-, -CO-O-, -O-CO-substitution, and wherein, in addition, one or more H atoms may be replaced by halogen, and X ¹ represents F, Cl, CN, OCN, SF ₅ , SCN, NCS a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkenyl group having 2 to 6 carbon atoms, a halogenated alkoxy group having 1 to 6 carbon atoms, a halogenated alkylalkane having 1 to 6 carbon atoms An oxy group, a halogenated alkenyloxy group having 2 to 6 carbon atoms, and Respectively independent of each other However, at least one of the rings A and B is a dioxane or a piper ring, and Y ¹ and Y ² each independently represent H or F, and Z ¹ and Z ^{1 '} 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-, a represents 1 or 2 b represents 1 or 2 R ^2A , R ^2B and R ^2C each independently represent H, an alkyl group having up to 15 C atoms, which is unsubstituted Monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, wherein, in addition, one or more CH ₂ groups in such groups may be such that O atoms are not directly connected to each other via -O-, -S- , , -C≡C-, -CF ₂ O-, -OCF ₂ -, - OC-O- or -O-CO-, L ¹ and L ² each independently represent F, Cl, CF ₃ or CHF ₂ , 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-, (O)C _v H _2v+1 means OC _v H _2v+1 or C _v H _{2v +1} p represents 1 or 2, q represents 0 or 1, and v represents 1 to 6. The liquid crystal medium of claim 1, wherein the compound of the formula I is selected from the group of compounds of the formulae I-1 to I-34. Wherein R ¹ and X ¹ have the meanings as given in claim 1. The liquid crystal medium of claim 1 or 2, wherein the medium comprises at least one compound of the following formula IIA, IIB and IIC Wherein: the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms, (O) alkyl group * represents an O alkyl group * or an alkyl group *, and an alkenyl group and an alkenyl group each The linear alkenyl group having 2 to 6 C atoms is represented independently of each other. The liquid crystal medium of any one of claims 1 to 3, wherein the medium additionally comprises one or more compounds of formula III, Wherein: R ³¹ and R ³² each independently represent a linear alkyl group, an alkoxyalkyl group, an alkenyl group or an alkoxy group having up to 12 C atoms, and Express Z ³ represents 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 -, -C ₄ H ₈ -, -CF=CF-. The liquid crystal medium of any one of claims 1 to 4, wherein the medium additionally comprises one or more compounds of the formulae IIIa to IIId, Wherein: the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms. The liquid crystal medium according to any one of claims 1 to 5, wherein the medium additionally comprises one or more compounds of the formulae L-1 to L-11, Wherein: R, R ¹ and R ² each independently have the meaning of R ^2A specified in claim 1, and alkyl represents an alkyl group having 1 to 6 C atoms, and (O)-alkyl represents O-alkane. Or an alkyl group, and s represents 1 or 2. The liquid crystal medium according to any one of claims 1 to 6, wherein the medium further comprises one or more compounds of the formulae O-1 to O-17, Wherein R ¹ and R ² have the meanings assigned to R ^{2A in} claim 1. The liquid crystal medium according to any one of claims 1 to 7, wherein the medium additionally comprises one or more terphenyls of the formula T-1 to the formula T-22, Wherein: R represents a linear alkyl group or alkoxy group having 1 to 7 C atoms, (O) C _m H _2m+1 represents OC _m H _2m+1 or C _m H _2m+1 , and m represents 1 to 6 And n represents 0 to 4. The liquid-crystalline medium according to any one of claims 1 to 8, wherein the medium additionally comprises one or more compounds selected from the group consisting of: The liquid crystal medium according to any one of claims 1 to 9, wherein the medium additionally comprises one or more indane compounds of the formula In, Wherein R ¹¹ , R ¹² and R ¹³ each independently represent a linear alkyl group, alkoxy group, alkoxyalkyl group or alkenyl group having 1 to 5 C atoms, and R ¹² and R ¹³ additionally represent a halogen. , Express i represents 0, 1, or 2. The liquid crystal medium according to any one of claims 1 to 10, wherein the medium additionally comprises one or more biphenyls of the formulae B-1 to B-4, Wherein: the alkyl group and the alkyl group * each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkoxy group means a linear alkoxy group having 1 to 6 C atoms, an alkenyl group and an alkenyl group * Each of them independently represents a linear alkenyl group having 2 to 6 C atoms. The liquid-crystalline medium according to any one of claims 1 to 11, wherein the medium additionally comprises one or more compounds selected from the group consisting of: The liquid-crystalline medium according to any one of claims 1 to 12, wherein the medium additionally comprises one or more compounds selected from the group consisting of difluorodibenzo compounds of the formula BC Alkane compound, formula CR Alkane, fluorinated phenanthrene of formula PH-1 and formula PH-2, fluorinated dibenzofuran of formula BF-1 and formula BF-2, Wherein: R ^B1 , R ^B2 , R ^CR1 , R ^CR2 , R ¹ , R ² each independently have the meaning of R ^2A in claim 1 and c represents 0, 1 or 2. The liquid crystal medium according to any one of claims 1 to 13, wherein the medium additionally comprises one or more compounds of the formula EY Wherein R ¹ , R ^1* , L ¹ and L ² have the meanings specified in the formula I and the formula II of claim 1. The liquid-crystalline medium according to any one of claims 1 to 14, wherein the medium additionally comprises one or more compounds selected from the group consisting of compounds of the formula EY-1 to EY-26: The liquid crystal medium according to any one of claims 1 to 15, wherein the medium additionally comprises one or more diphenylacetylene compounds of the formula To-1 to the formula To-12, Wherein: R ¹ and R ² each independently have the meaning of R ¹ of claim 1, and the alkyl group and the alkyl group each independently represent a linear alkyl group having 1 to 6 C atoms, and the alkenyl group has a linear alkenyl group of 2 to 6 C atoms. The liquid crystal medium according to any one of claims 1 to 16, wherein the medium further comprises one or more biphenyl compounds of the formula V-1 to the formula V-4, Wherein: R ¹ has the meaning of R ¹ of claim 1. The liquid crystal medium according to any one of claims 1 to 17, wherein the ratio of the compound of the formula I to the entire mixture is from 0.001 to 25% by weight. A liquid crystal medium according to any one of claims 1 to 18, which contains one or more additives selected from the group consisting of stabilizers, antioxidants, dopants, nanoparticles, and dyes. A liquid crystal medium according to any one of claims 1 to 19, which additionally comprises one or more polymerizable compounds. The liquid crystal medium according to any one of claims 1 to 20, wherein the concentration of the (the) polymerizable compound is from 0.01 to 5% by weight based on the medium. The liquid crystal medium according to any one of claims 1 to 21, wherein the (the) polymerizable compound is selected from the group consisting of a compound of the formula I*, R ^a -A ¹ -(Z ¹ -A ² ) _m -R ^b I* Wherein individual groups have the following meanings: R ^a and R ^b each independently represent P, P-Sp-, H, halogen, SF ₅ , NO ₂ , carbon or hydrocarbyl, wherein such radicals R ^a and R ^b At least one of them represents or contains a group P or P-Sp-, P represents the polymerizable group identically or differently at each occurrence, and Sp represents the spacer or single bond identically or differently at each occurrence, A ¹ and A ² each independently represent an aromatic, heteroaromatic, alicyclic or heterocyclic group, preferably have 4 to 25 ring atoms, which may also contain a fused ring, and which may also be monosubstituted by L. Or polysubstituted, L represents P-Sp-, H, OH, CH ₂ OH, halogen, SF ₅ , NO ₂ , carbon or hydrocarbyl, and Z ¹ represents the same or different -O-, -S at each occurrence -, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O -, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _n1 -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _n1 -, -CH =CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, CR ⁰ R ⁰⁰ or a single bond, and R ⁰ and R ⁰⁰ each independently represent H or an alkyl group having 1 to 12 C atoms, and m represents 0. 1, 2, 3 or 4, n1 represents 1, 2, 3 or 4. A method of preparing a liquid crystal medium according to any one of claims 1 to 22, characterized by mixing at least one compound of the formula I with at least one compound of the formulae IIA, IIB and IIC and optionally adding one or more liquid crystal primordial compounds and / or one or more additives and / or one or more polymerizable compounds. A use of a liquid crystal medium according to any one of claims 1 to 22 for use in an electro-optic display. A use of a liquid crystal medium according to any one of claims 1 to 22 for use in VA, PVA and PS-VA, IPS, PS-IPS, FFS, PS-FFS or PALC displays. Use of a liquid crystal medium according to any one of claims 1 to 22 for use in a PS and PSA display for the application of an electric field or a magnetic field by a polymerizable compound in the PSA or PS-VA display The bit is polymerized to produce a tilt angle in the liquid crystal medium. An electro-optic display having an active matrix addressing, characterized in that it contains a liquid crystal medium according to any one of claims 1 to 22 as a dielectric. An electro-optic display according to claim 27, wherein it is a VA, PSA, PS-VA, PALC, FFS, PS-FFS or PS-IPS display.