LIQUID CRYSTALLINE MEDIA WITH HOMEOTROPIC ALIGNMENT

Description

[0001] The present invention relates to liquid crystal media (LCM media) with negative or positive dielectric anisotropy, comprising a low-molecular-weight component and a polymerizable component. The polymerizable component comprises self-aligning, polymerizable mesogens (polymerizable self-orientation additives) that effect a homeotropic (vertical) alignment of the LCM media on a surface or the cell walls of a liquid crystal display (LCD). The invention therefore also includes LCD displays with a homeotropic alignment of the liquid crystal medium (LCM medium) without orientation layers. The invention discloses novel structures for polymerizable self-orientation additives that exhibit a specific position of the functional groups.

[0002] The principle of electrically controlled birefringence, the ECB effect (electrically controlled birefringence) or DAP effect (deformation of upright phases), was first described in 1971 (MF Schieckel and K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation in electrical fields", Appl. Phys. Lett. 19 (1971), 3912). This was followed by work by J.F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).

[0003] The work of J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3), and H. Schad (SID 82 Digest Techn. Papers (1982), 244) has shown that liquid-crystalline phases must exhibit high values ​​for the ratio of the elastic constants K3 / K1, high values ​​for the optical anisotropy Δn, and values ​​for the dielectric anisotropy of Δε ≤ -0.5 in order to be used for highly informative display elements based on the ECB effect. Electro-optical display elements based on the ECB effect exhibit a homeotropic edge orientation (VA technology = V ertical A ligned).

[0004] Advertisements that use the ECB effect have become known as VAN-( V ertically A ligned N ematic) Displays, for example in the MVA-( design. M ulti-Domain V ertical Alignment, e.g.: Yoshide, H. et al., Lecture 3.1: "MVA LCD for Notebook or Mobile PCs ...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6 to 9 and Liu, CT et al., Lecture 15.1: "A 46-inch TFT-LCD HDTV Technology ...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 750 to 753), PVA- ( P aterned V ertical A lignment, e.g.: Kim, Sang Soo, lecture 15.4: "Super PVA Sets New State-of-the-Art for LCD-TV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 760 to 763), ASV- ( A advanced S super V iew, e.g.: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Lecture 15.2: "Development of High Quality LCDTV", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 754 to 757) Displays, in addition to IPS- ( I n P lane Switching) (e.g.: Yeo, SD, Lecture 15.3: "A LC Display for the TV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pp. 758 & 759) and the long-known TN- ( T wisted NLCDs (ematic) are established as one of the three most important new types of liquid crystal displays, especially for television applications. In general terms, the technologies are compared, for example, in Souk, Jun, SIDSeminar 2004, Seminar M-6: "Recent Advances in LCD Technology", Seminar Lecture Notes, M-6 / 1 to M-6 / 26 and Miller, Ian, SIDSeminar 2004, Seminar M-7: "LCD-Television", Seminar Lecture Notes, M-7 / 1 to M-7 / 32. Although the switching times of modern ECB displays have already been significantly improved by overdrive control methods, e.g.: Kim, Hyeon Kyeong et al., Lecture 9.1: "A 57-in. Wide UXGA TFT-LCD for HDTV Application", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 106 to 109, achieving video-compatible switching times, especially when switching grayscale levels, is still a problem that has not yet been satisfactorily solved.

[0005] The production of VA displays with two or more domains of different preferred orientations involves considerable effort. One aim of this invention is to simplify the manufacturing processes and the display devices themselves, without sacrificing the advantages of VA technology, such as relatively fast switching times and good viewing angle dependency.

[0006] VA displays containing FK media with positive dielectric anisotropy are described in SH Lee et al. Appl. Phys. Lett. (1997), 71, 2851-2853. These displays use interdigital electrodes (in-plane drive electrode configuration of comb-like structure) arranged on a substrate surface, as found, for example, in commercially available IPS ( i n- p lane switching) displays are used (as disclosed, for example, in DE 40 00 451 and EP 0 588 568), and have a homeotropic arrangement of the liquid crystal medium, which changes to a planar arrangement when an electric field is applied.

[0007] Further developments of the aforementioned display can be found, for example, in KS Hun et al. J. Appl. Phys. (2008), 104, 084515 (DSIPS: 'double-side in-plane switching' for improvements in driver voltage and transmission), M. Jiao et al. App. Phys. Lett (2008), 92, 111101 (DFFS: 'dual fringe field switching' for improved switching times), and YT Kim et al. Jap. J. App. Phys. (2009), 48, 110205 (VAS: 'viewing angle switchable' LCD). VA-IPS displays are also known as Positive-VA and HT-VA.

[0008] In all such displays (hereinafter referred to generally as VA-IPS displays), an orientation layer for the homeotropic alignment of the FK medium is applied to both substrate surfaces, the production of which has so far been associated with considerable effort.

[0009] One aim of this invention is to simplify the manufacturing processes themselves without sacrificing the advantages of VA-IPS technology, such as relatively fast switching times, good viewing angle dependency and high contrast.

[0010] For the technical application of these effects in electro-optical display elements, FK phases are required that must meet a wide range of requirements. Particularly important are chemical resistance to moisture, air, the materials in the substrate surfaces, and physical influences such as heat, radiation in the infrared, visible and ultraviolet ranges, and static and alternating electric fields.

[0011] Furthermore, technically usable FK phases require a liquid crystalline mesophase in a suitable temperature range and a low viscosity.

[0012] VA and VA-IPS displays are generally designed to have a very high specific resistance combined with a large operating temperature range, short switching times and a low threshold voltage, which allows for the generation of various shades of gray.

[0013] In conventional VA and VA-IPS displays, a polyimide layer on the substrate surfaces ensures the homeotropic orientation of the liquid crystal. Manufacturing a suitable orientation layer within the display is quite complex. Furthermore, interactions between the orientation layer and the liquid crystal medium can worsen the display's electrical resistance. Because of these potential interactions, the number of suitable liquid crystal components is significantly reduced. Therefore, achieving homeotropic alignment of the liquid crystal medium without polyimide would be desirable.

[0014] The disadvantage of the frequently used active matrix TN displays lies in their comparatively low contrast, the relatively high viewing angle dependency and the difficulty of generating grayscale levels in these displays.

[0015] VA displays have significantly better viewing angle characteristics and are therefore mainly used for televisions and monitors.

[0016] A further development is represented by the so-called PS or PSA displays ("Polymer Sustained" or "Polymer Sustained Alignment"), for which the term "Polymer Stabilized" is also occasionally used. Without any significant loss of other parameters, such as the favorable viewing angle dependency of the contrast, PSA displays are characterized by shorter switching times.

[0017] In these displays, a small amount (for example, 0.3 wt.%, typically <1 wt.%) of one or more polymerizable compound(s) is added to the FK medium, which, after being poured into the FK cell, with or without an applied electrical voltage between the electrodes. in situThe polymerization or cross-linking is usually carried out by UV photopolymerization. The addition of polymerizable mesogenic or liquid-crystalline compounds, also known as reactive mesogens or "RM"s, to the polymer composite mixture has proven particularly suitable. PSA technology is currently used primarily for polymer composite media with negative dielectric anisotropy.

[0018] Unless otherwise stated, the term "PSA" is used below to refer to PS displays and PSA indicators.

[0019] The PSA principle is now used in various classic FK displays. For example, PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS, and PSA-TN displays are known. In PSA-VA and PSA-OCB displays, polymerization of the polymerizable compound(s) preferably occurs under applied electrical voltage, while in PSA-IPS displays it can occur with or without applied electrical voltage. As can be demonstrated in test cells, the PS(A) process leads to a 'pretilt' in the cell. In PSA-OCB displays, for example, the bend structure can be stabilized, thus eliminating or reducing the need for an offset voltage. In the case of PSA-VA displays, the 'pretilt' has a positive effect on switching times. A standard MVA or PVA pixel and electrode layout can be used for PSA-VA displays.Furthermore, it is also possible, for example, to manage with only one structured electrode side and without 'protrusions', which significantly simplifies the manufacturing process and simultaneously leads to very good contrast with very good light transmission.

[0020] PSA-VA indications are described, for example, in WO 2013 / 004372 A1, JP 10-036847 A, EP 1 170 626 A2, US 6,861,107, US 7,169,449, US 2004 / 0191428 A1, US 2006 / 0066793 A1 and US 2006 / 0103804 A1. PSA-OCB indications are described, for example, in T.-J. Chen et al., Jpn. J. Appl. Phys. (2006), 45, 2702-2704 and SH Kim, L.-C. Chien, Jpn. J. Appl. Phys. (2004), 43, 7643-7647. PSA-IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. (1999), 75(21), 3264. PSA-TN displays are described, for example, in Optics Express (2004), 12(7), 1221. PSA-VA-IPS displays are disclosed, for example, in WO 2010 / 089092 A1. Like the conventional FK displays described above, PSA displays can be operated as active-matrix or passive-matrix (PM) displays. In active-matrix displays, individual pixels are typically controlled by integrated, non-linear active elements such as transistors (e.g., thin-film transistors).'thin film transistor' or "TFT"), in passive matrix displays usually according to the multiplexing method, both methods being known from the prior art.

[0021] Especially for monitor and, above all, TV applications, optimizing switching times, as well as contrast and luminance (and therefore transmission) of the fixed-contrast display, remains crucial. Here, the PSA method can offer decisive advantages. Particularly with PSA-VA displays, switching times can be reduced without significant loss of other parameters, and these reductions correlate with a 'pretilt' measurable in test cells.

[0022] In the prior art, polymerizable compounds of the following formula are used for PSA-VA, for example. where P represents a polymerizable group, usually an acrylate or methacrylate group, as described, for example, in US 7,169,449.

[0023] The effort required to produce a polyimide layer, treat the layer, and improve it with raised areas or polymer layers is relatively high. A simplifying technology would therefore be desirable, one that both reduces production costs and helps optimize image quality (viewing angle dependency, contrast, switching times).

[0024] Publication WO 2012 / 038026 A1 describes self-aligning mesogens (non-polymerizable, conventional self-orientation additives) with a hydroxyl group attached to a mesogenic core structure consisting of two or more rings. The structures disclosed therein do not possess a polymerizable group arranged according to the invention.

[0025] However, existing approaches to achieving VA display applications without a polyimide layer are not yet fully satisfactory.

[0026] The present invention relates to an FK medium comprising a low molecular weight, non-polymerizable liquid crystalline component and a polymerizable or polymerized component comprising one or more compounds of formula I, wherein the polymerized component is obtainable by polymerizing the polymerizable component, R 1< -[A 3< -Z 3< ] m -[A 2< ] k -[Z 2< ] n -A 1< -R a< (I) wherein A1<, A2<, A3< each independently an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain annelated rings, and which may also be one or more times substituted by a group L or -Sp-P, L each independently H, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R0<)2, -C(=O)R0<, optionally substituted silyl, optionally substituted aryl or cycloalkyl with 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 25 C atoms, wherein one or more H atoms may also be replaced by F or Cl, Peine polymerizable group, spacing group (also called spacer or spacer group) or a single bond, Z 2< each independently of each other -O-, -S-, -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< ) n1 -, -CH(-Sp-P)-, -CH 2 CH(-Sp-P)-, -CH(-Sp-P)CH(-Sp-P)-, Z 3< each independently a single bond, -O-, -S-, -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< ) n1 -, -CH(-Sp-P)-, -CH 2 CH(-Sp-P)-, -CH(-Sp-P)CH(-Sp-P)-, n11, 2, 3 or 4, n0 or 1, m0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2 or 3, k0 or 1, R 0< each independently alkyl with 1 to 12 C atoms, R 00< each independently H or alkyl with 1 to 12 C atoms, R 1< independently H, halogen, straight-chain, branched or cyclic alkyl with 1 to 25 C atoms, wherein one or more non-adjacent CH 2 - R a< groups are also replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-,-O-CO-O- can be replaced in such a way that O and / or S atoms are not directly linked together and in which one or more H atoms can also be replaced by F or Cl, or a group -Sp-P, an anchor group of the formula , or p1 or 2, q2 or 3, a substituted or unsubstituted ring system or a condensed ring system, preferably a ring system selected from benzene, pyridine, cyclohexane, dioxane or tetrahydropyran, Y independently of one another -O-, -S-, -C(O)-, -C(O)O-, -OC(O)-, -NR 11< - or a single bond, o0 or 1, X 1< independently of one another H, alkyl, fluoroalkyl, OH, NH 2 , NHR 11< , NR 11< 2 , OR 11< , C(O)OH, -CHO, wherein at least one group X 1< means a residue selected from -OH, -NH 2 , NHR 11< , C(O)OH and -CHO, R 11< means alkyl with 1 to 12 C atoms, Sp a< , Sp c< , Sp d< each independently a distance group or a single bond Sp b< a trivalent or tetravalent group, preferably CH, N or C, mean, wherein the compound of formula I has at least one polymerizable group P within the groups A 1 , A 2 , A 3 , Z 2 and Z 3 , as they exist.

[0027] The polymerizable or polymerized component of the FK medium optionally contains further polymerizable compounds. Preference is given to those compounds suitable for the PSA principle.

[0028] The invention further relates to an FK display comprising an FK cell with two substrates and at least two electrodes, wherein at least one substrate is transparent and at least one substrate has one or two electrodes, as well as a layer of an FK medium according to the invention located between the substrates. The FK display is preferably of the PSA type.

[0029] The invention further relates to new compounds of formula I, as disclosed above and below, characterized in that they have two or more rings, i.e. compounds of formula I where k = 1.

[0030] Another aspect of the invention is the use of compounds of formula I as an additive for FK media to bring about a homeotropic orientation with respect to a surface limiting the FK medium.

[0031] Another aspect of the present invention is a method for producing an FK medium according to the invention, characterized in that one or more polymerizable self-orientation additives (compounds of formula I) are mixed with a low molecular weight, liquid crystalline component and optionally one or more polymerizable compounds and optionally a further, non-polymerizable, self-orientation additive (e.g. of formula I') and / or any additives are added.

[0032] A further object of the invention is a method for manufacturing an FK display comprising an FK cell with two substrates and at least two electrodes, wherein at least one substrate is transparent and at least one substrate has one or two electrodes, comprising the process steps: Filling the cell with an FK medium according to the invention, wherein a homeotropic (vertical) orientation of the FK medium is established relative to the substrate surfaces, and polymerizing the polymerizable component(s), optionally by applying a voltage to the cell or under the influence of an electric field, in one or more process steps.

[0033] The use of the self-orienting additives according to the invention as additives to FK media is not limited to specific FK media. The FK medium, or the non-polymerizable component contained therein, can exhibit positive or negative dielectric anisotropy. The FK medium is preferably nematic, since most displays based on the VA principle comprise nematic FK media.

[0034] The polymerizable self-orienting additive is incorporated into the liquid crystal medium. It causes a homeotropic alignment of the liquid crystal with respect to the substrate surfaces (such as a glass surface, or one coated with ITO or polyimide). Based on investigations related to this invention, it appears that the polar anchor group interacts with the substrate surface. This causes the organic compounds on the substrate surface to align and induce a homeotropic orientation of the liquid crystal. According to this view, the anchor group should be sterically accessible, i.e., not surrounded by ortho-oriented tert-butyl groups, as is the case, for example, with a phenolic (phenyl-substituted) OH group, as is the case with 2,6-di-tert-butylphenol. This means compounds with a head group of the formula are preferably not included in Formula I and its subformulas.

[0035] The FK cell of the FK display according to the invention preferably has no orientation layer, in particular no polyimide layer, for the homeotropic alignment of the FK medium. The polymerized component of the FK medium is not considered an orientation layer in this context. If an FK cell nevertheless has an orientation layer or a comparable layer, this layer is not responsible for the homeotropic orientation according to the invention. According to the invention, rubbing, for example, polyimide layers is not necessary to achieve a homeotropic orientation of the FK medium relative to the substrate surface. The FK display according to the invention is preferably a VA display with an FK medium having negative dielectric anisotropy and electrodes arranged on opposing substrates.Alternatively, it is a VA-IPS display with an FK medium having positive dielectric anisotropy and interdigital electrodes arranged on at least one substrate.

[0036] The polymerizable self-orientation additive of formula I is preferably used in a concentration of less than 10 wt%, particularly preferably ≤ 5 wt%, and most particularly ≤ 3 wt%. It is preferably used in a concentration of at least 0.05 wt%, and preferably at least 0.2 wt%. The use of 0.1 to 2.5 wt% of the self-orientation additive generally results in completely homeotropic orientation of the FK layer at the usual cell thicknesses (3 to 4 µm) with the usual substrate materials and under the usual conditions of the manufacturing processes for an FK indicator. Due to its polymerizable nature, higher concentrations of self-orientation additives are also possible without significantly affecting the FK medium, since the polymerizable substance is rebound by polymerization.

[0037] The FK medium according to the invention can contain, in addition to the polymerizable self-orientation additives of formula I, further self-orientation additives that are either non-polymerizable or of a different structure. In a preferred embodiment, the FK medium therefore contains one or more self-orientation additives without a polymerizable group (conventional self-orientation additives). The combined concentration of the polymerizable and conventional self-orientation additives is preferably the values ​​given above, for example, 0.1 to 2.5 wt.%. A combination of self-orientation additives with and without a polymerizable group offers the additional advantage that the self-orientation of the FK medium becomes more stable under stress (increased processability).

[0038] The other, non-polymerizable self-orienting additives can have a structure of formula I': R 1< -[A 3< -Z 3< ] m -[A 2< ] k -[Z 2< ] n -A 1< -R a< I' where m, k, n and the group R a< are defined as above for formula I, and A1<, A2<, A3< each independently an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be one or more times substituted by a group L, Z2< each independently -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2)n1-, -CF2CH2-, -CH2CF2-, -(CF2)n1-, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, -(CR0<R 00< ) n1 -, Z 3< each independently a single bond, -O-, -S-, -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< ) n1 -, n11, 2, 3, or 4, LEach independently of each other H, F, Cl, Br, I ,-CN, -NO₂, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R₀<)₂, -C(=O)R₀<, optionally substituted silyl, optionally substituted aryl or cycloalkyl with 3 to 20 carbon atoms, or straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy with 1 to 25 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F or Cl, R₀< each independently alkyl with 1 to 12 carbon atoms, R₀0< each independently H or alkyl with 1 to 12 carbon atoms, and R₁< independently H, halogen, straight-chain, branched or cyclic alkyl with 1 to 25 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F or Cl several non-adjacent CH 2 groups can be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-so that O and / or S atoms are not directly linked together and in which one or more H atoms can also be replaced by F or Cl.

[0039] Formula l', unlike formula I, does not include a polymerizable group -Sp-P or P.

[0040] Preferred and exemplary structures of the self-orientation additives, in particular the polymerizable self-orientation additives, are disclosed below: By definition, the anchor group R a< contains one, two, or three groups X 1<, which serve as a link to a surface. The spacer groups are intended to establish a flexible bond between the mesogenic group with rings and the group(s) X 1<. The structure of the spacer groups is therefore highly variable and, in the most general case of formula I, not definitively defined. Those skilled in the art will recognize that a multitude of possible chain variations are involved.

[0041] An anchor group of the formula As defined above and below, preferably represents an anchor group selected from the following formulas: or -Sp a< -X 1< , wherein the groups are defined independently as above and below, particularly preferably for a group of formulas -Sp a< -X 1< or or in each case the groups are defined independently as above and below.

[0042] Particularly preferred anchor groups of formula R a< are selected from the following subformulas, where the group R a< is linked to the group A 1< of formula I or I' via the dashed bond:

[0043] The anchor group R a< in the preceding formulas and subformulas particularly preferably comprises one, two or three OH groups.

[0044] The term "spacer" or "spacer group", generally denoted herein by "Sp" (or Sp a / c / d / 1 / 2< ), is known to those skilled in the art and described in the literature, e.g., in Pure Appl. Chem. 73(5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. (2004), 116, 6340-6368. In the present disclosure, the term "spacer" or "spacer group" denotes a connecting group, for example, an alkylene group, which links a mesogenic group to a polymerizable group. While the mesogenic group generally comprises rings, the spacer group is generally without ring systems, i.e., chain-like, and the chain may also be branched. An alkylene group, for example, is considered a chain. Substitutions on and within the chain, e.g., by -O- or -COO-, are generally included.Functionally, the spacer (the spacing group) is a bridge between attached functional structural parts, which allows a certain spatial flexibility in relation to each other.

[0045] The group Sp b< means preferred a trivalent group of the formula selected from CH, C(Me), C(CH 2 CH 3 ) or N, or the tetravalent group C (four-coordinate carbon atom).

[0046] The group Sp a< preferably means a group selected from the formulas -CH 2 -, -CH 2 CH 2 -, -OCH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -OCH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -OCH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -OCH 2 CH 2 OCH 2 CH 2 -,

[0047] The group Sp c< or Sp d< preferably means a group selected from the formulas -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -,

[0048] An anchor group of the formula defined above stands preferably for or where Y, Sp d< , and X 1< are defined as for Formula I.

[0049] The ring groups A1<, A2<, A3< each independently preferentially represent 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, wherein one or more CH groups in these groups may also be replaced by N, cyclohexane-1,4-diyl, wherein one or more non-adjacent CH2 groups may also be replaced by O and / or S, 3,3'-bicyclobutylidene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, Indan-2,5-diyl or octahydro-4,7-methano-indan-2,5-diyl, perhydro-cyclopenta[a]phenanthren-3,17-diyl (especially gonan-3,17-diyl), wherein all these groups may be unsubstituted or may be one or more times substituted by a group L or -Sp-P.

[0050] Preferably, at least one of the groups A 1< , A 2< and A 3< , insofar as they exist, is substituted by at least one group -Sp-P.

[0051] The groups A1<, A2<, and A3< are particularly preferred, each being independently selected from a group. a) the group consisting of 1,4-phenylenes and 1,3-phenylenes, wherein one or more H atoms may also be replaced by L or -Sp-P, b) the group consisting of trans-1,4-cyclohexylenes, 1,4-cyclohexenylenes, and 4,4'-bicyclohexylenes, wherein one or more non-adjacent CH₂ groups may also be replaced by -O- and / or -S-, and wherein one or more H atoms may also be replaced by F, L, or -Sp-P. Groups A₁< and A₂< particularly preferably denote a group according to the preceding subgroup a). Most preferably, A₁< and A₂< independently denote 1,4-phenylene or cyclohexane-1,4-diyl, which may be one or more times substituted by a group L or -Sp-P.

[0052] The compounds of formula I preferably comprise one or more compounds of formula I1, and more preferably the formulas IA, IB, IC or ID: wherein R 1< , R a< , A 1< , A 2< , A 3< , Z 2< , Z 3< , L, Sp, P, m, k and n are each independently defined as for formula I, and p1, p2, p3 independently 0, 1, 2 or 3, and r1, r2, r3 independently 0, 1, 2 or 3, wherein the compound of formula I as a whole (i.e. in sum) contains at least one polymerizable group P within the groups A 1< , A 2< , A 3< , Z 2< and Z 3< , as they are present.

[0053] Preferably, in formulas I1 and IA, IB and IC, p1 + p2 + p3 > 0, and for formulas ID and IE, p1 + p2 > 0, i.e., at least one polymerizable group P is present within the groups A1<, A2<, A3< or A1<, A2<, respectively, or within the corresponding rings in IA-IE. Furthermore, in a particular embodiment of the invention, it is preferred that in formulas I1 and IA, IB and IC, r1 + r2 + r3 > 0, and for formulas ID and IE, r1 + r2 > 0, and that L does not mean H, i.e., at least one lateral substituent L is present within the groups A1<, A2<, A3< or A1<, A2<. Alternatively, it is preferred that p1 + p2 + p3 > 1 or p1 + p2 > 1, i.e., that two or more lateral polymerizable groups are present. The compounds according to the invention with one such group L or two lateral P groups exhibit, among other things, improved solubility.

[0054] In the preceding and following formulas I and I' as well as in the preferred subformulas, regardless of the numerator n, preferably means 0.

[0055] Preferred compounds of formula I are represented and illustrated by the following formulas: wherein L, Sp, P, n and R a< are independent as defined for formula I, r1, r2, r3 independently mean 0, 1, 2 or 3, and Z 2< / Z 3< are independent as defined above, and wherein preferably Z 3< means a single bond or -CH 2 CH 2 - and most especially a single bond.

[0056] Particularly favored compounds of formula I are illustrated by the following formulas: where R< 1< , Sp, P, L and R a< are defined independently as for formula I. L is preferably a group other than H.

[0057] The compounds of formula I` (conventional self-orienting additives) preferably include compounds of formulas IA', IB', IC', ID' or IE': wherein R 1< , R a< , Z 2< , Z 3< , L and n are defined independently as for the preceding formulas IA to IE, and r1, r2, r3 independently mean 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0058] The production of conventional self-orientation additives can be found, for example, in publication WO 2012 / 038026.

[0059] The term "aryl" means an aromatic carbon group or a group derived therefrom. The term "heteroaryl" means "aryl" as defined above, containing one or more heteroatoms.

[0060] Aryl and heteroaryl groups can be mononuclear or polynuclear, meaning they can have one ring (such as phenyl) or two or more fused rings. At least one of the rings has an aromatic conjugation. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S, and Se.

[0061] Particularly preferred are mono-, di-, or trinuclear aryl groups with 6 to 25 carbon atoms, as well as mono-, di-, or trinuclear heteroaryl groups with 2 to 25 carbon atoms, which optionally contain fused rings. Also preferred are 5-, 6-, or 7-membered aryl and heteroaryl groups, wherein one or more CH groups may be replaced by N, S, or O in such a way that the O atoms and / or S atoms are not directly linked to each other.

[0062] Preferred aryl groups include, for example, phenyl, naphthyl, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc.

[0063] Bevorzugte Heteroarylgruppen sind beispielsweise 5-gliedrige Ringe wie Pyrrol, Pyrazol, Imidazol, 1,2,3-Triazol, 1,2,4-Triazol, Tetrazol, Furan, Thiophen, Selenophen, Oxazol, Isoxazol, 1,2-Thiazol, 1,3-Thiazol, 1,2,3-Oxadiazol, 1,2,4-Oxadiazol, 1,2,5-Oxadiazol, 1,3,4-Oxadiazol, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-Thiadiazol, 6-gliedrige Ringe wie Pyridin, Pyridazin, Pyrimidin, Pyrazin, 1,3,5-Triazin, 1,2,4-Triazin, 1,2,3-Triazin, 1,2,4,5-Tetrazin, 1,2,3,4-Tetrazin, 1,2,3,5-Tetrazin, oder kondensierte Gruppen wie Indol, Isoindol, Indolizin, Indazol, Benzimidazol, Benzotriazol, Purin, Naphthimidazol, Phenanthrimidazol, Pyridimidazol, Pyrazinimidazol, Chinoxalinimidazol, Benzoxazol, Naphthoxazol, Anthroxazol, Phenanthroxazol, Isoxazol, Benzothiazol, Benzofuran, Isobenzofuran, Dibenzofuran, Chinolin, Isochinolin, Pteridin, Benzo-5,6-chinolin, Benzo-6,7-chinolin, Benzo-7,8-chinolin, Benzoisochinolin, Acridin, Phenothiazin, Phenoxazin, Benzopyridazin, Benzopyrimidin,Quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, coumarin or combinations of these groups.

[0064] The (non-aromatic) alicyclic and heterocyclic groups include both saturated rings, i.e., those containing exclusively single bonds, and partially unsaturated rings, i.e., those that may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S, and Se.

[0065] The (non-aromatic) alicyclic and heterocyclic groups can be mononuclear, i.e., containing only one ring (such as cyclohexane), or polynuclear, i.e., containing several rings (such as decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Mono-, di-, or trinuclear groups with 3 to 25 carbon atoms are also preferred.

[0066] Furthermore, 5-, 6-, 7- or 8-membered carbocyclic groups are preferred, wherein 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-.

[0067] Preferred alicyclic and heterocyclic groups include, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine; 6-membered groups such as cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine; 7-membered groups such as cycloheptane; and fused groups such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methano-indan-2,5-diyl.

[0068] In the context of the present invention, the term "alkyl" means a straight-chain or branched, saturated or unsaturated, preferably saturated, aliphatic hydrocarbon residue having 1 to 15 (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15) carbon atoms.

[0069] The term "cyclic alkyl" encompasses alkyl groups that contain at least one carbocyclic component, including, for example, cycloalkylalkyl, alkylcycloalkyl, and alkylcycloalkylalkyl. The carbocyclic groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0070] In the context of the present invention, "halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

[0071] The preferred compounds of formula I listed above can in principle be prepared according to the following exemplary synthesis routes (Scheme 1 to 4): 1) Functionalization e.g. via:

[0072] n-BuLi and BF 3 *OEt 2 for ring opening with or via Sonogashira reaction with and subsequent hydrogenation, or via boronic acid oxidation to phenol with subsequent etherification with 2) Esterification with methacrylic acid.

[0073] Definitions: X = CH 2 , O or single bond, Pg 2< = e.g. Benzyl, Sp = spacer with e.g.: 0 - 3 C atoms.

[0074] The polymerizable component of the FK medium according to the invention preferably comprises, in addition to the compounds of formula I, further polymerizable or (partially) polymerized compounds. These are preferably conventional polymerizable compounds without an anchor group, preferably mesogenic compounds, in particular those suitable for PSA technology. Preferred polymerizable compounds for this purpose are the structures given below for formula M and its subformulas. The polymer formed therefrom can stabilize the orientation of the FK medium, optionally form a passivation layer, and optionally generate a pretilt.

[0075] The FK media according to the invention therefore preferably contain >0 to <5 wt.%, particularly preferably 0.05 to 1 wt.% and most preferably 0.2 to 1 wt.% of polymerizable compounds without anchor group Ra< , in particular compounds of formula M as defined below and the preferred formulas falling below.

[0076] The polymerization of the polymerizable components occurs together or in partial steps under different polymerization conditions. Preferably, polymerization takes place under the influence of UV light. Typically, polymerization is initiated using a polymerization initiator and UV light. With the preferred acrylates, practically complete polymerization is achieved in this way. Optionally, a voltage can be applied to the cell electrodes or another electric field can be used during polymerization to further influence the orientation of the polymer medium.

[0077] Particularly preferred are FK media according to the invention which, in addition to the compounds of formula I, contain further polymerizable or (partially) polymerized compounds (without an anchor group) and further self-orientation additives that are not polymerizable. These further non-polymerizable self-orientation additives are preferably those as described above, cf. formulas I', IA', IB', IC', ID', IE'.

[0078] The optionally included further monomers of the polymerizable component of the FK medium are preferably described by the following formula M: P 1< -Sp 1< -A 2< -(Z 1< -A 1< ) n -Sp 2-< P 2< M where the individual substituents have the following meaning: P1< , P2< each independently a polymerizable group, Sp1< , Sp2< the same or different in each occurrence a spacer group or a single bond, A1< , A2< , each independently a residue selected from the following groups: a) the group consisting of trans-1,4-cyclohexylenes, 1,4-cyclohexenylenes and 4,4'-bicyclohexylenes, in which one or more non-adjacent CH2 groups may also be replaced by -O- and / or -S- and in which one or more H atoms may also be replaced by a group L, or a residue of the formula b) the group consisting of 1,4-phenylenes and 1,3-phenylenes, wherein one or two CH groups may also be replaced by N and wherein one or more H atoms may also be replaced by a group L or -Sp 3< -P, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobut-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, which may also be substituted one or more times by a group L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic residues with 5 to 20 cyclic C atoms, one or more of which may also be replaced by heteroatoms, preferably selected from the group consisting of Bicyclo[1.1.1]pentane-1,3-diyl, Bicyclo[2.2.2]octane-1,4-diyl, Spiro[3.3]heptane-2,6-diyl, wherein in these residues one or more H atoms may also be replaced by a group L or -Sp 3< -P, and / or one or more double bonds may be replaced by single bonds, and / or one or more CH groups may be replaced by N, P 3< a polymerizable group, Sp 3< a spacer group, n0, 1, 2 or 3, preferably 1 or 2, Z 1< each independently of one another -CO-O-, -O-CO-, -CH 2 O-, -OCH 2-, -CF 2 O-, -OCF 2-, or -(CH 2 ) n-, wherein n is 2, 3 or 4, -O-, -CO-, -C(R c< R d< )-, -CH 2 CF 2-, -CF 2 CF 2-, or a single bond, L in each occurrence the same or different F, Cl, CN, SCN, SF 5 or straight-chain or branched, optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, R 0< , R 00< each independently H, F or straight-chain or branched alkyl with 1 to 12 C atoms, wherein one or more H atoms may also be replaced by F,MO-, -S-, -CH 2 -, -CHY 1< - or -CY 1< Y 2< -, and Y 1< , and Y 2< each independently of one of the meanings given above for R 0<, Cl or CN, and preferably H, F, Cl, CN, OCF 3 or CF 3 , W 1< , W 2< each independently of one of the meanings given above for R 0< , Cl or CN, and preferably H, F, Cl, CN, OCF 3 or CF 3 , W 1< , W 2< each independently of one of the meanings given above for R 0< , -CH 2 CH 2 -, -CH=CH-, -CH 2 -O-, -O-CH 2 -, -C(R c< R d< )- or -O- , R c< and R d< each independently of one of the meanings given above for R 0< , , where one or more of the groups P 1 -Sp 1 -, -Sp 2 -P 2 and -Sp 3 -P 3 a remainder R aa can mean, provided that at least one of the existing groups P 1 -Sp 1 -, -Sp 2 -P 2 and -Sp 3 -P 3 not R aa means, R aa< H, F, Cl, CN or straight-chain or branched alkyl with 1 to 25 C atoms, wherein one or more non-adjacent CH 2 groups may each be independently replaced by C(R 0< )=C(R 00< )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- such that O and / or S atoms are not directly linked to each other, and wherein one or more H atoms may also be replaced by F, Cl, CN or P 1< -Sp 1< -, particularly preferably straight-chain or branched, optionally mono- or multiply fluorinated, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy with 1 to 12 C atoms (where the alkenyl and alkynyl residues at least two and the branched residues have at least three C atoms), wherein the groups -OH, -NH 2 , -SH, -NHR, -C(O)OH and -CHO are not included in R aa<.

[0079] The polymerizable group P, P1<, P2<, and P3< in the preceding and following formulas is a group suitable for a polymerization reaction, such as radical or ionic chain polymerization, polyaddition, or polycondensation, or for a polymer-analogous reaction, such as addition or condensation to a polymer backbone. Groups suitable for chain polymerization, especially those containing a C=C double bond or a C≡C triple bond, as well as groups suitable for ring-opening polymerization, such as oxetane or epoxy groups, are particularly preferred.

[0080] Preferred groups P / P 1

[0081] Particularly preferred groups P / P 1

[0082] Particularly preferred groups P / P 1

[0083] Particularly preferred groups P / P 1

[0084] Preferred spacing groups Sp, Sp 1< and Sp 2< are a single bond or selected from the formula Sp"-X", such that the remainder P 1 / 2< -Sp 1 / 2< - corresponds to the formula P 1 / 2< -Sp"-X"-, where Sp" alkylene with 1 to 20, preferably 1 to 12 carbon atoms, which is optionally substituted once or multiple times by F, Cl, Br, I or CN, and in which one or more non-adjacent CH2 groups may each be replaced independently of one another by -O-, -S-, -Si(R00<R000<)-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N(R00<)-CO-O-, -O-CO-N(R00<)-, -N(R00<)-CO-N(R00<)-, -CH=CH- or -C≡C-, such that O and / or S atoms are not directly linked together, X"-O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R 00< )-, -N(R 00< )-CO-, -N(R 00< )-CO-N(R 00< )-, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CF 2 O-, R 00< -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-CO-O-, -O-CO-CH=CH- or a single bond means, each independently, alkyl with 1 to 12 C atoms means, R 000< each independently means H or alkyl with 1 to 12 C atoms,and Y2< and Y3< each independently represent H, F, Cl or CN.

[0085] X" is preferably -O-, -S -CO-, -COO-, -OCO-, -O-COO-, or a single binder.

[0086] Typical distance groups Sp" are, for example, a single bond, -(CH 2 ) p1 -, -(CH 2 CH 2 O) q1 -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, or -(SiR 00< R 000< -O) p1 -, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 00< and R 000< have the meanings given above.

[0087] Particularly preferred groups -Sp"-X"- are -(CH 2 ) p1 -, -(CH 2 ) p1 -O-, -(CH 2 ) p1 -O-CO-, -(CH 2 ) p1 -O-CO-O-, where p1 and q1 have the meanings given above.

[0088] Particularly preferred groups Sp" are, for example, straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

[0089] The substances of formula M do not contain -OH, -NH 2 , -SH, -NHR 11< , -C(O)OH and -CHO residues.

[0090] Suitable and preferred (co-)monomers for use in displays according to the invention are selected, for example, from the following formulas: wherein the individual substituents have the following meanings: P1<, P2< and P3< each independently of one another a polymerizable group, preferably with one of the meanings given above and below for P, particularly preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyloxy or epoxy group, Sp1<, Sp2< and Sp3< each independently of one another a single bond or a spacer group, preferably with one of the meanings given above and below for formula M, and particularly preferably -(CH2)p1-, -(CH2)p1-O-, -(CH2)p1-CO-O- or -(CH2)p1-O-CO-O-, wherein p1 is an integer from 1 to 12, and wherein in the latter groups the bonding to the adjacent ring is via the O atom, wherein one or more of the substituents P1<-Sp1<-, P2<-Sp2<- and P 3< -Sp 3< - can mean a residue R aa<, provided that at least one of the existing residues P 1< -Sp 1< -, P 2< -Sp 2< - and P 3< -Sp 3< - does not mean R aa<,R aa< H, F, Cl, CN or straight-chain or branched alkyl with 1 to 25 C atoms, wherein one or more non-adjacent CH 2 groups may each be independently replaced by C(R 0< )=C(R 00< )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- such that O and / or S atoms are not directly linked to each other, and wherein one or more H atoms may also be replaced by F, Cl, CN or P 1< -Sp 1< - , preferably straight-chain or branched, optionally mono- or multiply fluorinated, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy with 1 to 12 C atoms (where the alkenyl and alkynyl residues are at least two and the branched residues have at least three C atoms), wherein -OH, -NH 2 , -SH, -NHR, -C(O)OH and -CHO are not included in the group R aa<, R 0< , R 00< are each independently of each other and, at each occurrence, the same or different H or alkyl with 1 to 12 C atoms,R< y< and R< z< each independently H, F, CH3 or CF3, X< 1< , X< 2< and X< 3< each independently -CO-O-, O-CO- or a single bond, Z< 1< -O-, -CO-, -C(R< y< R< z< )-, or -CF2 CF2-, Z2 and Z3 each independently -CO-O-, -O-CO-, -CH2 O-, -OCH2-, -CF2 O-, -OCF2-, or -(CH2)<n-, where n is 2, 3 or 4, L in each occurrence the same or different F, Cl, CN, SCN, SF5 or straight-chain or branched, optionally mono- or polyfluorinated, alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or Alkoxycarbonyloxy with 1 to 12 C atoms, preferably F, L' and L" each independently of one another, H, F or Cl, r0, 1, 2, 3 or 4, s0, 1, 2 or 3, t0, 1 or 2, x0 or 1. ,

[0091] In the compounds of formulas M1 to M42, the ring group means preferably or wherein L, whether the same or different in each occurrence, has one of the foregoing meanings and preferably means F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , C(CH 3 ) 3 , CH(CH 3 ) 2 , CH 2 CH(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 or P-Sp-, particularly preferably F, Cl, CN, CH 3 , C 2 H 5 , OCH 3 , COCH 3 , OCF 3 or P-Sp-, most preferably F, Cl, CH 3 , OCH 3 , COCH 3 or OCF 3 , in particular F or CH 3 .

[0092] Preferably, the FK medium or polymerizable component comprises one or more compounds selected from the group of formulas M1-M28, particularly preferably from formulas M2-M15, and most preferably from formulas M2, M3, M9, M14 and M15. Preferably, the FK medium or polymerizable component does not comprise any compounds of formula M10, where Z2< and Z3< denote -(CO)O- or -O(CO)-.

[0093] To fabricate PSA displays, the polymerizable compounds in the FK medium between the FK display substrates are polymerized or crosslinked (if a polymerizable compound contains two or more polymerizable groups) by in-situ polymerization, optionally under voltage. The polymerization can be carried out in one step. Alternatively, in a first step, polymerization can be performed under voltage to create a pretilt angle, followed by a second polymerization step without voltage to polymerize or crosslink the compounds that did not react in the first step ("end curing").

[0094] Suitable and preferred polymerization methods include, for example, thermal or photopolymerization, preferably photopolymerization, particularly UV photopolymerization. Optionally, one or more initiators may be added. Suitable conditions for polymerization, as well as suitable types and amounts of initiators, are known to those skilled in the art and described in the literature. For radical polymerization, for example, the commercially available photoinitiators Irgacure651 ®<, Irgacure184 ®<, Irgacure907 ®<, Irgacure369 ®<, or Darocure1173 ®< (Ciba AG) are suitable. If an initiator is used, its proportion is preferably 0.001 to 5 wt.%, particularly preferably 0.001 to 1 wt.%.

[0095] The polymerizable component or the polymerization medium may also contain one or more stabilizers to prevent undesired spontaneous polymerization of the polymerization agents, for example, during storage or transport. Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature. Particularly suitable, for example, are the commercially available stabilizers of the Irganox® series (Ciba AG), such as Irganox® 1076. If stabilizers are used, their proportion, based on the total amount of polymerization agents or the polymerizable component, is preferably 10–10,000 ppm, and particularly preferably 50–500 ppm.

[0096] The FK media for use in the FK displays according to the invention contain, in addition to the self-orientation additives described above and the optional polymerizable compounds (M), an FK mixture ("host mixture") containing one or more, preferably two or more, low-molecular-weight (i.e., monomeric or unpolymerized) compounds. The latter are stable or unreactive towards a polymerization reaction under the conditions used for the polymerization of the polymerizable compounds. In principle, any dielectrically negative or positive FK mixture suitable for use in conventional VA and VA-IPS displays is suitable as a host mixture. The proportion of the host mixture is typically 95 wt.% or more, preferably 97 wt.% or more, for liquid crystal displays.

[0097] Suitable electrolytic capacitor mixtures are known to those skilled in the art and described in the literature. Electrolytic capacitor media for VA displays with negative dielectric anisotropy are described in EP 1 378 557 A1 or WO 2013 / 004372.

[0098] Suitable FK mixtures with positive dielectric anisotropy, suitable for LCDs and especially for IPS displays, are known, for example, from JP 07-181 439 (A), EP 0 667 555, EP 0 673 986, DE 195 09 410, DE 195 28 106, DE 195 28 107, WO 96 / 23 851 and WO 96 / 28 521.

[0099] The following are preferred embodiments for the liquid crystalline medium according to the invention with negative dielectric anisotropy:

[0100] FK medium, which additionally contains one or more compounds selected from the group of compounds of formulas A, B and C, wherein R 2A< , R 2B< and R 2C< each independently of each other H, an unsubstituted, an alkyl group simply substituted by CN or CF 3 or at least simply by halogen with up to 15 C atoms, wherein in these groups one or more CH 2 groups are also replaced by -O-, -S-, , -C≡C-, -CF2O-, -OCF2-, -OC-O- or -O-CO- can be replaced such that O atoms are not directly bonded to each other, L1-4< each independently F, Cl, CF3 or CHF2, Z2< and Z2'< each independently single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF-, -CH=CHCH2O-, p1 or 2, preferably 1, q0 or 1, and v1 to 6 mean.

[0101] In the compounds of formulas A and B, Z 2< can have the same or different meanings. In the compounds of formula B, Z 2< and Z 2'< can have the same or different meanings. In the compounds of formulas A, B, and C, R 2A<, R 2B<, and R 2C< each preferably denote alkyl with 1-6 carbon atoms, in particular CH 3, C 2 H 5, nC 3 H 7, nC 4 H 9, nC 5 H 11.

[0102] In the compounds of formulas A and B, L1<, L2<, L3< and L4< preferably denote L1< = L2< = F and L3< = L4< = F, furthermore L1< = F and L2< = Cl, L1< = Cl and L2< = F, L3< = F and L4< = Cl, L3< = Cl and L4< = F. Z2< and Z2'< in formulas A and B preferably each independently denote a single bond, furthermore a -C2H4 bridge.

[0103] If in formula BZ 2< = -C 2 H 4 -, then Z 2'< is preferably a single bond, or if Z 2'< = -C 2 H 4 -, then Z 2< is preferably a single bond. In the compounds of formulas A and B, (O)C v H 2v+1 preferably means OC v H 2v+1, and furthermore C v H 2v+1. In the compounds of formula C, (O)C v H 2v+1 preferably means C v H 2v+1. In the compounds of formula C, L 3< and L 4< preferably each mean F.

[0104] Preferred compounds of formulas A, B and C are, for example: wherein Alkyl and Alkyl* each independently represent a straight-chain alkyl group with 1-6 carbon atoms.

[0105] The FK medium preferably has a Δε of -1.5 to -8.0, in particular of -2.5 to -6.0.

[0106] The birefringence values ​​Δn in the liquid crystal mixture are typically between 0.07 and 0.16, preferably between 0.08 and 0.12. The rotational viscosity γ 1 at 20 °C before polymerization is preferably ≤ 165 mPa·s, particularly ≤ 140 mPa·s.

[0107] The following are preferred embodiments of the liquid crystalline medium according to the invention with negative or positive dielectric anisotropy: LC medium which additionally contains one or more compounds of formula II and / or III: wherein Ring A1,4-phenylene or trans-1,4-cyclohexylene, where a0 or 1 is, R3< each independently represents alkyl with 1 to 9 C atoms or alkenyl with 2 to 9 C atoms, preferably alkenyl with 2 to 9 C atoms, and R4< each independently represents an unsubstituted or halogenated alkyl group with 1 to 12 C atoms, wherein one or two non-adjacent CH2 groups may also be replaced by -O-, -CH=CH-, -CH=CF-, -(CO)-, -O(CO)- or -(CO)O- such that O atoms are not directly linked together, and preferably represents alkyl with 1 to 12 C atoms or alkenyl with 2 to 9 C atoms.

[0108] The compounds of formula II are preferably selected from the group consisting of the following formulas: wherein R3a< and R4a< each independently denote H, CH3, C2H5 or C3H7, and "alkyl" denotes a straight-chain alkyl group with 1 to 8, preferably 1, 2, 3, 4 or 5 carbon atoms. Compounds of formula IIa and IIf are particularly preferred, especially those in which R3a< denotes H or CH3, preferably H, and compounds of formula IIc, especially those in which R3a< and R4a< denote H, CH3 or C2H5.

[0109] The following are preferred embodiments for the liquid crystalline medium according to the invention with positive dielectric anisotropy:

[0110] The FK medium preferably contains one or more compounds of formulas IV and V: wherein R 0< Alkyl- or alkoxy residue with 1 to 15 C atoms, wherein optionally one or more CH 2 groups in these residues, independently of each other, are replaced by -C≡C-, -CF 2 O-, -CH=CH-, -O-, -(CO)O- or -O(CO)- are substituted in such a way that O atoms are not directly linked together, and in which one or more H atoms can optionally be replaced by halogen, ring A or Ring B independently of each other 1,4-phenylene, optionally substituted by one or two F or Cl, or X 0< F, Cl, CN, SF 5 , SCN, NCS, a halogenated alkyl group, a halogenated alkenyl group, a halogenated alkoxy group or a halogenated alkenyloxy group, each with up to 6 C atoms, Y 1-4< each independently H or F, Z 0< -CF 2 O-, -(CO)O- or a single bond, and c0, 1 or 2, preferably 1 or 2. means preferably R 0< preferably means straight-chain alkyl or alkenyl with 2 to 7 carbon atoms; X 0< preferably means F, OCF 3 , Cl or CF 3 , in particular F.

[0111] The nematic phase of the dielectrically negative or positive FK medium according to the invention preferably has a nematic phase in a temperature range of 10 °C or less to 60 °C or more, particularly preferably from 0 °C or less to 70 °C or more.

[0112] Within the scope of the present application, the two formulas for substituted benzene rings are synonymous. 1,4-Substituted cyclohexane is replaced by reproduced, which is preferably 1,4-trans-configured.

[0113] In the present application and in the following examples, the structures of the liquid crystal compounds are indicated by acronyms, with the transformation into chemical formulas taking place according to Tables A and B below. All CnH2n+1 and CmH2m+1 residues are straight-chain alkyl groups with n or m carbon atoms, respectively; n, m, z, and k are integers and preferably represent 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. The coding according to Table B is self-explanatory. In Table A, only the acronym for the parent compound is given. In individual cases, a code for the substituents R1*<, R2*<, L1*<, and L2*< follows separately from the acronym for the parent compound with a dash. Code for R 1*< , R 2*< , L 1*< , L 2*< , L 3*< R 1*< R 2*< L 1*< L 2*< nm C n H 2n+1 C m H 2m+1 H H nOm C n H 2n+1 OC m H 2m+1 H H nO.m OC n H 2n+1 C m H 2m+1 H H n C n H 2n+1 CN H H nN.F C n H 2n+1 CN F H nN.FF C n H 2n+1 CN F F nF C n H 2n+1 F H H nCl C n H 2n+1 Cl H H nOF OC n H 2n+1 F H H nF.F C n H 2n+1 F F H nF.FF C n H 2n+1 F F F nOCF 3 C n H 2n+1 OCF 3 H H nOCF 3 .F C n H 2n+1 OCF 3 F H n-Vm C n H 2n+1 -CH=CH-C m H 2m+1 H H nV-Vm C n H 2n+1 -CH=CH- -CH=CH-C m H 2m+1 H H

[0114] Preferred mixture components can be found in Tables A and B. Table B n, m, z independently mean preferably 1, 2, 3, 4, 5 or 6.

[0115] In a preferred embodiment of the present invention, the LC media according to the invention contain one or more compounds selected from the group consisting of compounds from Table A and B. Table C Table C lists possible chiral dopants that can be added to the FK media according to the invention.

[0116] Optionally, the FK media contain 0 to 10 wt.%, in particular 0.01 to 5 wt.%, most preferably 0.1 to 3 wt.% dopants, preferably selected from the group consisting of compounds in Table C. Table D Table D lists possible stabilizers that can be added to the FK media according to the invention. (n here means an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8; terminal methyl groups are not shown).

[0117] Preferably, the FK media contain 0 to 10 wt.%, in particular 1 ppm to 5 wt.%, most preferably 1 ppm to 1 wt.% of stabilizers. Preferably, the FK media contain one or more stabilizers selected from the group consisting of compounds in Table D. Table E Table E lists example compounds that can preferably be used as polymerizable compounds in the FK media according to the present invention.

[0118] In a preferred embodiment of the present invention, the mesogenic media contain one or more compounds selected from the group of compounds in Table E. Table F Table F lists example compounds that can preferably be used as non-polymerizable self-orientation additives in the FK media according to the present invention.

[0119] In this application, the term "compounds," also written as "compound(s)," means both one and multiple compounds unless explicitly stated otherwise. Conversely, the term "compound" generally includes multiple compounds, provided this is possible according to the definition and unless otherwise stated. The same applies to the terms FK media and FK medium. The term "component" comprises one or more substances, compounds, and / or particles.

[0120] The following abbreviations and symbols are also used: ne extraordinary refractive index at 20°C and 589 nm, no ordinary refractive index at 20°C and 589 nm, Δnopic anisotropy at 20°C and 589 nm, ε⊥ dielectric permittivity perpendicular to the director at 20°C and 1 kHz, ε∥ dielectric permittivity parallel to the director at 20°C and 1 kHz, Δεdielectric anisotropy at 20°C and 1 kHz, Kp., T(N,I) clearing point [°C], γ1 rotational viscosity at 20°C [mPa·s], K1 elastic constant, "splay" deformation at 20°C [pN], K2 elastic constant, "twist" deformation at 20°C [pN], K3 elastic constant, "bend" deformation at 20°C [pN], V 0 Capacitive threshold (Freedericks threshold) at 20°C [V].

[0121] Unless explicitly stated otherwise, all concentrations in this application are given in weight percent and refer to the corresponding total mixture containing all solid or liquid crystalline components, excluding solvents.

[0122] All physical properties are and were determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany and apply to a temperature of 20°C and Δn is determined at 589 nm and Δε at 1 kHz, unless explicitly stated otherwise.

[0123] The polymerizable compounds are polymerized in the display or test cell by irradiation with UVA light (usually 365 nm) of a defined intensity for a predetermined time, optionally with simultaneous application of a voltage to the display (usually 10 to 30 V AC, 1 kHz). Unless otherwise specified, the examples use a mercury vapor lamp with < 100 mW / cm², and the intensity is measured with a standard UV meter (Ushio UNI meter) equipped with a bandpass filter at 320 nm (optionally 340 nm).

[0124] The following examples illustrate the present invention without limiting it in any way. However, the physical properties clearly indicate to those skilled in the art which properties are to be achieved and in which areas they can be modified. In particular, the combination of the various properties that can preferably be achieved is thus well defined for those skilled in the art.

[0125] Further combinations of the embodiments and variants of the invention according to the description also arise from the claims. Examples

[0126] The compounds used, unless commercially available, are synthesized according to standard laboratory procedures. The FK media are from Merck KGaA, Germany. A) Synthesis examples Example 1 Synthesis of 2-methyl-acrylic acid 2-[2'-ethyl-4-(2-hydroxy-ethoxy)-4"-pentyl-[1,1';4',1"]terphenyl-3-yl]-ethyl ester 1

[0127] 1) Synthesis of 4'-Bromo-2'-ethyl-biphenyl-4-ol A

[0128]

[0129] 110.3 g (1.04 mol) Na 2 CO 3 are mixed with 223 ml of water and 154 g (0.49 mol) of 4-bromo-2-ethyl-1-iodobenzene, 75.1 g (0.54 mol) of 4-hydroxyphenylboronic acid and 850 ml of 1,4-dioxane are added and the mixture is degassed. The mixture is treated with 14.5 g (19.8 mmol) of bis(1,1-diphenylphosphinoferocene) palladium(II) chloride and stirred at 80°C for 18 h. After complete reaction (checked by thin-layer chromatography with heptane / ethyl acetate 1:1), the reaction mixture is cooled to room temperature, diluted with water and methyl tert-butyl ether, and acidified to pH 1–2 with 2 N HCl. The phases are separated, the aqueous phase is extracted with methyl tert-butyl ether, and the combined organic phases are dried over Na₂SO₄, filtered, and concentrated under vacuum. The resulting crude product is fried with heptane / ethyl acetate (8:2) over silica gel, yielding 96 g of the product. A as a brown oil. 2) Synthesis of 2'-Ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-ol B

[0130]

[0131] 102 g (514 mmol) 4-pentylphenylboronic acid and 135 g (467 mmol) bromide A are in a mixture of 743 ml toluene, 270 ml ethanol and 350 ml 2 N Na₂CO₂ was dissolved and degassed. 8.1 g (7.0 mmol) of tetrakis(triphenylphosphine)palladium were added and the mixture refluxed for 18 h. After complete reaction, the mixture was cooled to room temperature, the aqueous phase was removed, the organic phase was washed with methyl tert-butyl ether (MTB ether), and the combined organic phases were dried over Na₂SO₄, filtered, and concentrated under vacuum. The crude product was fried with dichloromethane over silica gel, and the product fractions were recrystallized from heptane, yielding 76.9 g of the product as colorless crystals. 1< H NMR (500 MHz, DMSO-d6) δ = 0.89 ppm (t, 6.88 Hz, 3H, CH 3 ), 1.08 (t, 7.51 Hz, 3H, CH 3 ), 1.31 (m c , 4H, CH 2 ), 1.61 (q, 7.58 Hz, 2H, CH 2 ), 2.62 (q. überlagert mit t, 4H, CH 2 benzylisch), 6.83 (d, 8.5 Hz, 2H, arom-H), 7.13 (d, 8.5 Hz, 2H, arom-H), 7.17 (d, 7.9 Hz, 1H, arom-H), 7.28 (d, 8.2 Hz, 2H, arom-H), 7.46 (dd, 7.93, 1.97 Hz, 1H, arom.-H), 7.54 (d, 1.88 Hz, 1H, arom.-H), 7.59 (d, 8.17 Hz, 2H, arom.-H), 9.44 (s, 1H, arom.-OH). 3) Synthese von 3-Bromo-2'-ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-ol C

[0132]

[0133] 30.0 g (85.9 mmol) Alkohol BThe mixture is dissolved in 1100 ml of dichloromethane and cooled to -48°C. At this temperature, 5.28 ml (103 mmol) of bromine in 1100 ml of dichloromethane is slowly added over 40 minutes. The mixture is stirred at this temperature for 1 hour and monitored by thin-layer chromatography (using toluene). The excess bromine is reduced with saturated NaHSO₃ solution, and the phases are separated. The aqueous phase is extracted with dichloromethane, and the combined organic phases are dried over Na₂SO₄ and concentrated under vacuum. The crude product is fried with toluene over silica gel, yielding 35.3 g of the product as a white solid. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.91 ppm (t, 6.99 Hz, 3H, CH 3 ), 1.15 (t, 7.53 Hz, 3H, CH 3 ), 1.36 (mc , 4H, CH 2 ), 1.66 (mc , 2H, CH 2 ), 2.65 (mc , 4H, CH 2 benzylic), 5.5 (s, 1H, arom-OH), 7.06 (d, 8.3 Hz, 1H, arom-H), 7.20 (dd, 8.28, 2.07 Hz superimposed with d 7.85 Hz, 2H, arom-H), 7.26 (d, 8.1 Hz, 2H, arom-H), 7.43 (dd, 7.87, 1.87 Hz, 2H, arom.-H), 7.46 (d, 2.01 Hz, 1H, arom.-H), 7.503 (d, 1.71 Hz, 1H, arom.-H), 7.54 (d, 8.1 Hz, 2H, arom.-H. 4) Synthesis of [2-(3-Bromo-2'-ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-yloxy)-ethoxy]-tert-butyl-dimethyl-silane D

[0134]

[0135] 2.9 g (71.7 mmol) of NaH (60% suspension in paraffin oil) were placed in 93 ml of dimethylformamide (DMF) and cooled to 2°C while stirring and treated with a solution of alcohol CThe solution was slowly added to DMF, ensuring the temperature did not exceed 12°C. After complete addition, the solution was allowed to rise to room temperature (RT) and stirred for 2 h (yellowish solution). 17.2 g (71.7 mmol) of (2-bromoethoxy)-tert-butyldimethylsilane dissolved in DMF was then slowly added and stirred for 18 h at 50°C. The reaction solution was carefully poured onto ice water and extracted with MTB ether. The combined organic phases were washed with water, dried over Na₂SO₄, filtered, and concentrated under vacuum. The resulting crude product was fried with toluene over silica gel, and the product fractions were concentrated under vacuum. 27.9 g of the desired product were obtained. MS (EI): 582.4 [M⁺<] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si-CH 3 ), 0.78 (s, 12H, Si-C(CH 3 ) 3 ), 1.01 (t, 7.52 Hz, CH 3 ), 1.23 (m c , 4H, CH 2 ), 1.52 (m c , 2H, CH 2 ), 2.51 (m c , 4H, CH 2 benzylisch), 3.91 (t, 5.24 Hz, 2H, CH 2 O), 4.02 (t, 5.24 Hz, 2H CH 2 O), 6.84 (d, 8.45 Hz, 1H, arom-H), 7.08 (dd, 8.37, 2.33 Hz überlagert mit d 7.66 Hz, 2H, arom-H), 7.12 (d, 8.2 Hz, 2H, arom-H), 7.29 (dd, 7.86, 1.9 Hz, 2H, arom-H) 7.36 (d, 1.79 Hz, 1H, arom.-H), 7.41 (d, 8.12 Hz überlagert mit d, 2.15 Hz, 3H, arom.-H). 5) Synthese von 2-{4-[2-(tert-Butyl-dimethyl-silanyloxy)-ethoxy]-2'-ethyl -4"-pentyl-[1,1';4',1"]terphenyl-3-yl}-ethanol E

[0136]

[0137] 8.5 g (14 mmol) von Bromid DThe mixture is dissolved in 41 ml of tetrahydrofuran (THF) and cooled to -78°C. 10.6 ml (17 mmol) of butyllithium (1.6 molar solution in THF) is then slowly added. Next, 6.23 ml (16 mmol) of ethylene oxide (2.5-3.3 molar in THF) is added and stirred for 30 min. At -78°C, 2.13 ml (17 mmol) of boron trifluoride-diethyl ether complex in 10 ml of cooled THF is slowly added (exothermic) and stirred at this temperature for 2 h. The reaction solution is then allowed to warm to room temperature (RT) within 2 h and poured onto ice water. Extraction is performed with MTB ether, and the organic phase is dried over Na₂SO₄, filtered, and concentrated under vacuum. The crude product obtained is purified over silica gel with heptane / ethyl acetate (H / EE) 9:1 and subsequently with H / EE (4:1), and the product fractions are concentrated under vacuum. 3.61 g of the product are obtained as oil. MS (EI): 546.4 [M +< ] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si-CH 3 ), 0.81 (s, 12H, Si-C(CH 3 ) 3 ), 1.03 (t, 7.53 Hz, CH 3 ), 1.24 (m c , 4H, CH 2 ), 1.54 (m c , 2H, CH 2 ), 1.73(t, 6.25 Hz, 1H, OH), 2.54 (m c , 4H, CH 2 benzylisch), 2.85 (t, 6.3 Hz, 2H, CH 2 -O), 3.76 (q, 6.15 Hz, 2H, CH2-OH) 3.88 (t, 5.18 Hz, 2H, CH 2 O), 3.99 (t, 5.18 Hz, 2H CH 2 O), 6.81 (d, 8.26 Hz, 1H, arom-H), 7.01-7.08 (m 2H, arom-H), 7.10-7.16 (d überlagert mit Singulett , 3H, arom-H), 7.30 (dd, 7.86, 1.92 Hz, 2H, arom-H), 7.38 (d, 1.8 Hz, 1H, arom.-H), 7.42 (d, 8.14, 2H, arom.-H). 6) Synthese von 2-Methyl-acrylic acid 2-{4-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-2'-ethyl-4"-pentyl-[1,1';4',1"]terphenyl-3-yl}-ethyl ester F

[0138]

[0139] 8.50 g (15.5 mmol) an Alkohol E,1.84 ml (21.8 mmol) of methacrylic acid and 0.19 g (1.55 mmol) of 4-(dimethylamino)pyridine are dissolved in 100 ml of dichloromethane and cooled to 5°C. 3.37 g (21.8 mmol) of 4-N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride dissolved in 40 ml of dichloromethane are slowly added, and the mixture is stirred at room temperature for 72 h. The reaction mixture is diluted with dichloromethane and filtered through silica gel. The product fractions are concentrated under vacuum at a maximum temperature of 30°C. 7.5 g of the product is obtained as a clear oil. MS (EI): 614.5 [M +< ] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si-CH 3 ), 0.81 (s, 12H, Si-C(CH 3 ) 3 ), 1.02(t, 7.49 Hz, CH 3 ), 1.24 (m c , 4H, CH 2 ), 1.55 (m c , 2H, CH 2 ), 1.79 (s, 3H, CH 3 ), 2.53 (m c , 4H, CH 2 benzylisch), 2.95 (t, 6.89 Hz, 2H, CH 2 -O), 3.89 (t, 5.11 Hz, 2H, CH 2 O), 3.99 (t, 5.14 Hz, 2H CH 2 O), 4.28 (t, 6.94, 2H, CH 2 -O), 5.39 (s, 1H, Olefin-H), 5.95, (s, 1H, Olefin-H), 6.8 (d, 8.24 Hz, 1H, arom-H), 7.03-7.06 (m 2H, arom-H), 7.10 (d, 7.86 Hz, 1H, arom-H), 7.14 (d, 8.76 Hz, 2H, arom-H), 7.30 (dd, 7.86, 1.82 Hz, 2H, arom-H), 7.38 (d, 1.63 Hz, 1H, arom.-H), 7.43 (d, 8.07, 2H, arom.-H). 7) Synthese von 2-Methyl-acrylic acid 2-[2'-ethyl-4-(2-hydroxy-ethoxy)-4"-pentyl-[1,1';4',1"]terphenyl-3-yl]-ethyl ester G

[0140]

[0141] 7.60 g (12.2 mmol) von Verbindung FThe mixture is dissolved in 150 ml of THF and cooled to 2°C. 7.01 ml (14.0 mmol) of 2 N HCl is then slowly added and stirred for 1 h at 2-4°C. The reaction solution is then warmed to room temperature over 3 h and carefully adjusted to pH 7 with NaHCO3 solution. It is extracted with MTB ether, and the organic phases are dried over Na2SO4 and concentrated under vacuum. The crude product is purified with heptane / ethyl acetate (1:1) on silica gel, and the product fractions are combined and recrystallized twice from acetonitrile (1:4) at -20°C. The resulting product is dried at 60°C using a bulb distillation apparatus (to remove acetonitrile). 3.2 g of the product are obtained as a white solid. Phasen: Tg -16 K 58 I MS (EI) 500.3 [M +< ] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.91 ppm (t, 6.88 Hz, CH 3 ), 1.14 (t, 7.52Hz, 3H, CH 3 ), 1.37 (m c , 4H, CH 2 ), 1.67 (m, 2H, CH 2 ), 1.04 (s, 3H, CH 3 ), 2.65 (m c , 4H, CH 2 benzylisch), 3.04 (t, 7.74 Hz, 2H, CH 2 -O), 3.19 (t, 6.81 Hz, 1H, OH), 4.03 (m c , 2H, CH 2 O), 4.15 (t, 4.02 Hz, 2H CH 2 O), 4.42 (t, 7.5 Hz, 2H, CH 2 -O), 5.56 (s, 1H, Olefin-H), 6.12, (s, 1H, Olefin-H), 6.91 (d, 8.32 Hz, 1H, arom-H), 7.30-7.13 (m 5H (überlagert mit CHCl 3 ), arom-H), 7.42 (dd, 7.87, 1.91 Hz, 1H, arom-H), 7.506 (d, 1.76 Hz, 1H, arom-H), 7.54 (d, 8.15 Hz, 2H, arom-H). Example 2 Synthese von 2-Methyl-acrylic acid 2'-ethyl-4"-(2-hydroxy-ethyl)-6"-(2-methyl-acryloyloxy)-4-pentyl-[1,1';4',1"]terphenyl-3"-yl ester 2

[0142] 1) Synthese von 4-Bromo-2-ethyl-4'-pentyl-biphenyl A2

[0143]

[0144] 45.0 g (234 mmol) of 4-pentylphenylboronic acid and 70.0 g (225 mmol) of 4-bromo-2-ethyl-1-iodobenzene are dissolved in a mixture of 300 ml toluene, 200 ml ethanol, and 200 ml Na₂CO₃ solution (2 molar) and inerted with argon. Then, 8.00 g (6.92 mmol) of tetrakis(triphenylphosphine)palladium(0) are added, and the reaction mixture is refluxed for 18 h. After complete conversion, the mixture is cooled to room temperature and treated with water. The phases are separated, the organic phase is washed with water and dried over Na₂SO₄, filtered, and concentrated under vacuum. The crude product (orange oil) is filtered with heptane over silica gel, yielding 56.2 g of the product as a colorless oil. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.91 ppm (t, 6.97Hz. 3H, CH 3 ), 1.09 (t, 7.58 Hz, 3H. CH 3 ), 1.36 (m c , 4H, CH 2 ), 1.66, (m c , 2H, CH 2 ), 2.56 (q, 7.55Hz, 2H, benz.-CH 2 ), 2.64 (dd, 7.71Hz, 2H, benz.-CH 2 ), 7.05 (d, 8.15Hz, 1H, arom.-H), 7.16 (d, 8.21 Hz, 2H, arom.-H), 7.21 (d, 8.14 Hz, 2H, arom.-H), 7.3 (dd, 8.14, 2.12Hz, 1H, arom.-H), 7.42 (d, 1H, 2.08Hz, 1H, benz.-H), 7.24 (d, 8.2Hz, 2H, arom.-H), 7.27 (d, 8.2Hz, 2H, arom.-H), 7.35 (dd, 7.87, 1.71Hz, 1H, arom.-H), 7.42 (d, 1.53 Hz, 1H, arom.-H) 2) Synthese 2-Ethyl-4'-pentyl-biphenyl-4-boronsäure B2

[0145]

[0146] Es werden 65.0 g (196mmol) Bromid A2Dissolved in 475 ml of tetrahydrofuran (THF), cooled to -78°C, and treated dropwise with 128.8 ml (206 mmol, 1.6 molar in n-hexane) of n-butyllithium. The reaction mixture was stirred for 60 min at -78°C, and at this temperature, 24.5 ml (216 mmol) of trimethyl borate was added dropwise. Stirring continued at this temperature for one hour, the mixture was then slowly thawed to 0°C and carefully acidified with 2 N hydrochloric acid at 0°C. After brief stirring, the phases were separated. The aqueous phase was extracted with MTB ether, and the combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated. The crude product was first filtered over silica gel with dichloromethane and then with MTB ether and concentrated under vacuum. 43.7 g of the product were obtained as a smectic solid. 3) Synthesis of 2-(4-Bromo-2,5-dimethoxy-phenyl)-ethanol C2

[0147]

[0148] 10.0 g (33.8 mmol) of 1,4-dibromo-2,5-dimethoxybenzene is dissolved in 300 ml of THF and cooled to -78°C. 23.0 ml (36.8 mmol, 1.6 molar in n-hexane) of n-butyllithium is added dropwise and stirred for 5 minutes. 1.70 g (38.6 mmol) of ethylene oxide dissolved in 20 ml of THF cooled to 2°C is then added to the reaction mixture. At -78°C, 5.00 ml (39.8 mmol) of boron trifluoride-diethyl ether complex is carefully added dropwise and stirred for 15 minutes. After checking the reaction by thin-layer chromatography, the reaction was quenched with 5.0 ml of isopropanol at low temperatures, allowed to thaw at 0°C, carefully treated with water and MTB ether, and stirred. The phases were separated, the aqueous phase extracted with MTB ether, the organic phases combined, washed with saturated sodium chloride solution, dried over sodium sulfate, and concentrated under vacuum.The crude product is filtered over silica gel with dichloromethane / MTB ether (9:1) and yields 5.8 g of the product as a light yellow oil. 4) Synthesis of 2-(2'-ethyl-2",5"-dimethoxy-4-pentyl-1,1';4',1"]terphenyl-4"-ethanol D2

[0149]

[0150] 23.0 g (25 wt% in toluene, 19.4 mmol) of alcohol C2 and 5.70 g (18.7 mmol, 85%) of B2The mixture is dissolved in a solution of 200 ml toluene, 100 ml ethanol, and 40 ml (1 mol / L, 40 mmol) Na₂CO₃ and degassed by argon injection. 100 mg (0.87 mmol) of tetrakis(triphenylphosphine)palladium (0) is added and refluxed for 60 min. The mixture is cooled to room temperature and treated with water. The phases are separated, the organic phase is washed with water, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product is filtered over silica gel with a mixture of dichloromethane and MTB ether (95:5) and concentrated under vacuum. 6.0 g of the product are obtained as a light brown oil. 1< H NMR (500 MHz, DMSO-d 6 ) δ = 0.89 ppm (t, 6.8 Hz, 3H, CH 3 ), 1.06 (t, 7.54 Hz, 3H, CH 3 ), 1.33 (mc , 4H, CH 2 ), 1.63 (quin., 7.51 Hz, 2H, CH 2 ), 2.67-2.54 (m, 4H, benz.-CH 2 ), 2.77 (t, 7.25Hz, 2H, benz.-CH 2 ), 3.60 (dt, 7.21, 5.49 Hz, 2H, CH 2 C H2 OH), 3.72 (s, 3H, OCH 3 ), 3.79 (s, 3H, OCH 3 ), 4.62 (t, 5.36 Hz, 1H, OH), 6.90 (s, 1H, arom-H), 6.95 (s, 1H, arom.-H), 7.15 (d, 7.86 Hz, 1H, arom.-H). 5) Synthese von 2'-Ethyl-4"-(2-hydroxy-ethyl)-4-pentyl-[1,1';4',1"]terphenyl-2",5"-diol E2

[0151]

[0152] 4.70 g (10.9 mmol) von Alkohol D2The mixture is dissolved in 50 ml of dichloromethane and cooled to -28°C. 2.3 ml (24.2 mmol) of boron tribromide are carefully added, and the mixture is stirred for 3 h at -25°C. After the reaction is complete, the mixture is stirred and poured onto ice water, then carefully neutralized with 2 N sodium hydroxide solution. The phases are separated, the aqueous phase is extracted with dichloromethane, and the combined organic phases are washed with water, dried over sodium sulfate, filtered, and concentrated. The crude product (orange oil) is first filtered with dichloromethane and MTB ether (9:1) and then with (3:1) over silica gel, and the product fractions are concentrated under vacuum. The resulting product is recrystallized from toluene at 5°C, yielding 1.7 g of the product as colorless crystals. 1< H NMR (500 MHz, DMSO-d 6 ) δ = 0.89 ppm (t, 6.83 Hz, 3H, CH 3 ), 1.07 (t, 7.55Hz, 3H, CH 3 ), 1.34 (m c , 4H, CH 2 ), 1.64 (quin., 7.3 Hz, 2H, CH 2 ), 2.71-2.55 (m, 6H, benz.-CH 2 ), 3.58 (dt, 7.0, 5.01 Hz, 2H, CH 2 C H 2 OH), 4.70, (t, 5.07 Hz, CH 2 O H ), 6.68 (s, 1H, arom-H), 6.74 (s, 1H, arom.-H), 7.15 (d, 7.89 Hz, arom.-H), 7.25 (d, 8.26 Hz, 2H, arom.-H), 7.28 (d, 8.26 Hz, 2H, arom.-H), 7.37 (dd, 7.9, 1.8 Hz, 1H, arom.-H), 7.43 (d, 1.60 Hz, 1H, arom.-H), 8.67 (s, 2H, arom.-OH). 6) Synthese von 4"-[2-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-2'-ethyl-4-pentyl-[1,1';4',1"]terphenyl-2",5"-diol F2

[0153]

[0154] 1.20 g (2.96 mmol) von Alkohol E20.214 ml (3.23 mmol) of imidazole are dissolved in 9.0 ml of THF and cooled to 2°C. Then, 490 mg (3.25 mmol) of tert-butylchlorodimethylsilane dissolved in 4 ml of THF are added dropwise over 30 minutes, and the mixture is stirred at this temperature for 60 minutes. The reaction mixture is treated with ammonium chloride solution and extracted with MTB ether. The organic phase is separated and dried over sodium sulfate, filtered, and concentrated under vacuum. An orange oil is obtained, which is filtered over silica gel with toluene and ethyl acetate (98:2). 1.0 g of the product is obtained as a yellow oil. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si(CH 3 ) 2 ), 0.82 (s, 12H, SiC(CH 3 ) 3 ),1.02 (t, 7.56Hz, 3H, CH 3 ), 1.26 (mc , 4H, CH 2 ), 1.57 (mc , 2H, CH 2 ), 2.55 (mc , 4H, benz.-CH), 2.78 (t, 4.98Hz, 2H, C H 2 CH 2 OSi), 3.85 (t, 5.1Hz, 2H, C H2 OSi), 4.82 (s, 1H, arom.-OH), 6.59 (s, 1H, arom.-H), 6.79 (s, 1H, arom.-H) 7.13 (2xd(überlagert) 4H, arom.-H), 7.18 (d, 7.78Hz, 1H, arom.-H), 7.21 (dd, 7.78, 1.7Hz, 1H, arom.-H), 7.29, (d, 1.4Hz, 1H, arom.-H), 7.82 (s, 1H, arom.-OH). 7) Synthese von 2-Methyl-acrylic acid 4"-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-2'-ethyl-6"-(2-methyl-acryloyloxy)-4-pentyl-[1,1';4',1"]terphenyl-3"-yl ester G2

[0155]

[0156] 2.30 g (4.43 mmol) an Phenol F2,1.0 ml (11.8 mmol) of methacrylic acid and 30.0 mg (0.25 mmol) of 4-(dimethylamino)pyridine are dissolved in 25 ml of dichloromethane and cooled to 1°C. 1.80 g (11.6 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDC) dissolved in 20 ml of dichloromethane at 1-4°C is added dropwise, and the mixture is stirred for 18 h at room temperature (RT). A further 0.4 ml of methacrylic acid and 0.6 g of EDC are then added at RT, and the mixture is stirred for another 18 h at RT. The reaction solution is then filtered directly through a 100 ml silica frit containing dichloromethane and concentrated under vacuum. 3.3 g of the yellow crude product are obtained as a semi-crystalline solid, which is dissolved in 10 ml of heptane / ethyl acetate (EE) (95:5) and filtered to remove undissolved components. The mixture is then filtered through 120 g of silica gel with heptane / EE (95:5). 2.4 g of the product are obtained as a yellow oil. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si(CH 3 ) 2 ), 0.86 (s, 12H, SiC(CH 3 ) 3 ),1.06 (t, 7.55Hz, 3H, CH 3 ), 1.35 (m c , 4H, CH 2 ), 1.65 (m c , 2H, CH 2 ), 1.93 (s, 3H, CH 3 ), 2.07 (s, 3H, CH 3 ), 2.58 (q, 7.52, 2H, benz.-CH 2 ), 2.63 (t, 7.91, 2H, benz.-CH 2 ), 2.78 (t, 7.23 Hz, 2H, C H 2 CH 2 OSi), 3.79 (t, 7.26 Hz, 2H, CH 2 OSi), 5.62 (s, 1H, olefin.-H), 5.77 (s, 1H, olefin.-H), 6.18 (s, 1H, olefin.-H), 6.37 (s, 1H, olefin.-H), 7.12 (s, 1H, arom.-H), 7.16 (d, 7.86 Hz, 1H, arom.-H), 7.18 (s, 1H, arom.-H), 7.19, (s, 4H, arom.-H), 7.24 (dd, (überlagert mit CHCl 3 , 1H, arom.-H), 7.32, (d, 1.39 Hz, 1H, arom.-H). 8) Synthese von 2-Methyl-acrylic acid 2'-ethyl-4"-(2-hydroxy-ethyl)-6"-(2-methyl-acryloyloxy)-4-pentyl-[1,1',4',1"]terphenyl-3"-yl ester 2

[0157]

[0158] 2.20 g (3.36 mmol) von Verbindung G2The mixture is dissolved in 50 ml of THF and cooled to 2 °C. 2.00 ml (4.00 mmol) of hydrochloric acid (2N) is then added slowly, dropwise, and stirred for 3 hours until it reaches room temperature (RT). The mixture is then neutralized with sodium bicarbonate solution while cooling, and treated with water and MTB ether. The phases are separated, and the aqueous phase is further extracted with MTB ether. The combined organic phases are washed with water, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product is obtained as a yellow oil, which is filtered over 200 g of silica gel with dichloromethane / MTB ether (98:2). The resulting product (colorless oil) is concentrated under vacuum and then dried at 60 °C and 0.09 mbar until no more solvent evaporates. The product (700 mg) is obtained as a colorless, viscous resin. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.92 (t, 6.63Hz, 3H, CH 3 ), 1.08 (t, 7.54Hz, 3H, CH 3 ), 1.37 (m c , 4H, CH 2 ), 1.67 (m c , 3H, CH 2 , OH), 1.94 (s, 3H, CH 3 ), 2.09 (s, 3H, CH 3 ), 2.60 (q, 7.53 Hz, 2H, benz.-CH 2 ), 2.70 (t, 7.9 Hz, 2H, benz.-H), 2.85, (t, 6.4 Hz, 2H, CH 2 C H 2 OH), 3.87 (q., 6.24 Hz, 2H, C H 2 OH), 5.66 (s, 1H, olefin.-H), 5.79 (s, 1H, olefin.-H), 6.21 (s, 1H, olefin.-H), 6.39 (s, 1H, olefin.-H), 7.17 (s, 1H, arom.-H), 7.19 (d, 7.87 Hz, 1 H, arom.-H), 7.21, 7.22 (2 x S (überlagert) 5H, arom.-H), 7.26 (dd (überlagert mit CHCl 3 ), 1H, arom.-H), 7.33 (d, 1.59 Hz, 1H, arom.-H). Example 3 Synthese von 2-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-[4-hydroxy-3-(hydroxymethyl)butoxy]phenyl}ethyl 2-methylprop-2-enoate 4

[0159] 1) Synthese von 4'-Bromo-2'-ethyl-biphenyl-4-ol A

[0160]

[0161] 110.3 g (1.04 mol) Na 2 CO 3 are mixed with 223 ml of water and 154 g (0.49 mol) of 4-bromo-2-ethyl-1-iodobenzene, 75.1 g (0.54 mol) of 4-hydroxyphenolboronic acid and 850 ml of 1,4-dioxane are added and the mixture is degassed. The mixture is treated with 14.5 g (19.8 mmol) of bis(1,1-diphenylphosphinoferocene) palladium(II) chloride and stirred at 80°C for 18 h. After complete reaction (checked by thin-layer chromatography with heptane / ethyl acetate 1:1), the reaction mixture is cooled to room temperature, diluted with water and methyl tert-butyl ether, and acidified to pH 1–2 with 2 N HCl. The phases are separated, the aqueous phase is extracted with methyl tert-butyl ether, and the combined organic phases are dried over Na₂SO₄, filtered, and concentrated under vacuum. The resulting crude product is fried with heptane / ethyl acetate (8:2) over silica gel, yielding 96 g of the product. A as a brown oil. 2) Synthesis of 2'-Ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-ol B

[0162]

[0163] 102 g (514 mmol) of 4-pentyl-1-benzeneboronic acid and 135 g (467 mmol) of bromide A The compounds are dissolved and degassed in a mixture of 743 ml toluene, 270 ml ethanol, and 350 ml 2 N Na₂CO₂. 8.1 g (7.0 mmol) of tetrakis(triphenylphosphine)palladium are added, and the mixture is refluxed for 18 h. After complete reaction, the mixture is cooled to room temperature, the aqueous phase is removed, the organic phase is washed with methyl tert-butyl ether (MTB ether), and the combined organic phases are dried over Na₂SO₄, filtered, and concentrated under vacuum. The crude product is fried with dichloromethane over silica gel, and the product fractions are recrystallized from heptane, yielding 76.9 g of the product as colorless crystals. 1< H NMR (500 MHz, DMSO-d6) δ = 0.89 ppm (t, 6.88 Hz, 3H, CH 3 ), 1.08 (t, 7.51 Hz, 3H, CH 3 ), 1.31 (m c , 4H, CH 2 ), 1.61 (q, 7.58 Hz, 2H, CH 2 ), 2.62 (q. überlagert mit t, 4H, CH 2 benzylisch), 6.83 (d, 8.5 Hz, 2H, arom-H), 7.13 (d, 8.5 Hz, 2H, arom-H), 7.17 (d, 7.9 Hz, 1H, arom-H), 7.28 (d, 8.2 Hz, 2H, arom-H), 7.46 (dd, 7.93, 1.97 Hz, 1H, arom.-H), 7.54 (d, 1.88 Hz, 1H, arom.-H), 7.59 (d, 8.17 Hz, 2H, arom.-H), 9.44 (s, 1H, arom.-OH). 3) Synthese von 3-Bromo-2'-ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-ol C

[0164] 30.0 g (85.9 mmol) Alkohol BThe mixture is dissolved in 1100 ml of dichloromethane and cooled to -48°C. At this temperature, 5.28 ml (103 mmol) of bromine in 1100 ml of dichloromethane is slowly added over 40 minutes. The mixture is stirred at this temperature for 1 hour and monitored by thin-layer chromatography (using toluene). The excess bromine is reduced with saturated NaHSO₃ solution, and the phases are separated. The aqueous phase is extracted with dichloromethane, and the combined organic phases are dried over Na₂SO₄ and concentrated under vacuum. The crude product is fried with toluene over silica gel, yielding 35.3 g of the product as a white solid. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.91 ppm (t, 6.99 Hz, 3H, CH 3 ), 1.15 (t, 7.53 Hz, 3H, CH 3 ), 1.36 (m c , 4H, CH 2 ), 1.66 (m c , 2H, CH 2 ), 2.65 (m c , 4H, CH 2 benzylisch), 5.5 (s, 1H, arom-OH), 7.06 (d, 8.3 Hz, 1H, arom-H), 7.20 (dd, 8.28, 2.07 Hz überlagert mit d 7.85 Hz, 2H, arom-H), 7.26 (d, 8.1 Hz, 2H, arom-H), 7.43 (dd, 7.87, 1.87 Hz, 2H, arom-H), 7.46 (d, 2.01 Hz, 1H, arom.-H), 7.503 (d, 1.71 Hz, 1H, arom.-H), 7.54 (d, 8.1 Hz, 2H, arom.-H. 4) Synthese von 6-(2-{2-bromo-4-[2-ethyl-4-(4-pentylphenyl)phenyl]-phenoxy}ethyl)-2,2,3,3,9,9,10,10-octamethyl-4,8-dioxa-3,9-disilaundecane D

[0165]

[0166] 10.0 g (24.0 mmol) Bromid C, 8.64 g (25.0 mmol) 4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]-methyl}butan-1-ol K7.03 g (26.81 mmol) of triphenylphosphine are dissolved in 76.5 ml of tetrahydrofuran (THF). The reaction solution is then treated dropwise with 5.46 ml (27.9 mmol) of diisopropyl azodicarboxylate at room temperature (RT). The resulting clear, slightly yellow reaction solution is stirred at RT for 20 h. The reaction mixture is then concentrated under vacuum and filtered through silica gel with heptane / dichloromethane. 17.45 g of the desired product are obtained. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 12H Si(CH 3 ) 2 ), 0.854 (mc , 21H, 2 4H), 1.61 (mc , 2H, CH 2 ), 1.83 (q, 6.58 Hz, 2H, CH 2 -benz.), 1.91 (sept., 5.64 Hz, 1H, CH 2 C H 1 (CH 2 OTBDMS) 2 ), 2.59 (mc , 4H, 2X CH 2 ), 3.62 (mc , 4H, CH 2 OTBDMS), 4.12 (t, 6.49 Hz, OCH 2 ), 6.87 (d, 8.43 Hz, 1H, arom.-H), 7.15 (dd (superimposed) , 7.83, 2.54 Hz,1H, arom.-H), 7.16 (d, 7.83 Hz, 1H, arom.-H), 7.21 (d, 7.25 Hz, 2H, arom.-H), 7.37 (dd, 7.86, 1.84 Hz, 1H, arom.-H), 7.44 (d, 1.68 Hz, 1H, arom.-H), 7.47 (d (superimposed) , 1.90 Hz, 1H, arom.-H), 7.49 (d (superimposed) , 8.22 Hz, 2H, arom.-H). 5) Synthesis of 2-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butoxy}-5-[2-ethyl-4-(4-pentylphenyl)-phenyl]phenyl)ethanol E

[0167]

[0168] 17.5 g (23.0 mmol) bromide DThe mixture is dissolved in 65.0 ml of tetrahydrofuran (THF) and cooled to -70°C. At this temperature, 17.1 ml (27.0 mmol) of butyllithium (1.6 M solution in hexane) is added dropwise. A solution of 8.70 ml (25.0 mmol) of ethylene oxide in 10.0 ml of cooled (-25°C) THF is then rapidly added. The reaction mixture is stirred for 45 minutes at -70°C and then carefully treated dropwise with a -25°C solution of 3.45 ml (27.0 mmol) of boron trifluoride in THF. The reaction mixture is then stirred at -70°C for 3 h, diluted with 20 ml of MTB ether, and allowed to reach room temperature within 2 h. It is then carefully poured onto ice water and extracted with MTB ether. The combined organic compounds... Phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated. The resulting crude product is filtered over silica gel with heptane / ethyl acetate (9:1 then 4:1), and the product fractions are concentrated under vacuum. Seven fractions are obtained.5 g of the product with a purity of 99.4% according to HPLC. 6) Synthesis of 2-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butoxy}-5-[2-ethyl-4-(4-pentylphenyl)-phenyl]phenyl)ethyl 2-methylprop-2-enoate F

[0169]

[0170] 17.2 g (24.0 mmol) alcohol E, 4.50 ml (53.1 mmol) of stabilized methacrylic acid and 0.33 g (2.71 mmol) of 4-(dimethylamino)pyridine are dissolved in 150 ml of dichloromethane (DCM) at room temperature and cooled to 2°C. 9.20 ml (53.3 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide solution in 50 ml of dichloromethane at 2-5°C is then added dropwise and stirred at room temperature for 20 h. The reaction solution is then filtered directly with DCM over silica gel, yielding 15.5 g of the product with 99.6% purity (HPLC). 7) Synthese von 2-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-[4-hydroxy-3-(hydroxymethyl)butoxy]phenyl}ethyl 2-methylprop-2-enoate G

[0171]

[0172] 15.5 g (19.6 mmol) von Ester FThe mixture is dissolved in 225 ml of tetrahydrofuran (THF) and cooled to 2°C. 23.5 ml (47.0 mmol) of HCl (2 mol / l) is then slowly added dropwise. The mixture is stirred for 3 h at room temperature, and the reaction mixture is carefully neutralized with saturated sodium bicarbonate solution. The reaction product is extracted with MTB ether, and the combined organic phases are washed with water, dried over sodium sulfate, filtered, and concentrated under vacuum at 30°C. The crude product is filtered over silica gel with heptane / ethyl acetate (2:1, 1:1, and finally 1:2), and the product fractions are concentrated under vacuum at 30°C. 10.9 g of a colorless solid is obtained, which is dissolved under reflux in 200 ml of pentane and 105 ml of MTB ether and subsequently crystallized with acetone / dry ice. After drying in a vacuum at room temperature, 9.0 g of the desired product is obtained as a colorless solid with 99.8% purity (HPLC). Phase behavior

[0173] Tg=-18°C / K (Schmelzpunk) =72°C / l (Isotrop) 1< H NMR (500 MHz, CDCl 3 ) δ = 0.95 ppm (t, 6.9 Hz, 3H, CH 3 ), 1.17 (t, 7.56 Hz, 3H, CH3), 1.39 (m c , 4H), 1.70 (quin. 7.33 Hz, 2H, CH 2 ), 1.92 (q, 6.35 Hz, 2H, CH 2 benz.), 1.95 (s, 3H, CH 3 ), 2.17 (m c , 1H,), 2.48 (s (breit) , 2H, 2 X OH), 2.68 (m c , 4H), 3.08 (t, 7.25 Hz, 2H), 3.82 (dd, 10.69 ,6.84 Hz 2H CH 2 HOC H a2 CH), 3.93 (dd, 10.77,3.99 Hz, 2H, HOC H b2 CH), 4.15 (t, 5.95 Hz, 2H, CH 2 ), 4.44 (t, 7.26 Hz, 2H, CH 2 ), 5.57 (s, 1H,), 6.11 (s, 1H), 6.93 (d, 8.27 Hz, 1H, arom-H), 7.19 (d, 2.05 Hz, 1H, arom-H), 7.21 (dd, 8.23, 2.28 Hz, 1H, arom.-H), 7.29 (d, 7.98 Hz, 2H, arom.-H) 7.45, (dd, 8.07, 2.02 Hz, 1H, arom.-H), 7.53 (d, 1.68 Hz, 1H, arom.-H), 7.58 (8.09 Hz, 2H, arom.-H). 8) Synthese von 1,3-diethyl 2-[2-(benzyloxy)ethyl]propanedioate H

[0174]

[0175] 240.0 ml (0.628 mol) of sodium methylate (20% solution in ethanol) are placed in 300 ml of ethanol and heated to 81°C. 180.0 ml (1.180 mol) of diethyl malonate is then rapidly added within 10 minutes, followed immediately by 100.0 g (0.451 mol) of 2-bromoethoxymethylbenzene within 15 minutes. The reaction mixture is stirred under reflux for 4 h, then cooled to room temperature and poured onto a mixture of ice water and MTB ether. The pH is carefully adjusted to 4–5 with 25% hydrochloric acid, and the organic phase is separated. The aqueous phase is extracted several times with MTB ether. The combined organic phases are washed with water, dried over sodium sulfate, filtered, and concentrated. 223.6 g of an orange liquid are obtained, from which the excess diethyl malonate is separated by distillation at a bath temperature of 100–150°C (head temperature 70–77°C) and a vacuum of 5 mbar. The resulting crude product (133 g) is then removed.2 g of orange liquid) is filtered with dichloromethane / MTB ether (8:2) over 2L silica gel and the product is obtained as a yellow liquid. 9) Synthesis of 2-[2-(benzyloxy)ethyl]propane-1,3-diol I

[0176]

[0177] 170.0 ml (340 mmol) of lithium aluminum hydride solution (2 molar in THF) are placed and, while cooling (to a maximum reaction temperature of 50°C), are mixed with a solution of 66.5 g (225.9 mmol) of ester. HThe mixture was dissolved in 350.0 ml of tetrahydrofuran (THF). The reaction mixture was then stirred for 5 h at 66°C. The mixture was cooled to room temperature (RT) and carefully treated dropwise with 100 ml of ethyl acetate. It was then carefully treated with 20 ml of water and with a hot solution of 27.8 ml (377.4 mmol) of sodium carbonate decahydrate (Emprove®) in 30 ml of water and stirred for 15 min. The colorless precipitate was filtered off and washed generously with THF. The filtrate was concentrated to obtain 45.4 g of the product as a colorless, slightly cloudy oil, which was filtered through 1.2 liters of silica gel with ethyl acetate (EE) and EE / methanol (95:5 and 9:1). The product fractions were concentrated to obtain 23.8 g of the product as a colorless oil. 1< H NMR (500 MHz, CDCl 3 ) δ = 1.74 ppm (q, 6.38 Hz, 2H CH 2 C H 2 CH 1 ), 1.91 (Sept., 5.17 Hz, 1H, CH 2 C H 1 (CH 2 OTBDMS) 2 ), 2.46 (s (broad) , 1H, 2 X OH), 3.61 (t, 5.77 Hz, 2H, CH 2 OCH 2 CH 2 ), 3.72 (dd, 10.9, 5.86 Hz, 2H,3.76 CH 1 C H 2 OTBDMS), (dd, 4.71,10.9 Hz, 2H, CH 1 C H 2 OTBDMS), 4.55 (s, 2H, CH 2 -benzyl.), 7.41-7.30 (m, 5H, arom.-H). 10) Synthese von 6-[2-(benzyloxy)ethyl]-2,2,3,3,9,9,10,10- octamethyl-4,8-dioxa-3,9-disilaundecane J

[0178]

[0179] 53.7 g (255.39 mmol) Diol I3.0 g (24.56 mmol) of 4-(dimethylamino)pyridine are dissolved in 600 ml of dichloromethane and cooled to 5°C. 110.0 ml (0.79 mmol) of triethylamine are added, followed by the addition of a solution of 100.0 g (0.66 mol) of tert-butyldimethylchlorosilane in 400 ml of dichloromethane (DCM) at 2-7°C, and the mixture is stirred at room temperature for 20 h. The precipitated ammonium salts are removed by filtration, washed with DCM, and the organic phase is washed with saturated sodium chloride solution and water, dried over sodium sulfate, filtered, and concentrated. The crude product (130.1 g) is obtained as an orange oil, which is filtered with toluene over 2 l of silica gel. After concentration of the product fractions, 113.2 g of the product is obtained as a light yellow oil. 11) Synthesis of 4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butan-1-ol

[0180]

[0181] 60.0 g (110.8 mmol) JThe compounds were dissolved in 600 ml of ethyl acetate and treated with 30.0 g of Pd-C (basic, 50% water) and debenzylated under a hydrogen atmosphere (1 bar, 50°C) for 24 h. The reaction mixture (50% product) was filtered off and debenzylated again with 15.0 g of Pd-C (basic, 50% water) under a hydrogen atmosphere (1 bar, 50°C) for a further 40 h. The reaction mixture was filtered and concentrated at room temperature. The crude product (50.0 g) was obtained as a colorless oil, which was filtered over 1 l of silica gel with pentane / MTB ether (9:1 to 7:3). 41.6 g of the product were obtained as a colorless oil. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (2, 12H, 2 X Si(CH 3 ) 2 ), 0.83 (s, 18H, 2 H 2 CH 1 ), 1.74 (Sept. 6.08 Hz, 1H, CH 2 C H 1 (CH 2 OTBDMS) 2 ), 3.16 (s (broad) , 1H, OH), 3.47 (dd,10.02, 6.26 Hz, 2H, CH 1 C H 2 OTBDMS), 3.57 (dd, 10.02, 5.72, 2H, CH 1 C H 2 OTBDMS), 3.62 (q (wide) , 5.37 Hz, 2H C H 2 OH). Example 4 Synthese von 3-{5-[2-Ethyl-4-(4-pentylphenyl)phenyl]-2-(3-hydroxy-propoxy)-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl}propyl 2-methylprop-2-enoat 13

[0182] 1) Synthese von 2,6-dibromo-4-[2-ethyl-4-(4-entylphenyl)phenyl]phenol A13

[0183]

[0184] 20.6 g (59.80 mmol) 2'-Ethyl-4"-pentyl-[1,1';4',1"]terphenyl-4-ol BThe components are placed in 150 ml of dichloromethane (DCM) and 1.50 ml (10.67 mmol) of diisopropylamine is added dropwise. The reaction solution is cooled to -5°C using a dry ice / acetone bath and then a solution of 21.6 g (121.4 mmol) of N-bromosuccinimide in 300 ml of DCM is added dropwise. The reaction solution is stirred at room temperature (RT) for 18 h, acidified with 2 M HCl, diluted with water, and the phases are separated. The aqueous phase is extracted with DCM, dried over sodium sulfate, filtered, and concentrated under vacuum. The crude product is filtered over 600 g of silica gel with toluene / heptane (1:1 + 1% triethylamine). The product fractions are combined and, after concentration, recrystallized from heptane at -30°C. The product is obtained as a viscous oil with a yield of 15.1 g and 99.1% purity (gas chromatography). 2) Synthesis of tert-butyl(2,6-dibromo-4-[2-ethyl-4-(4-pentylphenyl)phenyl]phenoxy)dimethylsilane B13

[0185]

[0186] 10.6 g (20.32 mmol) bromide A13 The mixture is placed in 150 ml of dichloromethane (DCM) and treated with 2.90 g (42.6 mmol) of imidazole, then stirred for 30 min at room temperature (RT). A solution of 4.00 g (26.54 mmol) of tert-butyldimethylchlorosilane in 20 ml of DCM is then added dropwise, and the mixture is stirred at RT for a further 18 h. The reaction mixture is concentrated under vacuum and dissolved in ethyl acetate (EE), water is added, and the phases are separated after stirring. The aqueous phase is extracted with EE, and the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, and concentrated under vacuum. The resulting crude product is filtered with heptane over 400 ml of silica gel, and the product fractions are combined and concentrated under vacuum. 6.6 g of the product are obtained as a colorless oil. MS (EI): 616.3 [M +< ] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.38 ppm (s, 6 H, Si(CH 3 ) 2 ), 0.88 (t, 6.6 Hz, 3H, CH 3 ), 1.06 (s, 9 H, Si(C(CH 3 ) 3 )), 1.13 (t, 8.06 Hz, 3H, CH 3 ), 1.38-1.27 (m, 4H, CH 2 ), 1.63 (quin., 7.7 Hz, 2H, CH 2 ), 2.66 - 2.59 (m, 4H, CH 2 ), 7.17 (d, 7.15 Hz, 1H, arom.-H), 7.23 (d, 7.62 Hz, 2H, arom.-H), 7.39 (dd, 7.86, 1.89 Hz, 1H, arom.-H), 7.44 (s, 2H, arom.-H), 7.462 (d, 1.75 Hz, 1H, arom.-H), 7.50 (d, 8.13 Hz, 2H, arom.-H). 3) Synthesis of 4-[2-ethyl-4-(4-pentylphenyl)phenyl]-2,6-bis(3-hydroxypropyl)phenol C13

[0187]

[0188] 2.90 g (27.4 mmol) sodium carbonate, 100.0 mg (0.56 mmol) palladium (II) chloride, 180.0 mg (0.39 mmol) 2-dicyclohexylphosphino-2',6'-di-isopropoxy-1,1'-biphenyl are placed in 30 ml of water and treated with a solution of 15.6 g (25.9 mmol) bromide B134.10 g (28.9 mmol) of 2-butoxy-1,2-oxaborolane are added to 135 ml of tetrahydrofuran (THF). 120 µL (0.87 mmol) of triethylamine is added, the mixture is degassed with nitrogen for 20 minutes, and then stirred under reflux for 18 hours. The reaction mixture is cooled to room temperature and treated with water and MTB ether. After stirring the reaction solution, the phases are separated, the aqueous phase is extracted with MTB ether, and the combined organic phases are washed with saturated sodium chloride solution, dried with sodium sulfate, filtered, and concentrated under vacuum. The crude product is filtered with toluene / ethyl acetate (1:1) through 350 ml of silica gel, and the product fractions are combined and concentrated under vacuum. 1< H NMR (500 MHz, DMSO-d6) δ = 0.89 ppm (t, 7.08 Hz, 3H, CH 3 ), 1.05 (t, 7.92 Hz, 3H, CH 3 ), 1.33 (m c , 4H, CH 2 ), 1.62 (quint, 7.29 Hz, 2H, CH 2 ), 1.73 (quint, 6.73 Hz, 2H, CH 2 ), 2.69 - 2.58 (m, 8H, benzyl-CH 2 ), 3.45 (q, 6.42 Hz, 4H, CH 2 ), 4.52 (t, 5.04 Hz, 2H, OH), 6.89 (s, 2H, arom.-H), 7.2 (d, 7.9 Hz, 1H, arom.-H), 7.29 (d, 8.98 Hz, 2H, arom.-H), 7.46 (dd, 7.92, 1.90 Hz, 1H, arom.-H), 7.54 (d, 1.78 Hz, 1H, arom.-H), 7.59 (d, 8.12 Hz, 2H, arom.-H), 8.25 (s, 1H, arom.-OH). 4) Synthese von 3-(2-{3-[(tert-butyldimethylsilyl)oxy]propoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]-3-(3-hydroxypropyl)phenyl)propan-1-ol D13

[0189]

[0190] 2.9 g (6.0 mmol) tris-Alkohol C13,2.40 g (9.0 mmol) of (3-bromopropoxy)-(tert-butyl)dimethylsilane and 1.70 g (12.3 mmol) of potassium carbonate are added to 20 ml of N,N-dimethylformamide and stirred at 80°C for 6 h. The reaction mixture is cooled to room temperature, treated with water and MTB ether, and the phases are separated after stirring. The aqueous phase is extracted with MTB ether, and the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and concentrated under vacuum. The resulting crude product is filtered with toluene / ethyl acetate (4:1) over 50 ml of silica gel, and the product fractions are combined and concentrated under vacuum. 1< H NMR (500 MHz, CDCl 3 ) δ = 0.00 ppm (s, 6H, Si(CH 3 ) 2 ), 0.81 (s, 9H, Si(C(CH 3 ) 3 )), 1.03 (t, 6.6 Hz, 3H, CH 3 ), 1.30 - 1.19 (m, 4H, CH 2 ), 1.58 - 1.49 (m, 2H, CH 2 ), 1.67 (quint., 5.5 Hz, 4H, CH 2 ), 1.88 (quint., 6.23 Hz, 2H, CH 2 ), 2.61 - 2.50 (m, 8H, CH 2 ), 3.37 (q, 6.41 Hz, 4H, CH 2 ), 3.76 (t, 6.2 Hz, 2H, CH 2 ), 3.79 (t, 5.69 Hz, 2H, CH 2 ), 4.33 (t, 5.5 Hz, 2H, OH), 6.92 (s, 2H, arom.-H), 7.14 (d, 7.89 Hz, 1H, arom.-H), 7.21 (d, 8.26 Hz, 2H, arom.-H), 7.39 (dd, 7.93, 1.76 Hz, 1H, arom.-H), 7.48 (d, 1.64 Hz, 1H, arom.-H), 7.52 (d, 8.08 Hz, 2H, arom.-H). 5) Synthese von 3-(2-{3-[(tert-butyldimethylsilyl)oxy]propoxy}-5-[2-ethyl-4-(4-pentylphenyl)phenyl]-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl)propyl 2-methylprop-2-enoat E13

[0191]

[0192] 2.5 g (4.0 mmol) bis-Alkohol D13,1.40 ml (16.5 mmol) of methacrylic acid (stabilized with hydroquinone monomethyl ether) and 55.0 mg (0.45 mmol) of 4-(dimethylamino)pyridine are dissolved in 25 ml of dichloromethane (DCM) and cooled to 2°C. A solution of 2.48 ml (16.52 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide in 25 ml of DCM is then added dropwise at 2-5°C and stirred for a further 18 h. The reaction mixture is filtered directly over 100 ml of silica gel containing DCM, and the product fractions are combined. The resulting crude product is filtered under basic conditions with DCM / heptane (4:1) over 200 ml of silica gel and 20 ml of Alox, and the product fractions are concentrated under vacuum. 6) Synthesis of 3-{5-[2-ethyl-4-(4-pentylphenyl)phenyl]-2-(3-hydroxypropoxy)-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl}propyl 2-methylprop-2-enoate 13

[0193]

[0194] 3.1 g (4.0 mmol) Ester E13The mixture is placed in 40 ml of tetrahydrofuran (THF) and cooled to 2°C. 2.40 ml (4.80 mmol) of hydrochloric acid (2 N) is then slowly added, and the mixture is stirred for 4 h at room temperature (RT). After complete reaction, the mixture is carefully neutralized with sodium bicarbonate, treated with MTB ether, and stirred. The organic phase is separated, the aqueous phase is extracted with MTB ether, the organic phases are combined, washed with water, dried over sodium sulfate, filtered, and concentrated under vacuum at a maximum of 30°C. The resulting crude product (viscous oil) is filtered with heptane / ethyl acetate (2:1) over 150 ml of silica gel, and the product fractions are concentrated under vacuum at a maximum of 30°C. The resulting product (highly viscous oil) is dried at room temperature under oil pump vacuum (10⁻² < mbar) for 72 h.

[0195] Melting point: highly viscous oil at room temperature. Tg (glass point) -39°C MS (EI): 654.5 [M +< ] 1< H NMR (500 MHz, CDCl 3 ) δ = 0.94 ppm (t, 7.02 Hz, 3H, CH 3 ), 1.18 (t, 7.56 Hz, 3H, CH 3 ), 1.44 - 1.36 (m, 4H, CH 2 ), 1.57 (s (wide) , 1H, OH), 1.69 (quint., 8.25 Hz, 2H, CH 2 ), 1.98 (s, 6H, CH 3 ), 2.14-2.04 (m, 6H, CH 2 ), 2.67 (q, 7.49 Hz, 4H, CH 2 ), 2.81 (t, 7.72 Hz, 4H, CH 2 ), 3.97 (t (wide) , 5.77 Hz, 2H, CH 2 ), 4.03 (t, 5.94 Hz, 2H, CH 2 ), 4.26 (t, 6.47 Hz, 4H, CH 2 ), 5.58 (t, 1.58 Hz, 1H), 6.13 (s, 1H), 7.06 (s, 2H, arom.-H), 7.26 (d, 7.87 Hz, 1H, arom.-H), 7.29 (d, 2H, arom.-H), 7.46 (dd, 7.87, 1.9 Hz, 1H, arom.-H), 7.53 (d, 1.78 Hz, 1H, arom.-H), 7.57 (d, 8.12 Hz, 2H, arom.-H). Examples 5 to 165

[0196] Analogous to examples 1 to 3, as well as schemes 1 to 3, the following connections are made. Example structure 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112. 113. 114. 115. 116. 117. 118. 119. 120. 121. 122. 123. 124. 125. 126. 127. 128. 129. 130. 131. 132. 133. 134. 135. 136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153. 154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. B) Mixture examples

[0197] For the production of FK media according to the invention, the following liquid crystalline mixtures consisting of low molecular weight components in the specified percentage weight proportions are used. H1: Nematic host mixing (Δε < 0)

[0198] CY-3-O2 15.50 % Clearing point [°C]: 75.1 CCY-3-O3 8.00 % Δn [589 nm, 20°C]: 0.098 CCY-4-O2 10.00 % Δε [1 kHz, 20°C]: -3.0 CPY-2-O2 5.50 % ε ∥ [1 kHz, 20°C]: 3.4 CPY-3-O2 11.50 % ε ⊥ [1 kHz, 20°C]: 6.4 CCH-34 9.25 % K 1 [pN, 20°C]: 13.1 CCH-23 24.50 % K 3 [pN, 20°C]: 13.3 PYP-2-3 8.75 % γ 1 [mPa·s, 20°C]: 113 PCH-301 7.00 % V 0 [20°C, V]: 2.22 H2: Nematic host mixing (Δε < 0)

[0199] CY-3-O4 14.00 % Clearing point [°C]: 80.0 CCY-3-O2 9.00 % Δn [589 nm, 20°C]: 0.090 CCY-3-O3 9.00 % Δε [1 kHz, 20°C]: -3.3 CPY-2-O2 10.00 % ε ∥ [1 kHz, 20°C]: 3.4 CPY-3-O2 10.00 % ε ⊥ [1 kHz, 20°C]: 6.7 CCY-3-1 8.00 % K 1 [pN, 20°C]: 15.1 CCH-34 9.00 % K 3 [pN, 20°C]: 14.6 CCH-35 6.00 % γ 1 [mPa·s, 20°C]: 140 PCH-53 10.00 % V 0 [20°C, V]: 2.23 CCH-301 6.00 % CCH-303 9.00 % H3: Nematic host mixing (Δε < 0)

[0200] CC-3-V1 9.00 % Clearing point [°C]: 74.7 CCH-23 18.00 % Δn [589 nm, 20°C]: 0.098 CCH-34 3.00 % Δε [1 kHz, 20°C]: -3.4 CCH-35 7.00 % ε ∥ [1 kHz, 20°C]: 3.5 CCP-3-1 5.50 % ε ⊥ [1 kHz, 20°C]: 6.9 CCY-3-O2 11.50 % K 1 [pN, 20°C]: 14.9 CPY-2-O2 8.00 % K 3 [pN, 20°C]: 15.9 CPY-3-O2 11.00 % γ 1 [mPa·s, 20°C]: 108 CY-3-O2 15.50 % V 0 [20°C, V]: 2.28 PY-3-O2 11.50 % H4: Nematic host mixing (Δε < 0)

[0201] CC-3-V 37.50 % Clearing point [°C]: 74.8 CC-3-V1 2.00 % Δn [589 nm, 20°C]: 0.099 CCY-4-O2 14.50 % Δε [1 kHz, 20°C]: -2.9 CPY-2-O2 10.50 % ε ∥ [1 kHz, 20°C]: 3.7 CPY-3-O2 9.50 % ε ⊥ [1 kHz, 20°C]: 6.6 CY-3-O2 15.00 % K 1 [pN, 20°C]: 12.2 CY-3-O4 4.50 % K 3 [pN, 20°C]: 13.4 PYP-2-4 5.50 % γ 1 [mPa·s, 20°C]: 92 PPGU-3-F 1.00 % V 0 [20°C, V]: 2.28 H5: Nematic host mixing (Δε < 0)

[0202] CCH-23 20.00 % Clearing point [°C]: 74.8 CCH-301 6.00 % Δn [589 nm, 20°C]: 0.105 CCH-34 6.00 % Δε [1 kHz, 20°C]: -3.2 CCP-3-1 3.00 % ε ∥ [1 kHz, 20°C]: 3.5 CCY-3-O2 11.00 % ε ⊥ [1 kHz, 20°C]: 6.8 CPY-2-O2 12.00 % K 1 [pN, 20°C]: 12.7 CPY-3-O2 11.00 % K 3 [pN, 20°C]: 13.6 CY-3-O2 14.00 % γ 1 [mPa·s, 20°C]: 120 CY-3-O4 4.00 % V 0 [20°C, V]: 2.16 PCH-301 4.00 % PYP-2-3 9.00 % H6: Nematic host mixing (Δε < 0)

[0203] CC-4-V 17.00 % Clearing point [°C]: 106.1 CCP-V-1 15.00 % Δn [589 nm, 20°C]: 0.120 CCPC-33 2.50 % Δε [1 kHz, 20°C]: -3.6 CCY-3-O2 4.00 % ε ∥ [1 kHz, 20°C]: 3.5 CCY-3-O3 5.00 % ε ⊥ [1 kHz, 20°C]: 7.0 CCY-4-O2 5.00 % K 1 [pN, 20°C]: 16.8 CLY-3-O2 3.50 % K 3 [pN, 20°C]: 17.3 CLY-3-O3 2.00 % γ 1 [mPa·s, 20°C]: 207 CPY-2-O2 8.00 % V 0 [20°C, V]: 2.33 CPY-3-O2 10.00 % CY-3-O4 17.00 % PYP-2-3 11.00 % H7: Nematic host mixing (Δε < 0)

[0204] CY-3-O2 15.00 % Clearing point [°C]: 75.5 CCY-4-O2 9.50 % Δn [589 nm, 20°C]: 0.108 CCY-5-O2 5.00 % Δε [1 kHz, 20°C]: -3.0 CPY-2-O2 9.00 % ε ∥ [1 kHz, 20°C]: 3.5 CPY-3-O2 9.00 % ε ⊥ [1 kHz, 20°C]: 6.5 CCH-34 9.00 % K 1 [pN, 20°C]: 12.9 CCH-23 22.00 % K 3 [pN, 20°C]: 13.0 PYP-2-3 7.00 % γ 1 [mPa·s, 20°C]: 115 PYP-2-4 7.50 % V 0 [20°C, V]: 2.20 PCH-301 7.00 % H8: Nematic host mixing (Δε < 0)

[0205] CY-3-O2 15.00 % Clearing point [°C]: 74.7 CY-5-O2 6.50 % Δn [589 nm, 20°C]: 0.108 CCY-3-O2 11.00 % Δε [1 kHz, 20°C]: -3.0 CPY-2-O2 5.50 % ε ∥ [1 kHz, 20°C]: 3.6 CPY-3-O2 10.50 % ε ⊥ [1 kHz, 20°C]: 6.6 CC-3-V 28.50 % K 1 [pN, 20°C]: 12.9 CC-3-V1 10.00 % K 3 [pN, 20°C]: 15.7 PYP-2-3 12.50 % γ 1 [mPa·s, 20°C]: 97 PPGU-3-F 0.50 % V 0 [20°C, V]: 2.42 H9: Nematic host mixing (Δε < 0)

[0206] CCH-35 9.50 % Clearing point [°C]: 79.1 CCH-501 5.00 % Δn [589 nm, 20°C]: 0.091 CCY-2-1 9.50 % Δε [1 kHz, 20°C]: -3.6 CCY-3-1 10.50 % ε ∥ [1 kHz, 20°C]: 3.5 CCY-3-O2 10.50 % ε ⊥ [1 kHz, 20°C]: 7.1 CCY-5-O2 9.50 % K 1 [pN, 20°C]: 14.6 CPY-2-O2 12.00 % K 3 [pN, 20°C]: 14.5 CY-3-O4 9.00 % γ 1 [mPa·s, 20°C]: 178 CY-5-O4 11.00 % V 0 [20°C, V]: 2.12 PCH-53 13.50 % H10: Nematic host mixing (Δε < 0)

[0207] BCH-32 4.00 % Clearing point [°C]: 74.8 CC-3-V1 8.00 % Δn [589 nm, 20°C]: 0.106 CCH-23 13.00 % Δε [1 kHz, 20°C]: -3.5 CCH-34 7.00 % ε ∥ [1 kHz, 20°C]: 3.6 CCH-35 7.00 % ε ⊥ [1 kHz, 20°C]: 7.1 CCY-3-O2 13.00 % K 1 [pN, 20°C]: 14.8 CPY-2-O2 7.00 % K 3 [pN, 20°C]: 15.8 CPY-3-O2 12.00 % γ 1 [mPa·s, 20°C]: 115 CY-3-O2 12.00 % V 0 [20°C, V]: 2.23 PCH-301 2.00 % PY-3-O2 15.00 % H11: Nematic host mixing (Δε < 0)

[0208] CY-3-O4 22.00 % Clearing point [°C]: 86.9 CY-5-O4 12.00 % Δn [589 nm, 20°C]: 0.111 CCY-3-O2 6.00 % Δε [1 kHz, 20°C]: -4.9 CCY-3-O3 6.00 % ε ∥ [1 kHz, 20°C]: 3.8 CCY-4-O2 6.00 % ε ⊥ [1 kHz, 20°C]: 8.7 CPY-2-O2 10.00 % K 1 [pN, 20°C]: 14.9 CPY-3-O2 10.00 % K 3 [pN, 20°C]: 15.9 PYP-2-3 7.00 % γ 1 [mPa·s, 20°C]: 222 CC-3-V1 7.00 % V 0 [20°C, V]: 1.91 CC-5-V 10.00 % CCPC-33 2.00 % CCPC-35 2.00 % H12: Nematic host mixing (Δε < 0)

[0209] CY-3-O4 12.00 % Clearing point [°C]: 86.0 CY-5-O2 10.00 % Δn [589 nm, 20°C]: 0.110 CY-5-O4 8.00 % Δε [1 kHz, 20°C]: -5.0 CCY-3-O2 8.00 % ε ∥ [1 kHz, 20°C]: 3.8 CCY-4-O2 7.00 % ε ⊥ [1 kHz, 20°C]: 8.8 CCY-5-O2 6.00 % K 1 [pN, 20°C]: 14.7 CCY-2-1 8.00 % K 3 [pN, 20°C]: 16.0 CCY-3-1 7.00 % γ 1 [mPa·s, 20°C]: 250 CPY-3-O2 9.00 % V 0 [20°C, V]: 1.90 CPY-3-O2 9.00 % BCH-32 6.00 % PCH-53 10.00 % H13: Nematic host mixing (Δε < 0)

[0210] CC-3-V1 10.25 % Clearing point [°C]: 74.7 CCH-23 18.50 % Δn [589 nm, 20°C]: 0.103 CCH-35 6.75 % Δε [1 kHz, 20°C]: -3.1 CCP-3-1 6.00 % ε ∥ [1 kHz, 20°C]: 3.4 CCY-3-1 2.50 % ε ⊥ [1 kHz, 20°C]: 6.4 CCY-3-O2 12.00 % K 1 [pN, 20°C]: 15.4 CPY-2-O2 6.00 % K 3 [pN, 20°C]: 16.8 CPY-3-O2 9.75 % γ 1 [mPa·s, 20°C]: 104 CY-3-O2 11.50 % V 0 [20°C, V]: 2.46 PP-1-2V1 3.75 % PY-3-O2 13.00 % H14: Nematic host mixing (Δε < 0)

[0211] CC-3-V 27.50 % Clearing point [°C]: 74.7 CC-3-V1 10.00 % Δn [589 nm, 20°C]: 0.104 CCH-35 8.00 % Δε [1 kHz, 20°C]: -3.0 CCY-3-O2 9.25 % ε ∥ [1 kHz, 20°C]: 3.4 CLY-3-O2 10.00 % ε ⊥ [1 kHz, 20°C]: 6.4 CPY-3-O2 11.75 % K 1 [pN, 20°C]: 15.3 PY-3-O2 14.00 % K 3 [pN, 20°C]: 16.2 PY-4-O2 9.00 % γ 1 [mPa·s, 20°C]: 88 PYP-2-4 0.50 % V 0 [20°C, V]: 2.44 H15: Nematic host mixing (Δε > 0)

[0212] CC-4-V 10.00 % Clearing point [°C]: 77.0 CC-5-V 13.50 % Δn [589 nm, 20°C]: 0.113 PGU-3-F 6.50 % Δε [1 kHz, 20°C]: 19.2 ACQU-2-F 10.00 % ε ∥ [1 kHz, 20°C]: 23.8 ACQU-3-F 12.00 % ε ⊥ [1 kHz, 20°C]: 4.6 PUQU-3-F 11.00 % K 1 [pN, 20°C]: 11.5 CCP-V-1 12.00 % K 3 [pN, 20°C]: 11.1 APUQU-2-F 6.00 % γ 1 [mPa·s, 20°C]: 122 APUQU-3-F 7.00 % V 0 [20°C, V]: 0.81 PGUQU-3-F 8.00 % CPGU-3-OT 4.00 % H16: Nematic host mixing (Δε > 0)

[0213] PGU-2-F 3.50 % Clearing point [°C]: 77.0 PGU-3-F 7.00 % Δn [589 nm, 20°C]: 0.105 CC-3-V1 15.00 % Δε [1 kHz, 20°C]: 7.2 CC-4-V 18.00 % ε ∥ [1 kHz, 20°C]: 10.3 CC-5-V 20.00 % ε ⊥ [1 kHz, 20°C]: 3.1 CCP-V-1 6.00 % K 1 [pN, 20°C]: 15.3 APPEAL-3-F 15.00 % K 3 [pN, 20°C]: 13.5 PUQ-3-F 5.50 % γ 1 [mPa·s, 20°C]: 63 PGP-2-4 3.00 % V 0 [20°C, V]: 1.53 BCH-32 7.00 % H17: Nematic host mixing (Δε > 0)

[0214] APPOINTMENT-2-F 6.00 % Clearing point [°C]: 74.0 APPEAL-3-F 12.00 % Δn [589 nm, 20°C]: 0.120 PUQ-3-F 18.00 % Δε [1 kHz, 20°C]: 17.4 CPGU-3-OT 9.00 % ε ∥ [1 kHz, 20°C]: 22.0 CCGU-3-F 3.00 % ε ⊥ [1 kHz, 20°C]: 4.5 BCH-3F.FF 14.00 % K 1 [pN, 20°C]: 10.1 CCQU-3-F 10.00 % K 3 [pN, 20°C]: 10.8 CC-3-V 25.00 % γ 1 [mPa·s, 20°C]: 111 PGP-2-2V 3.00 % V 0 [20°C, V]: 0.80 H18: Nematic host mixing (Δε > 0)

[0215] PUQ-3-F 15.00 % Clearing point [°C]: 74.3 APPOINTMENT-2-F 5.00 % Δn [589 nm, 20°C]: 0.120 APPEAL-3-F 12.00 % Δε [1 kHz, 20°C]: 14.9 CCQU-3-F 11.00 % ε ∥ [1 kHz, 20°C]: 19.1 CCQU-5-F 1.50 % ε ⊥ [1 kHz, 20°C]: 4.3 CPGU-3-OT 5.00 % K 1 [pN, 20°C]: 11.2 CCP-30CF3 4.50 % K 3 [pN, 20°C]: 10.8 CGU-3-F 10.00 % γ 1 [mPa·s, 20°C]: 98 PGP-2-3 1.50 % V 0 [20°C, V]: 0.91 PGP-2-2V 8.00 % CC-3-V 26.50 % H19: Nematic host mixing (Δε > 0)

[0216] CCQU-3-F 9.00 % Clearing point [°C]: 94.5 CCQU-5-F 9.00 % Δn [589 nm, 20°C]: 0.121 PUQ-3-F 16.00 % Δε [1 kHz, 20°C]: 20.4 APPOINTMENT-2-F 8.00 % ε ∥ [1 kHz, 20°C]: 24.7 APPEAL-3-F 9.00 % ε ⊥ [1 kHz, 20°C]: 4.3 PGUQU-3-F 8.00 % K 1 [pN, 20°C]: 12.1 CPGU-3-OT 7.00 % K 3 [pN, 20°C]: 13.9 CC-4-V 18.00 % γ 1 [mPa·s, 20°C]: 163 CC-5-V 5.00 % V 0 [20°C, V]: 0.81 CCP-V-1 6.00 % CCPC-33 3.00 % PPGU-3-F 2.00 % H20: Nematic host mixing (Δε > 0)

[0217] CC-3-V 28.50 % Clearing point [°C]: 85.6 CCP-V1 3.00 % Δn [589 nm, 20°C]: 0.121 CCPC-33 2.00 % Δε [1 kHz, 20°C]: 19.5 PGU-2-F 4.00 % ε ∥ [1 kHz, 20°C]: 23.8 CCQU-3-F 8.00 % ε ⊥ [1 kHz, 20°C]: 4.3 CCQU-5-F 6.00 % K 1 [pN, 20°C]: 11.6 CCGU-3-F 3.00 % K 3 [pN, 20°C]: 12.7 PUQU-2-F 2.00 % γ 1 [mPa·s, 20°C]: 126 PUQU-3-F 10.00 % V 0 [20°C, V]: 0.81 APUQU-2-F 6.00 % APUQU-3-F 9.00 % PGUQU-3-F 5.00 % PGUQU-4-F 5.00 % PGUQU-5-F 4.00 % CPGU-3-OT 4.00 % PPGU-3-F 0.50 %

[0218] The following polymerizable self-orienting additives are used: polymerizable Self-orientation additive Nr . structure Phase behavior (Tg: glass transition point, K: crystalline, I: isoptropic phase), transition temperatures in °C 1 2 3 4 T g -7 K 51 I 5 K 57 I 6 T g -16 K 86 I 7 8 T g -21 I 9 T g -26 I 10 T g -36 I 11 T g -3 I 12 K 40 I 13 T g -38 I 14 T g -26 K 54 I 15 T g -24 I 16 T g -21 I 17 T g -20 I 18 T g -14 I 19

[0219] The following polymerizable compound is used: Mixing example 1

[0220] To a nematic FK medium H1 of the VA type (Δε < 0) the polymerizable self-orientation additive 1 (2.0 wt.%) added and homogenized.

[0221] Use in test cells without a pre-alignment layer: The resulting mixture is filled into a test cell (without a polyimide alignment layer, layer thickness d ≈ 4.0 µm, double-sided ITO coating, structured ITO for multi-domain switching, without a passivation layer). The FK medium exhibits a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clearing point, and the resulting VA cell can be reversibly switched by applying a voltage.

[0222] VA orientation layers, which are used for PM-VA, PVA, MVA and analogous technologies, are achieved through the application of additives such as the polymerizable self-orientation additive. 1 no longer necessary. Mixing example 2

[0223] To a nematic FK medium H15 of the VA-IPS type (Δε > 0) the polymerizable self-orientation additive 1(2.0 wt.%) added and homogenized.

[0224] Use in test cells without a pre-alignment layer: The resulting mixture is filled into a test cell (without a polyimide alignment layer, layer thickness d ≈ 4 µm, ITO interdigital electrodes arranged on one substrate surface, glass on the opposite substrate surface, without a passivation layer). The FK medium exhibits a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clearing point, and the resulting VA-IPS cell can be reversibly switched by applying a voltage.

[0225] VA orientation layers, which are used for VA-IPS, HT-VA and analogous technologies, are enhanced by the application of additives such as the polymerizable self-orientation additive. 1 no longer necessary Mixture examples 3-20

[0226] The polymerizable self-orienting additives2-19 (wt.% according to Table 5) are analogous to mixture example 1 to a nematic FK medium H1 (Δε < 0) is added and homogenized. The resulting mixtures are filled into test cells without a pre-orientation layer. The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clarification point, and the resulting VA cells can be reversibly switched by applying a voltage. Mixture examples 21-33

[0227] The polymerizable self-orienting additives 2-4, 7, 10, 12-19 (wt.% according to Table 5) are analogous to mixture example 2 to form a nematic FK medium H15(Δε > 0) is added and homogenized. The resulting mixtures are filled into test cells without a pre-orientation layer. The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clarification point, and the resulting VA-IPS cells can be reversibly switched by applying a voltage. Mixture examples 34-98

[0228] The polymerizable self-orienting additives 1, 4 , 13 , 18 and 19 (Wt.% according to Table 5) are analogous to mixture example 1 for the nematic FK media. H2 - H14(Δε < 0) is added and homogenized. The resulting mixtures are filled into test cells without a pre-orientation layer (see mixture example 1). The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clarification point, and the resulting VA cells can be reversibly switched by applying a voltage. Mixture examples 99-123

[0229] The polymerizable self-orienting additives 1, 4 , 13 , 18 and 19 (Wt.% according to Table 5) are analogous to mixture example 2 for the nematic FK media. H16 - H20(Δε > 0) is added and homogenized. The resulting mixtures are filled into test cells without a pre-orientation layer. The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clarification point, and the resulting VA-IPS cells can be reversibly switched by applying a voltage. Mixture examples 1a, 3a-5a, 8a, 11a, 13a-19a (polymerization of mixture examples 1, 3-5, 8, 11, 13-19)

[0230] To a nematic FK medium H1 (Δε < 0) becomes a polymerizable self-orientation additive in each case. 1, 2-4, 7, 10, 12-18 (Wt.% according to Table 5) added and homogenized.

[0231] Use in test cells without a pre-alignment layer: The resulting mixtures are filled into test cells (without a polyimide alignment layer, layer thickness d ≈ 4.0 µm, ITO coating on both sides (structured ITO for multi-domain switching), without a passivation layer). The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clearing point, and the resulting VA cell can be reversibly switched by applying a voltage.

[0232] Applying a voltage greater than the optical threshold voltage (e.g., 14 Vpp), the VA cells are irradiated for 12 minutes with UV light at an intensity of < 100 mW / cm² at 20°C and a 340 nm bandpass filter. This causes polymerization of the polymerizable compounds. The homeotropic orientation is further stabilized, a pre-tilt is established, and a polymer layer forms (Table 1). The resulting PSA-VA cells can be reversibly switched to the clearing point by applying a voltage. The switching times are shorter compared to the unpolymerized cell. The threshold voltages (V10) change (Table 2). Depending on the chemical structure of the polymerizable component, the voltage-holding ratio (VHR) can improve slightly (Table 3).

[0233] Polymerization can also be carried out without applying a voltage. This further stabilizes the homeotropic orientation and creates a polymer layer without establishing a 'pre-tilt'. The polymer layer acts as a protective layer and improves the long-term stability of the PSA-VA cell.

[0234] VA orientation layers used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerizable self-orientation additives 1 - 4. Mixture examples 1b, 3b-5b, 8b, 11b, 13b-19b (polymer stabilization of mixture examples 1a, 3a-5a, 8a, 11a, 13a-19a)

[0235] To a nematic FK medium H1 (Δε < 0) become a polymerizable compound (RM-1, 0.3 wt.%) and a polymerizable self-orienting additive 1, 2-4, 7, 10, 12-18 (Wt.% according to Table 5) added and homogenized.

[0236] Use in test cells without a pre-alignment layer: The resulting mixtures are filled into test cells (without a polyimide alignment layer, layer thickness d ≈ 4.0 µm, ITO coating on both sides (structured ITO for multi-domain switching), without a passivation layer). The FK media exhibit a spontaneous homeotropic (vertical) orientation to the substrate surfaces. This orientation remains stable until the clearing point, and the resulting VA cell can be reversibly switched by applying a voltage.

[0237] Applying a voltage greater than the optical threshold voltage (e.g., 14 Vpp), the VA cells are irradiated for 12 minutes with UV light at an intensity of < 100 mW / cm² at 20°C and a 340 nm bandpass filter. This causes polymerization of the polymerizable compounds. The homeotropic orientation is further stabilized, a pre-tilt is established, and a polymer layer forms (Table 1). The resulting PSA-VA cells can be reversibly switched to the clearing point by applying a voltage. The switching times are shorter compared to the unpolymerized cell. The threshold voltages (V10) change (Table 2). Depending on the chemical structure of the polymerizable components, the voltage-holding ratio (VHR) can improve slightly (Table 4).

[0238] Polymerization can also be carried out without applying a voltage. This further stabilizes the homeotropic orientation and forms a polymer layer without establishing a 'pre-tilt'. The polymer layer acts as a protective layer and improves the long-term stability of the PSA-VA cell.

[0239] VA orientation layers used for PSA, PS-VA and analogous technologies are no longer necessary with the use of additives such as the polymerizable self-orientation additives 1 - 4. Table 1: H1 (PSOA). Layer thickness d and roughness Ra of the polymer layer formed after UV irradiation. Host in conjunction with polymerizable self-orienting additive, PSA-type test cell. Polymerization conditions: 0 Vpp, 15 min, 100 mW / cm², 340 nm bandpass filter, 40°C. Cell preparation for AFM measurements: After irradiation, the cells are rinsed with cyclohexane, the cell substrates are separated, and used for the measurements (Park or Veeco, room temperature). Mixture example PSOA Other polynomial verbs R a / nm d / nm 1a 1 1.4 12 3a 2 3.6 20 5a 4 2.2 - 6a 5 2.5 46 1b 1 RM-1 2.2 33 6b 5 RM-1 1.4 52 Table 2: H1 (PSOA). Switching times and threshold voltages V10 of VA and PSA cells. Host in conjunction with polymerizable self-orientation additive. Polymerization conditions: UV-1 (340 nm bandpass filter, 20°C, 14 Vpp, 2 min, 50 mW / cm²< ); UV-2 (340 nm bandpass filter, 20°C, 0 Vpp, 10 min, 100 mW / cm²< ). Mixture example PSOA Other polynomial verbs UV radiation. UV-1 + -2 Cell type V 10 / V Switching time / ms 0 V→5 V 1 1 No VA 2.50 32 3 2 No VA 2.43 35 4 3 No VA 2.45 33 5 4 No VA 2.51 31 7 6 No VA 2.47 34 8 7 No VA 2.48 31 10 9 No VA 2.42 34 13 12 No VA 2.48 28 14 13 No VA 2.48 34 15 14 No VA 2.50 28 17 16 No VA 2.51 28 19 18 No VA 2.49 31 1a 1 Yes PSA 2.58 23 3a 2 Yes PSA 1.57 20 4a 3 Yes PSA 2.53 16 5a 4 Yes PSA 2.47 27 8a 7 Yes PSA 2.53 16 14a 13 Yes PSA 2.53 29 1b 1 RM-1 Yes PSA 2.64 19 3b 2 RM-1 Yes PSA - - 4b 3 RM-1 Yes PSA 2.60 17 5b 4 RM-1 Yes PSA 2.57 29 14b 13 RM-1 Yes PSA 2.58 26 Table 3: H1 (PSOA). VHR (Voltage-Holding Ratio, 60 Hz, 100°C, 5 min) before and after heat exposure (2 h, 120°C). Host mixture in combination with polymerizable self-orienting additive. Mixture example PSOA UV irradiation. Cell type VHR / % Before heat stress After heat stress H1 - No 99.0 99.3 1 1 No VA 98.6 98.6 3 2 No VA 97.9 96.0 4 3 No VA 97.4 98.3 5 4 No VA 96.4 - 8 7 No VA 96.7 - 13 12 No VA 96.4 96.9 14 13 No VA 96.4 92.0 15 14 No VA 97.2 94.8 17 16 No VA 97.7 97.8 19 18 No VA 97.6 97.8 Table 4: H1 (PSOA). VHR (voltage holding ratio, 6 Hz, 100°C, 5 min) before and after UV irradiation. Host mixture in combination with polymerizable self-orienting additive. Polymerization conditions: UV-1 (340 nm bandpass filter, 20°C, 0 Vpp, 2 min, 50 mW / cm²< ); UV-2 (340 nm bandpass filter, 20°C, 0 Vpp, 10 min, 100 mW / cm²< ). Mixture example PSOA Other polynomial verbs UV radiation. UV-1 + -2 Type of cells UV protection After UV H1 - Yes 94.1 93.1 H1 - RM-1 Yes 93.1 94.7 1a 1 Yes PSA 92.5 85.9 3a 2 Yes PSA 89.6 92.8 1b 1 RM-1 Yes PSA 92.6 89.9 3b 2 RM-1 Yes PSA 90.6 97.4 5b 4 RM-1 Yes PSA 91.3 93.2 Table 5: 1-123 Weight % for the mixture examples PSOA wt.% PSOA wt.% 1 2.0 11 3.0 2 2.0 12 2.0 3 2.0 13 1.5 4 0.3 14 0.3 5 4.0 15 0.3 6 3.0 16 0.3 7 2.5 17 0.5 8 3.0 18 0.5 9 3.0 19 3.0 10 2.5

Claims

1. LC medium comprising a low-molecular-weight, non-polymerisable liquid-crystalline component and a polymerisable or polymerised component comprising one or more polymerisable compounds of the formula I, where the polymerised component is obtainable by polymerisation of the polymerisable component,         R1-[A3-Z3]m-[A2]k-[Z2]n-A1-Ra     (I) in which A1, A2, A3 in each case, independently of one another, denote an aromatic, heteroaromatic, alicyclic or heterocyclic group, which may also contain fused rings, and which may also be mono- or polysubstituted by a group L or -Sp-P, L in each case, independently of one another, denotes H, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)N(R0)2, -C(=O)R0, optionally substituted silyl, optionally substituted aryl or cycloalkyl having 3 to 20 C atoms, or straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, in which, in addition, one or more H atoms may be replaced by F or Cl, P denotes a polymerisable group, Sp denotes a spacer group or a single bond, Z2 in each case, independently of one another, denotes -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2)n1-, -CF2CH2-, -CH2CF2-, -(CF2)n1-, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, -(CR0R00)n1-, -CH(-Sp-P)-, -CH2CH(-Sp-P)-, -CH(-Sp-P)CH(-Sp-P)-, Z3 in each case, independently of one another, denotes a single bond, -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2)n1-, -CF2CH2-, -CH2CF2-, -(CF2)n1-, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, -(CR0R00)n1-, -CH(-Sp-P)-, -CH2CH(-Sp-P)-, -CH(-Sp-P)CH(-Sp-P)-, n1 denotes 1, 2, 3 or 4, n denotes 0 or 1, m denotes 0, 1, 2, 3, 4, 5 or 6, and k denotes 0 or 1, R0 in each case, independently of one another, denotes alkyl having 1 to 12 C atoms, R00 in each case, independently of one another, denotes H or alkyl having 1 to 12 C atoms, R1, independently of one another, denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that O and / or S atoms are not linked directly to one another and in which, in addition, one or more H atoms may be replaced by F or Cl, or a group -Sp-P, Ra denotes an anchor group of the formula or p denotes 1 or 2, q denotes 2 or 3, B denotes a substituted or unsubstituted ring system or condensed ring system, Y, independently of one another, denotes -O-, -S-, -C(O)-, -C(O)O-, -OC(O)-, -NR11- or a single bond, o denotes 0 or 1, X1, independently of one another, denotes H, alkyl, fluoroalkyl, OH, NH2, NHR11, NR112, OR11, C(O)OH, -CHO, where at least one group X1 denotes a radical selected from -OH, -NH2, NHR11, C(O)OH and -CHO, R11 denotes alkyl having 1 to 12 C atoms, Spa, Spc, Spd in each case, independently of one another, denote a spacer group or a single bond, and Spb denotes a tri- or tetravalent group, where the compound of the formula I contains at least one polymerisable group P within the groups A1, A2, A3, Z2 and Z3, as are present, and where the LC medium having negative or positive dielectric anisotropy additionally comprises one or more compounds of the formula II and / or III: in which ring A denotes 1,4-phenylene or trans-1,4-cyclohexylene, a is 0 or 1, R3 in each case, independently of one another, denotes alkyl having 1 to 9 C atoms or alkenyl having 2 to 9 C atoms, preferably alkenyl having 2 to 9 C atoms, and R4 in each case, independently of one another, denotes an unsubstituted or halogenated alkyl radical having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH2 groups may be replaced by -O-, -CH=CH-, -CH=CF-, -(CO)-, -O(CO)- or -(CO)O- in such a way that O atoms are not linked directly to one another, and preferably alkyl having 1 to 12 C atoms or alkenyl having 2 to 9 C atoms.

2. Medium according to Claim 1, characterised in that, for formula I, A1, A2, A3 in each case, independently of one another, denote 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, where, in addition, one or more CH groups in these groups may be replaced by N, cyclohexane-1,4-diyl, in which, in addition, one or more non-adjacent CH2 groups may be replaced by O and / or S, 3,3'-bicyclobutylidene, 1,4-cyclo-hexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]-octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-methanoindane-2,5-diyl, perhydrocyclopenta[a]phenan-threne-3,17-diyl (in particular gonane-3,17-diyl), where all these groups may be unsubstituted or mono- or polysubstituted by a group L or -Sp-P.

3. Medium according to Claim 1 or 2, characterised in that the compound of the formula I is a compound of the formula I1, in which R1, Ra, A1, A2, A3, Z2, Z3, L, Sp, P, k, m and n independently are as defined in Claim 1, and p1, p2, p3 independently denote 0, 1, 2 or 3, and r1, r2, r3 independently denote 0, 1, 2 or 3, where the compound of the formula I1 contains at least one polymerisable group P within the groups A1, A2, A3, Z2 and Z3, as are present.

4. LC medium according to one or more of Claims 1 to 3, characterised in that the compound of the formula I contains in total at least one polymerisable group -Sp-P on the groups A1, A2 and A3, as are present.

5. LC medium according to one or more of Claims 1 to 4, characterised in that the one or more compounds of the formula I are selected from compounds of the formulae IA, IB, IC, ID or IE: in which R1, Ra, Z2, Z3, L, Sp, P and n independently are as defined in Claim 1, and p1, p2, p3 independently denote 0, 1, 2 or 3, and r1, r2, r3 independently denote 0, 1, 2 or 3, where each of the compounds of the formulae IA, IB, IC, ID or IE contains at least one polymerisable group P.

6. LC medium according to one or more of Claims 1 to 5, characterised in that, besides one or more compounds of the formula I, the polymerisable or polymerised component comprises one or more further polymerisable or polymerised compounds, where the polymerised component is obtainable by polymerisation of the polymerisable component.

7. LC medium according to one or more of Claims 3 to 6, characterised in that in the formulae I1, IA, IB and IC, r1 + r2 + r3 > 0, and for formulae ID and IE, r1 + r2 > 0 and the substituent L does not denote H.

8. LC medium according to one or more of Claims 1 to 7, characterised in that k = 1.

9. LC medium according to one or more of Claims 1 to 8, characterised in that the compound of the formula I comprises one or more compounds selected from the following formulae: in which L, Sp, P, Ra and Z2 independently are as defined in Claim 1, and Z3 denotes a single bond or -CH2CH2-, n denotes 0 or 1, p1, p2, p3 independently denote 0, 1, 2 or 3, r1, r2, r3 independently denote 0, 1, 2 or 3, and R1 denotes H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that O and / or S atoms are not linked directly to one another and in which, in addition, one or more H atoms may be replaced by F or CI.

10. LC medium according to one or more of Claims 1 to 9, characterised in that the group Ra in formula I contains one, two or three OH groups.

11. LC medium according to one or more of Claims 1 to 10, characterised in that the group Ra denotes a group selected from         -Spa-X1 or in which Spa, Spb, Spc, p and X1 have the meaning as in Claim 1.

12. LC medium according to one or more of Claims 1 to 11, characterised in that the group Ra denotes a group selected from the part-formulae 13. LC medium according to one or more of Claims 1 to 12, characterised in that, for the compound of the formula I, the group P is selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxide.

14. LC medium according to one or more of Claims 1 to 13, characterised in that it comprises the compounds of the formula I in a concentration of less than 10% by weight.

15. LC medium according to one or more of Claims 1 to 14, characterised in that it comprises one or more polymerisable compounds of the formula M or a (co)polymer comprising compounds of the formula M:         P1-Sp1-A2-(Z1-A1)n-Sp2-P2     M in which the individual radicals have the following meaning: P1, P2 in each case independently denote a polymerisable group, Sp1, Sp2 in each case independently denote a spacer group, A1, A2 in each case, independently of one another, denote a radical selected from the following groups: a) the group consisting of trans-1,4-cyclohexylene, 1,4-cyclo-hexenylene and 4,4'-bicyclohexylene, in which, in addition, one or more non-adjacent CH2 groups may be replaced by -O- and / or -S- and in which, in addition, one or more H atoms may be replaced by a group L, or selected from b) the group consisting of 1,4-phenylene and 1,3-phenylene, in which, in addition, one or two CH groups may be replaced by N and in which, in addition, one or more H atoms may be replaced by a group L or -Sp3-P, c) the group consisting of tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobut-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl and selenophene-2,5-diyl, each of which may also be mono- or polysubstituted by a group L, d) the group consisting of saturated, partially unsaturated or fully unsaturated, and optionally substituted, polycyclic radicals having 5 to 20 cyclic C atoms, one or more of which may, in addition, be replaced by heteroatoms, preferably selected from the group consisting of bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, where, in addition, one or more H atoms in these radicals may be replaced by a group L or -Sp3-P, and / or one or more double bonds may be replaced by single bonds, and / or one or more CH groups may be replaced by N, P3 denotes a polymerisable group, Sp3 denotes a spacer group, n denotes 0, 1, 2 or 3, Z1 in each case, independently of one another, denotes -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CF2O-, -OCF2-, or -(CH2)n-, where n is 2, 3 or 4, -O-, -CO-, -C(RcRd)-, -CH2CF2-, -CF2CF2- or a single bond, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF5 or straight-chain or branched, in each case optionally fluorinated, alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, R0, R00 in each case, independently of one another, denote H, F or straight-chain or branched alkyl having 1 to 12 C atoms, in which, in addition, one or more H atoms may be replaced by F, M denotes -O-, -S-, -CH2-, -CHY1- or -CY1Y2-, Y1 and Y2 in each case, independently of one another, have one of the meanings indicated above for R0 or denote Cl or CN, and preferably H, F, Cl, CN, OCF3 or CF3, W1, W2 in each case, independently of one another, denote -CH2CH2-, -CH=CH-, -CH2-O-, -O-CH2-, -C(RcRd)- or -O-, and Rc and Rd in each case, independently of one another, denote H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl, where one or more of the groups P1-Sp1-, -Sp2-P2 and -Sp3-P3 may denote a radical Raa, with the proviso that at least one of the groups P1-Sp1-, -Sp2-P2 and -Sp3-P3 present does not denote Raa, Raa denotes H, F, CI, CN or straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may in each case be replaced, independently of one another, by C(R0)=C(R00)-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that O and / or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, CN or P1-Sp1-, where the groups -OH, -NH2, -SH, -NHR, -C(O)OH and -CHO are not present in Raa.

16. LC medium according to one or more of Claims 1 to 15, characterised in that the polymerisable or polymerised component comprises 0.01 to 5% by weight of one or more compounds of the formula M according to Claim 16.

17. LC medium according to one or more of Claims 1 to 16, characterised in that the polymerisable or polymerised component comprises one or more compounds selected from the compounds of the following formulae: in which the individual radicals have the following meaning: P1, P2 and P3 in each case, independently of one another, denote a polymerisable group, preferably having one of the meanings indicated above and below for P, particularly preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyloxy or epoxide group, Sp1, Sp2 and Sp3 in each case, independently of one another, denote a single bond or a spacer group, preferably having one of the meanings indicated above and below for Spa, and particularly preferably -(CH2)p1-, -(CH2)p1-O-, -(CH2)p1-CO-O- or -(CH2)p1-O-CO-O-, in which p1 is an integer from 1 to 12, and where the linking to the adjacent ring in the last-mentioned groups takes place via the O atom, where, in addition, one or more of the radicals P1-Sp1-, P2-Sp2- and P3-Sp3- may denote a radical Raa, with the proviso that at least one of the radicals P1-Sp1-, P2-Sp2- and P3-Sp3- present does not denote Raa, Raa denotes H, F, CI, CN or straight-chain or branched alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may in each case be replaced, independently of one another, by C(R0)=C(R00)-, -C≡C-, -N(R0)-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that O and / or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, CI, CN or P1-Sp1-, where -OH, -NH2, -SH, -NHR, -C(O)OH and -CHO are not present in the group Raa, R0, R00 in each case, independently of one another and identically or differently on each occurrence, denote H or alkyl having 1 to 12 C atoms, Ry and Rz in each case, independently of one another, denote H, F, CH3 or CF3, X1, X2 and X3 in each case, independently of one another, denote -CO-O-, O-CO- or a single bond, Z1 denotes -O-, -CO-, -C(RyRz)- or -CF2CF2-, Z2 and Z3 in each case, independently of one another, denote -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CF2O-, -OCF2- or -(CH2)n-, where n is 2, 3 or 4, L on each occurrence, identically or differently, denotes F, Cl, CN, SCN, SF5 or straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, preferably F, L' and L" in each case, independently of one another, denote H, F or Cl, r denotes 0, 1, 2, 3 or 4, s denotes 0, 1, 2 or 3, t denotes 0, 1 or 2, and x denotes 0 or 1.

18. LC medium according to one or more of Claims 1 to 17, characterised in that it additionally comprises one or more compounds selected from the group of the compounds of the formulae A, B and C, in which R2A, R2B and R2C in each case, independently of one another, denote H, an alkyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN or CF3 or at least monosubstituted by halogen, where, in addition, one or more CH2 groups in these radicals may be replaced by -O-, -S-, -C≡C-, -CF2O-, -OCF2-, -OC-O- or -O-CO- in such a way that O atoms are not linked directly to one another, L1-4 in each case, independently of one another, denote F, Cl, CF3 or CHF2, Z2 and Z2' in each case, independently of one another, denote a single bond, -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -COO-, -OCO-, -C2F4-, -CF=CF- or -CH=CHCH2O-, p denotes 1 or 2, q denotes 0 or 1, and v denotes 1 to 6.

19. LC display comprising an LC cell having two substrates and at least two electrodes, where at least one substrate is transparent to light and at least one substrate has one or two electrodes, and having a layer of an LC medium according to one or more of Claims 1 to 18 located between the substrates, where the compound of the formula I is suitable for effecting a homeotropic alignment of the LC medium with respect to the substrate surfaces.

20. LC display according to Claim 19, characterised in that the substrates have no alignment layers for homeotropic alignment.

21. LC display according to Claim 19 or 20, which is a VA display with an LC medium having negative dielectric anisotropy and electrodes arranged on opposite substrates.

22. LC display according to one or more of Claims 19 to 21, characterised in that it is a VA-IPS display with an LC medium having positive dielectric anisotropy and interdigital electrodes arranged on at least one substrate.

23. Compounds of the formula I         R1-[A3-Z3]m-[A2]k-[Z2]n-A1-Ra     (I) in which m, n and the groups A1, A2, A3, Z2, Z3 and Ra are defined as in Claim 1, and where R1, independently of one another, denotes halogen, straight-chain, branched or cyclic alkyl having 1 to 25 C atoms, in which, in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -OCO-O- in such a way that O and / or S atoms are not linked directly to one another and in which, in addition, one or more H atoms may be replaced by F or Cl, or a group -Sp-P, and k = 1.

24. Compounds according to Claim 23, characterised in that m = 1, 2 or 3.

25. Compound according to Claim 23 of the formula I1, in which R1, Ra, A1, A2, A3, Z2, Z3, L, Sp, P, k, m and n independently are defined as in Claim 23, and p1, p2, p3 independently denote 0, 1, 2 or 3, and r1, r2, r3 independently denote 0, 1, 2 or 3, where the compound of the formula I1 contains at least one polymerisable group P within the groups A1, A2, A3, Z2 and Z3, as they are present.

26. Compounds according to one or more of Claims 23 to 25, in which A1 and A2 independently denote 1,4-phenylene or cyclohexane-1,4-diyl, which may in each case be mono- or polysubstituted by a group L or -Sp-P.

27. Use of compounds of the formula I according to one or more of Claims 23 to 26 as additive for LC media for effecting a homeotropic alignment with respect to a surface delimiting the LC medium.