Compounds and liquid crystalline media

Abstract

The invention relates to compounds of formula (I), and preferably to liquid-crystalline media having a nematic phase and negative dielectric anisotropy, comprising a) one or more compounds of formula (I) and b) one or more compounds selected from the group of compounds of formulae (II) and (III) wherein the parameters have the meanings given in claim 1, the use thereof in electro-optical displays, especially in active matrix displays based on the VA, ECB, PALC, FFS or IPS effect, displays of this type comprising a liquid-crystalline medium of this type, and the use of compounds of formula (I) for stabilizing liquid-crystalline media comprising one or more compounds of formula (II) and one or more compounds selected from the group of compounds of formulae (III-1) to (III-4) and B.

Description

[0001] This application is a divisional application of patent application number 201980035960.2. Technical Field

[0002] This invention relates to novel compounds, particularly novel compounds for liquid crystal media, but also to the use of these liquid crystal media in liquid crystal displays, and to these liquid crystal displays, particularly liquid crystal displays using the ECB (electro-controlled birefringence) effect, which exhibit dielectric negative liquid crystals in initial vertical alignment. The liquid crystal media according to the invention are characterized by a particularly short response time in displays according to the invention, while simultaneously exhibiting a high voltage retention rate (VHR or simply HR). Background Technology

[0003] The principles of electrically controlled birefringence, the ECB effect, or the DAP (diametrically opposed phase distortion) effect were first described in 1971 (M. F. Chieckel and K. Fahrenschon, "Deformation of nematic liquid crystals with vertical orientation in electrical fields", Appl. Phys. Lett. 19 (1971), 3912). This was followed by papers by J. F. Kahn (Appl. Phys. Lett. 20 (1972), 1193) and G. Labrunie and J. Robert (J. Appl. Phys. 44 (1973), 4869).

[0004] Papers by J. Robert and F. Clerc (SID 80 Digest Techn. Papers (1980), 30), J. Duchene (Displays 7 (1986), 3), and H. Schad (SID 82 Digest Techn. Papers (1982), 244) have shown that liquid crystal phases must have high values ​​for the elastic constant ratio K3 / K1, high values ​​for optical anisotropy Δn, and dielectric anisotropy values ​​≤ -0.5 to be suitable for high-information display elements based on the ECB effect. Electro-optic display elements based on the ECB effect have vertical edge alignment (VA technology = vertical alignment, or also called VAN = vertical alignment nematic). Dielectric-negative liquid crystal media can also be used in displays using the so-called IPS (in-plane switching) effect.

[0005] This effect necessitates LC phases that meet a wide variety of requirements for industrial applications in electro-optic display elements. Of particular importance here is resistance to moisture, air, and physical influences such as heat, radiation in the infrared, visible, and ultraviolet regions, as well as DC and AC electric fields.

[0006] In addition, an industrially usable LC phase is required, which has a liquid crystal mesophase within a suitable temperature range and low viscosity.

[0007] None of the compounds disclosed to date that have a liquid crystal mesophase include a single compound that satisfies all of these requirements. Therefore, mixtures of 2 to 25, preferably 3 to 18, compounds are generally prepared to obtain a substance that can be used as an LC phase.

[0008] Matrix liquid crystal displays (MLC displays) are known. The nonlinear elements that can be used for independent switching of individual pixels are, for example, active elements (i.e., transistors). Thus, the term "active matrix" is used, where, generally, thin-film transistors (TFTs) are used, typically disposed on a glass plate serving as a substrate.

[0009] The distinction lies between the two technologies: TFTs incorporating compound semiconductors (such as CdSe) or TFTs based on polycrystalline and, especially, amorphous silicon. The latter technology currently holds the greatest commercial importance worldwide.

[0010] The TFT matrix is ​​positioned inside one glass panel of the display, while another glass panel carries a transparent anti-electrode inside it. Compared to the size of the pixel electrodes, the TFTs are very small and have almost no adverse effect on the image. This technology can also be extended to full-color displays, where mosaics of red, green, and blue filters are arranged so that the filter elements are positioned relative to each switchable pixel.

[0011] The most commonly used TFT displays to date typically operate with cross-polarizers and are backlit. For TV applications, IPS or ECB (or VAN) cells are used; however, monitors typically use IPS or TN (twisted nematic) cells, and laptops, notebook computers, and mobile applications typically use TN cells.

[0012] The term MLC display here encompasses any matrix display with integrated nonlinear elements, that is, in addition to active matrices, it also includes displays with passive elements such as rheostats or diodes (MIM = metal-insulator-metal).

[0013] This type of MLC display is particularly suitable for TV applications, monitors, and laptops, or for displays with high information density, such as in automotive manufacturing or aircraft construction. In addition to issues concerning contrast angle dependence and response time, MLC displays also suffer from problems due to insufficient specific resistivity of the liquid crystal mixture [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, Sept. 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp. 141 ff., Paris; STROMER, M., Proc. Eurodisplay 84, Sept. 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, pp. 145 ff., Paris]. As resistance decreases, the contrast of an MLC display deteriorates. Due to the interaction with the inner surface of the display, the specific resistivity of the liquid crystal mixture typically decreases with the lifespan of an MLC display; therefore, high (initial) resistance is crucial for displays that must maintain an acceptable resistance value after prolonged operation.

[0014] Apart from IPS displays (e.g., Yeo, SD, paper 15.3: “An LC Display for the TV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Vol. II, pp. 758 and 759) and the long-known TN displays, displays using the ECB effect, also known as VAN (Vertical Alignment Nematic) displays, are now recognized as one of the three newer types of liquid crystal displays that are most important, especially for television applications.

[0015] The most important designs mentioned here are: MVA (Multi-Domain Vertical Alignment, e.g., Yoshide, H. et al., Paper 3.1: "MVA LCD for Notebook or Mobile PCs...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume I, pp. 6-9, and Liu, CT et al., Paper 15.1: "A 46-inch TFT-LCD HDTV Technology...", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume II, pp. 750-753) and PVA (Patterned Vertical Alignment), e.g., Kim, Sang Soo, Paper 15.4: "Super PVA Sets New State-of-the-Art for LCD-TV", SID 2004 International Symposium, Digest of Technical Papers. Papers, XXXV, Volume II, pp. 760-763) and ASV (Advanced Hyperview, e.g., Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Paper 15.2: “Development of High Quality LCDTV”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume II, pp. 754-757).

[0016] In general, this technology is compared in, for example, Souk, Jun, SID Seminar 2004, Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6 / 1 to M-6 / 26, and Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7 / 1 to M-7 / 32. Although the response time of modern ECB displays has been significantly improved by overdrive addressing methods, for example, Kim, Hyeon Kyeong et al., Paper 9.1: “A 57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Volume I, pp. 106-109, the achievement of video compatibility response time, especially in grayscale switching, remains an unresolved issue.

[0017] For example, ASV and ECB displays use liquid crystal media with negative dielectric anisotropy (Δε), while TN and all conventional IPS displays to date use liquid crystal media with positive dielectric anisotropy.

[0018] In this type of liquid crystal display, liquid crystal is used as a dielectric, and its optical properties can be reversibly changed after a voltage is applied.

[0019] Since the operating voltage should be as low as possible in displays, i.e., displays based on the effects mentioned above, liquid crystal media are typically used, primarily composed of liquid crystal compounds with the highest possible dielectric anisotropy values ​​and all having the same dielectric anisotropy sign. Generally, at most a relatively small proportion of neutral compounds is used, and compounds with dielectric anisotropy signs opposite to those of the medium are avoided if possible. In the case of liquid crystal media with negative dielectric anisotropy used in ECB displays, compounds with negative dielectric anisotropy are therefore primarily employed. The liquid crystal media used generally consists primarily, and usually, even essentially, of liquid crystal compounds with negative dielectric anisotropy.

[0020] In the media used according to this application, at most a significant amount of dielectric neutral liquid crystal compound is typically used and generally only a very small amount of dielectric positive compound or even no dielectric positive compound is used, because, in general, liquid crystal displays are intended to have the lowest possible addressing voltage.

[0021] For many practical applications in liquid crystal displays, known liquid crystal media are not sufficiently stable. In particular, their stability under UV irradiation and even under conventional backlight irradiation is impaired, especially in terms of electrical properties. For example, conductivity increases significantly.

[0022] The use of so-called "hindered amine light stabilizers," or HALS for short, has been suggested for the stabilization of liquid crystal mixtures.

[0023] For example, WO 2009 / 129911 A1 and WO 2012 / 076105 A1 recommend the inclusion of small amounts of TINUVIN. ® 770, a nematic liquid crystal mixture with negative dielectric anisotropy, using the following compound as a stabilizer.

[0024]

[0025] However, the corresponding liquid crystal mixtures do not possess sufficient performance for some practical applications. In particular, they are not sufficiently stable under irradiation using typical CCFL (cold cathode fluorescent lamp) and especially typical modern LED (light emission diode) backlights.

[0026] For example, similar liquid crystal mixtures are also known from EP 2 182 046 A1, WO 2008 / 009417 A1, WO 2009 / 021671 A1 and WO2009 / 115186 A1. However, the use of stabilizers is not indicated in these documents.

[0027] According to the publications in these documents, these liquid crystal mixtures may optionally contain various stabilizers, such as phenol and hindered amines (hindered amine light stabilizers, abbreviated as HALS). However, these liquid crystal mixtures are characterized by relatively high threshold voltages and at most moderate stability. In particular, their voltage retention decreases after exposure. Furthermore, pale yellow fading is generally enhanced.

[0028] For example, various stabilizers used in liquid crystal media are described in JP(S)55-023169(A), JP(H)05-117324(A), WO 02 / 18515 A1 and JP(H)09-291282(A).

[0029] In particular, EP 2 993 216 A1 recommends stable compounds of the following formula for dielectric positive liquid crystal media.

[0030]

[0031] In addition to various other compounds used as secondary stabilizers and, except for nitrogen-containing heterocyclic substances, WO 2009 / 129911 A1 also recommends compounds of the following formula for stabilizing dielectric negative liquid crystal media.

[0032]

[0033]

[0034]

[0035] EP 2 514 800 A2 recommends the use of compounds of the following formula for the purpose of stabilizing liquid crystal media.

[0036]

[0037] and

[0038]

[0039] Where R 11 Besides other meanings, it can also be O. . Or OH, instead of H. However, the chemical stability of these compounds in terms of hydrolysis, and especially their solubility in liquid crystal media, is insufficient for practical applications in most cases.

[0040] WO 2016 / 146245 A1 recommends compounds of the following formula for stabilization purposes in liquid crystal media.

[0041]

[0042] DE 2016 005 083 A1 also recommends the above-mentioned compounds and compounds of the following formula for use in stabilizing liquid crystal media.

[0043]

[0044] However, the chemical stability, especially in terms of hydrolysis, and particularly in terms of solubility in liquid crystal media, of these compounds is insufficient for practical applications in most cases.

[0045] Unpublished application DE 10 2016 009485.0 suggests using ether-linked compounds of the following formula as stabilizers for liquid crystal mixtures.

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] Existing liquid crystal media with correspondingly low addressing voltages have relatively low resistivity or low VHR and typically result in undesirable flicker and / or insufficient transmittance in displays. Furthermore, they are insufficiently stable to thermal / UV exposure, at least if they have correspondingly high polarity, which is necessary for low addressing voltages.

[0052] On the other hand, the addressing voltage of existing displays with high VHR is often too high, especially for displays that are not directly or continuously connected to a power supply network, such as displays for mobile applications.

[0053] Furthermore, the phase range of the liquid crystal mixture must be sufficiently wide for the intended application of the display. Therefore, low-temperature storage at -30°C in a cell and preferably in bulk should be 240 hours or longer.

[0054] The response time of liquid crystal media in displays must be improved, i.e., reduced. This is especially important for displays used in television or multimedia applications. To improve response time, optimizing the rotational viscosity (γ1) of the liquid crystal media has been repeatedly proposed in the past, i.e., achieving a medium with the lowest possible rotational viscosity. However, the results achieved here are insufficient for many applications, thus necessitating the search for alternative optimization methods.

[0055] Sufficient stability of the medium under extreme loads, especially under UV exposure and heat, is particularly important. This makes it especially difficult to simultaneously optimize rotational viscosity. This can be particularly important in applications such as displays in mobile devices like mobile phones, where relatively low addressing frequencies are preferred, especially in these devices.

[0056] The drawbacks of MLC displays disclosed to date are attributed to their relatively low contrast, relatively high viewing angle dependence, and difficulty in grayscale generation in these displays, as well as their insufficient VHR and their short lifespan.

[0057] Therefore, there is still a great need for MLC displays with very high specific resistance, a wide operating temperature range, short response time, and low threshold voltage, which can produce a variety of gray levels, especially with good and stable VHR. Summary of the Invention

[0058] The object of this invention is to provide an MLC display for use not only in monitors and TV applications, but also in mobile phones and navigation systems, which is based on ECB, IPS, or FFS (fringe-field effect) effects, as described in Lee, SH, Lee, SL and Kim, HY “Electro-optical characteristics and switching principle of nematicliquid crystal cell controlled by fringe-field switching”, Appl. Phys. Letts., Vol. 73, No. 20, pp. 2881-2883 (1998), without having the disadvantages mentioned above, or having only a minor degree of the aforementioned disadvantages, and simultaneously possessing a very high resistivity. In particular, for mobile phones and navigation systems, it is essential to ensure their operation at extremely high and extremely low temperatures.

[0059] Surprisingly, it has been found that when nematic liquid crystal mixtures are used in these display elements, liquid crystal displays, particularly in FFS displays, can be achieved with low threshold voltage and short response time while simultaneously having a sufficiently wide nematic phase, advantageously relatively low birefringence (Δn), good stability against decomposition by heat and by UV exposure, good solubility, and stable and high VHR. The nematic liquid crystal mixture comprises at least one compound of formula I, and in each case at least one compound of formula II, preferably a compound of formula II-1, and / or at least one compound selected from formulas III-1 to III-4, preferably a compound of formula III-2 and / or a compound of B.

[0060] This type of media can be used, in particular, for electro-optic displays with active matrix addressing based on the ECB effect, and for IPS displays and FFS displays.

[0061] The present invention therefore relates to liquid crystal media based on mixtures of polar compounds, comprising at least one compound of formula I and at least one compound comprising one or more compounds of formula II and preferably additionally comprising one or more compounds selected from formulas III-1 to III-4 and / or formula B.

[0062] The mixtures according to the invention exhibit a very wide nematic phase range with a clearing point of ≥70°C, a very favorable capacitance threshold value, a relatively high retention rate, and good low-temperature stability at -20°C and -30°C, as well as very low rotational viscosity. A further feature of the mixtures according to the invention is a very good ratio of clearing point to rotational viscosity and high negative dielectric anisotropy.

[0063] It has been surprisingly discovered that liquid crystal media with appropriately high Δε, appropriate phase range, and Δn can be realized without the disadvantages of existing materials or at least with these disadvantages only to a significantly reduced extent.

[0064] Here, it has been surprisingly found that compounds of formula I, even when used alone without additional heat stabilizers, still result in significant, in many cases sufficient, stabilization of the liquid crystal mixture against UV exposure and against heat. Particularly noteworthy is the parameter p in most of the compounds of formula I used, which represents 2 and n This is the case when p represents 4 or 6. In one embodiment of the invention, compounds of formula I, where p represents 2 and n represents 3 or 4, are therefore particularly preferred, and the precise use of these compounds in the liquid crystal mixtures according to the invention is also particularly preferred. It is also preferred that the group -Z is present. 11 -S 11 -Z 12 - indicates ω-dioxanediol, i.e., -OS 11 Compounds of formula I with -O-.

[0065] However, especially when one or more other compounds, preferably phenolic stabilizers, are present in the liquid crystal mixture in addition to one or more compounds of Formula I, sufficient stabilization of the liquid crystal mixture against UV exposure and against heat can be achieved. These other compounds are suitable as heat stabilizers.

[0066] Therefore, the present invention relates to compounds of formula I and to liquid crystal media having a nematic phase and negative dielectric anisotropy, comprising...

[0067] a) One or more compounds of formula I, preferably at a concentration of 1 ppm to 2500 ppm, more preferably to 2000 ppm, more preferably to 1500 ppm, particularly preferably to 1000 ppm, preferably in the range of 1 ppm to 500 ppm, particularly preferably in the range of 1 ppm to 250 ppm.

[0068]

[0069] in

[0070] R 11Each occurrence independently represents H or F, a straight or branched alkyl chain with 1-20 C atoms, wherein one or more -CH2- groups, if present, can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more -CH2- groups, if present, can be replaced by -CH=CH- or -C≡C-, and one or more H atoms can be replaced by F, OR 13 N(R) 13 (R) 14 ) or R 15 replace,

[0071] R 11 Preferably H or alkyl, particularly alkyl, especially n-alkyl and very particularly n-butyl.

[0072] R 12 Each occurrence independently represents a straight-chain or branched alkyl chain having 1-20 C atoms, where one or more -CH2- groups can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and a hydrocarbon group containing cycloalkyl or alkylcycloalkyl units, where one or more -CH2- groups can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more H atoms can be replaced by F, OR 13 N(R) 13 (R) 14 ) or R 15 The substitution, or aromatic or heteroaromatic hydrocarbon group, wherein one or more H atoms can be replaced by F, OR 13 N(R) 13 (R) 14 ) or R 15 replace,

[0073] R 12 Preferably, H represents a non-branched alkyl group or a branched alkyl group; particularly preferably, H represents a non-branched alkyl group.

[0074] R 13 Each occurrence independently represents a straight-chain or branched alkyl or acyl group having 1 to 10 carbon atoms, preferably a n-alkyl group, or an aromatic hydrocarbon or carboxylic acid group having 6 to 12 carbon atoms.

[0075] R 14 Each occurrence independently represents a straight-chain or branched alkyl or acyl group having 1 to 10 carbon atoms, preferably a n-alkyl group, or an aromatic hydrocarbon or carboxylic acid group having 6 to 12 carbon atoms.

[0076] R15 Each occurrence independently represents a straight-chain or branched alkyl group having 1 to 10 carbon atoms. One or more -CH2- groups may be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-.

[0077] S 11 and S 12 Each occurrence independently represents an alkylene group having 1 to 20 carbon atoms, which is branched, or preferably straight-chain, preferably having 1-20 carbon atoms, more preferably having 1-10 carbon atoms, and particularly preferably having 1 to 8 carbon atoms -(CH2-). n One or more -CH2- groups, if present, can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more -CH2- groups, if present, can be replaced by -CH=CH- or -C≡C-, and one or more H atoms can be replaced by F, OR 13 N(R) 13 (R) 14 ) or R 15 Replacement, or to represent a single key.

[0078] X 11 Indicates C,

[0079] Y 11 To Y 14 Each of them independently represents either methyl or ethyl, particularly preferably both represent either methyl or ethyl, and very particularly preferably methyl.

[0080] Z 11 To Z 14 Each occurrence is independently represented as -O-, -(C=O)-, -O-(C=O)-, -(C=O)-O-, -O-(C=O)-O-, -(NR 13 )-,-NR 13 -(C=O)- or if S 11 If it's a single bond, it means a single bond, but Z... 11 and Z 12 The two do not both represent -O-, and however, if S 12 If it's a single key, then Z 13 and Z 14 Both are not simultaneously -O-, and however, if -X 11 [-R 11 ] o - If it's a single key, then Z 12 and Z 13 The two are not both -O-.

[0081] Z 11 Preferred representation -O-,

[0082] Z 13 Preferred to represent a single bond,

[0083] p represents 1 or 2,

[0084] o represents (3-p),

[0085] n p represents an integer from 3 to 10, preferably up to 8.

[0086] When p=1

[0087] n represents 3, 4, 5, 6, or 8, with a particular preference for 4, 6, or 8, and a very particular preference for 4 or 6.

[0088] m represents (10-n), and,

[0089] When p=2,

[0090] n represents an integer from 2 to 4, preferably 2 or 3, especially 3, and

[0091] m represents (4-n), and

[0092] This refers to an organic group having (m+n) binding sites, preferably having 4 binding sites, and preferably having 1 to 30 C atoms as an alkyldiyl, alkyltriyl, or alkyltetrayl unit, wherein, in addition to the m groups R present in the molecule... 12 Outside, but independently of its location, another H atom can be R 12 One or more other H atoms can be replaced by R 12 Instead, preferably, an alkyl tetrayl unit with one or two valences on each terminal C atom, wherein one or more -CH2- groups can be replaced by -O- or -(C=O)- such that the two -O- atoms are not directly bonded to each other, or a substituted or unsubstituted aromatic or heteroaromatic hydrocarbon group with up to 10 valences, wherein, in addition to the m groups R present in the molecule 12 Outside, but independently of its location, another H atom can be R 12 One or more other H atoms can be replaced by R 12 replace,

[0093] And when p=1, -X 11 [-R 11 ] o - Alternatively, it can also represent a single bond.

[0094] b) One or more compounds selected from compounds of formulas II and III, preferably dielectrically positive, and preferably having a dielectric anisotropy of 3 or greater:

[0095]

[0096] in

[0097] R 2 H represents an unfluorinated or fluorinated alkyl or unfluorinated or fluorinated alkoxy group having 1 to 17 carbon atoms, or an unfluorinated or fluorinated alkenyl group having 2 to 15 carbon atoms, an unfluorinated or fluorinated alkenyloxy group, or an unfluorinated or fluorinated alkoxyalkyl group, wherein one or more CH2- groups may be... , , , or Instead, alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy groups having 1 to 7 carbon atoms, alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl groups having 2 to 7 carbon atoms, and preferably alkyl or alkenyl groups.

[0098] and Each occurrence is represented independently.

[0099]

[0100] Where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, or

[0101]

[0102]

[0103] L 21 and L 22 H or F can be represented independently of each other, with L being preferred. 21 F represents

[0104] X 2 The halogen is represented by a haloalkyl or alkoxy group having 1-3 carbon atoms, or a haloalkenyl or alkenoxy group having 2 or 3 carbon atoms, preferably F, Cl, -OCF3, -O-CH2CF3, -O-CH=CH2, -O-CH=CF2 or -CF3, with F, Cl, -O-CH=CF2 or -OCF3 being very preferred.

[0105] m represents 0, 1, 2, or 3, preferably 1 or 2, and particularly preferably 1.

[0106] R 3 Having R2 The given meaning is one or more, namely, H, an unfluorinated or fluorinated alkyl or unfluorinated or fluorinated alkoxy group having 1 to 17 carbon atoms, or an unfluorinated or fluorinated alkenyl group having 2 to 15 C atoms, an unfluorinated or fluorinated alkenyl group or an unfluorinated or fluorinated alkoxyalkyl group, wherein one or more CH2- groups may be , , , or Instead, alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy groups having 1 to 7 carbon atoms, alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl groups having 2 to 7 carbon atoms, and preferably alkyl or alkenyl groups.

[0107] and Each time they appear, they independently possess the above-mentioned characteristics. and One of the given meanings, and preferably

[0108]

[0109] L 31 and L 32 H or F can be represented independently of each other, with L being preferred. 31 F represents

[0110] X 3 The halogen is represented by a haloalkyl or alkoxy group having 1 to 3 carbon atoms, or a haloalkenyl or alkenoxy group having 2 or 3 carbon atoms, preferably F, Cl, -OCF3, -OCHF2, -O-CH2CF3, -O-CH=CF2, -O-CH=CH2 or -CF3, very preferably F, Cl, -O-CH=CF2, -OCHF2 or -OCF3.

[0111] Z 3 This indicates -CH2CH2-, -CF2CF2-, -COO-, trans- CH=CH-, trans- CF=CF-, -CH2O- or a single bond, preferably -CH2CH2-, -COO-. trans- CH=CH- or a single bond, with -COO- being highly preferred. trans- CH=CH- or a single bond, and

[0112] n represents 0, 1, 2, or 3, preferably 1, 2, or 3, and particularly preferably 1.

[0113] c) Optionally one or more compounds selected from compounds of formulas IV and V, preferably dielectrically neutral:

[0114]

[0115] in

[0116] R 41 and R 42 Independently possessing the above properties under Equation II for R 2 Given the meaning, the preferred option is R. 41 Indicates alkyl and R 42 Indicates alkyl or alkoxy or R 41 Represents alkenyl and R 42 Indicates alkyl group,

[0117] and Independent of each other and, if If they appear twice, then these also independently possess the above-mentioned characteristics. and One of the given meanings and preferred representations

[0118]

[0119] Preferred and One or more representations in ,

[0120] Z 41 and Z 42 Independent of each other, and if Z 41 If they appear twice, then they independently represent -CH2CH2-, -COO-, trans- CH=CH-, trans- CF=CF-, -CH2O-, -CF2O-, -C≡C- or a single bond, preferably one or more of these representing a single bond, and

[0121] p represents 0, 1, or 2, preferably 0 or 1.

[0122] R 51 and R 52 They are independent of each other for R 41 and R 42 The term "alkyl" is given in one of the following meanings and is preferably indicated by having 1 to 7 carbon atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5 carbon atoms; alkoxy having 1 to 7 carbon atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 2 to 5 carbon atoms; alkoxyalkyl having 2 to 7 carbon atoms, preferably 2 to 4 carbon atoms; alkenyl or alkenyloxy, preferably alkenyloxy.

[0123] to If they exist, each possesses the above-mentioned characteristics independently of the others. and One of the given meanings and preferred representations

[0124]

[0125] Preferred

[0126]

[0127] Preferred

[0128]

[0129] And, if it exists

[0130]

[0131] Z 51 To Z 53 Each can independently represent -CH2-CH2-, CH2-O-, -CH=CH-, -C≡C-, -COO-, or a single bond, preferably -CH2-CH2-, -CH2-O-, or a single bond, and particularly preferably a single bond.

[0132] i and j each represent 0 or 1 independently.

[0133] (i+j) preferably represents 0, 1, or 2, more preferably 0 or 1, and most preferably 1.

[0134] d) Again, optionally, alternatively, or additionally, one or more compounds selected from formulas VI to IX, preferably dielectric negative:

[0135]

[0136] in

[0137] R 61 R 62 R 71 R 72 R 81 and R 82 They independently possess the above-mentioned properties for R 41 and R 42 One of the given meanings, preferably

[0138] R 61 This refers to an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl; an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms; or an unsubstituted alkenoxy group having 2 to 6 carbon atoms.

[0139] R 62 This refers to an unsubstituted alkyl group having 1 to 7 carbon atoms, an unsubstituted alkoxy group having 1 to 6 carbon atoms, or an unsubstituted olefinic group having 2 to 6 carbon atoms, and

[0140] l represents 0 or 1.

[0141] R 71 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl, or an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms.

[0142] R 72 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms; or an unsubstituted olefinic group having 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms.

[0143] R 81 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl, or an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms.

[0144] R 82 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms; or an unsubstituted olefinic group having 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms.

[0145]

[0146] Z 8 This represents -(C=O)-O-, -CH2-O-, -CF2-O-, or -CH2-CH2-, preferably -(C=O)-O- or -CH2-O-, and

[0147] o represents 0 or 1.

[0148] R 91 and R 92 Each independently possesses the above for R 72 The given meaning,

[0149] R 91 Preferably, it refers to an alkyl group having 2 to 5 carbon atoms, more preferably having 3 to 5 carbon atoms.

[0150] R 92Preferably, it refers to an alkyl or alkoxy group having 2 to 5 carbon atoms, more preferably an alkoxy group having 2 to 4 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms.

[0151]

[0152] p and q represent 0 or 1 independently of each other, and

[0153] (p+q) preferably represents 0 or 1, and in express In this case, alternatively, p=q=1 is preferred.

[0154] e) Optionally again, one or more compounds of formula IN having high dielectric constants perpendicular to and parallel to the pointing vector, preferably at a concentration in the range of 1% to 60%, more preferably in the range of 5% to 40%, and particularly preferably in the range of 8% to 35%.

[0155]

[0156] in

[0157]

[0158] n represents 0 or 1,

[0159] R 11 and R 12 The terms "alkyl", "alkoxy", "fluorinated alkyl", or "fluorinated alkoxy" are independently represented, preferably having 1 to 7 carbon atoms, or alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl having 2 to 7 carbon atoms, and more preferably alkyl, alkoxy, alkenyl, or alkenyloxy, with alkyl, alkoxy, or alkenyloxy being the most preferred, and R 11 Alternatively, R can be represented 1 And R 12 X can be represented alternatively 1 ,

[0160] R 1 The term represents an alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy group, preferably having 1 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl, and preferably an alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl group having 2 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentenylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl, and preferably alkyl or alkenyl.

[0161] 1,3-cyclopentenyl is a part selected from groups of the following formula:

[0162]

[0163] X 1 The groups represent F, Cl, fluorinated alkyl, fluorinated alkenyl, fluorinated alkoxy, or fluorinated alkenyloxy, with the latter four groups preferably having 1 to 4 carbon atoms, preferably F, Cl, CF3, or OCF3, especially F for formulas I-1 and I-2, and OCF3 for formula I-4.

[0164] f) Optionally again, one or more compounds of formula B having high dielectric constants perpendicular to and parallel to the pointer, preferably in a concentration ranging from 1% to 60%, more preferably from 5% to 40%, and particularly preferably from 8% to 35%.

[0165]

[0166] in

[0167]

[0168] R B1 and R B2 Independently representing alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy groups, preferably having 1 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl groups, and having 2 to 7 carbon atoms, alkenyl, alkoxyalkyl, or fluorinated alkenyl groups, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentenylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl groups, and preferably alkyl, alkoxy, alkenyl, or alkenyloxy groups, most preferably alkyl, alkoxy, or alkenyloxy groups, and

[0169] n represents 0 or 1, with 0 being preferred.

[0170] g) Optionally again, one or more compounds of formula S having a high dielectric constant perpendicular to and parallel to the directional vector, preferably at a concentration in the range of 1% to 60%, more preferably in the range of 5% to 40%, and particularly preferably in the range of 8% to 35%.

[0171]

[0172] in

[0173]

[0174]

[0175] R S1 and R S2 Independently representing alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy groups, preferably having 1 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl groups, and having 2 to 7 carbon atoms, alkenyl, alkoxyalkyl, or fluorinated alkenyl groups, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentenylene, or 1,3-cyclopentenyl, preferably by cyclopropylene or 1,3-cyclopentenyl groups, and preferably alkyl, alkoxy, alkenyl, or alkenyloxy groups, most preferably alkyl, alkoxy, or alkenyloxy groups, and

[0176] n represents 0 or 1, preferably 1.

[0177] The liquid crystal medium according to this application preferably has a nematic phase.

[0178] In the compound of formula I, the group N(R) 13 (R) 14 Amines can also be preferred.

[0179] The following implementation scheme is preferred:

[0180] p is 2,

[0181] The organic group is an organic group having four binding sites, preferably an alkyl tetrayl unit having 1 to 30 carbon atoms, wherein, in addition to the m groups R present in the molecule 12 In addition, but independently of its location, another H atom can also be R 12 R can also replace one or more other H atoms 12 Instead, preferably, each of the two terminal C atoms has a monovalent or divalent alkyl tetrayl unit, wherein one or more -CH2- groups can be replaced by -O- or -(C=O)- such that the two O atoms are not directly bonded to each other, or by substituted or unsubstituted aromatic or heteroaromatic hydrocarbon groups having a maximum octet valence, wherein, in addition to the m groups R present in the molecule, 12 Outside, but independently of its location, another H atom can be R 12 One or more other H atoms can be replaced by R 12 replace,

[0182] express , (biphenyl-1,1′,3,3′-tetramethyl), (Benzene-1,2,4,5-tetrayl), >CH-[CH2)r -CH<(where r∈{0,1,2,3,4,5 to 18},-CH2-(CH-)-[CH2]) q -(CH-)-CH2-<(where q∈{0,1,2,3,4,5 to 16},

[0183] express (Benzene-1,3,5-trimethyl), (Benzene-1,2,4-triyl) or >CH-[CH2] r -CH2- (where r∈{0,1,2,3,4,5 to 18}) or

[0184] It represents -CH2-[CH2] r -CH2- (where r∈{0,1,2,3,4,5 to 18}), octane-1,8-diyl, heptane-1,7-diyl, hexane-1,6-diyl, pentane-1,5-diyl, butane-1,4-diyl, propane-1,3-diyl, ethane-1,2-diyl, or (1,4-Phenylidene) (1,3-phenylene), (1,2-phenylene) or (1,4-Cyclohexane).

[0185] In an alternative preferred embodiment,

[0186] p represents 1.

[0187] In this application, all elements comprise their respective isotopes. In particular, one or more H atoms in the compound may be replaced by D atoms, and this is particularly preferred in some embodiments. The corresponding high degree of deuteration of the compounds enables, for example, the monitoring and identification of the compounds. This is very helpful in some cases, especially in the case of compounds of formula I.

[0188] In this application,

[0189] Alkyl particularly preferably refers to a straight-chain alkyl group, especially CH3-, C2H5-, n -C3H7-, n -C4H9- or n -C5H 11 -,and

[0190] alkenyl is particularly preferred to represent CH2=CH-. E -CH3-CH=CH-, CH2=CH-CH2-CH2-, E-CH3-CH=CH-CH2-CH2-, E -( n -C3H7)-CH=CH-.

[0191] The liquid crystal medium according to this application preferably contains a total of 1 ppm to 2500 ppm, more preferably 1 ppm to 1500 ppm, more preferably 1 to 600 ppm, even more preferably 1 to 250 ppm, more preferably up to 200 ppm, and very particularly preferably 1 ppm to 100 ppm of compound I.

[0192] In a preferred embodiment of the invention, in the compound of formula I,

[0193] express , (biphenyl-1,1′,3,3′-tetramethyl) or (Benzene-1,2,4,5-tetramethyl)

[0194] express (Benzene-1,3,5-trimethyl) or (Benzene-1,2,4-trimethyl)

[0195] The terms -(CH2-)2, -(CH2-)3, -(CH2-)4, -(CH2-)5, -(CH2-)6, -(CH2-)7, and -(CH2-)8 represent ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. (1,4-Phenylidene) (1,3-phenylene), (1,2-phenylene) or (trans-1,4-cyclohexanediol), and / or

[0196] -Z 12 -S 11 -Z 11 - Represents each occurrence independently of -O-, S 11 -O-, -OS 11 -O-,-(C=O)-OS 11 -O-,-O-(C=O)-S 11 -O-,-O-(C=O)-S 11 -(C=O)-O-,-OS 11 -(C=O)-O-,-(C=O)-OS 11-C,-(C=O)-OS 11 -O-(C=O)- or -(NR) 13 )-S 11 -O-,-(NR 13 -C(=O)-S 11 -(C=O)-O or a single bond, preferably -O-, -S 11 -O-,-OS 11 -O-,-(C=O)-OS 11 -O, -O-(C=O)-S 11 -O-- or -OS 11 -(C=O)-O-, and / or

[0197] S 11 Preferably, it represents an alkylene group having 1 to 20 carbon atoms, and / or

[0198] R 11 If present, it indicates alkyl, alkoxy, or H, preferably H or alkyl, and / or

[0199] R 12 It represents H, methyl, ethyl, propyl, isopropyl, or 3-heptyl, or cyclohexyl.

[0200] In a preferred embodiment of this application, in the compound of formula I,

[0201]

[0202] Groups selected from the following formulas

[0203]

[0204]

[0205] In a preferred embodiment of this application, in the compound of formula I,

[0206]

[0207] Groups selected from the following formulas

[0208]

[0209]

[0210]

[0211] In a preferred embodiment of this application, in the compound of formula I, p preferably represents 1.

[0212] express Preferred OS 11 -O-, -S 11 -O- or -OS 11 -, Specially Selected - OS 11 -O- or -S 11 -O-.

[0213] In a further preferred embodiment of this application, in the compound of formula I,

[0214]

[0215] Preferably, it represents a group selected from the following formula.

[0216]

[0217]

[0218]

[0219]

[0220] or

[0221]

[0222] In a further preferred embodiment of this application, p is 2, which may be the same as or different from those described above, in the compound of formula I.

[0223]

[0224] Preferably, it represents a group selected from the following formula.

[0225]

[0226]

[0227] and

[0228]

[0229] In a further preferred embodiment of this application, it may be the same as or different from those described above, in which the group in Formula I compound...

[0230]

[0231] Each occurrence is represented independently.

[0232]

[0233] In a particularly preferred embodiment of this application, all groups present in the compound of formula I are...

[0234]

[0235] They have the same meaning.

[0236] These compounds are well-suited for use as stabilizers in liquid crystal mixtures. In particular, they stabilize the VHR of the mixtures for UV exposure.

[0237] In a preferred embodiment of the invention, the medium according to the invention comprises, in each case, one or more compounds of formula I, said compounds of formula I being selected from the group consisting of compounds of formulas I-1 to I-13: preferably selected from compounds of formulas I-3, I-5, I-6, I-7, I-8, I-9, I-10, I-12, and I-13, particularly preferably selected from compounds of formulas I-6 to I-10, and very particularly preferably compounds of formula I-10.

[0238]

[0239]

[0240]

[0241]

[0242]

[0243] In one or even more preferred embodiment of the invention, the medium according to the invention comprises, in each case, one or more compounds of formula I selected from the following formulas I-1 and / or I-3 to I-8 and / or I-9 and / or I-10.

[0244] In one or even a more preferred embodiment of the invention, the medium according to the invention comprises, in each case, one or more compounds of formula I selected from the following formulas I-9 and / or I-10.

[0245] In addition to the compound of formula I or its preferred sub-formula, the medium according to the invention preferably also contains one or more compounds of formula II, with a total concentration of 1% or more up to 90% or less, preferably 10% or more up to 80% or less, and particularly preferably 20% or more up to 70% or less.

[0246] In a preferred embodiment of the invention, the liquid crystal medium comprises one or more compounds selected from formulas II-1 and II-2, preferably having a dielectric positive polarity and preferably a dielectric anisotropy of 3 or greater:

[0247]

[0248]

[0249] The parameters have the corresponding meanings indicated in Equation II above, and L 23 and L 24 H or F can be represented independently of each other, with L being preferred. 23 Let F be the value, and

[0250] Having for One of the given meanings is that, in the cases of equations II-1 and II-2, X 2 Preferably, it represents F or OCF3, with F being particularly preferred, and in the case of formula II-2, and Independently, preferred representation or .

[0251] In addition to compounds of Formula I or their preferred sub-formulas, the media according to the invention preferably contain one or more compounds of Formula III, with a total concentration of 1% or more up to 40% or less, preferably 3% or more up to 20% or less, and particularly preferably 4% or more up to 10% or less.

[0252] The compounds of formula III are preferably selected from compounds of formulas III-1 and III-2:

[0253]

[0254]

[0255] The parameters have the meanings given in Formula III, and the medium according to the invention may replace compounds of Formula III-1 and / or III-2, or, in addition to compounds of Formula III-1 and / or III-2, contain one or more compounds of Formula III-3.

[0256]

[0257] The parameters have the corresponding meanings indicated above, and parameter L 31 and L 32 H or F can be represented independently of each other and independently of other parameters.

[0258] The liquid crystal medium preferably comprises a compound selected from formulas II-1 and II-2, wherein L 21 and L 22 and / or L 23 and L 24 All represent F.

[0259] In a preferred embodiment, the liquid crystal medium comprises a compound selected from formulas II-1 and II-2, wherein L21 ,L 22 ,L 23 and L 24 All represent F.

[0260] The liquid crystal medium preferably comprises one or more compounds of formula II-1. The compounds of formula II-1 are preferably selected from compounds of formulas II-1a to II-1e, preferably one or more of formulas II-1a and / or II-1b and / or II-1d, more preferably formulas II-1a and / or II-1d or II-1b and / or II-1d, and most preferably compounds of formula II-1d.

[0261]

[0262] The parameters have the corresponding meanings indicated above, and L 25 and L 26 H or F are represented independently of each other and independently of other parameters, and preferably, in formulas II-1a and II-1b, L 21 and L 22 Both represent F, and in equations II-1c and II-1d, L 21 and L 22 Both represent F and / or L 23 and L 24 Both represent F, and in equation II-1e, L 21 L 22 and L 23 It represents F.

[0263] The liquid crystal medium preferably comprises one or more compounds of formula II-2, preferably selected from compounds of formula II-2a to II-2k, and more preferably one or more compounds of formula II-2a and / or II-2h and / or II-2j respectively:

[0264]

[0265]

[0266] The parameters have the corresponding meanings indicated above, and L 25 To L 28 H or F can be represented independently of each other, with L being preferred. 27 and L 28 Both represent H, with L being the preferred choice. 26 H represents H.

[0267] The liquid crystal medium preferably comprises a compound selected from formulas II-1a to II-1e, wherein L 21 and L 22 Both represent F and / or L 23 and L 24 All represent F.

[0268] In a preferred embodiment, the liquid crystal medium comprises a compound selected from formulas II-2a to II-2k, wherein L 21 L 22 L 23 and L 24 All represent F.

[0269] Particularly preferred compounds of formula II-2 are those of the following formulas, especially preferred are II-2a-1 and / or II-2h-1 and / or II-2k-2:

[0270]

[0271]

[0272] Where R 2 and X 2 Having the meanings indicated above, and X 2 The preferred option is F.

[0273] The liquid crystal medium preferably comprises one or more compounds of formula III-1. The compounds of formula III-1 are preferably selected from compounds of formulas III-1a to III-1j, and more particularly from formulas III-1c, III-1f, III-1g, and III-1j.

[0274]

[0275]

[0276] The parameters have the meanings given above, and preferably, the parameters have the corresponding meanings indicated above, parameter L 35 and L 36 H or F can be represented independently of each other and independently of other parameters, and parameter L 35 and L 36 H or F can be represented independently of each other and independently of other parameters.

[0277] The liquid crystal medium preferably comprises one or more compounds of formula III-1c, preferably selected from compounds of formulas III-1c-1 to III-1c-5, preferably of formula III-1c-1 and / or III-1c-2, and most preferably of formula III-1c-1:

[0278]

[0279] Where R 3 It has the meanings mentioned above.

[0280] The liquid crystal medium preferably comprises one or more compounds of formula III-1f, which are preferably selected from compounds of formula III-1f-1 to III-1f-6, preferably of formula III-1f-1 and / or III-1f-2 and / or III-1f-3 and / or III-1f-6, more preferably of formula III-1f-3 and / or III-1f-6, and even more preferably of formula III-1f-6:

[0281]

[0282] Where R 3 It has the meanings mentioned above.

[0283] The liquid crystal medium preferably comprises one or more compounds of formula III-1g, preferably selected from compounds of formula III-1g-1 to III-1g-5, and preferably of formula III-1g-3:

[0284]

[0285] Where R 3 It has the meanings mentioned above.

[0286] The liquid crystal medium preferably comprises one or more compounds of formula III-1h, preferably selected from compounds of formula III-1h-1 to III-1h-3, with formula III-1h-3 being the most preferred:

[0287]

[0288] The parameters have the meanings given above, and X 3 The preferred option is F.

[0289] The liquid crystal medium preferably comprises one or more compounds of formula III-1i, which are preferably selected from compounds of formula III-1i-1 and III-1i-2, with formula III-1i-2 being the most preferred:

[0290]

[0291] The parameters have the meanings given above, and X 3 The preferred option is F.

[0292] The liquid crystal medium preferably comprises one or more compounds of formula III-1j, which are preferably selected from compounds of formula III-1j-1 and III-1j-2, with formula III-1j-1 being the most preferred:

[0293]

[0294] The parameters have the meanings given above.

[0295] The liquid crystal medium preferably comprises one or more compounds of formula III-2. The compounds of formula III-2 are preferably selected from compounds of formula III-2a and III-2b, with formula III-2b being preferred:

[0296]

[0297] The parameters have the corresponding meanings indicated above, and parameter L 33 and L 34 H or F can be represented independently of each other and independently of other parameters.

[0298] The liquid crystal medium preferably comprises one or more compounds of formula III-2a, which are preferably selected from compounds of formula III-2a-1 to III-2a-6:

[0299]

[0300] Where R 3 It has the meanings mentioned above.

[0301] The liquid crystal medium preferably comprises one or more compounds of formula III-2b, preferably selected from compounds of formula III-2b-1 to III-2b-4, with formula III-2b-4 being the most preferred:

[0302]

[0303] Where R 3 It has the meanings mentioned above.

[0304] In addition to or in addition to compounds of formula III-1 and / or III-2, the medium according to the invention may also contain one or more compounds of formula III-3.

[0305]

[0306] The parameters have the corresponding meanings indicated in Equation III.

[0307] These compounds are preferably selected from formulas III-3a and III-3b:

[0308]

[0309] Where R 3 It has the meaning of the above instructions.

[0310] The liquid crystal medium according to the invention preferably comprises one or more dielectric neutral compounds, the dielectric anisotropy of which is preferably -1.5 to 3, and preferably selected from compounds of formulas VI, VII, VIII and IX.

[0311] In this application, all elements include their respective isotopes. In particular, one or more H atoms in the compound may be replaced by D atoms, and this is particularly preferred in some embodiments. The corresponding high degree of deuteration of the compounds makes it possible, for example, to detect and identify the compounds. This is particularly helpful in certain cases, especially in the case of compounds of formula I.

[0312] In this application,

[0313] Alkyl particularly preferably refers to a straight-chain alkyl group, especially CH3-, C2H5-, n -C3H7-, n -C4H9- or n -C5H 11 -,and

[0314] alkenyl is particularly preferred to represent CH2=CH-, E -CH3-CH=CH-, CH2=CH-CH2-CH2-, E -CH3-CH=CH-CH2-CH2- or E -( n -C3H7)-CH=CH-.

[0315] In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds of formula B, preferably formula B-1, preferably at a concentration of 1% to 20%, particularly preferably 2% to 15%, and very particularly preferably 3% to 9%.

[0316]

[0317] The parameters have the corresponding meanings given in Equation B above, and preferably...

[0318] R B1 and R B2 In each case, the terms "alkyl", "alkoxy", "oxaalkyl", or "alkoxyalkyl", or "alkenyl" or "alkenoxy", having 1 to 7 carbon atoms, are used independently, preferably all representing alkoxy.

[0319] L B1 and L B2 F or Cl is represented independently of each other in each case, with F being preferred.

[0320] In a particularly preferred embodiment, the medium according to the invention comprises one or more compounds selected from formulas OH-1 to OH-6.

[0321]

[0322] These compounds are well-suited for stabilizing media under heat load.

[0323] In another preferred embodiment of the invention, the medium according to the invention comprises, in particular, one or more compounds of formula I, wherein p represents 2 and n represents 2, 3 or 4, preferably 2 or 3, and particularly preferably 3, and these media have excellent stability.

[0324] In another preferred embodiment of the invention, the medium according to the invention comprises at least one or more compounds of formula I in each case, wherein p represents 1 and n represents 3, 4, 5 or 6, preferably 4, and the group -Z 11 -S 11 -Z 12 - indicates ω-dioxanediol, i.e., -OS 11 -O-, these media have excellent stability.

[0325] The present invention also relates to electro-optic displays or electro-optic components comprising a liquid crystal medium according to the invention. Preferably, they are based on the IPS, FFS, VA, or ECB effect, especially electro-optic displays based on the IPS or FFS effect, and particularly those addressed by active matrix addressing devices.

[0326] Therefore, the present invention also relates to the use of the liquid crystal medium according to the invention in electro-optic displays or electro-optic components, and to a method for preparing the liquid crystal medium according to the invention, characterized in that one or more compounds of formula I are mixed with one or more compounds of formula II, preferably with one or more compounds of sub-formula II-1, and with one or more other compounds, preferably selected from compounds of formulas III and IV and / or V and / or VI to IX and / or IN and / or B and / or S.

[0327] Furthermore, the present invention relates to a method for stabilizing a liquid crystal medium comprising one or more compounds of formula II and one or more compounds selected from formulas III-IX, B, S and IN, characterized in that one or more compounds of formula I are added to the medium.

[0328] In a particularly preferred embodiment, the medium comprises one or more compounds of formula IV, said formula IV compounds being selected from formulas IV-1 to IV-4, preferably compounds of formula IV-1 and / or IV-2.

[0329]

[0330]

[0331]

[0332]

[0333] in

[0334] alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms.

[0335] alkenyl and alkenyl' independently represent alkenyl groups having 2 to 5 C atoms, preferably having 2 to 4 C atoms, and particularly preferably having 2 C atoms.

[0336] 'alkenyl' indicates an alkenyl group having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and particularly preferably 2 to 3 carbon atoms.

[0337] alkoxy means an alkoxy group having 1 to 5 carbon atoms, preferably having 2 to 4 carbon atoms.

[0338] In a particularly preferred embodiment, the medium according to the invention comprises one or more compounds of formula IV-1 and / or one or more compounds of formula IV-2.

[0339] The particularly preferred compound of formula IV-1 is a compound selected from the following formulas.

[0340]

[0341]

[0342]

[0343]

[0344] The alkyl group has the meaning given above, and preferably in each case, it independently represents an alkyl group having 1 to 6, more preferably 2 to 5, carbon atoms, and particularly preferably a n-alkyl group.

[0345] Particularly preferred compounds of formula IV are those selected from the following formulas.

[0346]

[0347]

[0348]

[0349]

[0350]

[0351] In another preferred embodiment, the medium comprises one or more compounds of formula V, which are selected from formulas V-1 to V-11, preferably compounds selected from formulas V-1 to V-5.

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363] The parameters have the meanings given in equation V above, and

[0364] Y 5 Represents H or F, and preferably

[0365] R 51 This indicates an alkyl group having 1 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms, and

[0366] R 52 The term indicates an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, preferably an alkyl or alkenyl group, and particularly preferably an alkenyl group.

[0367] In another preferred embodiment, the medium comprises one or more compounds of formula V-1, which are selected from formulas V-1a and V-1b, preferably formula V-1b.

[0368]

[0369]

[0370] in

[0371] alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms.

[0372] alkoxy means an alkoxy group having 1 to 5 carbon atoms, preferably having 2 to 4 carbon atoms.

[0373] In another preferred embodiment, the medium comprises one or more compounds of formula V-3, which are selected from formulas V-3a and V-3b.

[0374]

[0375]

[0376] in

[0377] alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms, and

[0378] alkenyl refers to an alkenyl group having 2 to 7 carbon atoms, preferably having 2 to 5 carbon atoms.

[0379] In another preferred embodiment, the medium comprises one or more compounds of formula V-4, which are selected from formulas V-4a and V-4b.

[0380]

[0381]

[0382] in

[0383] Alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms.

[0384] In another preferred embodiment, the medium comprises one or more compounds of formula V-5, selected from formulas V-5a to V5d, preferably V-5a and / or V-5b.

[0385]

[0386]

[0387]

[0388]

[0389] in

[0390] alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms, and

[0391] alkenyl and alkenyl' independently represent alkenyl groups having 2 to 5 C atoms, preferably 2 to 4 C atoms, and particularly preferably 4 C atoms.

[0392] The liquid crystal medium according to the present invention may contain one or more chiral compounds.

[0393] A particularly preferred embodiment of the invention satisfies one or more of the following conditions, wherein the acronym (abbreviation) is explained in Tables A to C and illustrated by examples in Table D.

[0394] i. The birefringence of the liquid crystal medium is 0.060 or higher, particularly preferably 0.070 or higher.

[0395] ii. The birefringence of the liquid crystal medium is 0.130 or lower, particularly preferably 0.120 or lower.

[0396] iii. The birefringence of the liquid crystal medium is in the range of 0.090 or higher to 0.120 or lower.

[0397] iv. The liquid crystal medium has negative dielectric anisotropy, with a value of 2.0 or greater, particularly preferably 3.0 or greater.

[0398] v. The liquid crystal medium has a negative dielectric anisotropy, with a value of 5.5 or less, particularly preferably 5.0 or less.

[0399] vi. Liquid crystal media have negative dielectric anisotropy, with a value ranging from 3.6 or greater to 5.2 or less.

[0400] vii. The total concentration of the compound of formula II in the entire mixture is 25% or higher, preferably 30% or higher, and preferably in the range of 25% or higher to 49% or lower, particularly preferably in the range of 29% or higher to 47% or lower, and very particularly preferably in the range of 37% or higher to 44% or lower.

[0401] viii. The liquid crystal medium comprises one or more compounds of formula IV, which are selected from the following: CC-nV and / or CC-n-Vm, particularly preferably CC-3-V, preferably at a concentration of up to 50% or less, particularly preferably at a concentration of up to 42% or less, and optionally additionally comprising CC-3-V1, preferably at a concentration of up to 15% or less, and / or CC-4-V, preferably at a concentration of up to 20% or less, particularly preferably at a concentration of up to 10% or less.

[0402] ix. The total concentration of the compound of formula CC-3-V in the entire mixture is 20% or higher, preferably 25% or higher.

[0403] x. The proportion of compounds of formula II and III in the whole mixture is 10% or higher, and preferably 75% or lower.

[0404] xi. The liquid crystal medium is basically composed of compounds of formula I, II, III, IV, V and B and / or S, preferably composed of compounds of formula I, II, III, IV, V and S.

[0405] Furthermore, the present invention relates to an electro-optic display having active matrix addressing based on the VA or ECB effect, characterized in that it contains a liquid crystal medium according to the present invention as a dielectric.

[0406] The liquid crystal mixture preferably has a nematic phase range with a width of at least 80 degrees and a maximum of 30 mm at 20°C. 2 ·s -1 Flow viscosity 20 .

[0407] The liquid crystal mixture according to the invention has a Δε of -0.5 to -8.0, particularly -1.5 to -6.0, and very particularly preferably -2.0 to -5.0, wherein Δε represents dielectric anisotropy.

[0408] The rotational viscosity γ1 is preferably 150 mPa·s or less, particularly 120 mPa·s or less, and very especially preferably 120 mPa·s or less.

[0409] The mixtures according to the invention are suitable for all IPS and FFS-TFT applications. They are also suitable for all VA applications, such as VAN, MVA, (S)-PVA and ASV applications, as well as PALC applications with negative Δε.

[0410] The nematic liquid crystal mixture in the display according to the present invention typically comprises two components A and B, which are themselves composed of one or more individual compounds.

[0411] The liquid crystal medium according to the invention preferably contains 4 to 15, particularly 5 to 12, and especially preferably 10 or fewer compounds. These are preferably selected from compounds of formulas I, II and III-1 to III-4, and / or IV and / or V.

[0412] The liquid crystal media according to the invention may optionally also contain more than 18 compounds. In this case, they preferably contain 18 to 25 compounds.

[0413] In addition to the compounds of formulas I to V, other components may also be present, for example, in an amount of up to 45% of the whole mixture, but preferably up to 35%, and especially up to 10%.

[0414] The medium according to the invention may optionally contain a dielectric positive component, preferably 10% or less in total concentration based on the entire medium.

[0415] In a preferred embodiment, the liquid crystal medium according to the invention comprises a total of, based on the entire mixture.

[0416] Compounds of Formula I with concentrations of 100 ppm or more up to 2500 ppm or less, preferably 300 ppm or more up to 2000 ppm or less, particularly preferably 500 ppm or more up to 1500 ppm or less, and very particularly preferably 700 ppm or more up to 1200 ppm or less.

[0417] 20% or more to 60% or less, preferably 25% or more to 50% or less, particularly preferably 30% or more to 45% or less of the compound of formula II, and

[0418] 50% or more to 70% or less of compounds of formulas I to IX and / or IN and / or B and / or S.

[0419] In a preferred embodiment, the liquid crystal medium according to the invention comprises one or more compounds selected from formulas II, III, IV, V, VI, VII, VIII, and IX, preferably compounds selected from formulas II and / or III and / or IV and / or V, which independently comprise one or more rings selected from the following substituted 1,4-phenylene rings.

[0420]

[0421] In a particularly preferred embodiment of the above preferred embodiments, the liquid crystal medium according to the present invention comprises one or more compounds selected from the following

[0422]

[0423] In a preferred embodiment, the liquid crystal medium according to the invention comprises one or more compounds selected from formulas II, III, IV, V, VI, VII, VIII, and IX, preferably compounds selected from formulas II and / or III and / or IV and / or V, comprising one end group, or, if present, two end groups, preferably one end group, which is selected from the following end groups.

[0424] 3-Fluoropropyl, cyclopropyl, cyclopropylmethyl, 2-cyclopropylethyl, cyclobutyl, cyclobutylmethyl, cyclopentyl, and cyclopentylmethyl

[0425] Preferably selected from 3-fluoropropyl, cyclopropyl, cyclopropylmethyl, 2-cyclopropylethyl, cyclobutylmethyl and cyclopentylmethyl.

[0426] In a particularly preferred embodiment of the above preferred embodiments, the liquid crystal medium according to the present invention comprises one or more compounds selected from the following

[0427]

[0428]

[0429]

[0430]

[0431]

[0432]

[0433]

[0434] In a preferred embodiment, the liquid crystal medium according to the invention comprises compounds selected from formulas I, II, III, IV, V, In, B and S, preferably compounds selected from formulas I, II and / or III and / or B and / or S; they preferably consist primarily, particularly preferably substantially and very particularly preferably actually entirely of compounds of the formulas.

[0435] The liquid crystal medium according to the invention preferably has a nematic phase in each case at least -20°C or lower up to 70°C or higher, particularly preferably -30°C or lower up to 80°C or higher, very particularly preferably -40°C or lower up to 85°C or higher, and most preferably -40°C or lower up to 90°C or higher.

[0436] The phrase "having a nematic phase" here refers, on the one hand, to the absence of smectic phases and crystallization observed at the corresponding temperatures at low temperatures, and on the other hand, to the absence of clearing upon heating of the nematic phase. Studies at low temperatures are conducted in a flow viscometer at the corresponding temperatures and examined by storing the sample in a test chamber with a thickness appropriate for the electro-optical application for at least 100 hours. If the storage stability at -20°C in the corresponding test chamber is 1000 hours or longer, the medium is considered stable at that temperature. At -30°C and -40°C, the corresponding times are 500 hours and 250 hours, respectively. At high temperatures, the clearing point is measured in a capillary using conventional methods. Furthermore, the shelf life of the bulk (1 mL sample) at low temperatures is determined in glass vials at -20°C or -30°C. At these temperatures, preferably at -30°C, a stable shelf life is preferably 120 hours or longer, particularly preferably 240 hours or longer.

[0437] In a preferred embodiment, the liquid crystal medium according to the invention is characterized by optical anisotropy in a moderate to low range. The birefringence value is preferably in the range of 0.065 or greater to 0.130 or less, particularly preferably in the range of 0.080 or greater to 0.120 or less, and very particularly preferably in the range of 0.085 or greater to 0.110 or less.

[0438] In this embodiment, the liquid crystal medium according to the invention has negative dielectric anisotropy and a relatively high absolute value of dielectric anisotropy ( The preferred range is 2.7 or greater to 5.3 or less, preferably to 4.5 or less, preferably 2.9 or greater to 4.5 or less, particularly preferably 3.0 or greater to 4.0 or less, and very particularly preferably 3.5 or greater to 3.9 or less.

[0439] The liquid crystal medium according to the invention has a relatively low threshold voltage (V0) value, which is in the range of 1.7V or greater to 2.5V or less, preferably 1.8V or greater to 2.4V or less, particularly preferably 1.9V or greater to 2.3V or less, and very particularly preferably 1.95V or greater to 2.1V or less.

[0440] In another preferred embodiment, the liquid crystal medium according to the invention preferably has a relatively low average dielectric anisotropy value ( av. ≡( +2 ) / 3), preferably in the range of 5.0 or greater to 7.0 or less, preferably 5.5 or greater to 6.5 or less, still more preferably 5.7 or greater to 6.4 or less, particularly preferably 5.8 or greater to 6.2 or less and very particularly preferably 5.9 or greater to 6.1 or less.

[0441] Furthermore, the liquid crystal medium according to the present invention has a high VHR value in the liquid crystal cell.

[0442] In a box, in a freshly filled box at 20°C, these are preferably greater than or equal to 95%, preferably greater than or equal to 97%, particularly preferably greater than or equal to 98%, and very particularly preferably greater than or equal to 99%, and after being in an oven at 100°C for 5 minutes in the box, these are greater than or equal to 90%, preferably greater than or equal to 93%, particularly preferably greater than or equal to 96%, and very particularly preferably greater than or equal to 98%.

[0443] Typically, liquid crystal media with low addressing voltage or threshold voltage have lower VHR than those with higher addressing voltage or threshold voltage, and vice versa.

[0444] These preferred values ​​for each of the physical properties are also preferably maintained in each case by being combined with each other through the medium according to the invention.

[0445] In this application, unless otherwise expressly stated, the term "compound" is also written as "(one or more) compounds" and refers to both one or more compounds.

[0446] Unless otherwise indicated, the individual compounds are generally used in mixtures at a concentration of 1% or more up to 30% or less, preferably 2% or more up to 30% or less, and particularly preferably 3% or more up to 16% or less.

[0447] In a preferred embodiment, the liquid crystal medium according to the present invention comprises

[0448] One or more compounds of formula I, and

[0449] One or more compounds of formula IV, preferably selected from compounds of formula CC-nV and CC-n-Vm, preferably CC-3-V, CC-3-V1, CC-4-V and CC-5-V, particularly preferably selected from compounds CC-3-V, CC-3-V1 and CC-4-V, very particularly preferably compound CC-3-V, and optionally additionally one or more compounds CC-4-V and / or CC-3-V1.

[0450] In a preferred embodiment, the liquid crystal medium according to the present invention comprises:

[0451] One or more compounds of formula I and / or

[0452] One or more compounds of formula II, preferably PUQU-nF, CDUQU-nF, APUQU-nF, DPUQU-nF and PGUQU-nF and / or

[0453] One or more compounds of formula III, preferably CCG-n-FCCP-n-OT, CLP-nT, CGG-nF, CGG-n-OD and PPGU-nF and / or

[0454] One or more compounds of formula IV, preferably of formula CC-nV, CC-n-Vm, CC-nm, CC-VV, CCVC-nV and / or

[0455] One or more compounds of formula V, preferably of formulas CP-n-Om, CCP-nm, CCP-Vn, CCP-V2-n, CLP-Vn, CCVC-nV, CGP-nm, PGP-nm, PGP-n-mV and CPGP-nm and / or

[0456] Optionally, preferably necessarily, one or more compounds of formula VI, preferably of formula Yn-Om, Y-nO-Om and / or CY-n-Om, selected from formula Y-3-O1, Y-4O-O4, CY-3-O2, CY-3-O4, CY-5-O2 and CY-5-O4 and / or

[0457] Optionally, preferably necessarily, one or more compounds of formula VII-1, preferably compounds selected from formulas CCY-nm and CCY-n-Om, preferably compounds of formula CCY-n-Om, preferably compounds selected from formulas CCY-3-O2, CCY-2-O2, CCY-3-O1, CCY-3-O3, CCY-4-O2, CCY-3-O2 and CCY-5-O2, and / or

[0458] Optionally, preferably necessarily, one or more compounds of formula VII-2, preferably of formula CLY-n-Om, preferably selected from formula CLY-2-O4, CLY-3-O2, CLY-3-O3 and / or

[0459] One or more compounds of formula VIII, preferably of formulas CZY-n-On and CCOY-nm and / or

[0460] One or more compounds of formula IX, preferably compounds selected from formulas PYP-nm and PGIY.n-Om and / or

[0461] One or more compounds of formula B and / or

[0462] One or more compounds of formula S and / or

[0463] Optionally, preferably necessarily, one or more compounds of formula IV, preferably selected from compounds of formula CC-nV, CC-n-Vm and CC-nV-Vm, preferably CC-3-V, CC-3-V1, CC-4-V, CC-5-V and CC-VV, particularly preferably selected from compounds CC-3-V, CC-3-V1, CC-4-V and CC-VV, very particularly preferably compound CC-3-V, and optionally additionally one or more compounds CC-4-V and / or CC-3-V1 and / or CC-VV.

[0464] In a particularly preferred embodiment of the invention, the medium according to the invention comprises one or more compounds of the formula PPGU-nF. Compounds of the formula PPGU-nF are also very suitable for use as stabilizers in liquid crystal mixtures.

[0465] In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds of formula IX.

[0466] Compounds of formula IX are also well-suited for use as stabilizers in liquid crystal mixtures, especially those with p = q = 1 and ring A. 9 =1,4-phenylene. In particular, they stabilize the VHR of the mixture for UV exposure.

[0467] In a preferred embodiment, the medium according to the invention comprises one or more compounds of formula IX, selected from one or more compounds of formulas IX-1 to IX-4, with formulas IX-1 to IX-3 being particularly preferred.

[0468]

[0469] The parameters have the meanings given in Equation IX, where F / H represents F or H.

[0470] In another preferred embodiment, the medium comprises one or more compounds of formula IX-3, preferably formula IX-3-a.

[0471]

[0472] Alkyl and alkyl' independently represent alkyl groups having 1 to 7 carbon atoms, preferably having 2 to 5 carbon atoms.

[0473] When compounds of formula IX are used in the liquid crystal medium according to this application, they are preferably present at a concentration of 20% or less, more preferably 10% or less, and most preferably 5% or less, and for a single compound, i.e. (homologous) compound, the concentration is preferably 10% or less, and more preferably 5% or less.

[0474] For the purposes of this invention, unless otherwise stated, the following definitions relate to the description of the composition components:

[0475] - "Contains": The concentration of the discussed component in the composition is preferably 5% or higher, particularly preferably 10% or higher, and very particularly preferably 20% or higher.

[0476] - "Mainly composed of": The concentration of the discussed component in the composition is preferably 50% or higher, particularly preferably 55% or higher, and very particularly preferably 60% or higher.

[0477] - "consisting essentially of": The concentration of the discussed component in the composition is preferably 80% or higher, particularly preferably 90% or higher, and very particularly preferably 95% or higher, and

[0478] - "actually composed entirely of": The concentration of the discussed component in the composition is preferably 98% or higher, particularly preferably 99% or higher, and very particularly preferably 100.0%.

[0479] This applies to media having its components (which can be components and compounds) and also to components having its components (compounds). The term "comprising" means that the concentration of the compound in question is preferably 1% or higher, particularly preferably 2% or higher, and very particularly preferably 4% or higher, only when the concentration of the individual compounds relative to the entire medium is involved.

[0480] In this invention, "≤" means less than or equal to, preferably less than, and "≥" means greater than or equal to, preferably greater than.

[0481] For the present invention,

[0482]

[0483] express trans -1,4-cyclohexylene,

[0484]

[0485] This indicates 1,4-cyclohexylene, preferably... trans -1,4-cyclohexylene, and

[0486]

[0487] It represents 1,4-phenylene.

[0488] For the purposes of this invention, the term "dielectrically positive compound" refers to a compound having a Δε > 1.5, the term "dielectrically neutral compound" generally refers to those wherein -1.5 ≤ Δε ≤ 1.5, and the term "dielectrically negative compound" refers to those wherein Δε < -1.5. The dielectric anisotropy of the compounds is determined in each case by dissolving 10% of the compound in a liquid crystal matrix and measuring the capacitance of the resulting mixture at 20°C and a frequency of 1 kHz in at least one test cell with a vertical alignment and a surface alignment, and a cell thickness of 20 μm. The measurement voltage is typically 1.0 V, but is always below the capacitance threshold of the corresponding liquid crystal mixture under study.

[0489] The host mixtures for the dielectric positive and dielectric neutral compounds were ZLI-4792, and the host mixture for the dielectric negative compounds was ZLI-2857, both from Merck KGaA, Germany. The values ​​for the corresponding compounds under investigation were obtained by extrapolating the change in dielectric constant of the host mixture after the addition of the compound under investigation to 100% of the compound used. The compound under investigation was dissolved in the host mixture at 10%. If the solubility of the substance was too low for this purpose, the concentration was gradually halved until the study could be carried out at the desired temperature.

[0490] Compounds of Formula I according to the present invention, or compounds of Formula I used according to the present invention, can be advantageously prepared according to the following reaction scheme.

[0491] Synthesis Scheme 1:

[0492]

[0493] Where n preferably represents 2, 3 or 4, and particularly preferably 3 or 4.

[0494] Synthesis Scheme 2:

[0495]

[0496] Where n preferably represents 2, 3 or 4, and particularly preferably 3 or 4.

[0497] Synthesis Scheme 3:

[0498]

[0499] Where m represents an integer from 3 to 6, with 4 or 6 being particularly preferred.

[0500] In the above reaction scheme, Pg represents the protecting group, and Rg represents the leaving group, and the parameter n has the meaning given in Formula I. Furthermore, R...1 Having the condition for R in Equation I 11 The given meaning, the ring structure has the meaning given for ZG in the case of Equation I, Sp 1 and Sp 2 Each has the condition for S under equation I. 1 and S 2 The given meaning, and preferably n represents 3 or 4, the ring structure represents an aromatic or aliphatic group, Sp 1 and Sp 2 Indicates a single bond or an alkylene group having 1 to 8 carbon atoms, and R 1 This indicates an alkyl group having 1 to 8 carbon atoms.

[0501] For the purposes of this invention, unless otherwise stated, the following definitions relate to the description of the composition components:

[0502] - "Contains": The concentration of the discussed component in the composition is preferably 5% or higher, particularly preferably 10% or higher, and very particularly preferably 20% or higher.

[0503] - "Mainly composed of": The concentration of the discussed component in the composition is preferably 50% or higher, particularly preferably 55% or higher, and very particularly preferably 60% or higher.

[0504] - "consisting essentially of": The concentration of the discussed component in the composition is preferably 80% or higher, particularly preferably 90% or higher, and very particularly preferably 95% or higher, and

[0505] - "actually composed entirely of": The concentration of the discussed component in the composition is preferably 98% or higher, particularly preferably 99% or higher, and very particularly preferably 100.0%.

[0506] This applies to media having its components (which can be components and compounds) and also to components having its components (compounds). The term "comprising" means that the concentration of the compound in question is preferably 1% or higher, particularly preferably 2% or higher, and very particularly preferably 4% or higher, only when the concentration of the individual compounds relative to the entire medium is involved.

[0507] In this invention, "≤" means less than or equal to, preferably less than, and "≥" means greater than or equal to, preferably greater than.

[0508] For the present invention,

[0509]

[0510] express trans -1,4-cyclohexylene, and

[0511]

[0512] It represents 1,4-phenylene.

[0513] For the purposes of this invention, the term "dielectrically positive compound" refers to a compound having a Δε > 1.5, the term "dielectrically neutral compound" refers to those wherein -1.5 ≤ Δε ≤ 1.5, and the term "dielectrically negative compound" refers to those wherein Δε < -1.5. The dielectric anisotropy of the compounds is determined in each case by dissolving 10% of the compound in a liquid crystal matrix and measuring the capacitance of the resulting mixture at 1 kHz in at least one test cell with a 20 μm cell thickness and a vertical alignment and a planar alignment. The measurement voltage is typically 0.5 V to 1.0 V, but is always below the capacitance threshold of the corresponding liquid crystal mixture under study.

[0514] The host mixtures for the dielectric positive and dielectric neutral compounds were ZLI-4792, and the host mixture for the dielectric negative compounds was ZLI-2857, both from Merck KGaA, Germany. The values ​​for the corresponding compounds under investigation were obtained by extrapolating the change in dielectric constant of the host mixture after the addition of the compound under investigation to 100% of the compound used. The compound under investigation was dissolved in the host mixture at 10%. If the solubility of the substance was too low for this purpose, the concentration was gradually halved until the study could be carried out at the desired temperature.

[0515] If necessary, the liquid crystal medium according to the invention may also contain other additives, such as stabilizers and / or pleochroic dyes and / or chiral dopants, in typical amounts. Based on the total amount of the mixture, the amount of these additives used is preferably 0% or higher to 10% or lower, particularly preferably 0.1% or higher to 6% or lower. The concentration of the individual compound used is preferably 0.1% or higher to 3% or lower. When specifying the concentration and concentration range of the liquid crystal compound in the liquid crystal medium, the concentration of these and similar additives is generally not considered.

[0516] In a preferred embodiment, the liquid crystal medium according to the invention comprises a polymer precursor containing one or more reactive compounds, preferably reactive mesomorphs, and, if necessary, other additives, such as polymerization initiators and / or polymerization modifiers, in typical amounts. The total amount of these additives used is 0% to 10% or less, preferably 0.1% to 2% or less, based on the total amount of the mixture. The concentrations of these and similar additives are not considered when specifying the concentrations and concentration ranges of the liquid crystal compounds in the liquid crystal medium.

[0517] The composition comprises a plurality of compounds, preferably 3 or more to 30 or fewer, particularly preferably 6 or more to 20 or fewer, and very particularly preferably 10 or more to 16 or fewer, which are mixed in a conventional manner. Typically, the desired amount of the component used in a small quantity is dissolved in the component constituting the main component of the mixture. This is advantageously carried out at elevated temperatures. If the selected temperature is above the clearing point of the main component, the completion of the dissolution operation is particularly easily observed. However, liquid crystal mixtures can also be prepared in other conventional ways, such as using premixing or from a so-called “multi-bottle system.”

[0518] The mixtures according to the invention exhibit a very wide nematic phase range with a clearing point at 65°C or higher, a very favorable capacitance threshold, a relatively high retention value, and very good low-temperature stability at both -30°C and -40°C. Furthermore, the mixtures according to the invention are characterized by a low rotational viscosity γ1.

[0519] It will be self-evident to those skilled in the art that the medium according to the invention for use in VA, IPS, FFS or PALC displays may also contain compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.

[0520] The structure of the liquid crystal display according to the present invention corresponds to a general geometric structure, such as that described in EP-A0240379.

[0521] The liquid crystal phases according to the invention can be improved by suitable additives in a way that allows them to be used in any type of LCD display disclosed to date, such as ECB, VAN, IPS, GH, or ASM-VA LCD displays.

[0522] Table E below shows the possible dopants that can be added to the mixtures according to the invention. If the mixture contains one or more dopants, they are used in amounts of 0.01% to 4%, preferably 0.1% to 1.0%.

[0523] For example, stabilizers that can be added to the mixtures according to the invention in amounts of 0.01% to 6%, particularly 0.1% to 3%, are shown in Table F.

[0524] For the purposes of this invention, unless otherwise expressly stated, all concentrations are indicated as weight percentages, and unless otherwise expressly stated, refer to the respective mixtures or mixture components.

[0525] Unless otherwise expressly stated, all temperature values ​​indicated in this application, such as melting point T(C,N), transformation from smectic (S) phase to nematic (N) phase T(S,N), and clearing point T(N,I), are expressed in Celsius (°C), and all temperature differences are expressed accordingly in degrees (° or degrees).

[0526] For the purposes of this invention, unless otherwise explicitly stated, the term “threshold voltage” refers to the capacitive threshold (V0), also known as the Freedericks threshold.

[0527] In each case, unless otherwise expressly stated, all physical properties are and have been determined in accordance with "Merck LiquidCrystals, Physical Properties of Liquid Crystals", Status November 1997, Merck KGaA, Germany, at a temperature of 20°C, and Δn is measured at 589 nm and Δε at 1 kHz.

[0528] As for switching behavior, electro-optical properties, such as threshold voltage (V0) (capacitive measurement), were measured in a test chamber manufactured by Merck Japan. The test chamber has a soda-lime glass substrate and is constructed in an ECB or VA configuration with a polyimide alignment layer (using a diluent). SE-1211 (mixing ratio 1:1), 26 (both from Nissan Chemicals, Japan), the polyimide alignment layers have been rubbed perpendicularly to each other and affect the vertical alignment of the liquid crystal. The transparent, almost square ITO electrode has a surface area of ​​1 cm². 2 .

[0529] Unless otherwise stated, chiral dopants should not be added to the liquid crystal mixture used, but the latter is particularly suitable for applications where this type of doping is necessary.

[0530] VHR was measured in a test chamber manufactured by Merck Japan. The test chamber has a soda-lime glass substrate and is constructed using a 50 nm thick polyimide alignment layer (e.g., AL-3046 from Japan Synthetic Rubber, Japan, unless otherwise specified) that has been rubbed perpendicularly to each other, or using an alignment layer that has been rubbed perpendicularly to each other as described in the examples. The layer thickness is uniform at 6.0 µm. The surface area of ​​the transparent ITO electrode is 1 cm². 2 .

[0531] VHR at 20℃ (VHR) 20 ) and at 100℃ (VHR) 100After drying in an oven for 5 minutes, the sample was measured using an instrument commercially available from Autronic Melchers, Germany. The voltage used had a frequency of 60 Hz, or the conditions shown in the example.

[0532] The accuracy of VHR measurements depends on the corresponding value of VHR. Accuracy decreases as the value decreases. The deviations typically observed for values ​​in various orders of magnitude are compiled in the table below by their order of magnitude.

[0533]

[0534] Stability to UV radiation was investigated using the commercial instrument “Suntest CPS” from Heraeus, Germany. The sealed test chamber was irradiated for 2.0 hours without additional heating. The irradiation power was 765 W / m² in the wavelength range of 300 nm to 800 nm. 2 V, or the condition indicated in the examples. To simulate the so-called window glass pattern, a UV “cut-off” filter with a 310 nm edge wavelength was used. In each series of experiments, at least four test boxes were studied for each condition, and the corresponding results are expressed as the average of the respective individual measurements.

[0535] Voltage retention rate is typically caused by exposure, such as UV irradiation from an LCD backlight. The decrease in VHR can be determined according to the following equation (1):

[0536] (1).

[0537] The relative stability (S) of the LC mixture with respect to the load at time t is determined according to the following equation (2). rel ):

[0538] (2),

[0539] Here, "ref" represents the corresponding unstable mixture.

[0540] Besides VHR, another characteristic measure that can characterize the conductivity of liquid crystal mixtures is ion density. High ion density often leads to display malfunctions such as image stickiness and flicker. Ion density is preferably measured in a test chamber manufactured by Merck Japan Ltd. The test chamber has a substrate made of soda-lime glass and is designed with a polyimide alignment layer (e.g., AL-3046 from Japan Synthetic Rubber, Japan, unless otherwise specified) with a thickness of 40 nm. The liquid crystal mixture layer thickness is a uniform 6.0 μm. Additionally, a circular transparent ITO electrode with a protective ring has an area of ​​1 cm².2 The accuracy of the measurement method is approximately ±15%. The liquid crystal cell is dried overnight in an oven at 120°C, and then filled with the relevant liquid crystal mixture.

[0541] Ion density was measured using instruments commercially available from TOYO, Japan. The measurement method is essentially similar to cyclic voltammetry, as described in M. Inoue, “Recent Measurement of Liquid Crystal Material Characteristics,” Proceedings IDW 2006, LCT-7-1, 647. In this method, the applied DC voltage varies between positive and negative maxima according to a pre-specified triangular curve. Thus, a complete run through the curve forms a measurement cycle. If the applied voltage is large enough to allow ions in the field to move to the corresponding electrode, an ion current is formed due to ion discharge. The amount of charge transferred here is typically in the range of a few pC to a few nC. This makes the highly sensitive detection ensured by the aforementioned instrument essential. The results are expressed as current / voltage curves. The ion current here is evident from the peak appearing at a voltage less than the threshold voltage of the liquid crystal mixture. The integral of the peak area gives the value of the ion density of the mixture under study. Four test boxes were measured for each mixture. The repetition frequency of the triangular voltage is 0.033 Hz, the measurement temperature is 60 °C, and the maximum voltage is ±3 V to ±10 V, depending on the order of magnitude of the dielectric anisotropy of the relevant mixture.

[0542] Rotational viscosity was measured using a rotating permanent magnet method, and flow viscosity was measured in a modified Ubbelohde viscometer. For liquid crystal mixtures ZLI-2293, ZLI-4792, and MLC-6608 (all products from Merck KGaA, Darmstadt, Germany), the rotational viscosities measured at 20°C were 161 mPa·s, 133 mPa·s, and 186 mPa·s, respectively, and the flow viscosity (ν) was 21 mm·s, respectively. 2 ·s -1 14mm 2 ·s -1 and 27mm 2 ·s -1 .

[0543] Unless otherwise expressly stated, use the following symbols:

[0544] V0 represents the capacitive [V] threshold voltage at 20℃;

[0545] n e This indicates the unusual refractive index measured at 20°C and 589 nm.

[0546] n o This represents the ordinary refractive index measured at 20°C and 589 nm.

[0547] △n represents the optical anisotropy measured at 20℃ and 589nm.

[0548] ε ⊥ This represents the dielectric susceptibility perpendicular to the director at 20℃ and 1kHz.

[0549] ε || This represents the dielectric susceptibility parallel to the director at 20℃ and 1kHz.

[0550] Δε represents the dielectric anisotropy at 20℃ and 1kHz.

[0551] cl.p. or

[0552] T(N,I) represents the clearing point [°C].

[0553] ν represents the flow viscosity measured at 20°C [mm]. 2 ·s -1 ],

[0554] γ1 represents the rotational viscosity [mPa·s] measured at 20℃.

[0555] K1 represents the elastic constant [pN] for "stretching" deformation at 20℃.

[0556] K2 represents the elastic constant [pN] for "torsional" deformation at 20℃.

[0557] K3 represents the elastic constant [pN] for "bending" deformation at 20℃, and

[0558] LTS indicates the low-temperature stability of the phase measured in the test chamber.

[0559] VHR represents the voltage holding rate.

[0560] △VHR represents the decrease in voltage holding rate, and

[0561] S rel This indicates the relative stability of the VHR.

[0562] The following examples illustrate the invention, but are not intended to limit it. However, they demonstrate to those skilled in the art the concept of using preferred compounds to be employed and their respective concentrations, as well as preferred mixtures thereof. Furthermore, the examples illustrate the available properties and combinations of properties.

[0563] For the purposes of this invention and in the following embodiments, the structures of the liquid crystal compounds are represented by acronyms and converted into chemical formulas according to Tables A through C below. All groups C n H 2n+1 C m H 2m+1 and C l H 2l+1 Or C n H 2n C m H 2m and C l H 2l The groups are straight-chain alkyl or alkylene groups, each having n, m, and l carbon atoms respectively. Table A shows the codes for the ring elements of the compound core, Table B lists the bridging units, and Table C lists the symbol meanings for the left-hand and right-hand end groups of the molecule. Acronyms consist of the code for the ring element with an optional linking group, followed by a first hyphen and the code for the left-hand end group, and a second hyphen and the code for the right-hand end group. Table D shows exemplary structures of the compounds and their respective abbreviations.

[0564] Table A: Ring Elements

[0565]

[0566]

[0567]

[0568]

[0569]

[0570] Table B: Bridging Units

[0571]

[0572] Table C: End Groups

[0573]

[0574] Where n and m are integers, and the three dots “…” are placeholders for other abbreviations from the table.

[0575] In addition to the compound of formula I, the mixture according to the invention preferably also contains one or more of the compounds mentioned below.

[0576] Use the following abbreviations:

[0577] (n, m, and z are each independent integers, preferably 1 to 6)

[0578] Table D

[0579]

[0580]

[0581]

[0582]

[0583]

[0584]

[0585]

[0586]

[0587]

[0588]

[0589]

[0590]

[0591]

[0592]

[0593]

[0594]

[0595]

[0596]

[0597]

[0598]

[0599]

[0600]

[0601]

[0602]

[0603]

[0604]

[0605]

[0606]

[0607]

[0608]

[0609]

[0610]

[0611]

[0612]

[0613]

[0614]

[0615]

[0616]

[0617]

[0618]

[0619]

[0620]

[0621]

[0622]

[0623]

[0624]

[0625]

[0626]

[0627]

[0628]

[0629]

[0630]

[0631]

[0632]

[0633]

[0634]

[0635]

[0636]

[0637]

[0638]

[0639] Table E shows the chiral dopants preferably used in the mixtures according to the invention.

[0640] Table E

[0641]

[0642]

[0643] In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds selected from the compounds in Table E.

[0644] Table F shows stabilizers, in addition to compounds of Formula I, that may also be preferably used in the mixtures according to the invention. Here, the parameter n represents an integer in the range of 1 to 12. In particular, the phenolic derivatives shown can be used as additional stabilizers because they act as antioxidants.

[0645] Table F

[0646]

[0647]

[0648]

[0649] In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds selected from the compounds in Table F, particularly one or more compounds selected from the following two formulas.

[0650] Detailed Implementation

[0651] Example

[0652] The following embodiments illustrate the invention but do not limit it in any way. However, the physical properties described make it clear to those skilled in the art what properties can be achieved and to what extent they can be modified. In particular, this provides a good definition for those skilled in the art of the various combinations of properties that can be preferably achieved.

[0653] Material Examples

[0654] The following substances are preferred substances according to Formula I of this application or substances of Formula I that are preferred to be used according to this application.

[0655]

[0656]

[0657]

[0658]

[0659]

[0660] The following embodiments illustrate the invention but do not limit it in any way. However, the physical properties described make it clear to those skilled in the art what properties are to be achieved and to what extent they can be modified. In particular, this provides a good definition for those skilled in the art of the various combinations of properties that can be preferably achieved.

[0661] Synthesis Example 1: Synthesis of bis(2,2,6,6-tetramethylpiperidin-4-yl)2-{3-[2,5-bis({4-butyl-5-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]-4-{[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]carbonyl}-5-oxopentyl})phenyl]propyl}-2-butylmalonate 1

[0662] (Material Example 1)

[0663]

[0664] Step 1.1: Synthesis of 3-[3,4-bis(3-hydroxypropyl)phenyl]prop-1-ol A

[0665]

[0666] Dissolve 51.34 g (484.0 mmol) of anhydrous sodium carbonate in 171.7 mL of water. Add a solution of 25.0 g (79.0 mmol) of 1,2,4-tribromobenzene and 67.70 g (476.0 mmol) of 2-butoxy-1,2-oxacyclopentaborane in 965.2 mL of tetrahydrofuran (THF), add 1.65 mL (11.9 mmol) of triethylamine, stir the mixture, and degas it under an argon flow for 30 min. Add 1.40 g (7.49 mmol) of palladium(II) chloride (59% palladium, anhydrous) and 1.85 g (3.97 mmol) of 2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl, and reflux the reaction mixture with stirring for 18 hours. Cool the reaction mixture to room temperature (RT), add water and methyl tert-butyl ether (MTBE), and separate the phases. The aqueous phase was extracted with MTBE, and the combined organic phases were washed with saturated NaCl solution, dried over sodium sulfate, filtered, and evaporated under vacuum. The product was a pale yellow oil, which was filtered through silica gel using a mixture of ethyl acetate (EA) and methanol (9:1). The product fractions were combined and evaporated under vacuum to obtain the reaction product, a pale yellow oil. The product was characterized by NMR spectroscopy.

[0667] 1 H NMR (500MHz, DMSO-d6)

[0668] δ = 1.66 (m c , 6H, CH2), 2.42–2.69 (m (与DMSO叠加) , 6H, CH2,), 3.36–3.49 (m,6H, CH2), 4.44 (t, J = 5.15 Hz, 1H), 4.48 (m c , 2H), 6.92 (dd, J = 1.7, 7.72Hz, 1H), 6.95 (d, J = 1.53 Hz, 1H), 7.03 (d, J = 7.7 Hz, 1H).

[0669] Step 1.2: Synthesis of 1,2,4-tris(3-iodopropyl)benzene B

[0670]

[0671] 30.2 mL (138 mmol) of triphenylphosphine was dissolved in 513 mL of acetonitrile, and a solution of 34.92 g (138.0 mmol) of iodine was added dropwise to 513 mL of acetonitrile under mild cooling. An orange suspension was formed during this addition. When the addition was complete, the mixture was stirred for another 10 min. 13.3 g (197 mmol) of imidazole was added, followed by dropwise addition of a solution of 10.0 g (39.3 mmol) of triol A in 100 mL of acetonitrile (a clear yellow solution was formed during this addition). The reaction solution was stirred at RT for 3 h and carefully poured into a cold sodium thiosulfate solution (decolorization occurred), followed by the addition of heptane. After washing with stirring, the phases were separated, the aqueous phase was extracted with heptane, and the combined organic phases were washed with water, dried over sodium sulfate, filtered, and evaporated under vacuum. The crude product was filtered through silica gel with heptane (H) and ethyl acetate (8:2), and the product fraction was evaporated to give a colorless oily product. The product was characterized by mass spectrometry.

[0672] MS(EI) = 582.0

[0673] Step 1.3: Synthesis of 2-Butylmalonyl dichloride C

[0674]

[0675] First, 76.00 g (474.5 mmol) of 2-butylmalonic acid was introduced into the reaction apparatus and heated to 40 °C. Then, 90.00 mL (1.240 mol) of thionyl chloride was added dropwise over approximately 30 minutes (carefully, to avoid gas release), and the mixture was stirred at room temperature (RT) for another 5 hours (h). During this time, gas release decreased significantly. The reaction solution was then stirred at 50 °C for 18 hours, followed by stirring at 70 °C for 5 hours. Slight gas release occurred again with each increase in temperature. The reaction mixture was then cooled to room temperature and dissolved in 300 mL of anhydrous toluene, and excess thionyl chloride was separated from the toluene by distillation (8 mBar, RT to the maximum bath temperature of 80 °C) to give a crude product as a brownish liquid, which was used directly in the next synthetic step.

[0676] Step 1.4: Synthesis of bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)2-butylmalonate D

[0677]

[0678] 45.3 g (262.9 mmol) of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy (free radical) and 40.1 mL (289.15 mmol) of triethylamine were dissolved in 419 mL of dichloromethane (DCM) and cooled to -11 °C. Then, over 1.5 h, a solution of 25.9 g (131.4 mmol) of acyl chloride C in 252 mL of DCM was added dropwise from -11 °C to -6 °C. The reaction mixture was stirred at a maximum of 0 °C for about 3 h, slowly thawed, and stirred at room temperature (RT) for 18 h. A saturated NaHCO3 solution was added under cooling at 3–6 °C, the mixture was briefly stirred, and the phases were separated. The aqueous phase was extracted with DCM, and the organic phases were combined, washed with saturated NaCl solution, dried over sodium sulfate, filtered, and evaporated under vacuum. The resulting crude product (orange solid) was filtered through silica gel using DCM / MTBE (9:1), and the product fraction was evaporated under vacuum to give orange crystals.

[0679] Step 1.5: Synthesis of bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)2-{3-[2,5-bis({4-butyl-5-[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]-4-{[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]carbonyl}-5-oxopentyl})phenyl]propyl}-2-butylmalonate 1'

[0680]

[0681] 0.31 g (7.87 mmol) of sodium hydride (60% suspension in paraffin oil) was suspended in 9.7 mL of N,N-dimethylformamide (DMF). A solution of 3.75 g (7.87 mmol) of diradical D dissolved in 29.0 mL of DMF was added dropwise under mild cooling (gas release), and the mixture was stirred at RT for 1 hour. 1.40 g (2.39 mmol) of triiodide B was added dropwise to the reaction solution (exothermic reaction at 5°C over 5 minutes), and the mixture was stirred at room temperature for 3 hours. The reaction mixture was carefully added to an ammonium chloride solution and extracted with MTBE. The phases were separated, the aqueous phase was extracted with MTBE, washed with saturated NaCl solution, dried over sodium sulfate, filtered, and evaporated under vacuum. The resulting orange crude product was filtered through silica gel with ethyl acetate / heptane (1:1), and the product fraction was evaporated under vacuum to give an orange solid that effervesced in a glassy manner. This product has the following properties.

[0682] Phase: Glass transition temperature (TG) = 23.5℃, decomposition begins at 150℃.

[0683] MS(APCI) = 1605.1[M+H + ].

[0684] Step 1.6: Synthesis of bis(2,2,6,6-tetramethylpiperidin-4-yl)2-{3-[2,5-bis({4-butyl-5-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]-4-{[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]carbonyl}-5-oxopentyl})phenyl]propyl}-2-butylmalonate 1

[0685]

[0686] 1.5 g (0.1 mmol) of hexavalent 1' was dissolved in 20 mL of THF, and 1.5 g of sponge nickel (Johnson-Matthey A-7000) was added. The mixture was stirred at 5 bar hydrogen pressure and 50 °C for 17 hours. The reaction solution was cooled to room temperature, filtered, and evaporated under vacuum. The crude product was purified by column chromatography on basic alumina (RediSep Rf) in a CombiFlash apparatus using dichloromethane / methanol (95:5), and the product fractions were combined and evaporated under vacuum. The product was then heated in a bulb tube apparatus at 50 °C and 3.2 mL. 10 -1 Drying at mbar for 3 hours yields a foamy, glassy solid.

[0687] Phase: Tg (glass transition temperature) 39°C (melting point) 41°C (isotropic).

[0688] MS (APCI) = 1515.1 [M+H] + .

[0689] 1 H NMR (500 MHz, CDCl3)

[0690] δ = 0.54–0.99 (m (重叠的) ,16H, 6 X NH, CH2), 1.09–1.40 (m (重叠的) 97H, CH3,CH2), 1.48 (m c , 6H, CH2), 1.82–2.02 (m (重叠的) , 24H, CH2), 2.57 (t, J=7.63 Hz, 6H), 5.24 (m c , 6H, C H (CH2)2), 6.93 (d (与单重峰重叠) , J=7.87 Hz, 2H), 7.04 (d, J=7.72Hz, 1H).

[0691] Synthesis Example 2: Synthesis of bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)2-(3-{3,5-bis[({4-butyl-5-[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]-4-{[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]carbonyl}-5-oxopentyl}oxy)carbonyl]benzoyloxy}propyl)-2-butylmalonate 2

[0692]

[0693] Step 2.1: bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)2-butyl-2-[3-( Synthesis of alkyl-2-yloxy)propyl]malonate E

[0694]

[0695] 3.20 g (80.01 mmol) of sodium hydride (60% suspension in paraffin oil) was suspended in 30 mL of DMF. A solution of 32.40 g (69.14 mmol) of diradical D (from the synthesis of compound 1) in 300 mL of DMF was added dropwise to the reaction solution under mild cooling (gas release), and the mixture was stirred at room temperature for 1 hour. Then, a solution of 19.0 g (85.16 mmol) of 2-(3-bromopropoxy)tetrahydropyran in 200 mL of DMF was added dropwise at RT (exothermic at 0.5 °C). To degas the reaction mixture before temperature increase, a gentle argon flow was passed through the reaction mixture for 30 minutes using an immersion Pasteur pipette, and the mixture was subsequently stirred at 35 °C for 18 hours. The reaction solution was cooled to RT, added to a saturated NaCl solution, extracted with MTBE, and the phases were separated. The aqueous phase was extracted with MTBE, and the organic phases were combined, washed with saturated NaCl solution, dried with sodium sulfate, filtered and vacuum evaporated to obtain a crude product as a red oil. For purification, it was filtered through silica gel with DCM / MTBE (9:1) to obtain a product as a red oil.

[0696] Step 2.2: Synthesis of bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)2-butyl-2-(3-hydroxypropyl)malonate F

[0697]

[0698] 36.5 g (56.1 mmol) of diradical E and 9.50 g (55.2 mmol) of toluene-4-sulfonic acid monohydrate were dissolved in a mixture of 500 mL methanol and 50 mL water, and the mixture was stirred at 40 °C for 5 hours. The reaction solution was cooled to RT, and the pH was adjusted to 9 with NaHCO3 solution under cooling, followed by vacuum evaporation. The aqueous residue was extracted with MTBE, and the combined organic phases were washed with saturated NaCl solution, dried over sodium sulfate, filtered, and vacuum evaporated to give a red oil. This oil was dissolved in 250 mL DCM, and 6.00 g (55.6 mmol) of MnO2 was added. The mixture was stirred at RT for 1 hour. (In the case of removing the THP protecting group, the radicals may also be converted to OH compounds in some cases; MnO2 is used to reverse this conversion). The reaction mixture was filtered through silica gel with DCM and vacuum evaporated. The crude product obtained was filtered through silica gel with DCM / MTBE (7:3), and the product fraction was vacuum evaporated to give a red oil.

[0699] Step 2.3: Synthesis of bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)2-(3-{3,5-bis[({4-butyl-5-[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]-4-{[(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)oxy]carbonyl}-5-oxopentyl}oxy)carbonyl]-benzoyloxy}propyl)-2-butylmalonate 2')

[0700]

[0701] 6.70 g (11.7 mmol) of F and 50.0 mg (0.41 mmol) of 4-(dimethylamino)pyridine were dissolved in 100 mL of dichloromethane under RT, and the mixture was cooled to 4 °C. Then 5.00 mL (36.1 mmol) of triethylamine was added, followed by dropwise addition of 1.00 g (3.77 mmol) of 1,3,5-benzenetricarbonyl chloride in 10 mL of dichloromethane at 3-4 °C. The solution was prepared in DCM. When the exothermic reaction was complete, the mixture was warmed to RT and then stirred at RT for 18 h. Ammonium chloride solution was then added under cooling, the mixture was briefly stirred, and the phases were separated. The aqueous phase was extracted with DCM. The combined organic phases were washed with diluted NaCl solution (for better phase separation), dried over sodium sulfate, filtered, and evaporated under vacuum to give the reaction product as a red, solidifying foam. For further purification, the product was filtered through silica gel using DCM / MTBE (9:1 to 85:15), and the product fraction was evaporated under vacuum. The resulting reaction product was a red, solidifying foam. It possessed the following properties.

[0702] Phase: Tg (glass transition temperature) 52℃, C (melting point) 57℃, I, decomposition >175℃.

[0703] MS(APCI) = 1734.

[0704] The following compounds were prepared using a synthetic sequence similar to that described above.

[0705] Material / Synthesis Example 2'

[0706]

[0707] Material / Synthesis Example 2

[0708] (Formula I-7)

[0709]

[0710] Material / Synthesis Example 3'

[0711]

[0712] Phase: Tg (glass transition temperature) -3℃, I (isotropic), decomposition >100℃

[0713] Material / Synthesis Example 3

[0714]

[0715] Material / Synthesis Example 4'

[0716]

[0717] Phase: Tg (glass transition temperature) 5℃, I (isotropic), decomposition >180℃.

[0718] Material / Synthesis Example 4

[0719] (Formula I-9)

[0720]

[0721] Material / Synthesis Example 5'

[0722]

[0723] Phase: Tg (glass transition temperature) 5℃, I (isotropic), decomposition >170℃.

[0724] Material / Synthesis Example 5

[0725]

[0726] Material / Synthesis Example 6'

[0727] (Formula I-13)

[0728]

[0729] Phase: Tg (glass transition temperature) 27℃, I (isotropic).

[0730] Material / Synthesis Example 6

[0731] (Formula I-12)

[0732]

[0733] Material / Synthesis Example 7'

[0734]

[0735] Material / Synthesis Example 7

[0736] (Formula I-3)

[0737]

[0738] Phase: (Glass transition temperature) 14℃ I (Isotropic)

[0739] Material / Synthesis Example 8'

[0740] (Formula I-6)

[0741]

[0742] Material / Synthesis Example 8

[0743]

[0744] Phase: Tg (glass transition temperature) -3℃, I (isotropic)

[0745] Material / Synthesis Example 9'

[0746]

[0747] Material / Synthesis Example 9

[0748] (Formula I-5)

[0749]

[0750] Phase: Tg (glass transition temperature) -3℃, I (isotropic)

[0751] Material / Synthesis Example 10: Synthesis of 4-(3-{3-[3,5-bis({3-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]propoxy})phenyl]-5-{3-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]propoxy}phenoxy}propoxy)-2,2,6,6-tetramethylpiperidine

[0752]

[0753] Step 10.1: Synthesis of 1-benzyl-2,2,6,6-tetramethylpiperidine-4-ol A

[0754]

[0755] 37.80 ml (318.2 mmol) of benzyl bromide and 100.0 g (635.9 mmol) of 2,2,6,6-tetramethylpiperidin-4-ol were dissolved in 500 ml of N,N-dimethylformamide (DMF), and the mixture was stirred at 120 °C for 18 h. The reaction solution was cooled to room temperature (RT) and stirred into a mixture of water and ice. The mixture was stirred for 30 min, and the precipitated solid was filtered off and extracted with methyl tert-butyl ether (MTB ether). The product solution was washed several times with saturated sodium chloride solution, the organic phase was dried over sodium sulfate, filtered, and evaporated under vacuum. The resulting crude crystalline product was recrystallized from heptane / isopropanol (5:1) at 5 °C, and the crystals were filtered off and dried under vacuum at 40 °C for 18 h to obtain a colorless crystalline solid.

[0756] Step 10.2: 1-Benzyl-2,2,6,6-Tetramethyl-4-[3-( Synthesis of [alkyl-2-yloxy]-propoxy]piperidine B

[0757]

[0758] 35.00 g (141.5 mmol) of tetramethylpiperidine A, 47.20 g (211.5 mmol) of 2-(3-bromopropoxytetrahydropyran), and 20.00 g (62.04 mmol) of tetra-n-butylammonium bromide were suspended in 270 mL of toluene, and then 110 mL (2.10 mol) of sodium hydroxide solution (50%) was rapidly added dropwise at room temperature (RT). The reaction mixture was stirred at 60 °C for 16 h, and then cooled to RT. The reaction mixture was carefully added to a mixture of ice water and toluene, and the phases were separated. The aqueous phase was extracted with toluene, and the combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and evaporated under vacuum to give a yellow, partially crystalline crude product. 300 mL of heptane was added to the crude product, and the mixture was stirred and filtered. A yellow, oily reaction product was obtained in the mother liquor, which was filtered through silica gel using toluene / ethyl acetate (9:1 to 3:1). The product fractions were combined and vacuum evaporated to obtain a light yellow oily product.

[0759] Step 10.3: Synthesis of 3-[(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy]prop-1-ol C

[0760]

[0761] 34.60 g (80.91 mmol) of B and 20.00 g (116.1 mmol) of toluene-4-sulfonic acid monohydrate were dissolved in 700 mL of methanol, and 100 mL of water (exothermic / 7 K) was added at room temperature. The reaction solution was stirred at 40 °C for 1 h, followed by vacuum evaporation and dilution with methyl tert-butyl ether (MTBE). The mixture was carefully washed with saturated NaHCO3 solution, and the phases were separated. The organic phase was washed with saturated NaCl solution, dried over sodium sulfate, filtered, and vacuum evaporated to give a yellow oily crude product, which was filtered through silica gel using dichloromethane (DCM) and MTBE (3:1). The product fractions were combined to give an almost colorless oily reaction product.

[0762] Step 10.4: Synthesis of 1-benzyl-4-[3-(3-{3-[(1-benzyl-2,2,6,6-tetramethyl-piperidin-4-yl)oxy]propoxy]-5-bromophenoxy}propoxy]-2,2,6,6-tetramethylpiperidine D]

[0763]

[0764] 5.80 g (30.7 mmol) of 5-bromophenyl-1,3-diol, 21.50 g (70.4 mmol) of alcohol C from the previous step, and 18.51 g (70.58 mmol) of triphenylphosphine were dissolved in 120 mL of tetrahydrofuran (THF) and cooled to 0 °C. 14.70 mL (70.58 mmol) of diisopropyl azodicarboxylate was added dropwise to the reaction solution, and the mixture was stirred at room temperature for 16 h. The reaction mixture was evaporated under vacuum, 200 mL of heptane was added, and the mixture was stirred vigorously. The precipitated triphenylphosphine oxide was filtered off, and the mother liquor was washed with 100 mL of heptane and evaporated under vacuum. The obtained crude product was filtered through silica gel with heptane / MTBE (7:3), and the combined product fractions were evaporated under vacuum to give a viscous, oily reaction product.

[0765] Step 10.5: Synthesis of 1-benzyl-4-[3-(3-{3-[(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy]propoxy}-5-[3,5-bis({3-[(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy]propoxy})-phenyl]phenoxy)propoxy]-2,2,6,6-tetramethylpiperidine E]

[0766]

[0767] The 14.60 g (19.11 mmol) of bromide D, 2.54 g (10.0 mmol) of bis(pinacol) diborone, and 2.81 g (28.7 mmol) of potassium acetate from the previous step were first introduced into 150 ml of dioxin. The mixture was placed in an alkyl group and degassed under an argon atmosphere for 30 minutes. 220.00 mg (0.30 mmol) of PdCl₂-dppf was added, and the reaction mixture was stirred at 100 °C for 1 h. It was then cooled below the boiling point, and another 220.00 mg (0.30 mmol) of PdCl₂-dppf and 25 ml (50 mmol) of sodium carbonate solution (2 M) were added. The mixture was stirred at 100 °C for 20 h. The reaction mixture was cooled to room temperature, water and MTBE were added, and the phases were separated. The aqueous phase was extracted with MTBE, and the organic phases were combined, washed with water, dried over sodium sulfate, filtered, and evaporated under vacuum. A crude product as a black oil was obtained and filtered through silica gel using heptane / MTBE (8:2 to 7:3). The combined product fractions were evaporated under vacuum to give a reaction product as a yellow resin.

[0768] MS(APCI) = 1367.9 [M] +

[0769] 1H NMR (500 MHz, CDCl3)

[0770] δ=0.99(s, 24H, CH3),1.13(s, 24H, CH3),1.45(t, J=11.7 Hz, 8H, CH2),1.94 (dd, J=12.25, 3.84 Hz, 4H, CH2), 2.09 (quint, J = 6.16 Hz, 4 H, CH2),3.71 (t (与多重峰叠加) , J = 6.21 Hz, 6 H, CH2, CH), 3.83 (s, 8H, CH2), 4.15 (t, 6.15Hz), 6.53 (t, 2.06 Hz, 2H), 6.76 (d, J = 2.12 Hz, 4H), 7.16 (t, 7.26 Hz, 4H), 7.28 (t, 7.72 Hz, 8H), 7.43 (d, J = 7.49 Hz, 8 H).

[0771] Step 10.6: Synthesis of 4-(3-{3-[3,5-bis({3-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]propoxy})phenyl]-5-{3-[(2,2,6,6-tetramethylpiperidin-4-yl)oxy]-propoxy}phenoxy}propoxy)-2,2,6,6-tetramethylpiperidine 10)

[0772]

[0773] 8.50 g (6.21 mmol) of product E from the previous step was dissolved in 107 mL of tetrahydrofuran, 3.00 g of 5% Pd / C (50% water, Degussa) was added, and the mixture was stirred at atmospheric pressure and room temperature (RT) for 17 hours under a hydrogen atmosphere. The reaction mixture was filtered and evaporated under vacuum. The residue was dissolved in 100 mL of MTBE, 50 mL of 2N hydrochloric acid was added, and the phases were separated. The aqueous phase was extracted with MTBE, then adjusted to pH 12–13 using 32% sodium hydroxide solution and extracted with MTBE ether. The combined organic phases were washed with saturated sodium chloride solution, dried over sodium sulfate, filtered, and evaporated under vacuum. The resulting crude product was filtered through Al2O3 (“basic alumina”) with dichloromethane / methanol, the product fractions were combined, and evaporated under vacuum to give a solidified, pale yellow oily product.

[0774] Phase: Tg (glass transition temperature) -4℃, T(C,I) (melting point) 64℃, I (isotropic).

[0775] MS (APCI) = 1007.7 [M+H]+

[0776] 1H NMR (500 MHz, CDCl3)

[0777] δ = 0.62 (s (broad), 4H, NH), 1.02 (t, J = 11.76, 8H), 1.15 (s, 24H, CH3), 1.19 (s, 24H, CH3), 1.98 (dd, 12.49, 3.9 Hz 8H), 2.07 (quintet, 6.13 Hz, 8H), 3.69 (t ( 重叠的 ), J = 5.8 Hz, 12H), 4.12 (t, J = 6.1 Hz, 8 H), 6.50 (s( 宽 ) = 2H),6.73 (d, J = 2.1 Hz, 4H).

[0778] Material / Synthesis Example 11: Synthesis of the following substances

[0779]

[0780] The compound was prepared in a similar manner, yielding a colorless oil.

[0781] Phase: T g (Glass transition temperature) -118℃.

[0782] 1 H NMR (500 MHz, CDCl3)

[0783] δ=6.35 (dd, J = 13.3, 2.2 Hz, 6H), 4.05 (t, J = 6.1 Hz, 8H), 3.81 –3.51 (m, 12), 2.57 – 2.48 (m, 4H), 2.04 (p, J = 6.2 Hz, 8H), 1.98 (dd, J =12.5, 3.9 Hz, 8H), 1.67 – 1.56 (m, 4H), 1.36 (d, J = 4.1 Hz, 6H), 1.18 (d J =19.7 Hz, 48H), 1.02 (t, J = 11.7 Hz, 8H), 0.69 (s, 4H).

[0784] Mixture Examples

[0785] Liquid crystal mixtures with the compositions and properties shown in the table below were prepared and investigated. Improved stability of the mixtures containing compound I was demonstrated by comparison with an unstable base mixture used as a reference.

[0786] Example 1 and corresponding comparative examples

[0787] Prepare and study the following mixture (M-1).

[0788]

[0789] First, the stability of the voltage retention rate of the mixture (M-1) itself was determined. The stability of mixture M-1 to backlight irradiation was investigated in a test chamber containing an alignment material with a layer thickness of 6.0 μm for planar alignment and a flat ITO electrode. For this purpose, one or more mixtures were tested for exposure to backlight. The stability of the corresponding test chambers to LED (light-emitting diode) backlight illumination for LCDs was investigated. For this purpose, the corresponding test chambers were filled and sealed. These chambers were then exposed to commercial LCD backlight illumination multiple times. No additional heat was applied except for the heat generated by the backlight. The voltage retention rate was then determined after 5 minutes at 100°C in each case. The results are summarized in Table 1a below.

[0790] Here, as shown below, six test boxes were filled and studied for each individual mixture. The indicated value is the average of the six individual values.

[0791] In various measurement series, the relative deviation of the "voltage retention rate" value is typically in the range of about 3% to 4%.

[0792] Accordingly, reference compound R-1 at concentrations of 100 ppm, 500 ppm, or 1000 ppm was added to the other three portions of mixture M-1.

[0793]

[0794] And accordingly, 100 ppm, 500 ppm, or 1000 ppm of compound I-10 were added to the other three portions of mixture M-1.

[0795]

[0796] As described above, the stability of the resulting mixtures (C-1.1, C-1.2, and C-1.3, and M-1.1, M-1.2, and M-1.3) was investigated. The results are shown in the following tables, Tables 1a to 1c.

[0797] Table 1a

[0798]

[0799] Table 1b

[0800]

[0801] Table 1c

[0802]

[0803] Example 2 and corresponding comparative examples

[0804] Prepare and study the following mixture (M-2).

[0805]

[0806] The voltage retention rate of mixture M-2 and its stability under UV radiation were investigated below. For this purpose, the mixture was also divided into several portions.

[0807] First, the stability of the mixture (M-2) itself was determined. For this purpose, the stability of mixture M-1 to UV exposure was investigated in a test chamber with a suitable polyimide of 6.0 μm thickness as the alignment material for planar alignment and a flat ITO electrode. For this purpose, the corresponding test chamber was irradiated in Suntest for 30 minutes. The voltage retention rate was then determined after 5 minutes at 100 °C in each case. Unless otherwise specified, the addressing frequency (or measurement frequency) here is 60 Hz. The results are summarized in Table 2a.

[0808] Then, for comparison, reference compound R-1 was added at 100 ppm, 500 ppm, or 1000 ppm to three portions of mixture M-2, and the resulting mixtures (C-2.1, C-2.2, and C-2.3) were studied as described above. Then, compound I-9 was added at 100 ppm, 500 ppm, or 1000 ppm to three portions of mixture M-2, and the resulting mixtures (M-2.1, M-2.2, and M-2.3) were studied as described above.

[0809] Example 3

[0810] The following mixture (M-3) was prepared and studied.

[0811]

[0812] As described in Examples 1 and 2, mixture M-3 was also divided into several portions, and its exposure stability to LCD backlight and UV source was studied in a test box with planar aligned alignment materials and planar ITO electrodes, as well as with various additive compounds.

[0813] Example 4

[0814] The following mixture (M-4) was prepared and studied.

[0815]

[0816] As described in Examples 1 to 3, mixture M-4 was also divided into several portions, and its exposure stability to LCD backlight and UV source was studied in a test box with planar aligned alignment materials and planar ITO electrodes, as well as with various additive compounds.

[0817] Example 5

[0818] The following mixture (M-5) was prepared and studied.

[0819]

[0820] As described in Examples 1 to 4, mixture M-5 was also divided into several portions, and its exposure stability to LCD backlight and UV source was studied in a test box with planar aligned alignment materials and planar ITO electrodes, as well as with various additive compounds.

[0821] Example 6

[0822] The following mixture (M-6) was prepared and studied.

[0823]

[0824] As described in Examples 1 to 5, the mixture M-6 was also divided into several portions, and its exposure stability to LCD backlight and UV source was studied in a test box with planar aligned alignment materials and planar ITO electrodes, as well as with various additive compounds.

Claims

1. A liquid crystal medium, characterized in that... Include a) One or more compounds of formula I in R 11 Each occurrence independently represents H, F, a straight-chain or branched alkyl chain with 1-20 C atoms, wherein one or more -CH2- groups, if present, can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more -CH2- groups, if present, can be replaced by -CH=CH- or -C≡C-, and one or more H atoms can be replaced by F, OR. 13 ,N(R 13 (R) 14 ) or R 15 replace, R 12 Each occurrence independently represents H, a straight-chain or branched alkyl chain with 1-20 C atoms, wherein one or more -CH2- groups can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, a hydrocarbon group containing cycloalkyl or alkylcycloalkyl units, and wherein one or more -CH2- groups can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more H atoms can be replaced by F, OR 13 ,N(R 13 (R) 14 ) or R 15 The substitution, or aromatic or heteroaromatic hydrocarbon group, wherein one or more H atoms can be replaced by F, OR 13 ,N(R 13 (R) 14 ) or R 15 replace, R 13 Each occurrence independently represents a straight-chain or branched alkyl or acyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon or carboxylic acid group having 6 to 12 carbon atoms. R 14 Each occurrence independently represents a straight-chain or branched alkyl or acyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon or carboxylic acid group having 6 to 12 carbon atoms. R 15 Each occurrence independently represents a straight-chain or branched alkyl group having 1 to 10 carbon atoms. One or more -CH2- groups may be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-. S 11 and S 12 Each occurrence independently represents an alkylene group having 1 to 20 carbon atoms, where one or more -CH2- groups, if present, can be replaced by -O- or -C(=O)-, but no two adjacent -CH2- groups are replaced by -O-, and one or more H atoms can be replaced by F, OR. 13 ,N(R 13 (R) 14 ) or R 15 Replacement, or to represent a single key. Y 11 To Y 14 Each can be represented independently as either methyl or ethyl. Z 11 To Z 14 Each occurrence is independently represented as -O-, -(C=O)-, -O-(C=O)-, -(C=O)-O-, -O-(C=O)-O-, -(NR 13 )-,-NR 13 -(C=O)- or if S 11 If it's a single bond, it means a single bond, but Z... 11 and Z 12 The two do not both represent -O-, and however, if S 12 If it's a single key, then Z 13 and Z 14 The two cannot both represent -O-, and if -X 11 [-R 11 ] o - If it's a single key, then Z 12 and Z 13 They cannot both represent -O-. X 11 Indicates C, p represents 1 or 2, o represents (3-p), n p represents an integer from 3 to 10. When p=1 n represents 3, 4, 5, 6, or 8. m represents (10-n), and, When p=2, n represents an integer from 2 to 4, and m represents (4-n), and This indicates an organic group having (m+n) binding sites. And among them, when p=1, -X 11 [-R 11 ] o - Alternatively, it can also represent a single bond, and b) One or more compounds selected from formulas II and III, in R 2 H represents an unfluorinated or fluorinated alkyl or unfluorinated or fluorinated alkoxy group having 1 to 17 carbon atoms, or an unfluorinated or fluorinated alkenyl group having 2 to 15 carbon atoms, an unfluorinated or fluorinated alkenyloxy group, or an unfluorinated or fluorinated alkoxyalkyl group, wherein one or more CH2- groups may be... , , , or Instead, alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy groups having 1 to 7 carbon atoms, and alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl groups having 2 to 7 carbon atoms. and Each occurrence is represented independently. Where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, or L 21 and L 22 H or F can be represented independently of each other. X 2 The term indicates a halogen, which is a haloalkyl or alkoxy group having 1-3 carbon atoms or a haloalkenyl or alkenoxy group having 2 or 3 carbon atoms. m represents 0, 1, 2, or 3. R 3 H represents an unfluorinated or fluorinated alkyl or unfluorinated or fluorinated alkoxy group having 1 to 17 carbon atoms, or an unfluorinated or fluorinated alkenyl group having 2 to 15 carbon atoms, an unfluorinated or fluorinated alkenyloxy group, or an unfluorinated or fluorinated alkoxyalkyl group, wherein one or more CH2- groups may be... , , , or replace, and Each occurrence is represented independently. Where R L Each time it appears, it may represent H or an alkyl group having 1 to 6 carbon atoms, either the same or different; or L 31 and L 32 H or F can be represented independently of each other. X 3 The symbol represents a halogen, a haloalkyl or alkoxy group having 1 to 3 carbon atoms, or a haloalkenyl or alkenoxy group having 2 or 3 carbon atoms, F, Cl, -OCF3, -OCHF2, -O-CH2CF3, -O-CH=CF2, -O-CH=CH2, or -CF3. Z 3 This indicates -CH2CH2-, -CF2CF2-, -COO-, trans- CH=CH-, trans- CF = CF-, -CH2O- or a single bond, and n represents 0, 1, 2, or 3, and c) One or more compounds selected from formulas VI to IX: in R 61 R 62 R 71 R 72 R 81 and R 82 They independently possess the above-mentioned properties for R 41 and R 42 One of the given meanings, preferably R 61 This refers to an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl; an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms; or an unsubstituted alkenoxy group having 2 to 6 carbon atoms. R 62 This refers to an unsubstituted alkyl group having 1 to 7 carbon atoms, an unsubstituted alkoxy group having 1 to 6 carbon atoms, or an unsubstituted olefinic group having 2 to 6 carbon atoms, and l represents 0 or 1. R 71 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl, or an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms. R 72 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms; or an unsubstituted olefinic group having 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms. R 81 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably a straight-chain alkyl group, more preferably a n-alkyl group, and most preferably propyl or pentyl, or an unsubstituted alkenyl group having 2 to 7 carbon atoms, preferably a straight-chain alkenyl group, and particularly preferably having 2 to 5 carbon atoms. R 82 This indicates an unsubstituted alkyl group having 1 to 7 carbon atoms, preferably 2 to 5 carbon atoms; an unsubstituted alkoxy group having 1 to 6 carbon atoms, preferably 1, 2, 3, or 4 carbon atoms; or an unsubstituted olefinic group having 2 to 6 carbon atoms, preferably 2, 3, or 4 carbon atoms. Z 8 This represents -(C=O)-O-, -CH2-O-, -CF2-O-, or -CH2-CH2-, preferably -(C=O)-O- or -CH2-O-, and o represents 0 or 1. R 91 and R 92 Each independently possesses the above for R 72 The given meaning, R 91 Preferably, it refers to an alkyl group having 2 to 5 carbon atoms, more preferably having 3 to 5 carbon atoms. R 92 Preferably, it refers to an alkyl or alkoxy group having 2 to 5 carbon atoms, more preferably an alkoxy group having 2 to 4 carbon atoms, or an alkenyloxy group having 2 to 4 carbon atoms. p and q represent 0 or 1 independently of each other, and (p+q) preferably represents 0 or 1, and in express In the case of p=q=1, alternatively, p=q=1 is preferred.

2. The medium according to claim 1, characterized in that... The total concentration of Formula I compound in the entire medium is 1 ppm or higher up to 2000 ppm or lower.

3. The medium according to claim 1 or 2, characterized in that It contains one or more compounds of formula II.

4. The medium according to one or more of claims 1 to 3, characterized in that... It contains one or more compounds of formula III.

5. The medium according to one or more of claims 1 to 4, characterized in that... It contains one or more compounds selected from formulas B and S. in R B1 and R B2 Each of these groups independently represents an alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy group, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenyl; or an alkenyl, alkenoxy, alkoxyalkyl, or fluorinated alkenyl group having 2 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenyl. n represents 0 or 1, R S1 and R S2 Each of the following can independently represent an alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy group, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenylene; an alkenyl, alkenoxy, alkoxyalkyl, or fluorinated alkenyl group having 2 to 7 carbon atoms, wherein one of the -CH2- groups can be replaced by cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentenylene; and n represents 0 or 1, preferably 1.

6. The medium according to one or more of claims 1 to 5, characterized in that, It contains one or more compounds selected from formulas IV and V. in R 41 and R 42 Each having independently the above-mentioned properties for R in claim 1 2 The given meaning, and Independent of each other and, if The occurrence of these twice is also independent of each other, and if they exist, each independently possesses the meaning of claim 1 for... and One of the meanings given is Z 41 and Z 42 Independent of each other, and if Z 41 If they appear twice, then they independently represent -CH2CH2-, -COO-, trans- CH=CH-, trans- CF=CF-, -CH2O-, -CF2O-, -C≡C- or a single bond, preferably one or more of these representing a single bond, and p represents 0, 1, or 2. R 51 and R 52 They each have independent properties for R 41 and R 42 The given meaning, to If they exist, each possesses the above-mentioned characteristics independently of the others. and One of the meanings given Z 51 To Z 53 Each of these can be independently represented as -CH2-CH2-, -CH2-O-, -CH=CH-, -C≡C-, -COO-, or a single bond, and i and j each represent 0 or 1 independently.

7. The medium according to at least one of claims 1 to 6, characterized in that, It comprises one or more compounds of formula IX selected from one or more compounds of formula IX-1 to IX-4. The parameters have the meanings given in Equation IX, where F / H represents F or H.

8. The medium according to at least one of claims 1 to 6, characterized in that, It contains one or more compounds of the formula Yn-Om, Y-nO-Om and / or CY-n-Om.

9. The medium according to at least one of claims 1 to 6, characterized in that, It contains one or more compounds of formula VII-1 selected from CCY-nm and CCY-n-Om.

10. The medium according to at least one of claims 1 to 6, characterized in that, It contains one or more compounds selected from formula VII-2 of formula CLY-n-Om.

11. The medium according to at least one of claims 1 to 6, characterized in that, It contains one or more compounds selected from formula VIII of formula CZY-n-Om and CCOY-nm.

12. The medium according to at least one of claims 1 to 6, characterized in that, It contains one or more compounds of formula IX selected from formula PYP-nm and PGIY-n-Om.

13. The medium according to one or more of claims 1 to 12, characterized in that, It also contains one or more chiral compounds.

14. Compound of Formula I The parameters have the meanings given for Equation I in claim 1.

15. The compound of formula I according to claim 14, wherein p represents 2.

16. The compound of formula I according to claim 15, wherein it is a compound selected from formulas I-1 to I-13. 。 17. An electro-optic display or electro-optic component, characterized in that, It contains a liquid crystal medium according to one or more of claims 1 to 12.

18. The display according to claim 17, characterized in that, It is based on IPS, FFS, VA, or ECB effects.

19. The display according to claim 17 or 18, characterized in that, It includes active matrix addressing devices.

20. Use of a compound of formula I according to one or more of claims 14 to 16 in a liquid crystal medium.

21. Use of a liquid crystal medium according to one or more of claims 1 to 12 in an electro-optic display or electro-optic assembly.

22. The method for preparing a liquid crystal medium according to one or more of claims 1 to 12, characterized in that, One or more of the Formula I compounds according to one or more of claims 1 to 12, together with one or more of the Formula II compounds according to claim 1 and / or one or more selected from A mixture of compounds of formulas III-1 to III-4 according to claim 1.

23. A method for stabilizing a liquid crystal medium, characterized in that... One or more compounds of formula I as given in claim 1, and optionally one or more compounds selected from formulas OH-1 to OH-6, are added to the medium. 。 24. A method for preparing a compound of formula I according to one or more of claims 14 to 16, characterized in that, An alcohol containing two 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl groups is reacted with a suitable derivatized cyclic structure, such as a dicarboxylic acid dihalide or a tetracarboxylic acid tetrahalide.

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