Aromatic isothiocyanates

Abstract

Aromatic isothiocyanates are provided. The present invention relates to compounds of formula UI as defined in claim 1, to liquid crystalline media comprising compounds of formula UI, and to high frequency components, in particular microwave components for high frequency devices, comprising these media, such as devices for shifting the phase of microwaves, tunable filters, tunable material structures and electron beam steering antennas, e.g. phased array antennas. TIFF2023547643000328.tif42166

Description

[Technical Field]

[0001] The present invention relates to aromatic isothiocyanates, liquid crystalline media containing them, and high-frequency components containing these media, particularly microwave components for high-frequency devices, such as microwave phase-shifting devices, tunable filters, tunable material structures, and electron beam manipulation antennas (e.g., phased array antennas), and devices containing said components. [Background technology]

[0002] Liquid crystal media have long been used in electro-optical displays (liquid crystal displays: LCDs) for displaying information. However, in recent years, the use of liquid crystal media in components for microwave technology has also been proposed, for example, in German Patent Application No. 10 2004 029 429 (Patent Document 1) and Japanese Patent Publication No. 2005-120208 (Patent Document 2).

[0003] In "Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formulation of the Vector Variational Approach" by A. Gaebler, F. Goelden, S. Muller, A. Penirschke, and R. Jakoby, pp. 463-467 (Non-Patent Literature 1), 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), the corresponding properties of the known liquid crystal mixture E7 (Merck, Germany) are described.

[0004] German Patent Application No. 10 2004 029 429 (Patent Document 1) describes the use of liquid-crystalline media in microwave technology, particularly in phase shifters. It discusses liquid-crystalline media with respect to their properties in the corresponding frequency range, and presents liquid-crystalline media based mainly on mixtures of aromatic nitriles and isothiocyanates.

[0005] Fluorine atoms are commonly used in mesogenic compounds to introduce polarity. Especially in combination with a terminal NCS group, since the dipole of the entire molecule is the sum of all individual dipoles of the partial structures of the molecule, a high dielectric anisotropy value can be achieved particularly when the NCS group at the 1-position has two fluorine atoms in its ortho positions. On the other hand, since fluorine substitution often adversely affects the nematic phase properties of the compounds, a balanced compromise regarding the number of fluorine atoms must be found.

[0006] European Patent Application Publication No. 2 982 730 (Patent Document 3) describes a mixture consisting entirely of isothiocyanate compounds.

[0007] However, the compositions available for use in microwave applications still have several drawbacks. There is a need to improve these media with regard to their general physical properties, storage stability, and stability under operation in devices. In view of the large number of different parameters that must be considered and improved for the development of liquid-crystalline media for microwave applications, it is desirable to have a broader range of possible mixing components for the development of such liquid-crystalline media. [Prior Art Documents] [Patent Documents]

[0008] [Patent Document 1] German Patent Application No. 10 2004 029 429 [Patent Document 2] JP-A 2005-120208 [Patent Document 3] European Patent Application Publication No. 2 982730 Specification [Non-patent literature]

[0009] [Non-Patent Document 1] A. Gaebler, F. Goelden, S. Muller, A. Penirschke, and R. Jakoby, "Direct Simulation of Material Permittivites using an Eigen-Susceptibility Formulation of the Vector Variational Approach," 12MTC 2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467. [Overview of the project] [Problems that the invention aims to solve]

[0010] The object of the present invention is to provide compounds for use in liquid crystal media having improved properties relevant to applications in the microwave range of the electromagnetic spectrum. [Means for solving the problem]

[0011] To solve this problem, a compound of formula UI as defined below and a liquid crystal medium containing said compound are provided.

[0012] This invention relates to compounds of formula UI.

[0013] [ka]

[0014] During the ceremony, R Urepresents H, a linear or branched non-fluorinated alkyl group having 1 to 12 C atoms, or a non-fluorinated alkenyl group having 2 to 12 C atoms, in which one or more CH₂ groups in the group may be

Chemical formula

Chemical formula

[0015] According to another aspect of the present invention, a liquid crystal medium comprising one or more compounds of formula UI is provided.

[0016] Preferred embodiments of the present invention are the subject of the dependent claims and may also be addressed herein. [Modes for carrying out the invention]

[0017] Surprisingly, it was found that using compounds of formula UI in liquid crystal media makes it possible to realize liquid crystal media with excellent stability, high dielectric anisotropy, suitably fast switch time, suitable nematic phase range, high tunability, and low dielectric loss in the microwave region of the electromagnetic spectrum.

[0018] In particular, media according to the present invention, including compounds according to the present invention, are distinguished by improved material quality η due to higher adjustability τ and lower dielectric loss.

[0019] The media according to the present invention are further distinguished by their high transparency temperature, wide nematic phase range, and excellent low-temperature stability (LTS). As a result, devices containing the media can operate under extreme temperature conditions.

[0020] The media are further distinguished by high dielectric anisotropy and low rotational viscosity. As a result, the threshold voltage, i.e., the minimum voltage at which the device can be switched, is very low. Low operating voltage and low threshold voltage are desirable to realize devices with improved switching characteristics and high energy efficiency. Low rotational viscosity enables fast switching of the device according to the present invention.

[0021] These properties, as a whole, make the medium particularly suitable for use in components and devices for applications in high-frequency technology and the microwave range, especially in devices for shifting microwave phases, tunable filters, tunable material structures, and electron beam maneuvering antennas (e.g., phased array antennas).

[0022] Therefore, according to another aspect of the present invention, components and devices containing such components are provided, all of which are operable in the microwave range of the electromagnetic spectrum. Preferred components include phase shifters, varactors, radio and radio antenna arrays, matching circuits, and adaptive filters.

[0023] In this specification, “high-frequency technology” means electromagnetic wave applications having frequencies in the range of 1 MHz to 1 THz, preferably 1 GHz to 500 GHz, more preferably 2 GHz to 300 GHz, and particularly preferably about 5 GHz to 150 GHz.

[0024] When used herein, halogens are F, Cl, Br, or I, preferably F or Cl, and particularly preferably F.

[0025] In this specification, alkyls are linear or branched and have 1 to 15 carbon atoms, preferably linear and having 1, 2, 3, 4, 5, 6 or 7 carbon atoms unless otherwise indicated, and therefore preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl or n-heptyl.

[0026] In this specification, branched alkyl groups are preferably isopropyl, s-butyl, isobutyl, isopentyl, 2-methylbutyl, 2-methylhexyl, or 2-ethylhexyl.

[0027] As used herein, cyclic alkyl means linear or branched alkyl or alkenyl having up to 12 carbon atoms, preferably alkyl having 1 to 7 carbon atoms, wherein the CH2 group is replaced by a carbon ring having 3 to 5 carbon atoms, and is very preferably selected from the group consisting of cyclopropylalkyl, cyclobutylalkyl, cyclopentylalkyl and cyclopentenylalkyl.

[0028] In this specification, the alkoxy group is linear or branched and contains 1 to 15 carbon atoms. It is preferably linear and has 1, 2, 3, 4, 5, 6 or 7 carbon atoms unless otherwise indicated, and is therefore preferably methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy or n-heptoxy.

[0029] In this specification, the alkenyl group is preferably an alkenyl group having 2 to 15 carbon atoms, and the group is linear or branched and contains at least one carbon-C double bond. It is preferably linear and has 2 to 7 carbon atoms. Thus, it is preferably vinyl, propa-1- or -2-enyl, buta-1-, -2- or -3-enyl, penta-1-, -2-, -3- or -4-enyl, hexa-1-, -2-, -3-, -4- or -5-enyl, hepta-1-, -2-, -3-, -4-, -5- or -6-enyl. If two carbon atoms of the carbon-C double bond are substituted, the alkenyl group may be in the form of E and / or Z isomers (trans / cis). Generally, each E isomer is preferred. Among the alkenyl groups, propa-2-enyl, buta-2- and -3-enyl, and penta-3- and -4-enyl are particularly preferred.

[0030] In this specification, alkynyl is understood to mean an alkynyl group having 2 to 15 carbon atoms, the group being linear or branched and containing at least one carbon-carbon triple bond. 1- and 2-propynyl and 1-, 2- and 3-butynyl are preferred.

[0031] R F If the halogen is an alkyl-, alkoxy-, alkenyl or alkenyloxy, it may be branched or unbranched. It is preferably unbranched and monofluorinated, polyfluorinated or perfluorinated, preferably perfluorinated, and has 1, 2, 3, 4, 5, 6 or 7 C atoms; in the case of an alkenyl, it has 2, 3, 4, 5, 6 or 7 C atoms.

[0032] R P Preferably, CN, NCS, Cl, F, -(CH2) n -CH=CF2, -(CH2) n -CH=CHF, -(CH2) n -CH=Cl2, -C n F 2n+1 ,-(CF2) n -CF2H, -(CH2) n-CF3, -(CH2) n -CHF2, -(CH2) n CH2F, -CH=CF2, -O(CH2) n -CH=CF2, -O(CH2) n CHCl2, -OC n F 2n+1 -O(CF2) n -CF2H, -O(CH2) n CF3, -O(CH2) n -CHF2, -O(CF) n CH2F, -OCF=CF2, SC n F 2n+1 -S(CF) n - Selected from CF3, where n is an integer between 0 and 7.

[0033] Structurally related compounds having trifluorovinyl substituents are described in Chinese Patent Application Publication No. 105294526 for use as co-components in media for display devices.

[0034] Compounds of general formula UI can be prepared by methods known in themselves and under precise reaction conditions suitable for the reaction, as described in the literature (e.g., Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, and other standards). Modifications known in themselves but not described in more detail herein may be used herein.

[0035] If desired, the starting material can be formed in situ by immediately reacting it with a compound of general formula UI without isolating it from the reaction mixture.

[0036] A preferred synthetic route to the compound according to the present invention is illustrated in Scheme 1 below, where the groups and parameters appearing have the meaning given to formula UI. It is further illustrated by examples and can be adapted to specific desired compounds of general formula UI by selecting appropriate starting materials.

[0037] The preferred construction block 2 (Scheme 1) consists of 4-bromo-3,5-difluoroaniline, 4-bromo-3,5-dichloroaniline, and 4-bromo-3-chloro-5-fluoroaniline, all of which are documented in the literature, for example, the Sonogashira reaction (Scheme 1, however Z U1 ) is -C≡C- and G is H. ), Suzuki coupling (where Z U1 The compound of formula UI can be reacted with a suitable intermediate 1 by a known cross-coupling reaction, such as ( ), to obtain a compound of formula UI. The compound of formula N is reacted with a thiocarbonate derivative or CS2 to obtain a compound of formula UI. [ka] In the formula, X and Y are leaving groups.

[0038] [ka]

[0039] Similar synthesis toward structurally related compounds having trifluorovinyl substituents is shown in Chinese Patent Application Publication No. 105294526, which discloses compounds for use as co-components in media for display devices. Compounds of formula UII shown below are prepared similarly or as described in European Patent Application Publication No. 1054001. Preferred reagents for the method according to the present invention for converting compounds of formula N to compounds of formula UI are carbon disulfide, thiophosgene, thiocarbonyldiimidazole, di-2-pyridylthiocarbonate, bis(dimethylthiocarbamoyl) disulfide, dimethylthiocarbamoyl chloride, and phenylchlorothiobrome, very preferably thiophosgene.

[0040] The reactions described should be considered illustrative only. Those skilled in the art can perform corresponding modifications to the described synthesis and follow other suitable synthetic routes to obtain compounds of formula UI.

[0041] The compound of formula UI is preferably selected from the group consisting of compounds of formulas UI-1, UI-2, and UI-3. [ka]

[0042] In the formula, R U , [ka] X U1 and X U2 The expression UI has the meaning given above, however in expression UI-3 [ka] At least one of the groups represents trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetralin-2,6-diyl, tetralin-5,8-diyl, decalin-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, or spiro[3.3]heptane-2,6-diyl, where one or two CH groups in the group may be replaced by N, and one or more adjacent groups The CH2 group that is not fluorinated may be replaced with -O- and / or -S-, and one or more H atoms in the group may be replaced with L, where L is the same or different in each instance and represents F, Cl, CN, SCN, SF5, or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy which each has 1 to 12 C atoms and is linear or branched, and which may be fluorinated in each case.

[0043] and preferably X U1 and X U2 represents F, R UPreferably, represents a linear, branched, or cyclic alkyl or alkenyl having 1 to 7 carbon atoms, or a fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms. [ka] They are the same or different, preferably [ka] This represents, In the formula, R L Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms. or [ka] This represents, In the formula, one or more H atoms may be replaced by alkyl groups or F groups having 1 to 6 C atoms. [ka] Very preferably [ka] It represents. [ka] Preferably [ka] comfortably [ka] Very preferred [ka] This represents, During the ceremony, R L This represents an alkyl group having H or 1 to 6 C atoms.

[0044] A highly preferred compound of formula UI is selected from the following sub-formulas.

[0045] [ka]

[0046] [ka]

[0047] In the formula, R U The above has the meaning and preferably represents a linear or branched alkyl group having 1 to 7 C atoms, particularly methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or n-heptyl.

[0048] The liquid crystal medium according to the present invention preferably comprises one or more compounds of formula UI and additionally one or more compounds of formula UII.

[0049] [ka]

[0050] During the ceremony, R U This represents a linear or branched alkyl group having H, 1 to 12 C atoms, or an alkenyl group having 2 to 12 C atoms, and in this group, one or more CH2 groups are [ka] It may be replaced by, however, one or more non-adjacent CH2 groups may be replaced by O, or the group R P This represents, R P Halogen, CN, NCS, R F -, R F -O- or R F -S- represents, however R F This represents a fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms. Z U1 , Z U2 These are identical or different, representing -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -C≡CC≡C- or a single bond, preferably -CF=CF-, -C≡C- or a single bond, very preferably -C≡C- or a single bond. X U1 , X U2 These represent Cl or F, preferably F, and are the same or different. [ka] This represents a group selected from the following groups: a) A group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be replaced by N, and one or more H atoms may be replaced by L. b) The group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, tetralin-2,6-diyl, tetralin-5,8-diyl, decalin-2,6-diyl, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl and spiro[3.3]heptane-2,6-diyl, wherein one or two CH groups may be replaced by N, one or more non-adjacent CH2 groups may be replaced by -O- and / or -S-, and one or more H atoms may be replaced by L, c) A group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenofen-2,5-diyl, and each of these groups may be monosubstituted or polysubstituted with L. L represents, whether identical or different in each instance, an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy molecule having 1 to 12 C atoms each, and being linear or branched, which may be fluorinated in each case. u is 0, 1, or 2, preferably 1. However, compounds of formula UI are excluded from compounds of formula UII.

[0051] Preferably, the compound of formula UII is selected from compounds of formula UII-1, UII-2, and UII-3, preferably UII-1 and UII-2, and especially UII-1.

[0052] [ka]

[0053] In the formula, the bases that appear have the meanings given above in formula UII, preferably [ka] are the same or different [ka] This represents, X U1 and X U2 represents F, R U Preferably, represents a linear, branched, or cyclic alkyl or alkenyl having 1 to 7 carbon atoms, or a fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms.

[0054] A highly preferred compound of formula UII is selected from the following sub-formulas.

[0055] [ka]

[0056] In the formula, R U The above has the meaning and preferably represents a linear or branched alkyl group having 1 to 7 C atoms, particularly methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or n-heptyl.

[0057] In a preferred embodiment, the medium according to the present invention comprises one or more compounds selected from the group of formulas I, II, and III.

[0058] [ka]

[0059] During the ceremony, R 1 H represents a nonfluorinated alkyl or nonfluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a nonfluorinated alkenyl, nonfluorinated alkenyloxy or nonfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably a nonfluorinated alkyl or nonfluorinated alkenyl, and in this group one or more CH2 groups, [ka] It can be replaced with, n is 0, 1, or 2. [ka] (In the formula, R L (Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms, preferably H, methyl, or ethyl, particularly preferably H.) [ka] (In the formula, one or more H atoms may be replaced by alkyl groups or F atoms having 1 to 6 C atoms.) This represents, and however, [ka] This represents, If n=2, [ka] Preferably, [ka] This represents, more, [ka] This represents, [ka] This represents, [ka] This represents,

[0060] R 2 H represents a nonfluorinated alkyl or nonfluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a nonfluorinated alkenyl, nonfluorinated alkenyloxy or nonfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably a nonfluorinated alkyl or nonfluorinated alkenyl, and in this group one or more CH2 groups, [ka] It can be replaced with, Z 21 This represents trans-CH=CH-, trans-CF=CF- or -C≡C-, preferably -C≡C- or trans-CH=CH-, and [ka] (In the formula, R L (Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms, preferably H, methyl, or ethyl, particularly preferably H.) [ka] (In the formula, one or more H atoms may be replaced by alkyl groups or F atoms having 1 to 6 C atoms.) This represents, Preferably, [ka] This represents, [ka] Represents, and [ka] comfortably [ka] This represents,

[0061] R 3 H represents a nonfluorinated alkyl or nonfluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a nonfluorinated alkenyl, nonfluorinated alkenyloxy or nonfluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably a nonfluorinated alkyl or nonfluorinated alkenyl, and in this group one or more CH2 groups, [ka] It can be replaced with, Z 31 and Z 32 On the other hand, preferably Z 32 One represents trans-CH=CH-, trans-CF=CF-, or -C≡C-, and the other independently represents -C≡C-, trans-CH=CH-, trans-CF=CF-, or a single bond, preferably one of them, preferably Z 32 One represents -C≡C- or trans-CH=CH-, the other represents a single bond, and [ka] (In the formula, R L (Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms, preferably H, methyl, or ethyl, particularly preferably H.) [ka] (In the formula, one or more H atoms may be replaced by alkyl groups or F atoms having 1 to 6 C atoms.) This represents, and however, [ka] This represents, Preferably [ka] This represents, more, [ka] This represents, [ka] especially [ka] This represents, [ka] especially [ka] It represents.

[0062] In the compounds of formulas I, II, and III, R L preferably represents H. In another preferred embodiment, in compounds of formulas I, II, and III, one or two groups R L Preferably one base R L This is different from H.

[0063] In a preferred embodiment of the present invention, the compound of formula I is selected from the group of compounds of formula I-1 to I-5.

[0064] [ka]

[0065] During the ceremony, L 1 , L 2 and L 3 Each of these groups represents either H or F, either identically or differently in its respective appearance, and the other groups have the respective meanings shown above in formula I. Preferably R 1 This represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0066] Preferably, the medium comprises one or more compounds selected from the compounds of formula I-1 and optionally one or more compounds selected from the compounds of formula Cy-1.

[0067] [ka]

[0068] In the formula, the appearing groups have the meanings given above for formula I-1. The total amount of compounds of formula I-1 and / or Cy-I in the medium according to the present invention is preferably less than 10%, more preferably less than 5%, and particularly less than 2%. Particularly preferably, the medium does not contain compounds of formula Cy-1.

[0069] The medium preferably contains one or more compounds of formula I-1, preferably selected from the group of compounds of formula I-1a to I-1d, and more preferably from the group of compounds of formula I-1b.

[0070] [ka]

[0071] In the formula, R 1 The symbol in formula I has the meaning shown above and preferably represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0072] The medium preferably contains one or more compounds of formula I-2, preferably selected from the group of compounds of formula I-2a to I-2e, and more preferably from the group of compounds of formula I-2c.

[0073] [ka]

[0074] In the formula, R 1 The symbol in formula I has the meaning shown above and preferably represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0075] The medium preferably contains one or more compounds of formula I-3, preferably selected from the group of compounds of formula I-3a to I-3d, and more preferably from the group of compounds of formula I-3b.

[0076] [ka]

[0077] In the formula, R 1 The symbol in formula I has the meaning shown above and preferably represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0078] The medium preferably contains one or more compounds of formula I-4, preferably selected from the group of compounds of formula I-4a to I-4e, and more preferably from the group of compounds of formula I-4b.

[0079] [ka]

[0080] In the formula, R 1 The symbol in formula I has the meaning shown above and preferably represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0081] The medium preferably contains one or more compounds of formula I-5, preferably selected from the group of compounds of formula I-5a to I-5d, and more preferably from the group of compounds of formula I-5b.

[0082] [ka]

[0083] In the formula, R 1 The symbol in formula I has the meaning shown above and preferably represents a non-fluorinated alkyl group having 1 to 7 carbon atoms or a non-fluorinated alkenyl group having 2 to 7 carbon atoms.

[0084] The medium preferably contains one or more compounds of formula II, preferably selected from the group of compounds of formula II-1 to II-3, and preferably selected from the group of compounds of formula II-1 and II-2.

[0085] [ka]

[0086] In the formula, the bases that appear have the meanings given above in formula II, and Preferably R 2 This represents a non-fluorinated alkyl or alkoxy having 1 to 7 carbon atoms or a non-fluorinated alkenyl having 2 to 7 carbon atoms, and [ka] This represents, The other party, independently, [ka] Preferably [ka] Most preferably [ka] This represents, and preferably, R 2 represents C n H 2n+1 or CH2=CH-(CH2)-, and Z and n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0087] The compound of formula II-1 is preferably selected from the group of compounds of formulas II-1a to II-1e.

[0088] [Chemical Formula]

[0089] wherein R 2 has the meaning indicated above, and preferably represents C n H 2n+1 or CH2=CH-(CH2)-, and Z and n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0090] The compound of formula II-2 is preferably selected from the group of compounds of formulas II-2a and II-2b.

[0091] [Chemical Formula]

[0092] wherein R 2 has the meaning indicated above, and preferably represents C n H 2n+1 or CH2=CH-(CH2)-, Z represents, n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0093] The compound of Formula II-3 is preferably selected from the group of compounds of Formulas II-3a to II-3d.

[0094]

Chemical Formula

[0095] In the formula, R 2 has the meaning indicated above, and preferably represents C n H 2n+1 or CH2=CH-(CH2) Z , n represents an integer in the range of 1 to 7, preferably in the range of 2 to 6 and particularly preferably in the range of 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

[0096] The compound of Formula III is preferably selected from the group of compounds of Formulas III-1 to III-6, more preferably selected from the group of compounds of Formulas III-1, III-2, III-3 and III-4, and particularly preferably selected from the group of compounds of Formula III-1.

[0097]

Chemical Formula

[0098] In the formula, Z 31 and Z 32 independently of one another represent trans-CH=CH- or trans-CF=CF-, preferably trans-CH=CH-, or in Formula III-6 one of Z 31 and Z 32 may represent -C≡C-, and the other group has the meaning given above for Formula III, and preferably R 3 This represents a non-fluorinated alkyl or alkoxy having 1 to 7 carbon atoms or a non-fluorinated alkenyl having 2 to 7 carbon atoms, and [ka] Very preferred [ka] This represents, The other party operates independently of the other. [ka] Preferably [ka] comfortably [ka] This represents, However [ka] This represents, and preferably R 3 C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z This represents, n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0099] The compound of formula III-1 is preferably selected from the group of compounds of formulas III-1a to III-1j, more preferably from the group of compounds of formulas III-1a, III-1b, III-1g and III-1h, and particularly preferably from the group of compounds of formula III-1b and / or III-1h.

[0100] [ka]

[0101] [ka]

[0102] During the ceremony, R 3 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z This represents, n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0103] The compound of formula III-2 is preferably a compound of formula III-2a to III-2l, and very preferably a compound of formula III-2b and / or III-2j.

[0104] [ka]

[0105] [ka]

[0106] During the ceremony, R 3 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z This represents, n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0107] The compound of formula III-5 is preferably selected from the compounds of formula III-5a.

[0108] [ka]

[0109] R 3 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z This represents, n represents an integer within the range of 1 to 7, preferably within the range of 2 to 6.

[0110] In a preferred embodiment, the medium according to the present invention comprises one or more compounds selected from the group of compounds of formula IIA-1-1 to IIA-1-12, very preferably IIA-1-1 or IIA-1-2.

[0111] [ka]

[0112] [ka]

[0113] During the ceremony, R 1 represents an alkyl or alkenyl having up to 7 C atoms, preferably ethyl, n-propyl, n-butyl, or n-pentyl, n-hexyl. R L Each instance represents an alkyl or alkenyl having 1 to 5 C atoms, either identical or different, or a cycloalkyl or cycloalkenyl having 3 to 6 C atoms, preferably methyl, ethyl, n-propyl, n-butyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopenta-1-enyl, very preferably ethyl. Compounds of formula II-1 are excluded.

[0114] In addition, the liquid crystal medium according to the present invention in one embodiment, which may be the same as or different from the previously described preferred embodiment, preferably comprises one or more compounds of formula IV.

[0115] [ka]

[0116] During the ceremony, [ka] This represents, s is 0 or 1, preferably 1, and Preferably [ka] Particularly preferred [ka] This represents, L 4 This represents an alkyl group having H or 1 to 6 C atoms, a cycloalkyl group having 3 to 6 C atoms, or a cycloalkenyl group having 4 to 6 C atoms, preferably CH3, C2H5, n-C3H7, i-C3H7, cyclopropyl, cyclobutyl, cyclohexyl, cyclopenta-1-enyl, or cyclohexa-1-enyl, and particularly preferably CH3, C2H5, cyclopropyl, or cyclobutyl. X 4 This represents H, an alkyl or halogen having 1 to 3 C atoms, preferably H, F or Cl, more preferably H or F, and very preferably F. R 41 ~R 44Each independently represents a nonfluorinated alkyl or nonfluorinated alkoxy having 1 to 15 carbon atoms, a nonfluorinated alkenyl, nonfluorinated alkenyloxy or nonfluorinated alkoxyalkyl having 2 to 15 carbon atoms, or a cycloalkyl, alkylcycloalkyl, cycloalkenyl, alkylcycloalkenyl, alkylcycloalkylalkyl or alkylcycloalkenylalkyl having up to 15 carbon atoms, and alternatively R 43 and R 44 One or both of these also represent H, Preferably R 41 and R 42 Each of these independently represents a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 7 carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 6 carbon atoms. Particularly preferred R 41 This represents a non-fluorinated alkyl having 1 to 7 carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy, or non-fluorinated alkoxyalkyl having 2 to 6 carbon atoms each, and Particularly preferred R 42 Each represents a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 7 C atoms, and Preferably R 43 and R 44 H represents a nonfluorinated alkyl having 1 to 5 carbon atoms, a nonfluorinated cycloalkyl or cycloalkenyl having 3 to 7 carbon atoms, a nonfluorinated alkylcyclohexyl or nonfluorinated cyclohexylalkyl having 4 to 12 carbon atoms, or a nonfluorinated alkylcyclohexylalkyl having 5 to 15 carbon atoms, particularly preferably cyclopropyl, cyclobutyl or cyclohexyl, and very particularly preferably R 43 and R 44At least one of them represents an n-alkyl group, particularly preferably methyl, ethyl, or n-propyl, and the other represents H or an n-alkyl group, particularly preferably H, methyl, ethyl, or n-propyl.

[0117] More preferably, the compound of formula IV is selected from the compounds of formula IV-1.

[0118] [ka]

[0119] In the formula, R 41 and R 42 This represents an alkyl group having two, three, four, five, or six identical or different carbon atoms.

[0120] In a preferred embodiment of the present invention, the liquid crystal medium further comprises one or more compounds selected from the group of compounds of formulas V, VI, VII, VIII, and IX.

[0121] [ka]

[0122] During the ceremony, L 51 R 51 or X 51 This represents, L 52 R 52 or X 52 This represents, R 51 and R 52 Each of these independently represents H, a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably alkyl or non-fluorinated alkenyl. X 51and X 52 These independently represent H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or a fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 C atoms, preferably a fluorinated alkoxy, a fluorinated alkenyloxy, F or Cl, and [ka] Preferably [ka]

[0123] L 61 is R 61 Represents Z 61 and / or Z 62 If this represents trans-CH=CH- or trans-CF=CF-, or alternatively X 61 It also represents, L 62 is R 62 Represents Z 61 and / or Z 62 If this represents trans-CH=CH- or trans-CF=CF-, or alternatively X 62 It also represents, R 61 and R 62 Each of these independently represents H, a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably alkyl or non-fluorinated alkenyl. X 61 and X 62Each of these independently represents F or Cl, -CN, -SF5, a fluorinated alkyl or alkoxy having 1 to 7 C atoms, or a fluorinated alkenyl, alkenyloxy or alkoxyalkyl having 2 to 7 C atoms. Z 61 and Z 62 One of them represents trans-CH=CH-, trans-CF=CF-, or -C≡C-, and independently of that, the other represents trans-CH=CH-, trans-CF=CF-, or a single bond, preferably one of them represents -C≡C- or trans-CH=CH-, and the other represents a single bond. [ka] Preferably [ka] Represents, and

[0124] x represents either 0 or 1. L 71 R 71 or X 71 This represents, L 72 R 72 or X 72 This represents, R 71 and R 72 Each of these independently represents H, a non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 17, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably alkyl or non-fluorinated alkenyl. X 71 and X 72These independently represent H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or a fluorinated alkenyl having 2 to 7 C atoms, an unfluorinated or fluorinated alkenyloxy or an unfluorinated or fluorinated alkoxyalkyl, preferably a fluorinated alkoxy, a fluorinated alkenyloxy, F or Cl, and Z 71 ~Z 73 These independently represent trans-CH=CH-, trans-CF=CF-, -C≡C-, or single bonds, with one of them preferably representing a single bond, and particularly preferably all representing single bonds. [ka] Preferably [ka] This represents,

[0125] R 81 and R 82 Each independently represents a non-fluorinated alkyl or alkoxy having H, 1 to 15, preferably 2 to 10 C atoms, or a non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl, preferably a non-fluorinated alkyl or alkenyl, having 2 to 15, preferably 3 to 10 C atoms. Z 81 and Z 82 One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other one independently represents trans-CH=CH-, trans-CF=CF- or a single bond, and one of them preferably represents -C≡C- or trans-CH=CH-, and the other one represents a single bond, and [ka] [ka] This represents,

[0126] L 91 R 91 or X 91 This represents, L 92 R 92 or X 92 This represents, R 91 and R 92 Each independently represents a non-fluorinated alkyl or alkoxy having H, 1 to 15, preferably 2 to 10 C atoms, or a non-fluorinated alkenyl, alkenyloxy or alkoxyalkyl, preferably a non-fluorinated alkyl or alkenyl, having 2 to 15, preferably 3 to 10 C atoms. X 91 and X 92 These independently represent H, F, Cl, -CN, -NCS, -SF5, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, or a fluorinated alkenyl having 2 to 7 C atoms, an unfluorinated or fluorinated alkenyloxy or an unfluorinated or fluorinated alkoxyalkyl, preferably a fluorinated alkoxy, a fluorinated alkenyloxy, F or Cl, and Z 91 ~Z 93 These independently represent trans-CH=CH-, trans-CF=CF-, -C≡C-, or single bonds, with one of them preferably representing a single bond, and particularly preferably all representing single bonds. [ka] [ka] It represents.

[0127] In a preferred embodiment of the present invention, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formula V, preferably formulas V-1 to V-3, preferably formulas VI-1 and / or V-2 and / or V-3, and preferably formulas V-1 and V-2.

[0128] [ka]

[0129] Each parameter in the formula has the meaning shown in formula V above, preferably R 51 This represents an unfluorinated alkyl group having 1 to 7 carbon atoms or an unfluorinated alkenyl group having 2 to 7 carbon atoms. R 52 This represents an unfluorinated alkyl having 1 to 7 carbon atoms, an unfluorinated alkenyl having 2 to 7 carbon atoms, or an unfluorinated alkoxy having 1 to 7 carbon atoms. X 51 and X 52 These independently represent F, Cl, -OCF3, -CF3, -CN, -NCS, or -SF5, preferably F, Cl, -OCF3, or -CN. The compound of formula V-1 is preferably selected from the group of compounds of formulas V-1a to V-1d, preferably V-1c and V-1d.

[0130] [ka]

[0131] Each parameter in the formula has the meaning shown in formula V-1 above, however Y 51 and Y 52 Each of these represents H or F independently of the other, and preferably R 51 represents alkyl or alkenyl, and X 51 This represents F, Cl, or -OCF3. The compound of formula V-2 is preferably selected from the group of compounds of formulas V-2a to V-2e and / or the group of compounds of formulas V-2f and V-2g.

[0132] [ka]

[0133] In each case, the compound of formula V-2a is excluded from the compounds of formula V-2b and V-2c, the compound of formula V-2b is excluded from the compounds of formula V-2c, the compound of formula V-2f is excluded from the compounds of formula V-2g, and However, each parameter has the meaning shown in equation V-1 above, however Y 51 and Y 52 Each of these represents H or F independently of the other, and preferably Y 51 and Y 52 Each of these independently represents either H or F, and preferably similarly represents H.

[0134] The compound of formula V-3 is preferably the compound of formula V-3a.

[0135] [ka]

[0136] The parameters in the formula each have the meaning shown in formula V-1 above, however preferably X 51 This represents F, Cl, preferably F. X 52 represents F, Cl, or -OCF3, preferably -OCF3.

[0137] The compound of formula V-1a is preferably selected from the group of compounds of formula V-1a-1 and V-1a-2.

[0138] [ka]

[0139] During the ceremony, R 51The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably 2 to 6, and especially preferably 3 to 5.

[0140] The compound of formula V-1b is preferably the compound of formula V-1b-.

[0141] [ka]

[0142] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably 2 to 6, and especially preferably 3 to 5.

[0143] The compound of formula V-1c is preferably selected from the group of compounds of formulas V-1c-1 to V-1c-4, and particularly preferably selected from the group of compounds of formulas V-1c-1 and V-1c-2.

[0144] [ka]

[0145] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably 1 to 6, and especially preferably 3 to 5.

[0146] The compound of formula V-1d is preferably selected from the group of compounds of formula V-1d-1 and V-1d-2, and is particularly preferably the compound of formula V-1d-2.

[0147] [ka]

[0148] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably 1 to 6, and especially preferably 3 to 5.

[0149] The compound of formula V-2a is preferably selected from the group of compounds of formula V-2a-1 and V-2a-2, and is particularly preferably the compound of formula V-2a-1.

[0150] [ka]

[0151] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0152] In particular, in the case of formula V-2a-1 (R 51 and R 52 The preferred combination of ) is (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1and OC m H 2m+1 ), (CH2=CH-(CH2) Z and C m H 2m+1 ), (CH2=CH-(CH2) Z and OC m H 2m+1 ) and (C n H 2n+1 and (CH2) Z -CH=CH2)

[0153] The preferred compound of formula V-2b is the compound of formula V-2b-1.

[0154] [ka]

[0155] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0156] Here (R 51 and R 52 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 )

[0157] The preferred compound of formula V-2c is the compound of formula V-2c-1.

[0158] [ka]

[0159] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0160] Here (R 51 and R 52 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 )

[0161] The preferred compound of formula V-2d is the compound of formula V-2d-1.

[0162] [ka]

[0163] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 1 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0164] Here (R 51 and R 52 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 )

[0165] The preferred compound of formula V-2e is the compound of formula V-2e-1.

[0166] [ka]

[0167] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0168] Here (R51 and R 52 ) is particularly favored by (C n H 2n+1 and OC m H 2m+1 )

[0169] The preferred compound of formula V-2f is the compound of formula V-2f-1.

[0170] [ka]

[0171] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0172] Here (R 51 and R 52 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0173] The preferred compound of formula V-2g is the compound of formula V-2g-1.

[0174] [ka]

[0175] During the ceremony, R 51 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 52 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0176] Here (R 51 and R 52 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and OC m H 2m+1 )

[0177] The compound of formula VI is preferably selected from the group of compounds of formula VI-1 to VI-5.

[0178] [ka]

[0179] During the ceremony, Z 61 and Z 62 -C≡C-, trans--CH=CH- or trans-CF=CF-, preferably -C≡C- or trans-CH=CH-, And other appearing bases and parameters have the meanings given above in formula VI, preferably R 61 and R 62 Each of these independently represents a non-fluorinated alkyl or alkoxy group having H, 1 to 7 C atoms, or a non-fluorinated alkenyl group having 2 to 7 C atoms. X 62 This represents F, Cl, -OCF3, or -CN.

[0180] The compound of formula VI-1 is preferably selected from the group of compounds of formula VI-1a and VI-1b, and more preferably selected from the compound of formula VI-1a.

[0181] [ka]

[0182] During the ceremony, R 61 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 62 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0183] In this specification (R 61 and R 62 The preferred combination of ) is especially (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ) and in the case of formula U-1a, (C n H 2n+1 and C m H 2m+1 ) and in the case of formula U-1b, (C n H 2n+1 and OC m H 2m+1 )

[0184] The compound of formula VI-3 is preferably selected from the compounds of formulas VI-3a to VI-3e.

[0185] [ka]

[0186] In the formula, the parameter has the meaning given above in formula VI-3, preferably R 61 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and X 62 -F, -Cl, -OCF3, or -CN.

[0187] The compound of formula VI-4 is preferably selected from the compounds of formulas VI-4a to VI-4e.

[0188] [ka]

[0189] In the formula, the parameter has the meaning given above in formula VI-4, preferably R 61 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and X 62 -F, -Cl, -OCF3, or -CN.

[0190] The compound of formula VI-5 is preferably selected from the compounds of formulas VI-5a to VI-5d, preferably VI-5b.

[0191] [ka]

[0192] In the formula, the parameter has the meaning given above in formula VI-5, preferably R 61 The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably in the range of 1 to 5, and X 62 represents -F, -Cl, -OCF3, or -CN, with -OCF3 being particularly preferred.

[0193] The compound of formula VII is preferably selected from the group of compounds of formula VII-1 to VII-6.

[0194] [ka]

[0195] However, compounds of formula VII-5 are excluded from compounds of formula VII-6, and Each parameter in the formula has the meaning shown in formula VII above. Y 71 , Y 72 , Y73 These represent H or F independently of each other, and Preferably R 71 Each of these represents an unfluorinated alkyl or alkoxy having 1 to 7 carbon atoms, or an unfluorinated alkenyl having 2 to 7 carbon atoms. R 72 Each represents an unfluorinated alkyl or alkoxy having 1 to 7 carbon atoms, or an unfluorinated alkenyl having 2 to 7 carbon atoms, and X 72 represents F, Cl, NCS or -OCF3, preferably F or NCS, and Particularly preferred, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0196] The compound of formula VII-1 is preferably selected from the group of compounds of formula VII-1a to VII-1d.

[0197] [ka]

[0198] X in the formula 72 This has the meaning given to equation VII-2 above, and R 71The above has the meanings shown above, preferably C n H 2n+1 This represents, however n represents an integer in the range of 1 to 7, preferably 2 to 6, and particularly preferably 3 to 5, and z represents 0, 1, 2, 3 or 4, preferably 0 or 2, and X 72 Preferably, it represents F.

[0199] The compound of formula VII-2 is preferably selected from the group of compounds of formula VII-2a and VII-2b, and particularly preferably from the group of compounds of formula VII-2a.

[0200] [ka]

[0201] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0202] Here (R 71 and R 72 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0203] The compound of formula VII-3 is preferably the compound of formula VII-3a.

[0204] [ka]

[0205] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0206] Here (R 71 and R 72 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0207] The compound of formula VII-4 is preferably the compound of formula VII-4a.

[0208] [ka]

[0209] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0210] Here (R 71 and R 72 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0211] The compound of formula VII-5 is preferably selected from the group of compounds of formula VII-5a and VII-5b, more preferably from the group of compounds of formula VII-5a.

[0212] [ka]

[0213] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0214] Here (R 71 and R 72 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0215] The compound of formula VII-6 is preferably selected from the group of compounds of formula VII-6a and VII-6b.

[0216] [ka]

[0217] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1Alternatively, CH2 = CH - (CH2) Z Represents, and R 72 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0218] Here (R 71 and R 72 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0219] The compound of formula VII-7 is preferably selected from the group of compounds of formula VII-7a to VII-7d.

[0220] [ka]

[0221] During the ceremony, R 71 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z This represents, X 72 This represents F, -OCF3, or -NCS. n represents an integer in the range of 1 to 7, preferably 2 to 6 and particularly preferably 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0222] The compound of formula VIII is preferably selected from the group of compounds of formula VIII-1 to VIII-3, more preferably these compounds of formula VIII are predominant therein, even more preferably essentially therein, and very especially preferably completely therein.

[0223] [ka]

[0224] During the ceremony, Y 81 and Y 82 One of them represents H, and the other represents H or F, and R 81 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 82 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0225] Here (R 81 and R 82 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0226] The compound of formula VIII-1 is preferably selected from the group of compounds of formula VIII-1a to VIII-1c.

[0227] [ka]

[0228] During the ceremony, R 81 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 82 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0229] Here (R 81 and R 82 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0230] The compound of formula VIII-2 is preferably the compound of formula VIII-2a.

[0231] [ka]

[0232] During the ceremony, R 81 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 82 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0233] Here (R 81 and R 82 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ), (C n H 2n+1 and OC m H 2m+1 ) and (CH2=CH-(CH2) Z and C m H 2m+1 ), particularly preferably (C n H 2n+1 and C m H 2m+1 )

[0234] The compound of formula VIII-3 is preferably the compound of formula VIII-3a.

[0235] [ka]

[0236] During the ceremony, R 81 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 82 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0237] Here (R 81 and R 82 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 )

[0238] The compound of formula IX is preferably selected from the group of compounds of formula IX-1 to IX-3.

[0239] [ka]

[0240] Each parameter in the formula has the meaning shown in formula IX above, and preferably [ka] And in the formula, R91 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 92 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0241] Here (R 91 and R 92 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 )

[0242] The compound of formula IX-1 is preferably selected from the group of compounds of formula IX-1a to IX-1e.

[0243] [ka]

[0244] Each parameter in the formula has the meaning given above, preferably R 91 The above has the meanings shown above, preferably C n H 2n+1 Represents, and n represents an integer in the range of 0 to 15, preferably 1 to 7 and particularly preferably 1 to 5, and X 92 Preferably, represents F or Cl.

[0245] The compound of formula IX-2 is preferably selected from the group of compounds of formula IX-2a and IX-2b.

[0246] [ka]

[0247] During the ceremony, R 91 The above has the meanings shown above, preferably C n H 2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 92 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0248] Here (R 91 and R 92 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 )

[0249] The compound of formula IX-3 is preferably selected from the group of compounds of formula IX-3a and IX-3b.

[0250] [ka]

[0251] During the ceremony, R 91 The above has the meanings shown above, preferably C n H2n+1 Alternatively, CH2 = CH - (CH2) Z Represents, and R 92 The above has the meanings shown above, preferably C m H 2m+1 or OC m H 2m+1 or (CH2) Z -CH=CH2 represents, however n and m represent integers independently of each other, ranging from 1 to 7, preferably from 2 to 6 and particularly preferably from 3 to 5, and z represents 0, 1, 2, 3, or 4, preferably 0 or 2.

[0252] Here (R 91 and R 92 ) is particularly favored by (C n H 2n+1 and C m H 2m+1 ) and (C n H 2n+1 and OC m H 2m+1 ), particularly preferably (C n H 2n+1 and OC m H 2m+1 )

[0253] In a preferred embodiment of the present invention, the medium comprises one or more compounds of formula X.

[0254] [ka]

[0255] During the ceremony, R 101 H represents an alkyl or alkoxy having 1 to 15, preferably 2 to 10, carbon atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15, preferably 3 to 10 carbon atoms, preferably an alkyl or alkenyl. X 101This represents H, F, Cl, -CN, SF5, NCS, a fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms, or a fluorinated alkenyl, fluorinated alkenyloxy or fluorinated alkoxyalkyl having 2 to 7 carbon atoms, preferably a fluorinated alkoxy, a fluorinated alkenyloxy, F, Cl or NCS, particularly preferably NCS. Y 101 This represents methyl, ethyl, or Cl, Y 102 represents H, methyl, ethyl, F, or Cl, preferably H or F. Z 101 , Z 102 These are identical or different, representing a single bond, -CH=CH-, -CF=CF-, or -C≡C-. [ka] Preferably [ka] This represents, and however, or [ka] This represents, n is either 0 or 1.

[0256] Preferably, the compound of formula X is selected from sub-formulas X-1 and X-2.

[0257] [ka]

[0258] In the formula, the bases and parameters that appear have the meanings given above in formula X.

[0259] Particularly preferably, the medium according to the present invention comprises one or more compounds selected from the group of compounds of formula X-1-1 to X-1-9.

[0260] [ka]

[0261] In the formula, R 101 This represents an alkyl group having 1 to 7 carbon atoms.

[0262] In preferred embodiments, the medium according to the present invention comprises one or more compounds of formula XI.

[0263] [ka]

[0264] During the ceremony, R S This represents an alkyl or alkoxy group having H, 1 to 12 C atoms, or an alkenyl, alkenyloxy, or alkoxyalkyl group having 2 to 12 C atoms, and in this group, one or more CH2 groups are [ka] It may be replaced by, and in the group, one or more H atoms may be replaced by F. [ka] This represents, In the formula, R L Each occurrence may be the same or different, representing a linear, branched, or cyclic alkyl group having H, Cl, or 1 to 6 C atoms. L S1 , L S2 These represent H, Cl, or F, either identical or different. R S1 , R S2 These are identical or different alkyl or alkenyl compounds having H, up to 6 C atoms, or represented as cyclopropyl, cyclobutyl, cyclopentenyl, or cyclopentyl compounds. R Th1 , R Th2These are identical or different alkyl, alkenyl, or alkoxy compounds having H, up to 6 C atoms, or represented as cyclopropyl, cyclobutyl, cyclopentenyl, or cyclopentyl compounds. Z S1 , Z S2 , Z S3 These are identical or different, representing -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C-, or single bonds. a and b are either the same or different, and are either 0 or 1.

[0265] Preferably, the compound of formula XI is selected from the group of compounds of formulas XI-1 to XI-24.

[0266] [ka]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] In the formula, the bases appearing have the meanings given above for formula XI, and preferably R S This represents an alkyl or alkenyl having 2 to 6 C atoms, and in this group, one or more CH2 groups are [ka] It can be replaced with, R S1 and R S2This represents an alkyl group having H or 1 to 6 C atoms, preferably H, and is either the same or different. R S3 This represents an alkyl or cyclopropyl having H, F, or up to 6 C atoms, preferably H, F, or ethyl, very preferably H. L S1 and L S2 These represent H or F, preferably F, and are the same or different.

[0271] Preferably, the medium contains one or more compounds of formula XII.

[0272] [ka]

[0273] During the ceremony, R 12 This represents an alkyl or alkoxy group having H, 1 to 12 C atoms, or an alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 12 C atoms, and in this group one or more CH2 groups, [ka] It may be replaced with, or the base R P This represents, R P Halogen, CN, NCS, R F , R F -O- or R F -S- represents, however R F This represents a fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms. Z 121 , Z 122 These are identical or different, representing -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, preferably -C≡C- or a single bond. X 1 , X 2 , X 3 and X 4 These represent Cl or F, preferably F, and are the same or different. t is 0 or 1, and [ka] This represents a group selected from the following groups: a) A group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be replaced by N, and one or more H atoms may be replaced by L, except that tetrafluoro-1,4-phenylene is excluded. b) A group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, and spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be replaced with -O- and / or -S-, and one or more H atoms may be replaced with F. c) A group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenofen-2,5-diyl, and each of these groups may be monosubstituted or polysubstituted with L. L represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy that is linear or branched, having F, Cl, CN, SCN, SF5, or 1 to 12 C atoms, and which may be fluorinated in each case, whether identical or different in each instance.

[0274] The compound of formula XII is preferably selected from the compounds of sub-formulas XII-1 to XII-11.

[0275] [ka]

[0276] [ka]

[0277] During the ceremony, L 1 , L 2 and L 3 are identical or different, representing H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and R 12 , X 1 , X 2 , X 3 and X 4 It has the meaning given above.

[0278] Very preferably the medium comprises the compound of formula XII-3, wherein the resulting group has the meaning given above, and particularly preferably L 1 represents H, and X 1 , X 2 , X 3 and X 4 represents F, R 12 This represents an alkyl group having 1 to 7 carbon atoms.

[0279] The medium according to the present invention preferably comprises one or more compounds of formula XIII.

[0280] [ka]

[0281] During the ceremony, R 13 This represents an alkyl or alkoxy group having H, 1 to 12 C atoms, or an alkenyl, alkenyloxy or alkoxyalkyl group having 2 to 12 C atoms, and in this group one or more CH2 groups, [ka] It may be replaced with, or the base R P This represents, R P Halogen, CN, NCS, R F , R F -O- or R F-S- represents, however R F This represents a fluorinated alkyl or fluorinated alkenyl having up to 9 C atoms. Z 131 , Z 132 , Z 133 These are identical or different, representing -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, preferably -C≡C- or a single bond. X 1 , X 2 These are the same or different, representing H, Cl, F, CH3 or C2H5, preferably H or F. Y 1 , Y 2 , Y 3 , Y 4 represents a linear, branched, or cyclic alkyl, alkenyl, alkoxy, or alkenyloxy molecule having the same or different H, F, Cl, or up to 12 C atoms each, provided that at least one Y is present. 1 , Y 2 , Y 3 and Y 4 Unlike F, s is 0, 1, or 2, preferably 0 or 1. t is 0, 1 or 2, preferably 0 or 1, and s+t is 0, 1, or 2, preferably 0 or 1. [ka] This represents a group selected from the following groups: a) A group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups may be replaced by N, and one or more H atoms may be replaced by L. b) A group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, and spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH2 groups may be replaced with -O- and / or -S-, and one or more H atoms may be replaced with F. c) A group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenofen-2,5-diyl, and each of these groups may be monosubstituted or polysubstituted with L. L represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy that is linear or branched, having F, Cl, CN, SCN, SF5, or 1 to 12 C atoms, and which may be fluorinated in each case, whether identical or different in each instance.

[0282] In a preferred embodiment of the present invention, the compound of formula XIII is selected from the compounds of formula XIII-1 to XIII-20, and very preferably from the compounds of formula XIII-1 to XIII-13.

[0283] [ka]

[0284] [ka]

[0285] [ka]

[0286] [ka]

[0287] In the formula, the groups that appear have the meanings shown above in formula XIII and its subformulas, preferably R 13 represents an alkyl group having 1 to 7 C atoms, and Y 1 , Y 2 , Y 3 and Y 4 is the same or different and represents H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclopentenyl, more preferably Y 1 and Y 2 represents H or F independently, especially H, and Y 3 and Y 4 It is very preferably H, and L 1 and L 2 is the same or different, very preferably representing H, F, methyl, or ethyl, especially H.

[0288] Preferably, the medium according to the present invention comprises one or more compounds of formula T.

[0289] [ka]

[0290] During the ceremony, R T Halogen, CN, NCS, R F , R F -O- or R F -S- represents, and in the formula, R F This represents a fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms. [ka] This represents, L 4 and L 5 This represents a linear, branched, or cyclic alkyl or alkenyl molecule having the same or different F, Cl, or up to 12 C atoms. Z T3 , Z T4These represent, whether identical or different, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, and t is either 0 or 1.

[0291] In a preferred embodiment, the liquid crystal medium according to the present invention comprises one or more compounds selected from the group of compounds of the following formulas T-1a to T-3b.

[0292] [ka]

[0293] During the ceremony, [ka] It has the meaning given above, and n is 1, 2, 3, 4, 5, 6, or 7, preferably 1, 2, 3, or 4, and particularly preferably 1.

[0294] In a particularly preferred embodiment of the present invention, the medium comprises one or more compounds selected from the compounds of formula T-1a and formula T-2a.

[0295] The preferred compound of formula T-1a is selected from the group of compounds with the following sub-formulas.

[0296] [ka]

[0297] In the formula, n is 1, 2, 3, or 4, preferably 1.

[0298] The preferred compound of formula T-2a is selected from the group of compounds with the following sub-formulas.

[0299] [ka]

[0300] In the formula, n is 1, 2, 3, or 4, preferably 1.

[0301] More preferably, the medium according to the present invention comprises one or more compounds of formula T-1a-5.

[0302] In one embodiment, the medium according to the present invention is based on R 1 , R 2 , R 3 , R 41 , R 42 , R 51 , R 52 , R 61 , R 62 , R 71 , R 72 , R 81 , R 82 , R 91 , R 92 , R 101 , R 102 and R S However, each contains one or more compounds of formulas I, II, III, IV, V, VI, VII, VIII, IX, and X, which are cyclic alkyl groups.

[0303] Highly preferred compounds containing cyclic alkyl groups are selected from compounds of formula Cy-1 to Cy-14.

[0304] [ka]

[0305] [ka]

[0306] The medium according to the present invention comprises one or more chiral dopants. Preferably, these chiral dopants are 1 μm in size. -1 ~150μm -1 A range of preferably 10 μm -1 ~100μm -1The absolute value of the helical twisting power (HTP) is within the range. If the medium contains two or more chiral dopants, these may have opposite signs in their HTP values. This condition is preferable for some specific embodiments because it allows for some degree of compensation for the chirality of each compound, and can be used to compensate for various temperature-dependent properties of the medium obtained in the device. However, generally, it is preferable that most, preferably all, of the chiral compounds present in the medium according to the present invention have the same sign in their HTP values.

[0307] Preferably, the chiral dopants present in the medium according to this application are mesogenic compounds, and most preferably, they exhibit a mesophase on their own.

[0308] In a preferred embodiment of the present invention, the medium comprises two or more chiral compounds, all having the same arithmetic sign of HTP.

[0309] The temperature dependence of the HTP of individual compounds can be high or low. The temperature dependence of the pitch of the medium can be compensated for by mixing compounds with different HTP temperature dependencies in corresponding ratios.

[0310] As for optically active ingredients, a number of commercially available chiral dopants are available to those skilled in the art, such as cholesteryl nonanoate, R- and S-811, R- and S-1011, R- and S-2011, R- and S-3011, R- and S-4011, or CB15 (all from Merck, Darmstadt).

[0311] Particularly suitable dopants are compounds containing one or more chiral groups and one or more mesogenic groups, or one or more aromatic or alicyclic groups that form a mesogenic group together with a chiral group.

[0312] Suitable chiral groups include, for example, chiral branched hydrocarbon groups, chiral ethanediols, binaphthols or dioxolanes, as well as monovalent or polyvalent chiral groups selected from the group consisting of sugar derivatives, sugar alcohols, sugar acids, lactic acid, chiral-substituted glycols, steroid derivatives, terpene derivatives, amino acids, or sequences of several, preferably 1 to 5, amino acids.

[0313] Preferred chiral groups include sugar derivatives, such as glucose, mannose, galactose, fructose, arabinose, and dextrose; sugar alcohols, such as sorbitol, mannitol, isitol, galactitol, or their anhydro derivatives, particularly dianhydrohexitol, such as dianhydrosorbide (1,4:3,6-dianhydro-D-sorbide, isosorbide), dianhydromannitol (isosorbitol), or dianhydroiditol (isoiditol); sugar acids, such as gluconic acid, gulonic acid, and ketoguronic acid; and chiral-substituted glycol groups. For example, mono- or oligoethylene or propylene glycol in which one or more CH2 groups are substituted with alkyl or alkoxy groups; amino acids, such as alanine, valine, phenylglycine or phenylalanine, or sequences of 1 to 5 of these amino acids; steroid derivatives, such as cholesteryl or cholic acid groups; terpene derivatives, such as menthyl, neomentyl, campheyl, pinail, terpineil, isolongifolyl, phenthyl, kalyl, myrtenyl, nopyl, geranyl, linaloyl, neryl, citronellyl or dihydrocitronellyl.

[0314] The medium according to the present invention preferably comprises a chiral dopant selected from the group of known chiral dopants. Suitable chiral groups and mesogenic chiral compounds are described, for example, in German Patent Nos. 3425503, 3534777, 3534778, 3534779, and 3534780, 4342280, European Patent No. 01038941, and German Patent No. 19541820. Other examples are the compounds listed in Table F below.

[0315] The chiral compounds preferably used in accordance with the present invention are selected from the group consisting of the formulas shown below.

[0316] Chiral dopants selected from the group consisting of compounds of the following formulas AI~A-III and A-Ch are particularly preferred.

[0317] [ka]

[0318] During the ceremony, R a11 , R a12 and R b12 This represents an alkyl group having 1 to 15 C atoms independently of each other, where furthermore, one or more non-adjacent CH2 groups are independently of each other such that the O and / or S atoms are not directly bonded to each other, -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, where one or more H atoms may be replaced by F, Cl, Br, I or CN. Preferably, it represents alkyl, more preferably n-alkyl, however, R a12 is R b12 Unlike, R a21 and R a22This represents an alkyl group having 1 to 15 C atoms independently of each other, where furthermore, one or more non-adjacent CH2 groups are independently of each other such that the O and / or S atoms are not directly bonded to each other, -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, where one or more H atoms may be replaced by F, Cl, Br, I or CN. Preferably both represent alkyl, more preferably n-alkyl. R a31 , R a32 and R b32 This represents a linear or branched alkyl group having 1 to 15 C atoms independently of each other, where furthermore, one or more non-adjacent CH2 groups are independently of each other such that the O and / or S atoms are not directly bonded to each other, and -C(R z )=C(R z )-, -C≡C-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, where one or more H atoms may be replaced by F, Cl, Br, I or CN. Preferably, it represents alkyl, more preferably n-alkyl, however, R a32 is R b32 Unlike, R z represents H, CH3, F, Cl, or CN, preferably H or F. R 8 This is the R given above. a11 One of the meanings is an alkyl group having 1 to 15 C atoms, more preferably an n-alkyl group. Z 8 This represents -C(O)O-, -CH2O-, -CF2O- or a single bond, preferably -C(O)O-. A 11 A is below 12 As defined in, or [ka] This represents, A 12 teeth, [ka] Preferably [ka] This represents, During the ceremony, L 12 Each instance independently represents a halogen, CN, or an alkyl, alkenyl, alkoxy, or alkenyloxy having up to 12 C atoms, wherein one or more H atoms may be replaced by a halogen, preferably methyl, ethyl, Cl, or F, and particularly preferably F. A 21 teeth, [ka] This represents, A 22 is, A 12 It has meaning to be given to, A 31 is, A 11 It has meaning to be given to, or [ka] This represents, A 32 is, A 12 It has meaning to be given to, n2 is 0, 1, or 2, and is either the same or different in each occurrence. n3 is 1, 2, or 3. r is 0, 1, 2, 3, or 4.

[0319] A dopant selected from the group consisting of compounds of the following formula is particularly preferred.

[0320] [ka]

[0321] [ka]

[0322] During the ceremony, m is an integer from 1 to 9, and n is an integer between 2 and 9, which may be the same or different in each occurrence.

[0323] Particularly preferred compounds of formula A are those of formula A-III.

[0324] Further preferred dopants are derivatives of isosorbide, isomannitol, or isoiditol of the following formulas A-IV.

[0325] [ka]

[0326] In the formula, the group [ka] teeth, [ka] The most preferred is dianhydrosorbitol.

[0327] Furthermore, it includes chiral ethanediols such as diphenylethanediol (hydrobenzoin), particularly mesogenic hydrobenzoin derivatives of the following formula AV, which are (S,S) enantiomers not shown.

[0328] [ka]

[0329] During the ceremony, [ka] Each of these is 1,4-phenylene or 1,4-cyclohexylene, which may be monosubstituted, disubstituted, or trisubstituted at L, independently of each other. L is H, F, Cl, CN, or an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms that may be halogenated. c is either 0 or 1. X is either CH2 or -C(O)-, Z 0 These are -COO-, -OCO-, -CH2CH2-, or single bonds. R 0 These are alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy compounds having 1 to 12 carbon atoms.

[0330] This is an example of a compound of formula IV.

[0331] [ka]

[0332] [ka]

[0333] Compounds of formulas A-IV are described in International Publication No. 98 / 00428. Compounds of formula AV are described in British Patent Application Publication No. 2,328,207.

[0334] Particularly preferred dopants are the chiral binaphthyl derivatives described in International Publication No. 02 / 94805, the chiral binaphthol acetal derivatives described in International Publication No. 02 / 34739, the chiral TADDOL derivatives described in International Publication No. 02 / 06265, and the chiral dopants having at least one fluorinated crosslinking group and a terminal or central chiral group described in International Publication Nos. 02 / 06196 and International Publication No. 02 / 06195.

[0335] Chiral compounds of formulas A-VI are particularly preferred.

[0336] [ka]

[0337] During the ceremony, X 1 , X 2 , Y 1 and Y 2 Each of these groups is independently of the others, and consists of F, Cl, Br, I, CN, SCN, SF5, and linear or branched alkyl groups having 1 to 25 carbon atoms (which may be monosubstituted or polysubstituted with F, Cl, Br, I, or CN, where furthermore, one or more non-adjacent CH2 groups are independently of each other, such that the O and / or S atoms are not directly bonded to each other, and consist of -O-, -S-, -NH-, NR 0 -, -CO-, -COO-, -OCO-, -OCOO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- (which may be replaced by a polymerizable group or a cycloalkyl or aryl having up to 20 carbon atoms (which may be monosubstituted or polysubstituted with a halogen, preferably F, or a polymerizable group), x 1 and x 2 Each of these is independently 0, 1, or 2. y 1 and y 2 Each of these is independently 0, 1, 2, 3, or 4. B 1 and B 2 Each of these is an aromatic, partially saturated, or fully saturated aliphatic six-membered ring, where one or more CH groups may be replaced by N atoms, and one or more non-adjacent CH2 groups may be replaced by O and / or S atoms. W 1 and W 2 These are, independently of each other, -Z 1 -A 1 -(Z2 -A 2 ) m -R, or one of the two is R 1 Or A 3 However, neither is H at the same time, or [ka] teeth, [ka] And, U 1 and U 2 Each of these is independently CH2, O, S, CO, or CS. V 1 and V 2 Each of them operates independently of the other, (CH2) n (However, one or two non-adjacent CH2 groups may each be replaced with O or S.) Or a single bond, where n is 1, 2 or 3. Z 1 and Z 2 These are -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, and -CO-NR, each independent of the others. 0 -, -NR 0 -CO-, -O-CH2-, -CH2-O-, -S-CH2-, -CH2-S-, -CF2-O-, -O-CF2-, -CF2-S-, -S-CF2-, -CH2-CH2-, -CF2-CH2-, -CH2-CF2-, -CF2-CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, two combinations of these groups (where two O and / or S and / or N atoms are not directly bonded to each other), (preferably -CH=CH-COO- or -COO-CH=CH-), or single bonds, R x This represents an alkyl group having 1 to 6 carbon atoms. A 1 , A 2 and A 3Each of these is independently 1,4-phenylene, in which one or two non-adjacent CH groups may be replaced by N; 1,4-cyclohexylene, 1,3-dioxolane-4,5-diyl, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl (each of these groups may be monosubstituted or polysubstituted with L); and further A 1 It can be a single bond, L is a halogen atom, preferably F, CN, NO2, an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl or alkoxycarbonyloxy having 1 to 7 carbon atoms (where one or more H atoms may be replaced by F or Cl), m is independently 0, 1, 2, or 3. R and R 1 Each of these is independently a linear or branched alkyl group having 1 or 3 to 25 carbon atoms, consisting of H, F, Cl, Br, I, CN, SCN, SF5 (which may be monosubstituted or polysubstituted with F, Cl, Br, I, or CN, and one or more non-adjacent CH2 groups are -O-, -S-, -NH-, -NR such that two O and / or S atoms are not directly bonded to each other). 0 -, -CO-, -COO-, -OCO-, -O-COO-, -S-CO-, -CO-S-, -CH=CH- or -C≡C- may be substituted, or it is a polymerizable group.

[0338] Chiral binaphthyl derivatives of formula A-VI-1 are particularly preferred.

[0339] [ka]

[0340] In the formula, rings B, R 0 and Z0 This is as defined for equations A-IV and AV, where b is 0, 1, or 2.

[0341] In particular, it must be selected from the following equations A-VI-1a to A-VI-1c.

[0342] [ka]

[0343] In the formula, rings B, R 0 and Z 0 This is as defined for equation A-VI-1, R 0 This is either as defined for formulas A-IV, or an alkyl group having H or 1 to 4 carbon atoms. b is 0, 1, or 2. Z 0 These are specifically -OC(O)- or single bonds.

[0344] The concentration of one or more chiral dopants (one or more) in the LC medium is preferably in the range of 0.001% to 20%, preferably 0.05% to 5%, more preferably 0.1% to 2%, and most preferably 0.5% to 1.5%. These preferred concentration ranges apply in particular to chiral dopants S-4011 or R-4011 (both manufactured by Merck) and chiral dopants having the same or similar HTP. For chiral dopants with a higher or lower absolute value of HTP compared to S-4011, these preferred concentrations must be decreased or increased proportionally, respectively, according to the ratio of their HTP values ​​to the HTP value of S-4011.

[0345] The pitch p of the LC medium or host mixture according to the present invention is preferably in the range of 5 to 50 μm, more preferably 8 to 30 μm, and particularly preferably 10 to 20 μm.

[0346] Preferably, the medium according to the present invention comprises a stabilizer selected from the group of compounds of formulas ST-1 to ST-18.

[0347]

Chemical Formula

[0348]

Chemical Formula

[0349]

Chemical Formula

[0350]

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0351] Among the compounds of formula ST, the compound shown below is particularly preferred.

[0352] [ka]

[0353] [ka]

[0354] [ka]

[0355] In the compounds of formulas ST-3a and ST-3b, n preferably represents 3. In the compound of formula ST-2a, n preferably represents 7.

[0356] A particularly very preferred mixture according to the present invention comprises one or more stabilizers from the group of compounds of formula ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1, and ST-12.

[0357] [ka]

[0358] [ka]

[0359] The compounds of formulas ST-1 to ST-18 are preferably present in the liquid crystal mixture according to the present invention in an amount of 0.005 to 0.5% based on the mixture.

[0360] When the mixture according to the present invention contains two or more compounds from the group of compounds of formula ST-1 to ST-18, the concentration increases to 0.01 to 1% relative to the mixture, corresponding to the case of two compounds.

[0361] However, the total proportion of compounds of formulas ST-1 to ST-18 based on the mixture according to the present invention should not exceed 2%.

[0362] Other mesogenic compounds not explicitly stated above may also be optionally and advantageously used in the media according to the present invention. Such compounds are known to those skilled in the art.

[0363] In a preferred embodiment of the present invention, the total concentration of the compound of formula UI in the liquid crystal medium is 5% or 6% or more, preferably 7% or more, very preferably 10% or more, and particularly preferably 10% or 12% or more.

[0364] In a preferred embodiment of the present invention, the total concentration of the compound of formula UII in the liquid crystal medium is 5% or more, preferably 6% or more, very preferably 8% or more, and particularly preferably 10% or more.

[0365] In preferred embodiments of the present invention, the liquid crystal medium preferably contains a compound of formula UI in a total of 2% to 45%, preferably 5% to 40%, more preferably 6% to 30%, and particularly preferably 8% to 25%.

[0366] In preferred embodiments of the present invention, the liquid crystal medium preferably contains a total of 2% to 40%, preferably 5% to 30%, and particularly preferably 8% to 25% of the compound of formula UII.

[0367] In preferred embodiments of the present invention, the liquid crystal medium preferably contains compounds of formulas UI and UII in total at a concentration of 10% to 60%, preferably 12% to 55%, more preferably 15% to 50%, and particularly preferably 20% to 45%.

[0368] In a preferred embodiment of the present invention, the liquid crystal medium contains a total of 5% to 35%, preferably 6% to 30%, and particularly preferably 7% to 25%, of one or more compounds of formula T, preferably selected from formulas T-1a and T-2a, and very preferably from T-1a-5 and T-2a-2.

[0369] In preferred embodiments of the present invention, the medium contains one or more compounds of formula I, preferably formula I-2 or I-3, in a total concentration ranging from 1% to 30%, more preferably 2% to 25%, very preferably 3% to 20%, and particularly preferably 5% to 15%.

[0370] In preferred embodiments of the present invention, the medium contains one or more compounds of formula II, preferably formula II-1, in a total concentration ranging from 2% to 20%, more preferably 3% to 15%, and particularly preferably 5% to 10%.

[0371] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula IIA-1 in a total concentration of 5% to 25%, more preferably 8% to 20%, and particularly preferably 12% to 17%.

[0372] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula II-1 in a total concentration of 30% or less, more preferably 25% or less, and particularly preferably 20% or less.

[0373] In preferred embodiments of the present invention, the medium contains one or more compounds of formula III, preferably III-1 and / or III-2, more preferably III-1f and / or III-1b and / or III-1h, in a total concentration of 15% to 60% or 65% or 70%, more preferably 18% to 55%, and particularly preferably 20% to 50%.

[0374] In a preferred embodiment of the present invention, the medium contains one or more compounds of formula XII in a total concentration of 5% to 30%, more preferably 8% to 25%, and particularly preferably 10% to 20%.

[0375] In preferred embodiments, the medium contains, preferably at a total concentration of 90% or more, more preferably 95%, 96%, or 97% or more, very preferably 98% or more, and particularly 99% or more, one or more compounds of formula UI and / or UII, and one or more compounds selected from the group consisting of formula I, II and / or IIA, III, XII, and T.

[0376] In a preferred embodiment, the medium comprises one or more compounds of formula UI and / or UII, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII, and T, in a total concentration ranging from 40% to 90%, and one or more compounds of formula IV in a total concentration of 10% or more.

[0377] In a preferred embodiment, the medium comprises one or more compounds of formulas UI and UII, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII, and T, in a total concentration ranging from 40% to 70%, and one or more compounds of formula IV in a total concentration of 30% or more.

[0378] In a preferred embodiment, the medium comprises one or more compounds of formula UI and / or UII, and one or more compounds selected from the group consisting of formulas I, II and / or IIA, III, XII, and T, in a total concentration ranging from 40% to 60%, and one or more compounds of formula IV in a total concentration of 40% or more.

[0379] Further preferred embodiments of the present invention, either individually or in combination with each other, are as follows, although some compounds are as listed in Tables A and B and are abbreviated using the acronyms given in Table C below.

[0380] The medium comprises one, two, three, or four or more compounds selected from the compounds of formula III-1, preferably from the compounds of formula III-1b, III-1f, and III-1h, and more preferably from the compounds of III-1b and III-1h.

[0381] The medium preferably contains the compound of formula III-1b in a total concentration ranging from 5% to 35%, more preferably 10% to 30%, and particularly 15% to 25%.

[0382] The medium preferably contains the compound of formula III-1h in a total concentration ranging from 5% to 35%, more preferably 7% to 30%, and particularly 10% to 25%.

[0383] The medium contains the compound PPU-TO-S and / or PPTU-TO-S and / or PTPU-TO-S and / or PP(1)TO-nS.

[0384] The medium comprises one or more compounds of formula I-2d, preferably compound PGU-2-S and / or PGU-3-S and / or PGU-4-S and / or CPU-2-S and / or CPU-3-S and / or CPU-4-S.

[0385] The medium comprises one or more compounds of formula II-1b, preferably compound PTU-4-S and / or PTU-5-S.

[0386] The medium contains one or more compounds of the formula PPTU-nS and / or PTPU-nS in a total concentration ranging from 15 to 25%.

[0387] The medium contains one or more compounds of the formula PPTU-nS and / or PTPU-nS and / or PGTU-nS in a total concentration ranging from 15 to 30%, where n is 1, 2, 3, 4, 5, or 6.

[0388] The medium contains one or more compounds of formula ST-3, preferably ST-3a and / or ST-3b, particularly preferably ST-3b-1, in a total concentration ranging from 0.01 to 1%, preferably 0.05 to 0.5%, and particularly 0.10 to 0.15%.

[0389] The liquid crystal medium according to the present invention has a transparent point preferably at 90°C or higher, more preferably at 100°C or higher, even more preferably at 110°C or higher, even more preferably at 120°C or higher, even more preferably at 130°C or higher, particularly preferably at 140°C or higher, and very particularly preferably at 150°C or higher.

[0390] The liquid crystal medium according to the present invention preferably has a transparent point at 160°C or lower, more preferably 140°C or lower, particularly preferably 120°C or lower, and very particularly preferably 100°C or lower.

[0391] The nematic phase of the medium according to the present invention preferably extends from at least 0°C to 90°C or higher. It is advantageous for the medium according to the present invention to exhibit an even broader range of nematic phase, preferably at least -10°C to 120°C or higher, very preferably at least 20°C to 140°C or higher, particularly preferably at least 30°C to 150°C or higher, and very particularly preferably at least 40°C to 170°C or higher.

[0392] The Δε of the liquid crystal medium according to the present invention at 1 kHz and 20°C is preferably 5 or more, more preferably 7 or more, and very preferably 8 or more.

[0393] The liquid crystal medium according to the present invention has a wavelength of 589 nm (Na DThe birefringence (Δn) at 20°C is preferably 0.280 or higher, more preferably 0.300 or higher, even more preferably 0.320 or higher, very preferably 0.330 or higher, and especially preferably 0.350 or higher.

[0394] The liquid crystal medium according to the present invention has a wavelength of 589 nm (Na D ) and Δn at 20℃ are preferably in the range of 0.200 to 0.900, more preferably in the range of 0.250 to 0.800, even more preferably in the range of 0.300 to 0.700, and very particularly preferably in the range of 0.350 to 0.600.

[0395] In a preferred embodiment of the present invention, the Δn of the liquid crystal medium according to the present invention is preferably 0.50 or more, more preferably 0.55 or more.

[0396] In each case, the compounds of formulas I to III include dielectrically positive compounds with dielectric anisotropy greater than 3, dielectrically neutral compounds with dielectric anisotropy less than 3 and greater than -1.5, and dielectrically negative compounds with dielectric anisotropy of -1.5 or less.

[0397] Compounds of formulas UI, UII, I, II, and III are preferably dielectrically positive.

[0398] In the present application, the expression "dielectrically positive" describes a compound with Δε>3.0, "dielectrically neutral" describes a compound with -1.5≦Δε≦3.0, and "dielectrically negative" describes a compound with Δε<-1.5. Δε is determined at a frequency of 1 kHz and 20°C. The dielectric anisotropy of each compound is determined from the results of a 10% solution of the respective individual compound in a nematic host mixture. If the solubility of the respective compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitance of the test mixture is determined in both a cell having homeotropic alignment and a cell having homogeneous alignment. The cell thickness of both types of cells is approximately 20 μm. The applied voltage is a rectangular wave having a frequency of 1 kHz and an effective value of typically 0.5 V to 1.0 V, which is selected to be always lower than the capacitive threshold of each test mixture.

[0399] Δε is (ε ∥ -ε ⊥ ), while ε ave is (ε ∥ +2ε ⊥ ) / 3.

[0400] The host mixture used to determine the physical constants of the pure compound by extrapolation is ZLI-4792 from Merck KGaA, Germany. The absolute value of the dielectric constant, birefringence (Δn) and rotational viscosity (γ1) of the compound are determined from the change in the respective values of the host mixture when the compound is added. The concentration in the host is 10%, or 5% if the solubility is insufficient. The values are those obtained by extrapolating the concentration of the added compound to 100%.

[0401] In the examples, the phase sequence of the pure compound is given using the following abbreviations: K: crystal, N: nematic, SmA: smectic A, SmB: smectic B, I: isotropic.

[0402] A component having a nematic phase at a measurement temperature of 20°C is measured as it is, and the others are treated in the same manner as the compound.

[0403] In either case, unless otherwise specified, the expression "threshold voltage" in this application refers to the optical threshold voltage, specifically the 10% relative contrast (V) 10 ) quotes the expression "saturation voltage," which refers to optical saturation at 90% relative contrast (V 90 ) is cited. Also, the capacitance threshold voltage (V0) is the Frederick threshold voltage (V Fr Also known as ), this term is used only when making a specific statement.

[0404] Unless otherwise specified, the parameter ranges shown in this application include all limit values.

[0405] When combined with each other, different upper and lower limits are shown for various ranges of characteristics, resulting in an additional preferred range.

[0406] Unless otherwise specified throughout this application, the following conditions and definitions apply. All concentrations are cited in weight percent, all temperatures in Celsius, and all temperature differences in degrees of difference for each mixture as a whole. All physical properties are determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals," published November 1997, Merck AG, Germany, and are cited at a temperature of 20°C unless otherwise specified. Optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. Dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. Threshold voltage and all other electro-optical properties are determined using a test cell manufactured by Merck AG. The test cell for determining Δε has a cell thickness of approximately 20 μm. The electrodes are 1.13 cm². 2 It is a circular ITO electrode with a surface area and a guard ring. The orientation layer is homeotropically oriented (ε ∥ For this purpose, it is SE-1211 manufactured by Nissan Chemical Corporation in Japan, and is homogeneous oriented (ε ⊥ For this purpose, the material used is polyimide AL-1054 manufactured by Nippon Synthetic Rubber Co., Ltd. of Japan. The capacitance is 0.3V. rmsThe characteristic voltage is determined using a Solatron 1260 frequency response analyzer that employs a sine wave with a voltage of . White light is used for the electro-optical measurements. In this specification, an instrumentation configuration using a DMS device commercially available from Autronic-Melchers GmbH in Germany is used. The characteristic voltage was determined under vertical observation. Threshold (V) 10 ), medium gray (V 50 ) and saturated (V 90 The voltages were determined at relative contrasts of 10%, 50%, and 90%, respectively.

[0407] The characteristics of liquid crystal media in the microwave frequency range are examined as described in "Cavity Perturbation Method for Characterization of Liquid Crystals up to 35GHz" by A. Penirschke et al., 34th European Microwave Conference - Amsterdam, pp. 545-548. Furthermore, this is compared with "Direct Simulation of Material Permittivites" by A. Gaebler et al., 12MTC2009 - International Instrumentation and Measurement Technology Conference, Singapore, 2009 (IEEE), pp. 463-467, and German Patent Application Publication No. 10 2004 029 429, both of which describe measurement methods in similar detail.

[0408] Liquid crystal is introduced into a cylindrical polytetrafluoroethylene (PTFE) or quartz capillary. The capillary has an inner diameter of 180 μm and an outer diameter of 350 μm. The effective length is 2.0 cm. The filled capillary is introduced into the center of a cylindrical cavity with a resonant frequency of 19 GHz. This cavity has a length of 11.5 mm and a radius of 6 mm. An input signal (signal source) is then applied, and the output signal result is recorded using a commercially available vector network analyzer (N5227A PNA Microwave Network Analyzer, Keysight Technologies, USA). For other frequencies, the dimensions of the cavity are adapted accordingly.

[0409] Using the change in resonant frequency and the Q factor between measurements with and without a liquid crystal-filled capillary, the dielectric constant and loss angle at the corresponding target frequency are determined using equations 10 and 11 as described in the aforementioned publication, A. Penirschke et al., "Cavity Perturbation Method for Characterisation of Liquid Crystals up to 35GHz," 34th European Microwave Conference - Amsterdam, pp. 545-548.

[0410] The values ​​of the characteristic components perpendicular and parallel to the liquid crystal director are obtained by the orientation of the liquid crystal in a magnetic field. For this purpose, a magnetic field from a permanent magnet is used. The strength of the magnetic field is 0.35 Tesla.

[0411] Preferred components include phase shifters, varactors, wireless and radio wave antenna arrays, matching circuit adaptive filters, and others.

[0412] In this application, unless otherwise specified, the term "compound" shall be interpreted as meaning both one type of compound and multiple types of compounds.

[0413] All mixtures according to the present invention are nematic. The liquid crystal media according to the present invention preferably have a nematic phase within the preferred range given above. Here, having a nematic phase means, on the one hand, that no smectic phase and crystallization are observed at low temperatures at the corresponding temperature, and on the other hand, that no transparency occurs upon heating from the nematic phase. At high temperatures, the point of transparency in the capillary is measured using conventional methods. Low-temperature studies are performed at the corresponding temperature using a fluid viscometer and confirmed by the storage of bulk samples. The bulk storage stability (LTS) of the media according to the present invention at a given temperature T is determined by visual inspection. 2 g of the media under consideration is filled into a suitably sized sealed glass container (bottle) placed in a refrigerator at the given temperature. The bottle is checked at predetermined time intervals for the occurrence of the smectic phase and crystallization. Two bottles are stored for each material and each temperature. If crystallization or the appearance of the smectic phase is observed in at least one of the two corresponding bottles, the test is terminated, and the time of the last inspection before the appearance of a higher phase is recorded as the respective storage stability. The test is finally completed after 1000 hours, meaning that the LTS value of 1000 hours indicates that the mixture is stable at a given temperature for at least 1000 hours.

[0414] The liquid crystal used preferably has a positive dielectric anisotropy. This is preferably 2 or more, preferably 4 or more, particularly preferably 6 or more, and very particularly preferably 10 or more.

[0415] Furthermore, the liquid crystal medium according to the present invention is characterized by having a high anisotropy value in the microwave region. The birefringence at approximately 19 GHz is preferably 0.14 or higher, particularly preferably 0.15 or higher, particularly preferably 0.20 or higher, particularly preferably 0.25 or higher, and very particularly preferably 0.30 or higher. In addition, the birefringence is preferably 0.80 or lower.

[0416] The dielectric anisotropy in the microwave region is defined as follows:

[0417]

number

[0418] Adjustability (τ) is defined as follows:

[0419]

number

[0420] Material quality (η) is defined as follows:

[0421]

number

[0422] In the equation, the maximum dielectric loss is shown below.

[0423]

number

[0424] The adjustability τ of the medium according to the present invention, measured at 20°C and 19GHz, is 0.250 or higher, preferably 0.300 or higher, 0.310 or higher, 0.320 or higher, 0.330 or higher, or 0.340 or higher, very preferably 0.345 or higher, and particularly 0.350 or higher.

[0425] The preferred material quality (η) of the liquid crystal material is 6 or higher, preferably 8 or higher, preferably 10 or higher, preferably 15 or higher, preferably 17 or higher, preferably 20 or higher, particularly preferably 25 or higher, and very particularly preferably 30 or higher.

[0426] In the corresponding components, preferred liquid crystal materials have a phase shift amount of 15° / dB or more, preferably 20° / dB or more, preferably 30° / dB or more, preferably 40° / dB or more, preferably 50° / dB or more, particularly preferably 80° / dB or more, and very particularly preferably 100° / dB or more.

[0427] However, depending on the embodiment, a liquid crystal having a negative dielectric anisotropy can also be used.

[0428] The liquid crystals used are either individual substances or mixtures. They preferably have a nematic phase.

[0429] The liquid crystal medium according to the present invention may contain further additives and chiral dopants at normal concentrations. The total concentration of these further components is in the range of 0% to 10%, preferably 0.1% to 6%, based on the whole mixture. The concentration of each individual compound used is preferably in the range of 0.1% to 3%. The concentrations of these and similar additives are not considered when referring to the values ​​and concentration ranges of liquid crystal compounds in the liquid crystal medium in this application.

[0430] Preferably, the media according to the present invention contains one or more chiral compounds as chiral dopants to adjust their cholesteric pitch. The total concentration of these compounds in the media according to the present invention is preferably in the range of 0.05% to 15%, more preferably 1% to 10%, and most preferably 2% to 6%.

[0431] The medium according to the present invention optionally contains further liquid crystal compounds to adjust its physical properties. Such compounds are known to those skilled in the art. Their concentrations in the medium according to the present invention are preferably 0% to 30%, more preferably 0.1% to 20%, and most preferably 1% to 15%.

[0432] The response time is the time (t) for the change in relative tuning from 0% to 90% for each electro-optic response. 90 -t0), i.e., delay time (t 10 (τ) including the rising time (t0) on ) as the time (t) for the change in relative tuning for the electro-optic response, from 100% back to 10%. 100 -t 10 ) with respect to decay time (τ off ) as, and total response time (τ total =τ on +τoff These are shown below.

[0433] The liquid crystal medium according to the present invention consists of a plurality of compounds, preferably 3 to 30 types, more preferably 4 to 20 types, and very preferably 4 to 16 types. These compounds are mixed by conventional methods. Generally, a desired amount of compound to be used in smaller quantities is dissolved in a larger quantity of the compound to be used. When the temperature is higher than the transparency point of the compound to be used at higher concentrations, it is particularly easy to observe the completion of the dissolution process. However, it is also possible to prepare the medium using other conventional methods, such as so-called premixes which may be homogeneous or eutectic mixtures of components, or using a so-called "multi-bottle" system, for example.

[0434] For example, all temperatures, such as the melting point T(C,N) or T(C,S), the transition from the smectic (S) phase to the nematic (N) phase T(S,N), and the transparency point T(N,I) of liquid crystals, are cited in degrees Celsius. All temperature differences are cited in degrees of difference.

[0435] In the present invention and especially in the following examples, the structure of a mesogenic compound is represented by an abbreviation, also called an acronym. In these acronyms, the chemical formula is abbreviated as follows using Tables A to C below. All groups C n H 2n+1 , C m H 2m+1 and C l H 2l+1 and C n H2 n-1 , C m H 2m-1 and C l H 2-1 Each represents a linear alkyl or alkenyl group, having n, m, and l carbon atoms, respectively, where n and m are independently 1, 2, 3, 4, 5, 6, or 7, and l is 1, 2, or 3. Table A lists the codes used for the ring elements of the core structure of the compounds, while Table B shows the linking and terminal groups. Table C shows exemplary structures of the compounds, along with their respective abbreviations.

[0436] <Table A: Ring elements>

[0437] [Table 1] TIFF0007933760000208.tif133166

[0438] [Table 2]

[0439] [Table 3]

[0440] [Table 4]

[0441] [Table 5]

[0442] <Table B: Linking group>

[0443] [Table 6]

[0444] <Table B: Terminal group>

[0445] [Table 7]

[0446] In the table, n and m represent integers, and the three dots "..." are spaces for other abbreviations from this table.

[0447] The branching lateral chain bases are numbered starting from the position next to ring (1) where the longest chain is selected, with smaller numbers indicating the length of the branch and superscript numbers in parentheses indicating the position of the branch. For example, below.

[0448] [ka]

[0449] [ka]

[0450] The following table shows exemplary structures along with their respective abbreviations. These are provided to illustrate the meaning of the abbreviation rules. They represent compounds that are more preferably used.

[0451] <Table C: Exemplary Structure> The following exemplary structures are examples and compounds that are preferably used additionally in the medium.

[0452] [Table 8]

[0453] [Table 9]

[0454] [Table 10]

[0455] [Table 11]

[0456] [Table 12]

[0457] Table 13

[0458] Table 14

[0459] Table 15

[0460] Table 16

[0461] Table 17

[0462] Table 18

[0463] Table 19

[0464] Table 20

[0465] Table 21

[0466] Table 22

[0467] Table 23

[0468] [Table 24]

[0469] In the table, m and n are either the same or different, and are 1, 2, 3, 4, 5, 6, or 7.

[0470] Preferably, the medium according to the present invention comprises one or more compounds selected from the compounds in Table C.

[0471] Table D, shown below, lists exemplary compounds that can be used as alternative stabilizers in the mesogenic medium according to the present invention. The total concentration of these and similar compounds in the medium is preferably 5% or less.

[0472]

[0473] [Table 25]

[0474] [Table 26]

[0475] In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group of compounds in Table D.

[0476] Table E, shown below, lists exemplary compounds that can be preferably used as chiral dopants in the mesogenic medium according to the present invention.

[0477]

[0478] [Table 27]

[0479] [Table 28]

[0480] [Table 29]

[0481] In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group of compounds in Table E.

[0482] The mesogenic medium according to this application preferably comprises two or more compounds selected from the group consisting of the compounds in the table above, preferably four or more compounds.

[0483] Unless otherwise indicated, part or percentage data represents parts by weight or percentage by weight.

[0484] Above and below: V0 represents the capacitance threshold voltage [V] at 20°C. n e This represents the anomalous refractive index at 20°C and 589nm. n0 represents the typical refractive index at 20°C and 589nm. Δn represents the optical anisotropy at 20°C and 589 nm. ε ⊥ This represents the dielectric constant perpendicular to the director at 20°C and 1kHz. ε ∥ This represents the dielectric constant parallel to the director at 20°C and 1kHz. Δε represents the dielectric anisotropy at 20°C and 1kHz. cl.p. and T(N,I) represent the point of transparency [°C]. γ1 represents the rotational viscosity [mPa·s] measured at 20℃, K1 represents the elastic constant [pN] for "splay" deformation at 20°C. K2 represents the elastic constant [pN] for "twist" deformation at 20°C. K3 represents the elastic constant [pN] for "bend" deformation at 20°C. K avg. teeth,

number

[0485] Unless otherwise specified, all temperature values ​​expressed in this application, such as the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N), and the transparency point T(N,I) or cl.p, are expressed in degrees Celsius (°C). Mp represents the melting point. Furthermore, Tg represents the glassy state, C represents the crystalline state, N represents the nematic phase, S represents the smectic phase, and I represents the isotropic phase. The numbers between these symbols represent the transition temperature.

[0486] In this invention, the term "threshold voltage" refers to the capacitance threshold (V0), also known as the Frederick's threshold, unless otherwise specified. Furthermore, in the example, although generally typical, 10% relative contrast (V0) is used. 10 The optical threshold for ) may also be indicated.

[0487] The display used for measuring capacitance threshold voltage consists of two flat, parallel glass outer plates separated by a 20 μm gap. Each outer plate has an electrode layer on the inside and an unrubbed polyimide orientation layer on top, which causes homeotropic edge orientation of liquid crystal molecules.

[0488] The so-called "HTP (helical twisting power)" represents the helical twisting force of an optically active or chiral substance in an LC medium (unit: μm). Unless otherwise specified, HTP is measured at 20°C in the commercially available nematic LC host mixture MLD-6260 (Merck).

[0489] The transparency point is measured using a Mettler Thermosystem FP900. Optical anisotropy (n) is measured using an Abbe refractometer H005 (sodium spectral lamp Na10, 589 nm, at 20°C). Dielectric anisotropy (Δε) is measured at 20°C using an LCR meter E4980A / Agilent (G005) (ε-parallel cell equipped with JALS2096-R1). Start-up voltage (V0) is measured at 20°C using an LCR meter E4980A / Agilent (G005) (ε-parallel cell equipped with JALS2096-R1). Rotational viscosity (γ1) is measured at 20°C using a Toyo Technica LCM-2 (0002) (gamma 1 negative cell equipped with JALS-2096-R1). The elastic constant (K1, spray) is measured at 20°C using an LCR meter E4980A / Agilent Corporation (G005) (ε-parallel cell equipped with JALS2096-R1). K3: The elastic constant (K3, bend) is measured at 20°C using an LCR meter E4980A / Agilent Corporation (G005) (ε-parallel cell equipped with JALS2096-R1).

[0490] Unless otherwise explicitly stated, all concentrations in this application are expressed as weight percentages of the entire corresponding mixture, including all solid or liquid crystal components, excluding the solvent. All physical properties are determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals," published November 1997, Merck, Germany, and a temperature of 20°C is applied unless otherwise explicitly stated. [Examples]

[0491] The following examples illustrate the present invention without limiting it in any way. From the physical properties, it will be clear to those skilled in the art what properties can be achieved and to what extent they can be modified. Therefore, the various combinations of properties that can be particularly preferably achieved are well defined to those skilled in the art. The following examples include reference examples.

[0492] <Example of synthesis>

[0493] abbreviation distillation DABCO 1,4-Diazabicyclo[2.2.2]octane THF (Tetrahydrofuran) MTB ether methyl-tert-butyl ether distillation XPhos 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl XPhos Pd G2 Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)palladium(II)]

[0494] <Synthesis Example 1>: 2-[4-(4-butylcyclohexyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0495] <Step 1.1>: 4-[4-(4-butylcyclohexyl)phenyl]-3,5-difluoroaniline

[0496] [ka]

[0497] Bis(dibenzylidene-acetone)palladium (0) (20 mg, 0.04 mmol) and tris(o-tolyl)phosphine (50 mg, 0.2 mmol) are added to a mixture of [4-(4-butylcyclohexyl)phenyl]boronic acid (CAS 516510-90-0) (4.5 g, 17 mmol) and 3,5-difluoro-4-iodoaniline (4.3 g, 17 mmol) in acetone (50 ml) at 50°C under an argon atmosphere. Slowly add aqueous sodium hydroxide (2N) (17.0 ml, 34 mmol) at reflux temperature, and heat the reaction mixture overnight at reflux temperature. Then cool to room temperature, quench with distilled water and hydrochloric acid (2N), and dilute with MTB ether. Separate the aqueous phase and extract with MTB ether. Wash the combined organic layers with brine, dry with sodium sulfate, and concentrate under vacuum. The residue was purified by silica gel chromatography (eluent 1-chlorobutane) to obtain 4-[4-(4-butylcyclohexyl)phenyl]-3,5-difluoroaniline as a yellow solid.

[0498] <Step 1.2>: 2-[4-(4-butylcyclohexyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0499] [ka]

[0500] Thiophosgene (1.3 ml, 16 mmol) is slowly added at 0°C under an argon atmosphere to a solution of 4-[4-(4-butylcyclohexyl)phenyl]-3,5-difluoroaniline (4.8 g, 12 mmol) and DABCO (4.0 g, 36 mmol) in dichloromethane (60 ml). The reaction mixture is stirred overnight at room temperature. Then it is quenched with distilled water and brine. The aqueous phase is separated and extracted with dichloromethane. The combined organic phase is washed with brine, dried (sodium sulfate), filtered, and concentrated under vacuum. The residue is purified by silica gel chromatography (eluent heptane) and crystallization (heptane) to obtain colorless crystals of 2-[4-(4-butylcyclohexyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene. [Table 30]

[0501] <Synthesis Example 2>: 2-[4-(4-butylphenyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0502] <Step 2.1>: 4-[4-(4-butylphenyl)phenyl]-3,5-difluoroaniline

[0503] [ka]

[0504] Bis(dibenzylidene-acetone)palladium (0) (20 mg, 0.04 mmol) and tris(o-tolyl)phosphine (50 mg, 0.2 mmol) are added to a mixture of [4-(4-butylphenyl)phenyl]boronic acid (CAS 145413-17-8; 4.5 g, 17 mmol) and 3,5-difluoro-4-iodoaniline (4.3 g, 17 mmol) in acetone (50 ml) at 50°C under an argon atmosphere. Slowly add aqueous sodium hydroxide (2N) (18.0 ml, 36 mmol) at reflux temperature, and heat the reaction mixture overnight at reflux temperature. Then cool to room temperature, quench with distilled water and hydrochloric acid (2N), and dilute with MTB ether. Separate the aqueous phase and extract with MTB ether. Wash the combined organic layers with brine, dry with sodium sulfate, and concentrate under vacuum. The residue was purified by silica gel chromatography (eluent 1-chlorobutane) to obtain 4-[4-(4-butylphenyl)phenyl]-3,5-difluoroaniline as a yellow solid.

[0505] <Step 2.2>: 2-[4-(4-butylphenyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0506] [ka]

[0507] Thiophosgene (1.3 ml, 16 mmol) is slowly added at 0°C under an argon atmosphere to a solution of 4-[4-(4-butylphenyl)phenyl]-3,5-difluoroaniline (4.7 g, 14 mmol) and DABCO (4.0 g, 36 mmol) in dichloromethane (60 ml). The reaction mixture is stirred overnight at room temperature. Then it is quenched with distilled water and brine. The aqueous phase is separated and extracted with dichloromethane. The combined organic phase is washed with brine, dried (sodium sulfate), filtered, and concentrated under vacuum. The residue is purified by silica gel chromatography (heptane eluent) and crystallization (heptane) to obtain colorless crystals of 2-[4-(4-butylphenyl)phenyl]-1,3-difluoro-5-isothiocyanatobenzene. [Table 31]

[0508] <Synthesis Example 3>: 2-[2-(4-butylphenyl)ethynyl]-1,3-difluoro-5-isothiocyanatobenzene

[0509] <Step 3.1>: 4-[2-(4-butylphenyl)ethynyl]-3,5-difluoroaniline

[0510] [ka]

[0511] XPhos Pd G2 (40 mg, 0.05 mmol), XPhos (25 mg, 0.05 mmol), and copper(I) iodide (5 mg, 0.03 mmol) are added to a mixture of 1-butyl-4-ethynylbenzene (4.0 g, 25 mmol) and 3,5-difluoro-4-iodoaniline (6.3 g, 25 mmol) in diisopropylamine (60 ml) and THF (60 ml) under an argon atmosphere slightly below the boiling point. The reaction mixture is heated overnight at reflux temperature. It is then cooled to room temperature, the precipitate is filtered, and washed with THF. The filtrate is concentrated under vacuum. The residue is purified by silica gel chromatography (eluent 1-chlorobutane) to obtain 4-[2-(4-butylphenyl)ethynyl]-3,5-difluoroaniline (3) as a brown oil.

[0512] <Step 3.2>: 2-[2-(4-butylphenyl)ethynyl]-1,3-difluoro-5-isothiocyanatobenzene

[0513] [ka]

[0514] Thiophosgene (1.9 ml, 24 mmol) was slowly added under an argon atmosphere at 0°C to a solution of 4-[2-(4-butylphenyl)ethynyl]-3,5-difluoroaniline (6.1 g, 20 mmol) and DABCO (6.0 g, 53 mmol) in dichloromethane (100 ml), and the reaction mixture was stirred at room temperature for 1 hour. The mixture was then quenched with distilled water and brine. The aqueous phase was separated and extracted with dichloromethane. The combined organic phase was washed with brine, dried (sodium sulfate), filtered, and concentrated under vacuum. The residue was purified by silica gel chromatography (eluent heptane) and crystallization (heptane) to obtain colorless crystals of 2-[2-(4-butylphenyl)ethynyl]-1,3-difluoro-5-isothiocyanatobenzene. [Table 32]

[0515] <Synthesis Example 4>: 1,3-difluoro-5-isothiocyanato-2-[4-[4-(trifluoromethoxy)phenyl]phenyl]benzene

[0516] <Step 4.1>: 3,5-difluoro-4-[4-[4-(trifluoromethoxy)phenyl]phenyl]aniline

[0517] [ka]

[0518] Bis(dibenzylidene-acetone)palladium (0) (20 mg, 0.04 mmol) and tris(o-tolyl)phosphine (45 mg, 0.1 mmol) are added to a mixture of [4-(trifluoromethoxy)phenyl)phenyl]boronic acid (CAS 501944-50-9) (4.0 g, 14 mmol) and 4-bromo-3,5-difluoroaniline (3.0 g, 14 mmol) in acetone (40 ml) at 50°C under an argon atmosphere. Slowly add aqueous sodium hydroxide (2N) (15 ml, 30 mmol) at reflux temperature, and heat the reaction mixture overnight at reflux temperature. Then cool to room temperature, quench with distilled water, and dilute with MTB ether. Separate the aqueous phase and extract with MTB ether. Wash the combined organic layers with brine, dry with sodium sulfate, and concentrate under vacuum. The residue was purified by silica gel chromatography (eluent 1-chlorobutane) to obtain 3,5-difluoro-4-[4-[4-(trifluoromethoxy)phenyl]phenyl]aniline as a yellow solid.

[0519] <Step 4.2>: 1,3-difluoro-5-isothiocyanato-2-[4-[4-(trifluoromethoxy)phenyl]phenyl]benzene

[0520] [ka]

[0521] Thiophosgene (1.0 ml, 13 mmol) is slowly added at 0°C under an argon atmosphere to a solution of 3,5-difluoro-4-[4-[4-(trifluoromethoxy)phenyl]phenyl]aniline (3.9 g, 11 mmol) and DABCO (3.0 g, 27 mmol) in dichloromethane (50 ml). The reaction mixture is stirred overnight at room temperature. Then it is quenched with distilled water and brine. The aqueous phase is separated and extracted with dichloromethane. The combined organic phase is washed with brine, dried (sodium sulfate), filtered, and concentrated under vacuum. The residue is purified by silica gel chromatography (eluent heptane) and crystallization (heptane) to obtain white crystals of 1,3-difluoro-5-isothiocyanato-2-[4-[4-(trifluoromethoxy)phenyl]phenyl]benzene. [Table 33]

[0522] Similar to synthesis examples 1-4, the following compounds were obtained.

[0523] [Table 34]

[0524] [Table 35]

[0525] [Table 36]

[0526] [Table 37]

[0527] [Table 38]

[0528] [Table 39]

[0529] [Table 40]

[0530] [Table 41]

[0531] [Table 42]

[0532] [Table 43]

[0533] Preferred compounds of formula UII are prepared as follows.

[0534] <Synthesis Reference Example 1>: 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0535] <Step 1.1>: 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0536] [ka]

[0537] XPhos Pd G2 (170 mg, 0.2 mmol), XPhos (100 mg, 0.2 mmol), and copper(I) iodide (20 mg, 0.1 mmol) are added to a mixture of 1-butyl-4-ethynylbenzene (18.0 g, 0.1 mol) and 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (30.0 g, 0.1 mol) in diisopropylamine (250 ml) and THF (27 ml) at 55°C under an argon atmosphere. The reaction mixture is heated overnight at reflux temperature. It is then cooled to room temperature, filtered, and concentrated under vacuum. The residue is dissolved in toluene, washed with distilled water, dried (with sodium sulfate), filtered, and concentrated under vacuum. The crude product was purified by silica gel chromatography (eluent toluene) and crystallization (heptane) to obtain 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as yellow crystals.

[0538] <Step 1.2>: 4-[4-[2-(4-butylphenyl)ethynyl]phenyl]-3,5-difluoroaniline

[0539] [ka]

[0540] Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (7 mg, 0.01 mmol) is added to a mixture of 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.5 g, 10 mmol) and 4-bromo-3,5-difluoroaniline (2.0 g, 10 mmol) in ethylene glycol (20 ml) and THF (20 ml) at 60°C under an argon atmosphere. Slowly add aqueous sodium hydroxide (2N) (7.5 ml, 15 mmol) at reflux temperature, and heat the reaction mixture overnight at reflux temperature. Then cool to room temperature and quench with acetic acid (0.9 ml, 16 mmol) and distilled water. Add MTB ether, separate the aqueous phase, and extract with MTB ether. The combined organic phases are washed with brine, dried (with sodium sulfate), filtered, and concentrated under vacuum. The residue is purified by silica gel chromatography (eluent: dichloromethane) to obtain 4-[4-[2-(4-butylphenyl)ethynyl]phenyl]-3,5-difluoroaniline as a yellow solid.

[0541] <Step 1.3>: 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-1,3-difluoro-5-isothiocyanatobenzene

[0542] [ka]

[0543] Thiophosgene (0.7 ml, 9 mmol) is slowly added at 0°C under an argon atmosphere to a solution of 4-[4-[2-(4-butylphenyl)ethynyl]phenyl]-3,5-difluoroaniline (2.9 g, 8 mmol) and DABCO (2.3 g, 21 mmol) in dichloromethane (40 ml). The reaction mixture is stirred at room temperature for 1 hour. Then it is quenched with distilled water and brine. The aqueous phase is separated and extracted with dichloromethane. The combined organic phase is washed with brine, dried (sodium sulfate), filtered, and concentrated under vacuum. The residue is purified by silica gel chromatography (eluent heptane) and crystallization (heptane) to obtain colorless crystals of 2-[4-[2-(4-butylphenyl)ethynyl]phenyl]-1,3-difluoro-5-isothiocyanatobenzene. [Table 44]

[0544] Similar to Reference Example 1, the following compounds are obtained.

[0545] [Table 45]

[0546] [Table 46]

[0547] [Table 47]

[0548] [Table 48]

[0549] [Table 49]

[0550] [Table 50]

[0551] <Mixture example> Comparative Examples C1 and C2, and Mixture Examples M1 to M13 were prepared and examined as follows.

[0552] <Comparative Example C1>

[0553] [Table 51]

[0554] <Mixture example M1>

[0555] [Table 52]

[0556] Mixture example M1 differs from comparative example C1 in that it contains the additional compounds PTPUI-4-S, PPTUI-4-S, and PTUI-4-S. As a result, medium M1 exhibits higher adjustability τ and lower loss tanδ. εr,⊥ This shows the improved material quality η.

[0557] <Comparative mixture C2>

[0558] [Table 53]

[0559] <Mixture example M2>

[0560] [Table 54]

[0561] Mixture example M2 differs from comparative example C2 in that it includes the compound PTUI-4-S. As a result, medium M2 exhibits lower loss tanδ εr,⊥This shows the improved material quality η.

[0562] <Mixture example M3>

[0563] [Table 55]

[0564] <Mixture example M4>

[0565] [Table 56]

[0566] <Mixture example M5>

[0567] [Table 57]

[0568] <Mixture example M6>

[0569] [Table 58]

[0570] <Mixture example M7>

[0571] [Table 59]

[0572] <Mixture example M8>

[0573] [Table 60]

[0574] <Mixture example M9>

[0575] [Table 61]

[0576] <Mixture Example M10>

[0577] Table 62

[0578] <Mixture Example M11>

[0579] Table 63

[0580] <Mixture Example M12>

[0581] Table 64

[0582] <Mixture Example M13>

[0583] Table 65

Claims

1. A liquid crystal medium comprising one or more compounds selected from the group consisting of compounds of formula UI-1, UI-2, or UI-3, and one or more compounds selected from the group consisting of compounds of formula UII-1, UII-2, or UII-3. 【Chemistry 1】 (In the formula, X Ｕ１ and X Ｕ２ This represents F R Ｕ This represents a linear or branched non-fluorinated alkyl group having 1 to 7 carbon atoms. 【Chemistry 2】 These represent 1,4-phenylene or trans-1,4-cyclohexylene, either identically or differently. however 【Transformation 3】 (The condition is that neither of them simultaneously represents 1,4-phenylene.) 【Chemistry 4】 (In the formula, X Ｕ１ and X Ｕ２ This represents F R Ｕ This represents a linear or branched non-fluorinated alkyl group having 1 to 7 carbon atoms. 【Transformation 5】 These represent 1,4-phenylene or trans-1,4-cyclohexylene, either identically or differently. However, compounds of formulas UI-1, UI-2, and UI-3 are excluded.

2. The liquid crystal medium according to claim 1, wherein the total concentration of the compounds of formulas UI-1, UI-2, and UI-3 is in the range of 5% by weight to 40% by weight.

3. The liquid crystal medium according to claim 1 or 2, wherein the total concentration of the compounds of formulas UII-1, UII-2, and UII-3 is in the range of 2% by weight to 40% by weight.

4. A liquid crystal medium according to any one of claims 1 to 3, comprising one or more compounds selected from the group consisting of compounds of formula UI-1 or UI-2.

5. The liquid crystal medium according to claim 4, comprising one or more compounds of formula UI-1.

6. The liquid crystal medium according to claim 4, comprising one or more compounds of formula UI-2.

7. A liquid crystal medium according to any one of claims 1 to 6, comprising one or more compounds selected from the group consisting of compounds of formula UII-1 or UII-2.

8. The liquid crystal medium according to claim 7, comprising one or more compounds of formula UII-1.

9. The liquid crystal medium according to claim 7, comprising one or more compounds of formula UII-2.

10. A liquid crystal medium according to any one of claims 1 to 9, further comprising one or more compounds selected from the group of compounds of formulas I, II, and III. 【Transformation 6】 (In the formula, R １ This represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and the group contains one or more CH ２ The basis is, 【Transformation 7】 It can be replaced with, n is 0, 1, or 2. 【Transformation 8】 (wherein, R Ｌ is identical or different at each occurrence and represents H or an alkyl having 1 to 6 C atoms.) 【Chemistry 9】 (In the formula, one or more H atoms may be replaced by alkyl groups or F groups having 1 to 6 C atoms.) This represents, and however, 【Chemistry 10】 This represents, R ２ This represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and the group contains one or more CH ２ The basis is, 【Chemistry 11】 It can be replaced with, Z ２１ This represents trans-CH=CH-, trans-CF=CF-, or -C≡C-, and 【Chemistry 12】 (In the formula, R Ｌ (Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms.) 【Chemistry 13】 (In the formula, one or more H atoms may be replaced by alkyl groups or F groups having 1 to 6 C atoms.) This represents, R ３ This represents a non-fluorinated alkyl or non-fluorinated alkoxy having H, 1 to 17 C atoms, or a non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl having 2 to 15 C atoms, and the group contains one or more CH ２ The basis is, 【Chemistry 14】 It can be replaced with, Z ３１ and Z ３２ One of them represents trans-CH=CH-, trans-CF=CF- or -C≡C-, and the other independently represents -C≡C-, trans-CH=CH-, trans-CF=CF- or a single bond, and 【Chemistry 15】 (In the formula, R Ｌ (Each occurrence represents an alkyl group having the same or different H or 1 to 6 C atoms.) 【Chemistry 16】 (In the formula, one or more H atoms may be replaced by alkyl groups or F groups having 1 to 6 C atoms.) This represents, and however, 【Chemistry 17】 (This represents...)

11. The liquid crystal medium according to claim 10, comprising one or more compounds selected from the group of compounds of formulas I-1 to I-5. [Chemistry 18] (In the formula, L １ , L ２ and L ３ In each occurrence, they represent H or F, and R １ 、 【Chemistry 19】 (This has the meaning given to formula I in claim 10.)

12. A liquid crystal medium according to claim 10 or 11, comprising one or more compounds selected from the group of compounds of formula II-1 to II-3. 【Chemistry 20】 (In the formula, R ２ 、 【Chemistry 21】 (This has the meaning given to formula II in claim 10.)

13. A liquid crystal medium according to any one of claims 10 to 12, comprising one or more compounds of formula III selected from the group consisting of compounds of formula III-1 to III-6. 【Chemistry 22】 (In the formula, Z ３１ and Z ３２ These are mutually independent of trans-CH=CH- or trans-CF=CF-, or Z in equation III-6. ３１ and Z ３２ One of them may represent -C≡C-, and the other base has the meaning given in formula III in claim 10. R ３ This represents a non-fluorinated alkyl or alkoxy having 1 to 7 carbon atoms or a non-fluorinated alkenyl having 2 to 7 carbon atoms, and 【Chemistry 23】 This represents, The other party operates independently of the other. 【Chemistry 24】 This represents, however 【Chemistry 25】 (This represents...)

14. A liquid crystal medium according to any one of claims 1 to 13, comprising one or more compounds of formula T. 【Chemistry 26】 (In the formula, R Ｔ Halogen, CN, NCS, R Ｆ , R Ｆ -O- or R Ｆ -S- represents, where R Ｆ This represents a fluorinated alkyl or fluorinated alkenyl having up to 12 C atoms. 【Chemistry 27】 This represents, L ４ and L ５ These represent identical or distinct linear, branched, or cyclic alkyl or alkenyl groups having F, Cl, or up to 12 C atoms each. Z Ｔ３ Z Ｔ４ These are identical or different, representing -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C- or a single bond, and t is either 0 or 1.

15. A liquid crystal medium according to any one of claims 1 to 14, comprising one or more compounds of formula U. 【Chemistry 28】 (In the formula, R Ｕ This represents an alkyl or alkoxy group having H, 1 to 12 carbon atoms, or an alkenyl, alkenyloxy, or alkoxyalkyl group having 2 to 12 carbon atoms, and the group contains one or more CH ２ The basis is, 【Chemistry 29】 It may be replaced with, or base R Ｐ This represents, R Ｐ Halogen, CN, NCS, R Ｆ , R Ｆ -O- or R Ｆ -S- represents, where R Ｆ This represents a fluorinated alkyl or fluorinated alkenyl having up to nine carbon atoms. Z Ｕ１ Z Ｕ２ These represent identical or different -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, or single bonds. X １ , X ２ , X ３ and X ４ These represent Cl or F, either identically or differently. t is either 0 or 1. 【Transformation 30】 This represents a group that is identical or different and selected from the following groups: a) A group consisting of 1,4-phenylene, 1,4-naphthylene, and 2,6-naphthylene, wherein one or two CH groups in the group may be replaced by N, and one or more H atoms in the group may be replaced by L, except that tetrafluoro-1,4-phenylene is excluded. b) The group consisting of trans-1,4-cyclohexylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, 4,4'-bicyclohexylene, bicyclo[2.2.2]octane-1,4-diyl, and spiro[3.3]heptane-2,6-diyl, wherein one or more non-adjacent CH groups are present in the group. ２ The group may be replaced with -O- and / or -S-, and one or more H atoms in the group may be replaced with F. c) A group consisting of thiophene-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, and selenofen-2,5-diyl, wherein each of these groups may be monosubstituted or polysubstituted with L. L is the same or different in each occurrence as F, Cl, CN, SCN, SF ５ Alternatively, it represents an alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy molecule having 1 to 12 C atoms that may be fluorinated, either linear or branched.

16. The liquid crystal medium according to claim 15, comprising one or more compounds selected from the group consisting of compounds of formulas U-1 to U-11. 【Chemistry 31】 【Chemistry 32】 (In the formula, L １ , L ２ and L ３ are identical or different, representing H, F, Cl, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclopentenyl, and R Ｕ , X １ , X ２ , X ３ and X ４ (This has the meaning given in claim 15.)

17. A component for high-frequency technology, characterized by including a liquid crystal medium as described in any one of claims 1 to 16.

18. The component according to claim 17, which is a liquid crystal antenna element, a phase shifter, a tunable filter, a tunable material structure, a matching network, or a varactor.

19. A microwave antenna array characterized by comprising one or more components as described in claim 17 or 18.

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