LCD Media

Abstract

We provide liquid crystal media. [Solution] The present invention relates to a dichroic dye compound of formula I as defined in claim 1, based on a donor-acceptor structure in which the donor portion comprises a polycyclic heteroaromatic group consisting of at least four fused rings, a mesogenic medium comprising one or more compounds of formula I, and optical, electronic and electro-optical applications of these compounds, mesogenic mediums and liquid crystal materials, in particular devices for controlling the passage of energy from external space to internal space, for example, in switchable windows for solar energy control in smart buildings and vehicles, which would result in energy saving and improved comfort.

Description

[Technical Field]

[0001] The present invention relates to a dichroic dye compound of formula I as defined below, based on a donor-acceptor structure in which the donor portion comprises a polycyclic heteroaromatic group consisting of at least four fused rings; a mesogenic medium comprising one or more compounds of formula I; and optical, electronic, and electro-optical applications of these compounds and mesogenic media, particularly devices for controlling the passage of energy from external to internal space, such as in switchable windows for solar energy control in smart buildings and vehicles, which contribute to energy saving and improved comfort. [Background technology]

[0002] A review article by R. Baetens et al., "Properties, requirements and possibilities of smart windows for dynamic daylight and solar energy control in buildings: A state-of-the-art review," Solar Energy Materials & Solar Cells, Vol. 94 (2010), pp. 87-105 (Non-Patent Literature 1), describes colorable smart windows. Smart windows can utilize various technologies to adjust light transmittance, such as electrochromism-based devices, liquid crystal devices, electrophoretic devices, or suspended particle devices. Liquid crystal-based devices change transmittance by altering the orientation of liquid crystal molecules by applying an electric field between two conductive electrodes.

[0003] Liquid crystal materials are used particularly as dielectrics in display devices, and their optical properties can be altered by the applied voltage. Electro-optic devices based on liquid crystals are well known in this art and can be based on a variety of effects. Examples of this type of device include dynamic scattering cells, DAP (orientation phase deformation) cells, TN cells with twisted nematic structures, STN (super-twisted nematic) cells, SBE (super-birefringence effect) cells, OMI (optical mode interference) cells, and guest-host cells.

[0004] Devices based on the guest-host effect were first reported by Heilmeier and Zanoni (GH. Heilmeier et al., Appl. Phys. Lett., 1968, Vol. 13, 91f. (Non-Patent Literature 2)) and have since been widely used, mainly in liquid crystal (LC) display elements. In a guest-host system, the LC medium contains one or more dichroic dyes in addition to the liquid crystal. Due to the directional dependence of absorption by the dye molecules, the light transmittance of the dye-doped liquid crystal can be modulated by changing the orientation of the dye together with the liquid crystal.

[0005] In addition to applications in liquid crystal displays, this type of device can also be used as a switching element to control the transmission of light or energy, as described, for example, in International Publication No. 2009 / 141295 (Patent Document 1) and International Publication No. 2010 / 118422 (Patent Document 2).

[0006] Various technological solutions have been proposed for devices that control the transfer of energy from the external space to the internal space.

[0007] Some devices can reversibly change the light transmittance, allowing the intensity of incident light to be attenuated, dimmed, or colored. Therefore, such devices can operate in both light and dark states, i.e., states with relatively high and relatively low light transmittance, and can switch between these states.

[0008] One possible mode of this device is the use of a liquid crystal medium combined with one or more dichroic dyes as described above as the switching layer. By applying a voltage, a change in the orientation of the dichroic dye molecules in these switching layers can be achieved. Direction-dependent absorption results in a change in the transmittance of the switching layer. A corresponding device is described, for example, in International Publication No. 2009 / 141295 (Patent Document 1).

[0009] Alternatively, such a change in transmission behavior can be achieved without applying a voltage by a temperature-induced transition from an isotropic state to a liquid crystal state of the liquid crystal medium, as described, for example, in U.S. Patent Application Publication No. 2010 / 0259698 (Patent Document 3).

[0010] International Publication No. 2009 / 141295 (Patent Document 1) and International Publication No. 2010 / 118422 (Patent Document 2) describe liquid crystal media for guest-host optical devices comprising a cyanobiphenyl derivative and one or more dichroic dyes. Rylene dyes are described for use in the above devices, for example, in International Publication No. 2009 / 141295 (Patent Document 1), International Publication No. 2013 / 004677 (Patent Document 4), and International Publication No. 2014 / 090373 (Patent Document 5). The use of benzothiadiazole in the above-mentioned device is described in International Publication No. 2014 / 187529 (Patent Document 6) and International Publication No. 2020 / 104563 (Patent Document 7), and the use of thiadiazoloquinoxaline in the above-mentioned device is described in International Publication No. 2016 / 177449 ​​(Patent Document 8) and International Publication No. 2020 / 104563 (Patent Document 7).

[0011] In this field, there is still a need for dichroic dye compounds and media containing these compounds that offer advantages in terms of device performance and reliability. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] International Publication No. 2009 / 141295 [Patent Document 2] International Publication No. 2010 / 118422 [Patent Document 3] U.S. Patent Application Publication No. 2010 / 0259698 [Patent Document 4] International Publication No. 2013 / 004677 [Patent Document 5] International Publication No. 2014 / 090373 [Patent Document 6] International Publication No. 2014 / 187529 [Patent Document 7] International Publication No. 2020 / 104563 [Patent Document 8] International Publication No. 2016 / 177449 [Non-patent literature]

[0013] [Non-Patent Document 1] Review article by R. Baetens et al., "Properties, requirements and possibilities of smart windows for dynamic daylight and solar energy control in buildings: A state-of-the-art review," Solar Energy Materials & Solar Cells, Vol. 94 (2010), pp. 87-105. [Non-Patent Document 2] G.H. Heilmeier et al., Appl. Phys. Lett., 1968, Vol. 13, 91f. [Disclosure of the Invention] [Problems that the invention aims to solve]

[0014] Therefore, an object of the present invention is to provide an improved dye compound that is particularly suitable for guest-host applications and can advantageously contribute to the effective and efficient performance of switching devices.

[0015] Furthermore, an object of the present invention is to provide an improved mesogenic medium that contains these compounds, exhibits a wide and stable liquid crystal phase range, particularly good low-temperature stability, and can provide an appropriate high degree of order.

[0016] A further objective is to provide a stable and reliable switching medium for electro-optical applications that enables performance particularly beneficial with respect to contrast, stability against prolonged exposure to direct sunlight, or aesthetic impression in devices that control the passage of energy from external space to internal space, particularly in smart switching windows. Further objectives of the present invention will be immediately apparent to those skilled in the art from the following detailed description.

[0017] These objectives are addressed by the subject matter set forth in the independent claims, and preferred embodiments are described in their respective dependent claims and further explained below.

[0018] The present invention provides, in particular, the following items, including main aspects, preferred embodiments, and specific features, each of which, individually or in combination, contributes to solving the above objectives and ultimately brings further advantages. [Means for solving the problem]

[0019] A first aspect of the present invention provides a compound of formula I.

[0020] [ka]

[0021] During the ceremony, R 1 and R 2 They are the same or different, H, F, CN, N(R z)2. represents a linear alkyl having 1 to 20 C atoms, or a branched or cyclic alkyl having 3 to 20 C atoms, provided that in addition, one or more non-adjacent CH2 groups are independently of each other such that O atoms and / or S atoms are not directly connected to each other, -C(R z )=C(R z )-, -C≡C-, [Chemical formula] -N(R z )-, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- may be replaced, provided that in addition, one or more H atoms may be replaced by F, Cl, Br, I or CN, R z represents, in each occurrence, the same or different, H, halogen, a linear alkyl having 1 to 12 C atoms, or a branched or cyclic alkyl having 3 to 12 C atoms, provided that in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- such that O atoms and / or S atoms are not directly connected to each other, provided that in addition, one or more H atoms may be replaced by F or Cl, Q 1 and Q 2 are the same or different and represent a single bond, -O-, -S-, -CF2O-, -OCF2-, -CF2-, -CF2CF2-, -CO-, -CR x1 =CR x2 -, -C≡C-, -NR x1 -, -N=N-, or preferably an alicyclic or heterocyclic group having 4 to 25 ring atoms, which may contain a fused ring and which is unsubstituted or mono- or polysubstituted by L, Z 1 and Z 2 are the same or different and represent a single bond, -O-, -S-, -C(O)-, -CR y1 R y2-, -CF2O-, -OCF2-, -C(O)-O-, -OC(O)-, -OC(O)-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2S-, -SCF2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -(CF2) n1 -, -CR x1 =CR x2 -, -C≡C-, -CR x1 =CR x2 -CO-, -CO-CR x1 =CR x2 -, -CR x1 =CR x2 -COO-, -OCO-CR x1 =CR x2 - or -N=N- represents, R x1 , R x2 Each of these independently represents an alkyl group having H, F, Cl, CN, or 1 to 12 C atoms. R y1 This represents an alkyl group having H or 1 to 12 C atoms. R y2 This represents an alkyl group having 1 to 12 carbon atoms. n1 represents 1, 2, 3, or 4. A 1 and A 2 represents an aromatic, heteroaromatic, alicyclic, or heterocyclic group which is identical or different and preferably has 4 to 25 ring atoms, and which may include a fused ring, which is unsubstituted, monosubstituted, or polysubstituted with L. L represents F, Cl, -CN, or a linear alkyl group having 1 to 25 C atoms, or a branched or cyclic alkyl group having 3 to 25 C atoms, wherein one or more non-adjacent CH2 groups may be replaced with -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that the O atoms and / or S atoms are not directly linked to each other, and one or more H atoms may each be replaced with F or Cl. D represents a donor group selected from heteroaromatic groups comprising at least four fused rings, preferably at least four linearly fused rings, preferably an electron-rich conjugated substructure, wherein each ring may be unsubstituted, monosubstituted, or polysubstituted with L. A represents an acceptor group, preferably an electron-deficient substructure. n represents 0, 1, 2 or 3, preferably 0, 1 or 2, and o represents 0 or 1, However, the number of rings in the compound, including fused rings, is at least five.

[0022] In this specification, the term “ring” refers to a closed ring structure, i.e., a cyclic group having a closed ring structure of atoms. In this specification, a ring also includes ring formation, condensation, or fused rings, in particular fused rings where ends are joined. In this case, a ring is condensed when it shares two or more atoms. In this regard, a compound, in particular a polycyclic compound, is considered to contain a number of rings equal to the number of cleavages required to convert it into an open-chain compound.

[0023] In this specification, the bond between an acceptor group A and a donor group D preferably forms a π-conjugated system. The donor group D includes an unsubstituted or substituted heteroaromatic group, particularly a polycyclic heteroaromatic group including a fused ring, preferably an unsubstituted or substituted heteroacene, and more preferably an unsubstituted or substituted S,N-heteroacene having extended π-conjugation.

[0024] The acceptor group A is preferably an electron-withdrawing group, and more preferably an electron-deficient portion lacking π electrons.

[0025] If present, group Z is directly adjacent to group D and group A. 1 and base Z 2 These are preferably single bonds or π-conjugated groups.

[0026] Surprisingly, the compounds of Formula I described herein have been found to exhibit excellent combined properties and characteristics, such as extinction coefficient, stability, and solubility, and to provide beneficial performance in optical, electro-optical, and electronic applications, particularly in guest host applications such as dimmable smart windows. In particular, the compounds of the present invention have excellent solubility and stability in liquid crystal media.

[0027] In particular, it was found that the compounds of formula I exhibit good solubility in liquid crystal media, while simultaneously showing appropriate photostability and temperature stability. Furthermore, these compounds exhibit good compatibility and stability as mixtures and have high color purity, making it possible to impart a neutral or gray appearance to the media as needed. At the same time, these compounds may exhibit little to no fluorescence.

[0028] Compounds of formula I have been found to exhibit advantageously large extinction coefficients in the VIS and / or NIR light regions, and furthermore, to have a moderately high dichromatic ratio. It is now recognized that the combination of these properties contributes favorably to effective and efficient device performance. The high extinction coefficient, especially in conjunction with the high dichromatic ratio, can be beneficial in that it allows the use of lower dye concentrations and / or a single switching layer to suffice, and / or the desired contrast and effective dark state to be achieved with smaller switching layer thicknesses or cell gaps. Lower dye concentrations may also have advantages in terms of solubility and viscosity.

[0029] Therefore, the compounds of formula I are particularly useful for guest-host applications, and the dye-doped mesogenic media can exhibit a moderately broad and stable liquid crystal phase range, especially good low-temperature stability. Thus, the mesogenic media of the present invention can provide advantages in terms of device performance and reliability, particularly in smart switching windows.

[0030] These compounds not only exhibit good solubility on their own in liquid crystal media, but have also been found to mix well with other dichroic dye compounds in the media. This greatly contributes to improving the ability to provide customized dye-doped liquid crystal media, particularly in terms of imparting specific colors or achieving a black appearance by covering the entire visible light spectrum. In this regard, the compounds of Formula I can be selected and adjusted to exhibit the desired color with very weak fluorescence or no fluorescence at all.

[0031] Accordingly, in a further embodiment, compositions, particularly mixtures, comprising two or more compounds, preferably three or more compounds, more preferably four or more compounds, according to the present invention are provided.

[0032] As described herein, the compounds according to the present invention can be suitably used in liquid crystal media.

[0033] Therefore, another embodiment relates to a liquid crystal medium comprising, in addition to at least one mesogenic compound, one or more compounds according to the present invention. Preferably, the liquid crystal medium comprises two or more compounds of formula I or each of preferred subformulas, and more preferably, three or more compounds of formula I or each of preferred subformulas.

[0034] The liquid crystal medium according to the present invention is a switching medium with stability, reliability, and high efficiency in electro-optical applications, and has been found to exhibit particularly beneficial performance in smart switching windows, especially in devices that control the passage of energy from the external space to the internal space. In this regard, the high extinction coefficient and good dichromatic ratio of the compound of formula I in the medium contribute to beneficial performance in guest host applications such as dimmable smart windows.

[0035] Accordingly, in a further aspect of the present invention, a device is provided for controlling the passage of energy from an external space to an internal space, the device comprising a switching layer containing the liquid crystal medium of the present invention as described herein. In particular, the device can be incorporated into a window.

[0036] In another aspect of the present invention, the compounds and mesogenic media according to the present invention are used in electro-optical displays, devices that control the passage of energy from external space to internal space, electrical semiconductors, organic field-effect transistors, printed circuits, radio frequency identification elements, diodes, organic light-emitting diodes, lighting elements, photovoltaic devices (particularly as sensitizers or semiconductors therein), light sensors, effect pigments, decorative elements, or, for example, polymer coloring dyes in the automotive field.

[0037] In a further embodiment, a window is provided that includes a device for regulating the passage of energy from an external space to an internal space, the device including a switching layer containing a liquid crystal medium according to the present invention.

[0038] The liquid crystal window according to the present invention can be used for sustainable glazing applications in buildings and vehicles by saving energy, particularly in relation to lighting, cooling, and / or heating, and by having a positive impact on the lifecycle, for example in terms of maintenance, and further improving thermal and visual comfort.

[0039] In a further aspect of the present invention, a method for producing the compound of formula I is provided. In particular, this method provides a simple process that facilitates the production of the compound of the present invention. [Modes for carrying out the invention]

[0040] This does not limit the present invention, but the present invention will be illustrated below by a detailed description of its aspects, embodiments, and specific features, and specific embodiments will be described in more detail.

[0041] In the present invention, a device that controls the passage of energy from external space to internal space is preferably understood to mean a device that controls the passage of energy, particularly light, particularly sunlight, passing through a region located within a structure with relatively low energy transmittance. A structure with low energy transmittance is, for example, a wall. Therefore, energy can pass through, for example, openings in a wall, particularly glass portions. For this reason, it is preferable that the device be arranged as a component of a window, for example, an insulated glass unit.

[0042] The controlled passage of energy occurs from an external space, preferably an environment exposed to direct or indirect solar radiation, to an internal space such as a building or vehicle, or to another unit substantially enclosed from the environment.

[0043] For the purposes of this invention, the term "energy" refers to specific energy from electromagnetic radiation in the UV-A, VIS, and NIR regions. In particular, it refers to energy from radiation that is not absorbed, or absorbed only slightly, by materials commonly used in windows, such as glass. Here, the UV-A region is considered to be the wavelength range from 320 nm to 380 nm, the VIS region the wavelength range from 380 nm to 780 nm, and the NIR region the wavelength range from 780 nm to 2000 nm. Correspondingly, the term "light" is generally considered to refer to electromagnetic radiation with wavelengths from 320 nm to 2000 nm, and especially from 380 nm to 780 nm.

[0044] Here, a dichroic dye refers to a light-absorbing compound whose absorption properties depend on the orientation of the compound with respect to the polarization direction of light. According to the present invention, dichroic dye compounds usually have an elongated shape, that is, they are considerably longer in the spatial direction (vertical axis) than in the other two spatial directions.

[0045] The term "organic group" refers to a carbon or hydrocarbon group.

[0046] The term "carbon group" refers to a monovalent or polyvalent organic group containing at least one carbon atom, which may contain no other atoms (e.g., -C≡C-) or may selectively contain one or more atoms. Examples include N, O, S, P, Si, Se, As, Te, Ge, etc., such as carbonyl groups. The term "hydrocarbon group" refers to a carbon group containing one or more H atoms, and may optionally include one or more heteroatoms (e.g., N, O, S, P, Si, Se, As, Te, Ge, etc.).

[0047] "Halogen" refers to F, Cl, Br, or I, preferably F or Cl.

[0048] A carbon group or hydrocarbon group can be either a saturated or unsaturated group. Examples of unsaturated groups include aryl groups, alkenyl groups, and alkynyl groups. A carbon group or hydrocarbon group containing three or more atoms can be linear, branched, and / or cyclic, and may contain spirolinks or fused rings.

[0049] Terms such as "alkyl," "aryl," and "heteroaryl" also include polyvalent groups such as alkylene, arylene, and heteroarylene.

[0050] The term "allyl" refers to an aromatic carbon group or a group derived therefrom. The term "heteroallyl," as defined above, refers to an "aryl" that contains one or more heteroatoms.

[0051] Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynnyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonyloxy, and alkoxycarbonyloxy groups, which have 1 to 40, preferably 1 to 25, particularly 1 to 18 C atoms, optionally 6 to 40, preferably 6 to 25 C atoms, or optionally substituted alkyl, allylcarbonyl, allylcarbonyl, aryloxycarbonyl, aryloxycarbonyl, or alkyloxy, allylcarbonyl, aryloxycarbonyl, or alkylcarbonyl groups, which have 6 to 40, preferably 6 to 25 C atoms.

[0052] Further preferred carbon and hydrocarbon groups are C1~C 40 Alkyl, C2~C 40 Alkenyl, C2~C 40 Alkinyl, C3~C 40 Allyl, C4~C 40 Alkyldienyl, C4~C 40 Polyenyl, C6~C 40 Aryl, C6~C 40 Alkylaryl, C6~C 40 Arylalkyl, C6~C 40 Alkylaryloxy, C6~C 40 Arylalkyloxy, C2~C 40 Heteroaryl, C4~C 40 Cycloalkyl, C4~C 40 Examples include cycloalkenyls. C1~C 22 Alkyl, C2~C 22 Alkenyl, C2~C 22 Alkinyl, C3~C 22 Allyl, C4~C 22 Alkyldienyl, C6~C 12 Aryl, C6~C 20 Arylalkyl and C2-C 20 Heteroaryls are particularly preferred.

[0053] Further preferred carbon and hydrocarbon groups are linear, branched, cyclic alkyl radicals having 1 to 40, preferably 1 to 25, C atoms, which are unsubstituted or monosubstituted or polysubstituted with F, Cl, Br, I, CN, except that non-adjacent CH2 groups are each independently not directly bonded to O and / or S atoms, -C(R z )=C(R z )-, -C≡C-, N(R z )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be used as substitutes.

[0054] R z Preferably, represents H, a halogen, a linear, branched, or cyclic alkyl chain having 1 to 25 C atoms (where one or more non-adjacent C atoms may be replaced with -O-, -S-, -CO-, -CO-O-, -O-CO, or -OCO-O-, and one or more H atoms may be replaced with fluorine (an allyl or allylxy group having 6 to 40 selectively replaceable C atoms)), or a substituted heteroallyl or heteroallyxy group having 2 to 40 C atoms.

[0055] Preferred alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, and perfluorohexyl.

[0056] Preferred alkenyl groups include, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, and cyclooctenyl.

[0057] Preferred alkynyl groups include, for example, ethinyl, propynyl, butynyl, pentynyl, hexynyl, and octinyl.

[0058] Preferred alkoxy groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, and n-dodecoxy.

[0059] Preferred amino groups include, for example, dimethylamino, methylamino, methylphenylamino, and phenylamino.

[0060] Aryl and heteroaryl groups can be monocyclic or polycyclic and may include one ring, such as a phenyl group, or two or more rings, such as a fused ring, such as a naphthyl group, a covalent ring, such as a biphenyl group, or a combination of a fused ring and a bonded ring. Heteroaryl groups preferably contain one or more heteroatoms selected from O, N, S, and Se. This type of ring system may also contain individual non-conjugated units, such as in the basic structure of fluorene.

[0061] Particularly preferred are monocyclic, bicyclic, or polycyclic aryl groups having 6 to 50 carbon atoms, and monocyclic, bicyclic, or polycyclic heteroaryl groups having 2 to 50 carbon atoms, which optionally include fused rings and are optionally substituted. Even more preferred are 5-membered, 6-membered, or 7-membered aryl and heteroaryl groups, in which one or more CH groups in these groups may be substituted with N, S, or O such that the O atoms and / or S atoms are not directly bonded to each other.

[0062] Preferred aryl groups can be derived from parent structures such as benzene, biphenyl, terphenyl, [1,1':3',1”]terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, and spirobifluorene.

[0063] Preferred heteroaryl groups include, for example, five-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, as well as six-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, and 1,3,5-triazine. 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensation groups, e.g., indole, isoindole, indidine, indazole, benzimidazole, benzotriazole, purine, naphthoimidazole, phenanthrimidazole, pyridimidazole, pyrazineimidazole, quinoxalineimidazole, benzoxazole, naphthoxazole, anthroxazole, fenantroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, i Soquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarbolin, phenantholidine, phenanthroline, thieno[2,3b]-thiophene, thieno[3,2b]-thiophene, dithienothiophene, dihydrothieno[3,4-b]-1,4-dioxin, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations of these groups. The heteroaryl group may be substituted with an alkyl group, alkoxy group, thioalkyl group, fluorine group, fluoroalkyl group, or further aryl or heteroaryl groups.

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

[0065] (Non-aromatic) alicyclic and heterocyclic groups may be monocyclic groups, i.e., those containing only one ring, such as cyclohexane, or polycyclic groups, i.e., those containing multiple rings, such as decahydronaphthalene or bicyclooctane. Saturated groups are particularly preferred. Furthermore, monocyclic, bicyclic, or tricyclic groups having 3 to 25 carbon atoms, optionally containing a fused ring, and optionally substituted are preferred. Furthermore, carbocyclic groups of 5, 6, 7, or 8 membered rings are preferred, in which case one or more carbon atoms may be replaced by silicon, and / or one or more CH groups may be replaced by nitrogen, and / or one or more non-adjacent CH2 groups may be replaced by oxygen and / or sulfur.

[0066] Preferred alicyclic and heterocyclic groups include, for example, five-membered ring groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, and pyrrolidine; six-membered ring groups such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, and piperidine; seven-membered ring groups such as cycloheptane; and condensed ring groups such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, and octahydro-4,7-methanoindan-2,5-diyl.

[0067] The aryl, heteroaryl, carbon, and hydrocarbon radicals optionally have one or more substituents, preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, and C 1~12 Alkyl, C 6~12 Ariel, C1~12 The group is selected from those comprising alkoxy, hydroxyl, or combinations thereof.

[0068] Preferred substituents include, for example, dissolution-promoting groups such as alkyl or alkoxy groups, electron-withdrawing groups such as fluorine, nitro or nitrile groups, or substituents that increase the glass transition temperature (Tg) of the polymer, particularly bulky groups such as t-butyl or optionally substituted aryl groups.

[0069] Preferred substituents are F, Cl, Br, I, CN, NO2, -NCO, -NCS, -OCN, SCN, -C(=O)N(R z )2, -C(=O)Y 1 -C(=O)R z , N(R z )2, and here R z The above has the meaning, Y 1 This represents a halogen, an optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20, carbon atoms, and a linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 carbon atoms, where one or more H atoms may optionally be replaced with F or Cl.

[0070] More preferred substituents include, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, and phenyl.

[0071] Here, the substituents represented by L in each appearance are the same or different, preferably F, Cl, CN, SCN, SF5, or in each case optionally fluorinated linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, or alkoxycarbonyloxy having 1 to 12 C atoms.

[0072] Preferably, in each appearance, L represents the same or different alkyl or alkoxy having 1 to 7 C atoms, which are either fluorinated, linear or branched, and in either case optionally fluorinated.

[0073] "Substituting silyl or aryl" is preferably halogen, -CN, R y1 , -OR y1 ,-CO-R y1 , -CO-OR y1 ,-O-CO-R y1 or -O-CO-OR y1 This means that it is replaced by R y1 This has the meanings shown above.

[0074] As described herein, the compounds of Formula I have donor-acceptor groups in their molecular structure and give very high extinction coefficients, particularly in the visible light region, while exhibiting preferred suitability for use in guest-host applications, and showing appropriate solubility and stability, especially in liquid crystal media.

[0075] According to the present invention, the group D in formula I represents a donor group selected from unsubstituted or substituted heteroaromatic groups comprising at least four fused rings, preferably at least four linear fused rings that provide an electron-rich conjugated moiety.

[0076] The donor group D is preferably a polycyclic group, particularly a tetracyclic, pentacyclic, hexacyclic, or heptacyclic group, which is a heterocyclic aromatic group, i.e., an aromatic group containing at least one non-carbon atom in at least one ring, preferably containing sulfur, nitrogen, and / or oxygen. In particular, this polycyclic heteroaromatic group contains at least four fused rings, each fused ring may be substituted or substituted, for example, containing a thienopyrrole fused group.

[0077] In preferred embodiments, group D is selected from groups comprising a linear fused ring, preferably an unsubstituted or substituted heteroacene, and more preferably a group consisting of a linear fused ring. Particularly preferably, group D comprises a heterocyclic thiophene ring and a pyrrole ring, preferably a fused heterocyclic thiophene ring and a pyrrole ring, preferably a substituted pyrrole ring, and more preferably so-called S,N-heteroacenes. Preferably, tetracyclic, pentacyclic, and hexacyclic systems, particularly S,N-heterotetracene, S,N-heteropentacene, and S,N-heterohexacene, and these systems may be symmetric or asymmetric.

[0078] In this specification, heteroacene refers to an acene compound containing, or preferably consisting of, a heteroatom-substituted aromatic group. In this regard, acene in this specification refers to a polycyclic aromatic hydrocarbon in which fused benzene rings are arranged in a linear chain.

[0079] Preferably, the donor group D is a heteroacene having linearly fused rings, where each ring may be unsubstituted or monosubstituted or polysubstituted by L, where L is defined above and below.

[0080] In one embodiment, Z 1 and Z 2 These independently represent a single bond, -CH=CH-, -CF=CF-, or -C≡C-. In particular, Z 1 and Z 2 It is preferable that this represents a single bond.

[0081] Base R in Equation I 1 and R 2are preferably, independently of each other, an alkyl group, preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, or a branched alkyl group having 3 to 12 carbon atoms, preferably a group in which a methyl, ethyl, n-propyl, n-butyl, or n-pentyl group is bonded to an ethyl, n-propyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl group, such as 2-ethylhexyl, 2-ethylheptyl, 2-ethyloctyl, 2-ethylnonyl, 2-ethyldecyl, 3-ethylhexyl, 3-ethylheptyl, 3-ethyloctyl, 3-ethylnonyl, 3-ethyldecyl, etc.

[0082] In another embodiment, the group R 1 and R 2 each independently represent a linear or branched alkyl or dialkylamino group having 1 to 12 carbon atoms per alkyl group.

[0083] In one embodiment, the compound of formula I is selected from the group of compounds of formula I-1 and I-2.

[0084]

Chemical formula

[0085] wherein R 1 , R 2 , A 1 , Z 1 , Z 2 , D, A, n and o have the meanings shown in formula I above, the number of rings in the compound is at least 5, preferably R 1 and R 2 are the same or different and are H, N(R z)2. represents a linear alkyl having 1 to 12 carbon atoms, or a branched or cyclic alkyl having 3 to 18 carbon atoms, provided that in addition, one or more non-adjacent CH2 groups may be independently replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that O atoms and / or S atoms are not directly linked to each other, and provided that in addition, one or more H atoms may be replaced by F, R z represents, in each occurrence, the same or different, H, a linear alkyl having 1 to 12 carbon atoms, or a branched or cyclic alkyl having 3 to 12 carbon atoms, provided that in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that O atoms and / or S atoms are not directly linked to each other, and provided that in addition, one or more H atoms may be replaced by F, Z 1 and Z 2 represent the same or different, a single bond, -O-, -S-, -C(O)-, -CF2O-, -OCF2-, -C(O)-O-, -O-C(O)-, -OCH2-, -CH2O-, -C≡C- or -N=N-, A 1 represents, in each occurrence, the same or different, an aromatic, heteroaromatic, alicyclic or heterocyclic group having 4 to 25 ring atoms, which may contain a fused ring and which is unsubstituted or mono- or polysubstituted by L, L represents F, Cl, -CN, or a linear alkyl having 1 to 25 carbon atoms, or a branched or cyclic alkyl having 3 to 25 carbon atoms, provided that in addition, one or more non-adjacent CH2 groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that O atoms and / or S atoms are not directly linked to each other, and provided that in addition, one or more H atoms may be replaced by F respectively, D represents a heteroacene group comprising at least four fused rings, preferably each ring being unsubstituted, monosubstituted, or polysubstituted with L, except that in formula I-2, if group A does not contain any rings, group D comprises at least five fused rings. A represents an acceptor group, preferably an electron-deficient substructure. n represents 1, 2, or 3, preferably 1 or 2, more preferably 1, and o represents 0 or 1, preferably 0.

[0086] In preferred embodiments, in formulas I, I-1 and I-2, and their preferred sub-formulas described herein, base D is selected from bases Da, Db and Dc.

[0087] [ka]

[0088] In the formula, Ar 1 Ar 2 Ar 3 Ar 4 Ar 5 and Ar 6 represents a fused ring, and Ar 1 These are independently selected from the following formulas, [ka] Ar 4 These are independently selected from the following formulas, [ka] Ar 2 Ar 3 Ar 5 Ar 6 These are independently selected from the following formulas, [ka] W 1 is S, O, or Se, U1 CR a R b , SiR a R b , GeR a R b or NR a And, however R a and R b R is independent 4 It is defined as follows: However, [ka] This is a different base [ka] Not adjacent to, R 4 , R 5 , R 6 and R 7 Each instance of represents, identical or different, a halogen, or a linear alkyl or alkoxy having 1 to 20 carbon atoms, or a branched alkyl or alkoxy having 3 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by fluorine. In the middle * This represents a carbon atom shared by an adjacent fused ring. Base Ar 1 and Ar 4 On the single bond inside * This represents the bonding of the groups Da, Db, and Dc to other groups of the compound.

[0089] In the present invention, particularly in the compounds of formula I, all atoms also include their isotopes. In particular, one or more hydrogen atoms (H) may be substituted with deuterium (D), which is particularly preferred in some embodiments. The higher the degree of deuteration, the easier or simpler the analytical quantification of the compound becomes, especially at low concentrations.

[0090] In the compounds of formulas I, I-1, and I-2, and their preferred sub-formulas described herein, the group D is particularly preferably selected from the following formulas.

[0091] [ka]

[0092] In the formula, R 4 Each instance of represents, whether identical or different, a halogen, or a linear alkyl or alkoxy having 1 to 20 carbon atoms, or a branched alkyl or alkoxy having 3 to 20 carbon atoms, where one or more hydrogen atoms may be replaced by fluorine.

[0093] According to the present invention, in the compound of formula I, the chromophore system in the molecular structure is composed of groups in which the donor group D is directly adjacent to the acceptor group.

[0094] Here, acceptor group A is an electron-deficient substructure and can exhibit electron-withdrawing properties. Acceptor group A is preferably a group having π electron deficiency properties.

[0095] Surprisingly, certain groups consisting of donor D and acceptor described herein have been found to offer advantages in terms of the performance of the dye, particularly in terms of its extinction coefficient and reliability.

[0096] In one embodiment, the acceptor group A, particularly the electron-withdrawing group A, is preferably selected from carbonyl and carbonyl-containing groups, sulfonyl and sulfonyl-containing groups, cyano and cyano-containing groups, nitro and nitro-containing groups, haloalkyl and haloalkyl-containing groups, electron-deficient aryl and electron-deficient aryl-containing groups, electron-deficient heteroaryl and electron-deficient heteroaryl-containing groups, benzothiadiazole groups, quinoxaline groups, particularly nitrile-containing quinoxaline groups, thiadiazoloquinoxaline groups, liylene groups, perylene groups, benzotriazole groups, anthraquinone groups, thiazolothiazole groups, bis(thiadiazolo)phenylene groups, pyridine groups, and diketopyrrolopyrrole groups.

[0097] In preferred embodiments, the base A in formulas I, I-1 and I-2, and their preferred sub-formulas described herein, is selected from the following formulas.

[0098] [ka]

[0099] [ka]

[0100] During the ceremony, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 Each occurrence may be the same or different, representing H, halogen, CN, or a linear alkyl having 1 to 20 C atoms, or a branched alkyl having 3 to 20 C atoms, where one or more H atoms may be replaced by F. R 15 represents halogens, CN, or linear alkyls having 1 to 20 carbon atoms, or branched alkyls having 3 to 20 carbon atoms, and The dashed lines indicate the bond with the rest of the compound.

[0101] In one embodiment, formula I and the base A in the preferred subformula 1In each occurrence, the group is selected from alicyclic groups, heterocyclic groups, aryl groups and heteroaryl groups, which may be the same or different, and which may be substituted with one or more groups L as defined herein, preferably selected from 1,4-cyclohexylene (where one or two non-adjacent CH2 groups may be replaced by O), 1,4-cyclohexenylene, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, selenofen-2,5-diyl, thienopyrrole-2,5-diyl, dithienopyrrolediyl, dithienosilodiyl, and cyclopentadithiophenediyl. A group selected from pyridine-2,5-diyl, pyrimidinediyl, and pyridazinediyl (wherein one or more H atoms may be replaced by the group L as defined herein), more preferably 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, selenofen-2,5-diyl, and thienopyrrole-2,5-diyl The group is selected from dithienopyrrole diyl, dithienosilo diyl, cyclopentadithiophene diyl, pyridine-2,5-diyl, pyrimidine diyl, and pyridazine diyl (wherein one or more H atoms may be replaced by a group L as defined herein), and in particular, the group is selected from 1,4-phenylene (wherein L is preferably F), where one or more H atoms may be replaced by a group L as defined herein.

[0102] In a preferred embodiment, the compound of formula I is selected from the compounds of formula IA.

[0103] [ka]

[0104] In the formula, the number of rings in the compound is at least 5, and R 1 H, N(R z)2, represents a linear alkyl group having 1 to 12 carbon atoms, or a branched or cyclic alkyl group having 3 to 18 carbon atoms, provided that in addition, one or more non-adjacent CH2 groups are independent of each other such that the oxygen atom and / or sulfur atom are not directly bonded to each other, -N(R z ) may be replaced with -, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, provided that one or more H atoms are replaced with F. Preferably, H, N(R z )2. Represents a linear alkyl group having 1 to 12 carbon atoms, or a branched or cyclic alkyl group having 3 to 18 carbon atoms, wherein one or more non-adjacent CH2 groups may be independently replaced by -O-, but preferably R z Each occurrence represents a linear alkyl group having the same or different H, 1 to 12 C atoms, or a branched or cyclic alkyl group having 3 to 12 C atoms. R z Each occurrence represents, identical or different, a linear alkyl group having H, 1 to 12 C atoms, or a branched or cyclic alkyl group having 3 to 12 C atoms, wherein one or more non-adjacent CH2 groups may be replaced with -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that the O and / or S atoms are not directly linked to each other, wherein one or more H atoms may be replaced with F. Z 1 This represents a single bond, -CF2O-, -OCF2-, -C(O)-O-, -OC(O)-, -OCH2-, -CH2O-, -C≡C-, or -N=N-. Preferably, it represents a single bond, A 1Each occurrence may be identical or different and represent 1,4-cyclohexylene (where one or two non-adjacent CH2 groups may be replaced by O), 1,4-cyclohexenylene, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, selenofen-2,5-diyl, thienopyrrole-2,5-diyl, dithienopyrrolediyl, dithienosyldiyl, cyclopentadithiophenediyl, pyridine-2,5-diyl, pyrimidinediyl, or pyridazinediyl (where one or more H atoms may be replaced by the group L), L represents F, Cl, -CN, or a linear alkyl group having 1 to 25 C atoms, or a branched or cyclic alkyl group having 3 to 25 C atoms, wherein one or more non-adjacent CH2 groups may be replaced with -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- so that the O atoms and / or S atoms are not directly linked to each other, and one or more H atoms may each be replaced with F. D represents a heteroacene group comprising at least four fused rings, preferably each ring being unsubstituted, monosubstituted, or polysubstituted with L. However, if n is 0, the group D contains at least 5 fused rings, A represents an acceptor group, preferably an electron-deficient substructure. n represents 0, 1, or 2, preferably 0 or 1.

[0105] The compound of formula I is particularly preferably selected from the group of compounds of the following formulas.

[0106] [ka]

[0107] [ka]

[0108] [Chemistry]

[0109] [Chemistry]

[0110] [Chemistry]

[0111] [Chemistry]

[0112] [Chemistry]

[0113] [Chemistry]

[0114] [Chemistry]

[0115] [Chemistry]

[0116] [Chemistry]

[0117] [Chemistry]

[0118] In the formula, Alk represents unsubstituted or substituted alkyl, or R represented by Formula I 1It has the same meaning as above. Preferably, it is a linear alkyl having 1 to 20 carbon atoms, or a branched or cyclic alkyl having 3 to 20 carbon atoms, and more preferably, a linear alkyl having 1 to 12 carbon atoms, or a branched alkyl having 3 to 18 carbon atoms.

[0119] In one embodiment, the compound of formula I comprises exactly one donor group and exactly one acceptor group, each selected from groups D and A as defined herein.

[0120] The method for producing the compound of formula I may be based on, for example, a known method described in standard organic chemistry literature, such as Houben-Weyl's "Methoden der organischen Chemie [Methods of Organic Chemistry]" (Thieme Verlag, Stuttgart), or a similar method. For specific methods of producing the compound of formula I, please refer to further examples and known literature.

[0121] In one aspect of the present invention, a method for producing a compound of formula I is provided, by which a bromine compound of formula I-Br is produced or provided.

[0122] [ka]

[0123] In the formula, D, A, Z 2 , A 2 Q 2 , R 2 and o have meanings relating to the compound of formula I described herein, and thereafter the compound of formula I-Br is subjected to a chemical reaction, preferably a cross-coupling reaction.

[0124] As described herein, the compounds of formula I exhibit preferably large extinction coefficients, in the visible light spectrum and / or the near-infrared spectrum, and particularly in the visible light spectrum.

[0125] In one embodiment, the compound of Formula I has an isotropic absorption coefficient of at least 500 (wt%·cm) -1 , preferably at least 650 (wt%·cm) -1 , more preferably at least (wt%·cm) -1 , even more preferably at least 875 (wt%·cm) -1 .

[0126] The isotropic absorption coefficient is preferably measured according to the method described below in this specification.

[0127] A high extinction coefficient, in combination with a particularly high dichroic ratio, provides several advantages. For example, by using a lower dye concentration, it is possible to obtain a desired contrast between the bright state and the dark state, i.e., a state with a relatively high light transmittance and a state with a relatively low light transmittance, and to achieve an effective dark state. Also, a lower dye concentration may have advantages from the viewpoints of solubility and viscosity. Similarly, also in the case of the dye compounds of the present invention having a high extinction coefficient, a single switching layer may be sufficient to obtain the desired switching contrast and the desired dark state performance, and / or a thinner switching layer thickness or cell gap may be sufficient.

[0128] The compound of Formula I is preferably a positive dichroic dye, i.e., a dye having a positive anisotropy degree R.

[0129] The degree of anisotropy R is determined for the LC mixture containing the dye from the values of the extinction coefficients of the parallel and perpendicular alignments of the molecules with respect to the direction of polarization of light.

[0130] According to the present invention, the anisotropy degree R is preferably greater than 0.4, more preferably greater than 0.6, even more preferably greater than 0.7, even more preferably greater than 0.75, and particularly greater than 0.8.

[0131] Absorption is preferably maximized when the polarization direction of the light is parallel to the direction of the longest molecular elongation of the compound of formula I, and preferably minimized when the polarization direction of the light is perpendicular to the direction of the longest molecular elongation of the compound of formula I.

[0132] The compounds according to the present invention preferably exhibit an absorption maximum at wavelengths in the visible light or near-infrared spectrum, and more preferably at wavelengths in the visible light spectrum.

[0133] The compound of formula I can be suitably used as a guest compound in a liquid crystal host mixture, particularly as a dichroic dye. Therefore, in a preferred embodiment, the compound of formula I is dissolved in a liquid crystal medium.

[0134] In one aspect of the present invention, the mesogenic medium comprises one or more compounds of formula I described above and below, preferably two or more compounds of formula I described above and below, and more preferably three or more compounds of formula I described above and below.

[0135] In a preferred embodiment, the mesogenic medium comprises at least one compound selected from the group of compounds of formulas I-1 and I-2 described herein.

[0136] In a particularly preferred embodiment, the mesogenic medium comprises at least one compound of formula IA as described herein, and more preferably at least two compounds of formula IA as described herein.

[0137] In principle, a suitable host mixture is a dielectrically negative or positive LC mixture suitable for use in conventional VA, TN, STN, IPS, or FFS displays.

[0138] Suitable LC mixtures are known in the art and have been documented in the literature. An LC medium for VA displays having negative dielectric anisotropy is described, for example, in European Patent Application Publication No. 1 378 557.

[0139] Suitable LC mixtures having positive dielectric anisotropy, suitable for LCDs, particularly IPS displays, are known from, for example, Japanese Patent Publication No. 07-181439, European Patent No. 0667555, European Patent No. 0673986, German Patent No. 19509410, German Patent No. 19528106, German Patent No. 19528107, International Publication No. 96 / 23851, International Publication No. 96 / 28521, and International Publication No. 2012 / 079676.

[0140] Preferred embodiments of the liquid crystal medium having negative or positive dielectric anisotropy according to the present invention are shown below.

[0141] The LC host mixture is preferably a nematic LC mixture. In one embodiment, the LC mixture does not have a chiral LC phase.

[0142] In one embodiment of the present invention, the liquid crystal medium comprises a liquid crystal host mixture having negative dielectric anisotropy. Therefore, in a preferred embodiment, the mesogenic medium according to the present invention comprises components selected from the following a) to x).

[0143] a) A mesogenic medium comprising one or more compounds selected from the group of compounds of formulas CY, PY, and AC.

[0144] [ka]

[0145] During the ceremony, a represents 0, 1, or 2, preferably 1 or 2. b represents 0 or 1, c is 0, 1, or 2. d is either 0 or 1, [ka] [ka] [ka] R 1 , R 2 , R AC1 , R AC2 Each of these independently represents an alkyl group having 1 to 12 carbon atoms (in addition, in the group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other), preferably an alkyl or alkoxy group having 1 to 6 carbon atoms. Z x and Z y Each of these independently represents -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O-, or a single bond, preferably a single bond. L 1~4 These each represent F, Cl, CN, OCF3, CF3, CH3, CH2F, and CHF2, respectively, independently of each other.

[0146] However, each unit has the following meaning: Each independently represents an alkyl group having 1 to 12 carbon atoms, and one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -O-CO-, or -CO-O-, in which case the oxygen atoms must not be directly bonded to each other. Z AC -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O, or a single bond, preferably a single bond.

[0147] Preferably, L 1 and L 2 Both of them represent F, or L 1 and L 2 One of them represents F and the other represents Cl, or L 3 and L 4Both of them represent F, or L 3 and L 4 One of them represents F, and the other represents Cl.

[0148] Compounds of formula CY are preferably selected from the group consisting of the following sub-formulas.

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] [ka]

[0155] In the formula, a represents 1 or 2, and alkyl and alkyl * Each of the following independently represents a linear alkyl group having 1 to 6 carbon atoms, alkenyl represents a linear alkenyl group having 2 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. Alkenyl preferably represents CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0156] Compounds of formula PY are preferably selected from the group consisting of the following sub-formulas. [ka]

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] In the formula, alkyl and alkyl * Each of the following independently represents a linear alkyl group having 1 to 6 carbon atoms, alkenyl represents a linear alkenyl group having 2 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. Alkenyl preferably represents CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0162] Compounds of formula AC are preferably selected from the group consisting of the following sub-formulas. [ka]

[0163] b) A mesogenic medium containing one or more compounds of the following formula. [ka]

[0164] In the formula, each base has the following meaning: [ka] [ka]

[0165] R 3 and R 4 Each of these independently represents an alkyl group having 1 to 12 carbon atoms, and in this group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other. Z y -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O-, or a single bond, preferably a single bond.

[0166] Compounds of formula ZK are preferably selected from the group consisting of the following sub-formulas. [ka]

[0167] [ka]

[0168] In the formula, alkyl and alkyl *Each of the following independently represents a linear alkyl group having 1 to 6 carbon atoms, alkenyl represents a linear alkenyl group having 2 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. Alkenyl preferably represents CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0169] Compounds of formulas ZK1 and ZK3 are particularly preferred.

[0170] Particularly preferred compounds of formula ZK are selected from the following sub-formulas.

[0171] [ka]

[0172] [ka]

[0173] In the formula, the propyl group, butyl group, and pentyl group are linear groups.

[0174] Compounds of formulas ZK1a and ZK3a are most preferred.

[0175] c) A mesogenic medium containing one or more compounds of the following formula. [ka]

[0176] In the formula, each base, whether identical or different in its respective appearance, has the following meaning: R 5 and R 6Each of these independently represents an alkyl group having 1 to 12 carbon atoms (in addition, in the group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other), preferably an alkyl or alkoxy group having 1 to 6 carbon atoms. [ka] [ka]

[0177] 'e' represents either 1 or 2.

[0178] Compounds of formula DK are preferably selected from the group consisting of the following sub-formulas.

[0179] [ka]

[0180] [ka]

[0181] In the formula, alkyl and alkyl * Each of the following independently represents a linear alkyl group having 1 to 6 carbon atoms, alkenyl represents a linear alkenyl group having 2 to 6 carbon atoms, and (O) represents an oxygen atom or a single bond. Alkenyl preferably represents CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0182] Compounds of formulas DK1, DK4, DK7, DK9, DK10, and DK11 are particularly preferred.

[0183] d) A mesogenic medium containing one or more compounds of the following formula. [ka]

[0184] In the formula, each base has the following meaning: [ka]

[0185] However, at least one ring F, unlike cyclohexylene, f represents either 1 or 2. R 1 and R 2 Each of these independently represents an alkyl group having 1 to 12 carbon atoms, and in this group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other. Z y This represents -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O- or a single bond, preferably a single bond. L 1 and L 2 These represent F, Cl, OCF3, CF3, CH3, CH2F, and CHF2, respectively, independently of each other.

[0186] Preferably, base L 1 and L 2 Both of them represent F, or the base L 1 and L 2 One of them represents F, and the other represents Cl.

[0187] Compounds of formula LY are preferably selected from the group consisting of the following sub-formulas.

[0188] [ka]

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] [ka]

[0193] In the formula, R 1 The above has the meanings shown, where alkyl represents a linear alkyl group having 1 to 6 carbon atoms, (O) represents an oxygen atom or a single bond, and v represents an integer from 1 to 6. 1 Preferably, a linear alkyl group having 1 to 6 carbon atoms or a linear alkylene group having 2 to 6 carbon atoms, particularly CH3, C2H5, n-C3H, n-C4H9, n-C5H 11 These represent CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0194] e) A mesogenic medium containing one or more compounds selected from the group consisting of the following formulas.

[0195] [ka]

[0196] [ka]

[0197] In the formula, alkyl is C 1~6 Represents alkyl, L x ∫ represents H or F, and X represents F, Cl, OCF3, OCHF2, or OCH=CF2. Compounds of formula G1 in which X represents F are particularly preferred.

[0198] f) A mesogenic medium containing one or more compounds selected from the group consisting of the following formulas.

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] In the formula, R 5 is R 1 It has one of the meanings shown above, and alkyl is C 1~6 R represents alkyl, d represents 0 or 1, and z and m each represent an integer from 1 to 6 independently of each other. 5 C is particularly preferred. 1~6 Alkyl or alkoxy or C 2~6 The compound is an alkenyl, and d is preferably 1. The LC medium according to the present invention preferably contains one or more compounds of the above formula in an amount of 5% by weight or more.

[0204] g) A mesogenic medium comprising one or more biphenyl compounds selected from the group consisting of the following formulas. [ka]

[0205] In the formula, alkyl and alkyl * Each of these represents a linear alkyl group having 1 to 6 carbon atoms independently of each other, and alkenyl and alkenyl * () represents a linear alkenyl group, each having 2 to 6 carbon atoms independently of the others, and (O) represents an oxygen atom or a single bond. * Preferably, CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0206] The proportion of biphenyls of formulas B1 to B3 in the LC mixture is preferably at least 3% by weight, and more preferably at least 5% by weight.

[0207] Compound B2 is particularly preferred.

[0208] Compounds of formulas B1 to B3 are preferably selected from the group consisting of the following sub-formulas.

[0209] [ka]

[0210] In the formula, alkyl * represents an alkyl group having 1 to 6 C atoms. The medium according to the present invention is particularly preferably comprised of one or more compounds of formula B1a and / or B2c.

[0211] h) A mesogenic medium containing one or more terphenyl compounds of the following formula. [ka]

[0212] In the formula, R 5 and R 6 Each of these has one of the meanings shown above, and [ka]

[0213] In the formula, R 5 represents F or Cl, preferably F, and R 6 represents F, Cl, OCF3, CF3, CH3, CH2F, or CHF2, preferably F.

[0214] Compounds of formula T are preferably selected from the group consisting of the following sub-formulas.

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] [ka]

[0219] [ka]

[0220] In the formula, R represents a linear alkyl or alkoxy group having 1 to 7 C atoms, * (O) represents a linear alkylene group having 2 to 7 carbon atoms, (O) represents an oxygen atom or a single bond, and m represents an integer from 1 to 6. *Preferably, CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0221] R preferably represents methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, or pentoxy.

[0222] i) A mesogenic medium containing one or more compounds of the following formula O. [ka]

[0223] During the ceremony [ka]

[0224] R O1 and R O2 Each represents an alkyl group having 1 to 12 carbon atoms, either identical or different, and in the group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other. Z O1 -CH2CH2-, -CF2CF2-, -C=C-, or a single bond. Z O2 This represents CH2O, -C(O)O-, -CH2CH2-, -CF2CF2-, or a single bond. o is either 1 or h².

[0225] Compounds of formula O are preferably selected from the group consisting of the following sub-formulas.

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] In the formula, R O1 and R O2 The above has the meanings shown, and preferably each represents a linear alkyl or linear alkylene having 1 to 6 carbon atoms independently of each other.

[0230] A preferred medium comprises one or more compounds selected from formulas O3, O4, and O5.

[0231] k) A mesogenic medium containing one or more compounds selected from the group consisting of the following formulas. [ka]

[0232] During the ceremony [ka]

[0233] In the formula, R 9 (F) represents H, CH3, C2H5, or n-C3H7, (Q) represents any fluorine substituent, and R represents 1, 2, or 3. 7 is R 1 It has one of the meanings indicated by and is preferably more than 3% by weight, particularly 5% by weight or more, and very preferably 5 to 30% by weight.

[0234] Particularly preferred compounds of formula FI are selected from the group consisting of the following sub-formulas.

[0235] [ka]

[0236] [ka]

[0237] In the formula, R 7 R preferably represents a linear alkyl group, 9 is represented by CH3, C2H5, or n-C3H7. Compounds of formulas FI1, FI2, and FI3 are particularly preferred.

[0238] l) A mesogenic medium containing one or more compounds selected from the group consisting of the following formulas. [ka]

[0239] In the formula, R 8 is R 1 It has one of the meanings shown, and alkyl represents a linear alkyl group having 1 to 6 carbon atoms.

[0240] m) A mesogenic medium comprising one or more compounds containing tetrahydronaphthyl or naphthyl units, such as compounds selected from the group consisting of the following formulas. [ka]

[0241] [ka]

[0242] [ka]

[0243] During the ceremony, R 10 and R 11Each of these independently represents an alkyl group having 1 to 12 carbon atoms (in addition, in the group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other), preferably an alkyl or alkoxy group having 1 to 6 carbon atoms. and R 10 and R 11 Preferably, represents a linear alkyl or alkoxy having 1 to 6 carbon atoms or a linear alkylene having 2 to 6 carbon atoms. Z 1 and Z 2 Each of these independently represents -C2H4-, -CH=CH-, -(CH2)4-, -(CH2)3O-, -O(CH2)3-, -CH=CH-CH2CH2-, -CH2CH2CH=CH-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CF=CH-, -CH=CF-, -CH2-, or a single bond.

[0244] n) A mesogenic medium containing one or more difluorodibenzochromans and / or chromans of the following formula. [ka]

[0245] During the ceremony, R 11 and R 12 Each of them operates independently on R 11 It has one of the meanings shown, Ring M is trans-1,4-cyclohexylene or 1,4-phenylene. Z m These are -C2H4-, -CH2O-, -OCH2-, -CO-O-, or -O-CO-, c is 0, 1, or 2. Preferably, the amount is 3 to 20% by weight, and more preferably 3 to 15% by weight.

[0246] Particularly preferred compounds of formulas BC, CR, and RC are selected from the group consisting of the following sub-formulas.

[0247] [ka]

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] In the formula, Alkyl and Alkyl * (O) represents a linear alkyl group having 1 to 6 C atoms independently of each other, c is 1 or 2, and Alkenyl and Alkenyl * These represent linear alkenyl groups, each independently containing 2 to 6 carbon atoms. * Preferably, CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0252] A mixture containing one, two, or three compounds of formula BC-2 is particularly preferred.

[0253] o) A mesogenic medium comprising one or more fluorinated phenanthrenes and / or dibenzofurans of the following formula. [ka]

[0254] In the formula, R 11 and R 12 Each of them operates independently on R 11 It has one of the meanings shown, where b represents 0 or 1, L represents F, and r represents 1, 2, or 3.

[0255] Particularly preferred compounds of formulas PH and BF are selected from the group consisting of the following sub-formulas.

[0256] [ka]

[0257] [ka]

[0258] In the formula, R and R' each represent a linear alkyl or alkoxy group having 1 to 7 carbon atoms, independently of each other.

[0259] In another embodiment, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formula B-1, B-2, and B-3.

[0260] [ka]

[0261] During the ceremony, R 11 and R 12 These are identical or different linear alkyl or alkoxy groups having H or 1 to 15 C atoms (wherein one or more CH2 groups in these groups are independent of each other and the O atoms are not directly linked to each other, such as -C≡C-, -CF2O-, -OCF2-, -CH=CH-, [ka] It may be replaced by -O-, -CO-O-, or -O-CO-, provided that one or more H atoms are replaced by halogens. ), preferably it represents a linear alkoxy group having 1 to 7 C atoms.

[0262] The compound of formula B-1 is preferably selected from the group of compounds of formulas B-1-a to B-1-e.

[0263] [ka]

[0264] During the ceremony, R 11 and R 12 represents an alkyl group having 1 to 7 carbon atoms, preferably ethyl, n-propyl, n-butyl, or n-pentyl, which may be the same or different.

[0265] The compound of formula B-2 is preferably selected from the group of compounds of formulas B-2-a to B-2-e.

[0266] [ka]

[0267] During the ceremony, R 11 and R 12 This represents an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms, and which may be identical or different.

[0268] The compound of formula B-3 is preferably selected from the group of compounds of formulas B-3-a to B-3-j.

[0269] [ka]

[0270] [ka]

[0271] In the formula, R 12 represents an alkyl group having 1 to 7 carbon atoms, preferably ethyl, n-propyl, or n-butyl.

[0272] In a preferred embodiment, one or more compounds selected from the group of compounds of formula B-1, B-2, and B-3 are selected from the group of compounds BA to BJ.

[0273] [ka]

[0274] [ka]

[0275] One or more compounds selected from the group of compounds of formulas B-1, B-2, and B-3 are included in the liquid crystal medium in a total amount preferably 0 to 15% by weight, more preferably 10% by weight or less, and even more preferably 5% by weight or less.

[0276] p) A mesogenic medium containing one or more monocyclic compounds of the following formula. [ka]

[0277] During the ceremony, R 1 and R 2 Each of these independently represents an alkyl group having 1 to 12 carbon atoms (in addition, in the group, one or two non-adjacent CH2 groups may be replaced with -O-, -CH=CH-, -CO-, -OCO-, or -COO-, so that the oxygen atoms are not directly bonded to each other), preferably an alkyl or alkoxy group having 1 to 6 carbon atoms. L 1 and L 2 These represent F, Cl, OCF3, CF3, CH3, CH2F, and CHF2, respectively, independently of each other.

[0278] Preferably, L 1 and L 2 Both represent F, or L 1 and L 2 One of them represents F, and the other represents Cl.

[0279] Compounds of formula Y are preferably selected from the group consisting of the following sub-formulas.

[0280] [ka]

[0281] [ka]

[0282] In the formula, Alkyl and Alkyl * Each of these independently represents a linear alkyl group having 1 to 6 carbon atoms, Alkoxy represents a linear alkoxy group having 1 to 6 carbon atoms, and Alkenyl and Alkenyl * Each represents a linear alkenyl group having 2 to 6 C atoms independently of each other, and O represents an oxygen atom or a single bond. * Preferably, CH2=CH-, CH2=CHCH2CH2-, CH3-CH=CH-, CH3-CH2-CH=CH-, CH3-(CH2)2-CH=CH-, CH3-(CH2)3-CH=CH-, or CH3-CH=CH-(CH2)2-.

[0283] Particularly preferred compounds of formula Y are selected from the group consisting of the following sub-formulas. [ka] In the formula, Alkoxy preferably represents a linear alkoxy having 3, 4, or 5 carbon atoms.

[0284] q) A mesogenic medium containing 1 to 15 types, preferably 3 to 12 types, of compounds of formula CY1, CY2, PY1, PY2, AC1, AC2, and / or AC3. The proportion of these compounds in the whole mixture is preferably 20 to 99%, more preferably 30 to 95%, and particularly preferably 40 to 90%. The content of each of these individual compounds is preferably 2 to 20% in each case.

[0285] r) A mesogenic medium containing 1 to 10 types, preferably 1 to 8 types, of compounds of formula ZK, particularly compounds ZK1, ZK2 and / or ZK6. The proportion of these compounds in the whole mixture is preferably 3 to 25%, particularly preferably 5 to 45%. The content of each of these individual compounds is preferably 2 to 20% in each case.

[0286] s) A mesogenic medium in which the proportion of compounds of formulas CY, PY, and ZK in the whole mixture is greater than 70%, preferably greater than 80%.

[0287] t) A mesogenic medium comprising one or more compounds selected from formulas PY1 to PY8, very preferably formula PY2, and preferably 1 to 5 compounds. The proportion of these compounds in the whole mixture is preferably 1 to 30%, particularly preferably 2 to 20%. The content of each of these individual compounds is preferably 1 to 20% in each case.

[0288] u) A mesogenic medium comprising one or more compounds of formula T2, preferably one, two, or three compounds. The content of these compounds in the whole mixture is preferably 1 to 20%. The LC medium according to the present invention preferably contains 0.5 to 30% by weight, particularly 1 to 20% by weight, of terphenyl compounds of formula T and its preferred subformulas. Compounds of formulas T1, T2, T3, and T21 are particularly preferred. In these compounds, R preferably represents alkyl, and more preferably alkoxy, each having 1 to 5 C atoms. Terphenyl compounds are preferably used in the mixture according to the present invention when the Δn value of the mixture is 0.1 or higher. A preferred mixture contains 2 to 20% by weight of one or more terphenyl compounds of formula T, preferably selected from the group of compounds T1 to T22.

[0289] v) A mesogenic medium comprising one or more compounds of formula BF1 and / or BSF1, preferably one, two, or three compounds. The total content of these compounds in the whole mixture is preferably 1-15%, preferably 2-10%, and particularly preferably 4-8%.

[0290] w) A preferred medium contains one or more compounds of formula O, preferably selected from formulas O3, O4, and O5, in a total concentration of 2-25%, preferably 3-20%, and particularly preferably 5-15%.

[0291] x) A preferred medium contains one or more compounds of formula DK, preferably selected from formulas DK1, DK4, DK7, DK9, DK10, and DK11. The total concentration of the compounds of formulas DK9, DK10, and DK11 is preferably 2-25%, more preferably 3-20%, and particularly preferably 5-15%.

[0292] In another embodiment of the present invention, the LC medium comprises an LC host mixture having positive dielectric anisotropy. Therefore, in a more preferred embodiment, the mesogenic medium according to the present invention comprises components selected from the following items aa) to zz).

[0293] aa) A mesogenic medium comprising one or more compounds selected from the group of compounds of formulas II to VIII below, particularly from the group of compounds of formulas II and III.

[0294] [ka]

[0295] During the ceremony, R 20 Each represents a halogenated or unsubstituted alkyl or alkoxy group having 1 to 15 C atoms, either identical or different, except that one or more CH2 groups are independently -C≡C-, -CF2O-, -CH=CH-, such that the O atoms in these groups are not directly bonded to each other. [ka] -O-, -CO-O-, or -O-CO- may be replaced. X 20 Each of these represents, either identical or different, a halogenated alkyl group, halogenated alkenyl group, halogenated alkoxy group, or halogenated alkenyloxy group, each having up to six carbon atoms, F, Cl, CN, SF5, SCN, NCS, Y 20~24 These are either the same or different, representing H or F. [ka]

[0296] The compound of formula II is preferably selected from the following formulas.

[0297] [ka]

[0298] [ka]

[0299] In the formula, R 20 and X 20 It has the meaning shown above.

[0300] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 X preferably represents F. Compounds of formulas IIa and IIb, particularly those of formulas IIa and IIb in which X represents F, are especially preferred.

[0301] In one embodiment, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formulas II-1 and II-2.

[0302] [ka]

[0303] During the ceremony, R 2 This represents an alkyl, alkoxy, fluorinated alkyl, or fluorinated alkoxy having 1 to 7 carbon atoms, or an alkenyl, alkenyloxy, alkoxyalkyl, or fluorinated alkenyl having 2 to 7 carbon atoms, provided that one or more CH2 groups are independently of each other. [ka] It can be replaced with, [ka] And, L 21 , L 22 , L 23 and L 24 Each of these independently represents either H or F. L 25 represents H or CH3, and X 2 This represents a halogen, alkyl halide, or alkoxy having 1 to 3 carbon atoms, or an alkenyl halide or alkenyloxy having 2 or 3 carbon atoms.

[0304] In further embodiments, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formulas II-1-a to II-1-h.

[0305] [ka]

[0306] [ka]

[0307] In the formula, R 2 This has the meaning given in equation II-1.

[0308] In further embodiments, the liquid crystal medium comprises one or more compounds selected from the group of compounds of formulas II-2-a to II-2-l.

[0309] [ka]

[0310] [ka]

[0311] In the formula, R 2 This has the meaning given in equation II-2 above.

[0312] The compound of formula III is preferably selected from the following formulas.

[0313] [ka]

[0314] In the formula, R 20 and X 20 It has the meaning shown above.

[0315] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 preferably represents F. Compounds of formula IIIa and IIIe, particularly compounds of formula IIIa, are especially preferred.

[0316] bb) A mesogenic medium comprising one or more compounds selected from the following formulas, either as a substitute or in addition.

[0317] [ka]

[0318] During the ceremony, R 20 , X 20 and Y 20~23 This has the meanings shown above, and Z 20 This represents -C2H4-, -(CH2)4-, -CH=CH-, -CF=CF-, -C2F4-, -CH2CF2-, -CF2CH2-, -CH2O-, -OCH2-, -COO- or -OCF2-, as well as single bonds in formulas V and VI, and -CF2O- in formulas V and VIII. r represents 0 or 1, and 's' represents either 0 or 1.

[0319] The compound of formula IV is preferably selected from the following formulas.

[0320] [ka]

[0321] In the formula, R 20 and X 20 It has the meaning shown above.

[0322] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 is preferably F, CN, or OCF3, and more preferably OCF=CF2 or Cl.

[0323] Compounds of formula V are preferably selected from the following formulas.

[0324] [ka]

[0325] [ka]

[0326] In the formula, R 20 and X 20 It has the meaning shown above.

[0327] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 Preferably, F and OCF3, and more preferably OCHF2, CF3, OCF=CF2 and OCH=CF2.

[0328] The compound of formula VI is preferably selected from the following formulas.

[0329] [ka]

[0330] In the formula, R 20 and X 20 It has the meaning shown above.

[0331] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 is preferably F, and more preferably OCF3, CF3, CF=CF2, OCHF2, and OCH=CF2.

[0332] The compound of formula VII is preferably selected from the following formulas.

[0333] [ka]

[0334] In the formula, R 20 and X 20 It has the meaning shown above.

[0335] R 20 X preferably represents an alkyl group having 1 to 6 carbon atoms. 20 is preferably F, and more preferably OCF3, OCHF2, and OCH=CF2.

[0336] cc) The mesogenic medium further comprises one or more compounds selected from the formulas ZK1 to ZK10 given above. Compounds of formulas ZK1 and ZK3 are particularly preferred. Particularly preferred compounds of formula ZK are selected from the sub-formulas ZK1a, ZK1b, ZK1c, ZK3a, ZK3b, ZK3c and ZK3d.

[0337] The mesogenic medium further comprises one or more compounds selected from the formulas DK1 to DK12 given above. Particularly preferred compounds are DK1, DK4, DK7, DK9, DK10, and DK11.

[0338] ee) The mesogenic medium contains one or more compounds selected from the following formulas. [ka]

[0339] In the formula, X 20 It has the meanings shown above, and L represents H or F, and "alkenyl" is C 2~6 Represents Alkenil

[0340] Compounds of formula DK-3a and IX are preferably selected from the following formulas. [ka]

[0341] In the formula, "alkyl" means C 1~6 Alkyl, preferably n-C3H7, n-C4H9, or n-C5H 11 , in particular, represents n-C3H7.

[0342] The medium (gg) further comprises one or more compounds selected from formulas B1, B2, and B3 given above, preferably from formula B2. The compounds of formulas B1 to B3 are particularly preferably selected from formulas B1a, B2a, B2b, and B2c.

[0343] The HH) medium contains one or more compounds selected from the following formulas. [ka]

[0344] In the formula, L 20 , L 21 represents H or F, and R 21 and R 22 Each represents an n-alkyl, alkoxy, oxaalkyl, fluoroalkyl, or alkenyl, each having the same or different carbon atoms and up to six carbon atoms, and preferably each represents an alkyl, each having the same or different carbon atoms and one to six carbon atoms.

[0345] ii) The medium contains one or more compounds of the following formula: [ka]

[0346] In the formula, R 20 , X 20 and Y 20~23 This has the meaning shown in Equation III, and [ka] and [ka]

[0347] Compounds of formulas XI and XII are preferably selected from the following formulas.

[0348] [ka]

[0349] [ka]

[0350] [ka]

[0351] In the formula, R 20 and X 20 The above has the meanings shown above, and preferably R 20 represents an alkyl group having 1 to 6 C atoms, and X 20 represents F. The mixture according to the present invention is particularly preferably comprising at least one compound of formula XIIa and / or XIIe.

[0352] The medium comprises one or more compounds selected from the group of compounds of formula T, preferably formulas T21-T23 and T25-T27, given above.

[0353] Compounds of formulas T21 to T23 are particularly preferred. Compounds of the following formulas are very particularly preferred.

[0354] [ka]

[0355] [ka]

[0356] The medium (kk) contains one or more compounds selected from the group DK9, DK10, and DK11 given above.

[0357] ll) The medium further contains one or more compounds selected from the following formulas.

[0358] [ka]

[0359] [ka]

[0360] In the formula, R 20 and X 20 Each of these independently has one of the meanings shown above, and Y 20~23 Each of these independently represents either H or F. 20 Preferably, it is F, Cl, CF3, OCF3, or OCHF2. 20 Preferably, each represents an alkyl, alkoxy, oxaalkyl, fluoroalkyl, or alkenyl having up to six carbon atoms.

[0361] The mixture according to the present invention is particularly preferably comprised of one or more compounds of formula XVIII-a. [ka]

[0362] In the formula, R 20 It has the meaning shown above. R 20 is preferably a linear alkyl, particularly ethyl, n-propyl, n-butyl, and n-pentyl, and very preferably n-propyl. Compounds of formula XVIII, particularly formula XVIII-a (one or more), are used in the mixture according to the present invention in an amount of 0.5 to 20% by weight, particularly preferably 1 to 15% by weight.

[0363] The medium (mm) contains one or more compounds of formula XIX in addition. [ka]

[0364] In the formula, R 20 , X 20 and Y 20~25 has the meaning shown in Equation III, where s represents 0 or 1, and [ka] It represents.

[0365] In equation XIX, also X 20 This may also represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The alkyl or alkoxy group is preferably linear.

[0366] R 20 Preferably, represents an alkyl group having 1 to 6 carbon atoms. 20 Preferably, it represents F.

[0367] The compound of formula XIX is preferably selected from the following formulas.

[0368] [ka]

[0369] [ka]

[0370] In the formula, R 20 , X 20 and Y 20 It has the meaning shown above. R 20 Preferably, represents an alkyl group having 1 to 6 carbon atoms. 20 preferably represents F, and Y 20 It is preferably F.

[0371] [ka]

[0372] ·R 20 These are linear alkyl groups or alkenyl groups having 2 to 6 carbon atoms.

[0373] The medium is of formulas G1 to G4 given above, preferably alkyl with C 1~6 It contains one or more compounds selected from G1 and G2 representing alkyl, L x represents H, and X represents F or Cl. In G2, X particularly preferably represents Cl.

[0374] The medium contains one or more compounds of the following formula: [ka]

[0375] In the formula, R 20 and X 20 It has the meaning shown above. R 20 Preferably, represents an alkyl group having 1 to 6 carbon atoms. 20 preferably represents F. The medium according to the present invention is particularly preferably X 20 The mixture preferably contains one or more compounds of formula XXII, where F is preferably represented. The compounds of formulas XX to XXII (one or more) are preferably used in the mixture according to the present invention in an amount of 1 to 20% by weight, particularly preferably 1 to 15% by weight. The particularly preferred mixture contains at least one compound of formula XXII.

[0376] The pp) medium contains one or more pyrimidine or pyridine compounds of the following formula: [ka]

[0377] In the formula, R 20and X 20 It has the meaning shown above. R 20 Preferably, represents an alkyl group having 1 to 6 carbon atoms. 20 preferably represents F. The medium according to the present invention is particularly preferably X 20 The mixture preferably contains one or more compounds of formula M-1 where F is represented. The compounds of formulas M-1 to M-3 (one or more) are preferably used in the mixture according to the present invention in an amount of 1 to 20% by weight, particularly preferably 1 to 15% by weight.

[0378] The medium qq) contains two or more compounds of formula XII, particularly formula XIIa and / or XIIe.

[0379] The medium contains 2 to 30% by weight, preferably 3 to 20% by weight, and particularly preferably 3 to 15% by weight, of the compound of formula XII.

[0380] ss) In addition to the compound of formula XII, the medium includes further compounds selected from the group of compounds of formulas II to XVIII.

[0381] The proportion of compounds of formulas II to XVIII in the whole mixture is 40 to 95% by weight, preferably 50 to 90% by weight, and particularly preferably 55 to 88% by weight.

[0382] The medium preferably contains 10-40% by weight, more preferably 12-30% by weight, and particularly preferably 15-25% by weight of the compound of formula II and / or III.

[0383] The medium contains 1 to 10% by weight, particularly preferably 2 to 7% by weight, of the compound of formula XV and / or XVI.

[0384] The media comprises at least one compound of formula XIIa and / or at least one compound of formula XIIe and at least one compound of formula IIIa and / or IIa.

[0385] xx) A preferred medium contains one or more compounds of formula O, preferably selected from formulas O3, O4, and O5, in a total concentration of 2-25%, preferably 3-20%, and particularly preferably 5-15%.

[0386] A preferred medium contains one or more compounds of formula DK, preferably selected from formulas DK1, DK4, DK7, DK9, DK10, and DK11. The total concentration of the compounds of formulas DK9, DK10, and DK11 is preferably 2-25%, more preferably 3-20%, and particularly preferably 5-15%.

[0387] zz) A preferred medium contains one or more compounds selected from formulas IV to VI, preferably IVa, IVb, IVc, IVd, Va, Vc, and VIb, at a concentration of 10 to 80%, preferably 12 to 75%, and particularly preferably 15 to 70%.

[0388] When the medium has negative dielectric anisotropy, the value of dielectric anisotropy (Δε) is preferably in the range of -2.0 to -8.0, more preferably in the range of -3.0 to -6.0, and particularly preferably in the range of -3.5 to 5.0.

[0389] When the medium has positive dielectric anisotropy, the value of Δε is preferably in the range of 2.5 to 50.0, more preferably in the range of 5.0 to 25.0, and particularly preferably in the range of 8.0 to 15.0.

[0390] The liquid crystal medium according to the present invention preferably has a transparency point of 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 105°C or higher, and particularly preferably 110°C or higher. In one embodiment, the liquid crystal medium according to the present invention has a transparency point in the range of 70°C to 170°C.

[0391] The defined high transparency point can be beneficial in terms of performance and reliability for devices using liquid crystal media. In particular, this medium can maintain its functional properties over a moderately wide temperature range, and even at high temperatures. This is especially advantageous for use in window elements to control the transmission of sunlight, particularly when the window element is exposed to direct or prolonged sunlight. Furthermore, the high transparency point contributes to a good degree of order in the liquid crystal host molecules, and consequently the dichroic dye guest molecules, at typical operating temperatures, improving the contrast between switching states.

[0392] The transparency point, particularly the phase transition temperature between the nematic and isotropic phases, can be measured and determined by known methods such as a Mettler oven, a hot stage under a polarizing microscope, or differential scanning calorimetry (DSC). According to the present invention, the transparency point is preferably measured using a Mettler oven.

[0393] The nematic phase of the medium according to the present invention preferably spans a range from at least -10°C to 80°C or higher. A wider nematic phase range is more preferable, particularly a range up to 90°C or higher, more preferably a range from at least -20°C to 100°C or higher, and particularly preferably a range from 30°C to 110°C or higher.

[0394] In a preferred embodiment of the present invention, the birefringence (Δn) of the liquid crystal medium is in the range of 0.010 to 0.350, more preferably in the range of 0.035 to 0.300, even more preferably in the range of 0.050 to 0.250, even more preferably in the range of 0.075 to 0.200, and particularly preferably in the range of 0.010 to 0.150.

[0395] Compounds selected from the above and the group of compounds of formula I below are present in the mesogenic medium in a proportion preferably of 0.01% to 15% by weight, more preferably 0.025% to 10% by weight, even more preferably 0.05% to 7.5% by weight, even more preferably 0.1% to 5% by weight, and particularly 0.2% to 2% by weight. In certain embodiments, the dye compounds of the present invention are present in the medium at a concentration in the range of 0.05% to 1% by weight.

[0396] In embodiments in which two or more compounds selected from the group of compounds of formula I described above and below are present in the mesogenic medium, the total concentration of these compounds in the medium is particularly preferably in the range of 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, and especially 0.2% to 5% by weight. In this case, it is particularly preferable that the individual dye compounds are present in the medium at a concentration in the range of 0.025% to 5% by weight, more preferably 0.05% to 2.5% by weight, and especially 0.1% to 1% by weight.

[0397] The medium preferably comprises one, two, three, four, five, six, seven, eight, or nine compounds of formula I according to the present invention. In a particular embodiment, the medium comprises at least three compounds selected from the group of compounds of formula I-1 and I-2.

[0398] The LC medium according to the present invention is preferably a nematic liquid crystal.

[0399] The medium according to the present invention is prepared by conventional methods. Generally, the components are preferably heated to dissolve each other. Mixing is preferably carried out under an inert gas, for example, nitrogen or argon. Subsequently, one or more dyes of formula I and any further dichroic dyes are added, preferably heated to above 40°C, more preferably above 50°C. Generally, a desired amount of the component to be used in smaller quantities is dissolved in the components constituting the main component. It is also possible to mix solutions of the components in an organic solvent, for example, acetone, toluene, chloroform or methanol, and then remove the solvent again after mixing, for example by distillation. The present invention further relates to a method for preparing the LC medium according to the present invention.

[0400] The present invention further relates to a method for producing a mesogenic medium according to the present invention.

[0401] The present invention further relates to the use of a liquid crystal medium comprising at least one compound of formula I in a guest-host type liquid crystal device (particularly a window component or display). In the device, the compounds and medium according to the present invention are preferably provided in one or more switching layers.

[0402] In a preferred embodiment, the device, in particular the window, includes only a single switching layer.

[0403] The present invention further relates to a guest-host type liquid crystal display comprising a liquid crystal medium containing at least one compound of formula I.

[0404] The present invention further relates to the use of a mixture comprising a liquid crystal medium and at least one compound of formula I in a device for controlling the passage of energy from an external space to an internal space.

[0405] In certain embodiments, the device according to the present invention preferably includes one or more compounds selected from the compounds of formula I, preferably a liquid crystal medium, as well as further dichroic dyes having a structure different from that of formula I in the switching layer. Particularly preferably, it includes one, two, three, four, five, six, seven, or eight further dyes having a structure different from that of formula I, and most preferably two or three further dyes.

[0406] Regarding the dichroic properties, the preferred properties described for the compound of formula I are also preferred for any further dichroic dyes.

[0407] The absorption spectra of the dichroic dyes in the switching layer(s) preferably complement each other so that they appear black, gray, or colorless. The two or more dichroic dyes in the liquid crystal medium according to the present invention preferably cover most of the visible spectrum, and more preferably cover the entire visible spectrum. Precise methods for preparing dye mixtures that appear black or gray are known in the art and are described, for example, in M. Richter's "Introduction to Colorimetry," 2nd edition (1981, ISBN 3 11-008209-8, Walter de Gruyter & Co.).

[0408] The setting of color positions in pigment mixtures is explained in the field of colorimetry. For this purpose, the spectra of individual pigments are calculated considering the Lambert-Beer law, and the overall spectrum is determined. Then, according to the rules of colorimetry, this is converted into color positions and luminance values ​​under corresponding illumination conditions, such as a D65 daylight source. The position of the white point is determined by each light source (e.g., D65) and is shown, for example, in the table in the references above. By changing the proportions of the various pigments, different color positions can be set.

[0409] According to a preferred embodiment, the switching layer includes one or more dichroic dyes that absorb light in the red and near-infrared regions, i.e., wavelengths of 600 nm to 2000 nm, preferably in the range of 600 nm to 1800 nm, and particularly preferably in the range of 650 nm to 1300 nm.

[0410] In preferred embodiments, the mesogenic medium further contains at least one dichroic dye in addition to the compound of formula I. Preferably, these additional one or more dichroic dyes are selected from azo dyes, anthraquinones, methine compounds, azomethine compounds, merocyanine compounds, naphthoquinones, tetrazine, perylene, terylene, quaterylene, higher rylene, pyromethene, thiadiazole, benzothiadiazole, nickeldithiolene, (metallic)phthalocyanine, (metallic)naphthalocyanine, and (metallic)porphyrin. Of these, azo dyes, thiadiazole, and benzothiadiazole are particularly preferred.

[0411] Further dichroic dyes having a structure different from formula I of the switch layer are preferably selected from the dyes shown in Chapter 11.2.1 of Liquid Crystals—Applications and Uses, Vol. 3, 1992, World Scientific Publishing, by B. Bahadur, and particularly preferably from the explicit compounds given in the table present herein.

[0412] The aforementioned dyes belong to the dichroic dyes known in the prior art and described in the literature. For example, anthraquinone dyes are described in European Patent No. 34832, European Patent No. 44893, European Patent No. 48583, European Patent No. 54217, European Patent No. 56492, European Patent No. 59036, British Patent No. 2065158, British Patent No. 2065695, British Patent No. 2081736, British Patent No. 2082196, and British Patent No. 2094822. The specifications, British Patent No. 2094825, Japanese Patent Publication No. 55-123673, German Patent No. 3017877, German Patent No. 3040102, German Patent No. 3115147, German Patent No. 3115762, German Patent No. 3150803 and German Patent No. 3201120 describe the naphthoquinone dye, and German Patent No. 3126108 and German Patent No. 3202761 describe the naphthoquinone dye. As described in the book, azo dyes are used in European Patent No. 43904, German Patent No. 3123519, International Publication No. 82 / 2054, British Patent No. 2079770, Japanese Unexamined Patent Publication No. 56-57850, Japanese Unexamined Patent Publication No. 56-104984, U.S. Patent No. 4308161, U.S. Patent No. 4308162, U.S. Patent No. 4340973, T. Uchida, C. Shishido, H. Seki and M. Wada Perylenes are described in: Mol.Cryst.Lig.Cryst. Vol. 39, pp. 39-52 (1977), and in: Jpn.J.Appl.Phys. Vol. 21, pp. 191-192 (1982) by H. Seki, C. Shishido, S. Yasui, and T. Uchida, and perylenes are described in: European Patent No. 60895, European Patent No. 68427, and International Publication No. 82 / 1191. Rylene dyes are described, for example, in: European Patent No. 2166040, U.S. Patent Application Publication No. 2011 / 0042651, European Patent No. 68427, European Patent No. 47027, European Patent No. 60895, German Patent No. 3110960, and European Patent No. 698649.

[0413] Examples of preferred additional dichroic dyes that may be present in the device's switch layer are shown below.

[0414] [Table 1]

[0415] [Table 2]

[0416] [Table 3]

[0417] [Table 4]

[0418] [Table 5]

[0419] [Table 6]

[0420] [Table 7]

[0421] In a particularly preferred embodiment, the mesogenic medium further comprises at least one compound selected from the group of compounds of the following formula.

[0422] [Table 8]

[0423] [Table 9]

[0424] [Table 10]

[0425] [Table 11]

[0426] In certain embodiments, the medium according to the present invention comprises one or more quencher compounds. This is preferable when the device according to the present invention comprises one or more fluorescent dyes in the switching layer.

[0427] Quencher compounds are compounds that quench fluorescence. Quencher compounds can absorb the electronic excitation energy of adjacent molecules in the switch layer, such as fluorescent dyes, and allow them to transition to the ongoing electronically excited state. As a result, the quenched fluorescent dye is converted back to its electronic ground state, thus preventing it from emitting fluorescence and subsequent reactions. The quencher compound itself returns to its ground state either through non-radioactive inactivation or by emitting light, allowing for further quenching.

[0428] Quencher compounds may have various functions in the medium and switch layer of the device according to the present invention. Firstly, quencher compounds can contribute to extending the lifetime of the dye system by deactivating the electronic excitation energy. Secondly, quencher compounds can eliminate additional coloring effects that may be aesthetically undesirable, such as coloring radiation in the internal space emitted from fluorescent dyes in the switch layer.

[0429] To achieve effective quenching, the quencher compound must be adapted to the dye system, particularly the dye with the longest wavelength absorption in the dye combination. Methods for doing this are known from the prior art.

[0430] Preferred quencher compounds are, for example, described in JRLakowicz, Principles of Fluorescence Spectroscopy, 3rd edition, 2010, ISBN 10:0-387-31278-1, Springer Science and Business Media, p. 279, Table 8.1. Further classes of compounds, such as so-called dark quenchers and black hole quenchers, are known in the art. Examples include azo dyes and aminoanthraquinones. Furthermore, the quencher compound used in the switch layer of the device according to the present invention may be a non-fluorescent dye, or a dye that fluoresces only in NIR.

[0431] In a preferred embodiment of the switch layer according to the present invention, the quencher compound of the present invention is optionally selected so as to suppress fluorescence in the visible portion of the spectrum.

[0432] Preferably, the device according to the present invention is suitable for controlling the passage of energy in the form of sunlight from the environment to the interior space. The energy passage controlled herein occurs from the environment, i.e., the external space, to the interior space.

[0433] In this specification, the interior space may be any desired space that is substantially sealed from the environment, such as a building, a vehicle, or a container.

[0434] Therefore, the present invention further relates to the use of a device that controls the passage of energy from an external space to an internal space.

[0435] However, for example, the device can also be used in aesthetic room design, such as for lighting and color effects. For example, door and wall elements containing the device according to the present invention in gray or color can be switched to transparent. The device may also further include a white or colored flat backlight modulated in a high-brightness or yellow flat backlight whose color is modulated using a blue guest-host display. If a glass substrate is used in the device, roughened or structured glass can be provided on one or both sides of the glass of the device according to the present invention for connection to lighting and / or to produce lighting effects.

[0436] Therefore, the liquid crystal medium according to the present invention is suitably used in building windows and automobiles, such as car sunroofs. In particular, this switchable optical device can be incorporated into building windows and facades. Furthermore, the device according to the present invention can also be applied to commercial vehicles, ships, trains, or airplanes.

[0437] In a further alternative use, the device could be used in protective goggles, visors, or sunglasses to control the incidence of light to the eyes, with one switch state maintaining low light incidence to the eyes and the other switch state reducing light incidence.

[0438] Preferably, the device according to the present invention is placed in an opening in a relatively large two-dimensional structure, where the two-dimensional structure itself allows only a small amount of energy to pass through or not at all, and the opening has a relatively high energy permeability. Preferably, the two-dimensional structure is a wall or another boundary of the internal space to the external space. More preferably, in the two-dimensional structure in which the device according to the present invention is placed, the two-dimensional structure covers an area of ​​at least the size of the opening, and particularly preferably at least twice the size.

[0439] Preferably, the device has a minimum of 0.05 m 2 Preferably at least 0.1 m 2 Particularly preferably at least 0.5 m 2And very preferably at least 1.0 m 2 It is characterized by having an area of ​​the following size. In the case of a window equipped with a device, the device area is preferably 0.1 m². 2 ~10m 2 , more comfortable 0.5m 2 ~5m 2 , especially 1m 2 ~3m 2 It is within the range.

[0440] Preferably, the device is housed in an opening having a relatively high energy transmittance as described above, within a building, container, vehicle, or other substantially enclosed space. The device can generally be used for any desired interior space, especially if it has a light-transmitting interface that allows external energy input in the form of light energy, where air exchange with the environment is limited. It is particularly preferable to use the device for interior spaces that receive strong solar radiation through light-transmitting regions, such as window regions.

[0441] The device according to the present invention is switchable. In this specification, "switch" is understood to mean a change in the passage of energy through the device. Preferably, the device according to the present invention is electrically switchable, for example, as described in International Publication No. 2009 / 141295 and International Publication No. 2014 / 090373.

[0442] However, the device according to the present invention may also be thermally switchable, for example, as described in International Publication No. 2010 / 118422. In this case, the switch preferably occurs by a transition from a nematic state to an isotropic state via a change in temperature of the switch layer containing the compound of formula I and a liquid crystal medium. In the nematic state, the molecules of the liquid crystal medium are in an oriented form, and so is the compound of formula I oriented parallel to the surface of the device by the action of an orientation layer. In the isotropic state, the molecules are in an unoriented form, and so is the compound of formula I. According to the principle that the dichroic compound has a higher or lower absorption coefficient depending on its orientation with respect to the plane of polarization of light, the difference in whether the dichroic compound of formula I is oriented or unoriented results in a difference in the light transmittance of the switch layer of the device according to the present invention.

[0443] If the device is electrically switchable, it preferably includes two or more electrodes positioned on either side of a switch layer. The electrodes preferably consist of ITO, or a thin, preferably transparent, metal and / or metal oxide layer, such as silver or FTO (fluorine-doped tin oxide), or an alternative material known in the prior art for this use. The electrodes preferably have electrical connections. The voltage is preferably provided by a battery, a rechargeable battery, or an external power supply.

[0444] When switching electrically, the switch operates due to the (re)orientation of the molecules in the liquid crystal medium caused by the application of voltage.

[0445] In one embodiment, the device switches from a high-absorption state, i.e., a state with low light transmittance that appears without voltage, to a lower-absorption state, i.e., a state with higher light transmittance. Preferably, the liquid crystal medium of the switching layer is nematic in both states. Preferably, the state without applied voltage is characterized in that the molecules of the liquid crystal medium and thus the molecules of the compound of formula I are oriented parallel to the switching layer surface. This is preferably achieved with a correspondingly selected orientation layer. Preferably, the state with applied voltage is characterized in that the molecules of the liquid crystal medium and thus the molecules of the compound of formula I are perpendicular to the switching layer surface.

[0446] In an embodiment that differs from the above-described embodiment, the device switches from a low-absorption state, i.e., a state with high light transmittance that appears without voltage, to a higher-absorption state, i.e., a state with lower light transmittance. Preferably, the liquid crystal medium of the switch layer is nematic in both states. The state without applied voltage is preferably characterized in that the molecules of the liquid crystal medium of the switch layer and thus the molecules of the compound of formula I are oriented perpendicular to the switch layer surface. This is preferably achieved with a correspondingly selected orientation layer. The state with applied voltage is preferably characterized in that the molecules of the liquid crystal medium of the switch layer and thus the molecules of the compound of formula I are parallel to the switch layer surface.

[0447] The device according to the present invention preferably has the following layer order, and further layers may be present. The layers shown below are preferably directly adjacent to each other in the device: • Substrate layer, preferably glass or polymer • A conductive layer, preferably containing ITO. • Oriented layer • Switch layer containing one or more compounds of formula I • Oriented layer • A conductive layer, preferably containing ITO. • A substrate layer, preferably glass or polymer, is included.

[0448] In another embodiment, the device includes two switching layers, which may be arranged in a so-called double cell.

[0449] The device according to the present invention preferably includes one or more, and more preferably two, orientation layers. The orientation layers are preferably directly adjacent to both sides of the switch layer containing the compound of formula I.

[0450] The orientation layer used in the device according to the present invention can be any layer known to those skilled in the art. Preferably, it is a polyimide layer, and particularly preferably a layer comprising rubbed polyimide. In one embodiment, a planar orientation is provided, more preferably with a small pretilt angle. In another embodiment, a homeotropic orientation is provided, more preferably with a high pretilt angle.

[0451] Furthermore, by using a polymer obtained by a polarized exposure process as an alignment layer, the compounds in the liquid crystal medium can be aligned along the alignment axis (i.e., photo-aligned).

[0452] The switching layer in the device according to the present invention is more preferably positioned between or surrounded by two substrate layers. The substrate is preferably optically transparent. The substrate layer can be made of, for example, glass or polymer, preferably a light-transmitting polymer.

[0453] Suitable glass substrates include, for example, float glass, downdrawn glass, chemically or heat-treated tempered glass, borosilicate glass, and aluminosilicate glass.

[0454] Suitable polymer substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), polycarbonate (PC), polyimide (PI), COP (cyclic olefin polymer), and cellulose triacetate (TAC).

[0455] Two substrates are arranged as a cell, and a gap is formed between the two substrates. The size of the gap, i.e., the thickness of the switching layer, is preferably 1 μm to 100 μm, preferably 2 μm to 50 μm, more preferably 3 μm to 25 μm, and most preferably 5 μm to 10 μm. The cell is usually sealed by an adhesive layer located at or near its edge. In a preferred embodiment, the cell gap is 25 μm or less, preferably 10 μm or less, and more preferably 6 μm or less.

[0456] The device is preferably characterized by not including polymer-based polarizers, particularly preferably not including solid material phase polarizers, and very preferably not including any polarizers at all.

[0457] However, according to an alternative embodiment, the device may include one or more polarizing plates. In this case, the polarizing plates are preferably linear polarizing plates.

[0458] When only one polarizing plate is present, its absorption direction is preferably perpendicular to the molecular orientation axis of the liquid crystal medium of the device according to the present invention on the switch layer side where the polarizing plate is placed.

[0459] In the device according to the present invention, both absorbing and reflective polarizers can be used. It is preferable to use polarizers in the form of optical films. Examples of reflective polarizers that can be used in the device according to the present invention are DRPF (diffusive reflective polarizer film, 3M), DBEF (dual brightness enhanced film, 3M), DBR (layered-polymer distributed Bragg reflectors, as described in U.S. Patent No. 7,038,745 and U.S. Patent No. 6,099,758), and APF film (advanced polarizer film, 3M, see Technical Digest SID 2006, p. 45.1, U.S. Patent Application Publication No. 2011 / 0043732 and U.S. Patent No. 7,023602). Furthermore, it is possible to use wire-grid polarizers (WGP, wire-grid polarizers) that reflect infrared or VIS light. Examples of absorbing polarizers that can be used in the device according to the present invention are Itos XP38 polarizing film and Nitto Denko GU-1220DUN polarizing film. An example of a circular polarizer that can be used according to the present invention is the APNCP37-035-STD polarizer (American Polarizers). A further example is the CP42 polarizer (ITOS).

[0460] In a preferred embodiment, the device according to the present invention is a window component, more preferably a window component including at least one glass surface, and particularly preferably a component of an insulated glass unit.

[0461] In this context, a window preferably refers to a structure within a building that includes a frame and at least one glass pane enclosed by this frame. Preferably, it includes an insulating frame and two or more glass panes, i.e., double-glazed insulating glass.

[0462] In a preferred embodiment, the device according to the present invention is applied directly to the glass surface of a window, and particularly preferably to the gap between two glass panes of double-glazed insulated glass.

[0463] The present invention further relates to a window including a device according to the present invention, preferably having the above-described desirable features.

[0464] Due to the electronic properties of the compounds according to the present invention, these compounds are suitable not only for use as dyes but also as organic semiconductors.

[0465] Due to the electronic properties of the compounds according to the present invention, these compounds are suitable not only for use as dyes but also as organic semiconductors. Accordingly, the present invention further relates to the use of compounds of formula I in organic electronic components such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), printed circuits, radio frequency identification elements (RFIDs), lighting elements, photovoltaic devices, and light sensors.

[0466] Because of its excellent color development and solubility in organic materials, the compounds according to the present invention are very suitable as dyes.

[0467] Accordingly, the present invention also relates to the use of dyes of formula I for coloring polymers.

[0468] In the present invention and especially in the following examples, the structure of the mesogenic compound is indicated by an abbreviation, also called an initial letter. In these initial letters, 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 or C n H 2n-1 , Cm H 2m-1 and C l H 2l-1 Each represents a linear alkyl or alkenyl, preferably a 1E alkenyl, having n, m, and l carbon atoms, respectively. Table A lists the codes used for the ring elements of the compound's core structure, while Table B shows the linking groups. Table C gives the meaning of the codes for the left-terminal or right-terminal group. The acronym consists of the code for the ring element having any linking group, followed by a first hyphen and the code for the left-terminal group, and a second hyphen and the code for the right-terminal group. Table D shows exemplary structures of the compounds, each with their abbreviations.

[0469] [Table 12]

[0470] [Table 13]

[0471] [Table 14]

[0472] [Table 15]

[0473] [Table 16]

[0474] In the table, n and m represent integers, respectively, and the three dots "..." are placeholders for other abbreviations from this table.

[0475] The following table shows example structures, each with its abbreviation. These are provided to explain the meaning of the abbreviation rules. They also represent compounds that are preferably used.

[0476] Table 17

[0477] Table 18

[0478] Table 19

[0479] Table 20

[0480] Table 21

[0481] Table 22

[0482] Table 23

[0483] Table 24

[0484] Table 25

[0485] Table 26

[0486] Table 27

[0487] Table 28

[0488] Table 29

[0489] Table 30

[0490] Table 31

[0491] Table 32

[0492] Table 33

[0493] Table 34

[0494] Table 35

[0495] Table 36

[0496] Table 37

[0497] [Table 38]

[0498] [Table 39]

[0499] [Table 40]

[0500] [Table 41]

[0501] [Table 42]

[0502] [Table 43]

[0503] In the table, n, m, and l preferably represent 1 to 7 independently of each other.

[0504] The following table, Table E, shows exemplary compounds that can be optionally used as stabilizers in the mesogenic medium according to the present invention.

[0505] Table E shows stabilizers that may be added to the LC medium according to the present invention. In the formula, n represents an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7, or 8.

[0506] [Table 44]

[0507] [Table 45]

[0508] [Table 46]

[0509] [Table 47]

[0510] [Table 48]

[0511] [Table 49]

[0512] [Table 50]

[0513] The LC medium preferably contains 0 to 10% by weight of a stabilizer, particularly 1 ppm to 5% by weight, and especially preferably 1 ppm to 1% by weight.

[0514] Table F below shows exemplary compounds that can be preferably used as chiral dopants in the mesogenic medium according to the present invention.

[0515] [Table 51]

[0516] [Table 52]

[0517] [Table 53]

[0518] [Table 54]

[0519] In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group of compounds in Table F.

[0520] The mesogenic medium according to the present invention preferably comprises two or more compounds selected from the group consisting of compounds from Tables D, E, and F above, more preferably four or more compounds.

[0521] The liquid crystal medium according to the present invention preferably comprises seven or more individual compounds selected from the group of compounds from Table D, and three or more different formulas selected from the formulas shown in Table D, particularly preferably four or more.

[0522] Furthermore, the LC medium according to the present invention may also include compounds in which, for example, H, C, N, O, Cl, or F are replaced with corresponding isotopes.

[0523] All percentage data and volume ratios presented herein are weight percentages unless explicitly stated otherwise.

[0524] Unless explicitly stated in each case, all physical properties are determined according to "Merck Liquid Crystals, Physical Properties of Liquid Crystals," published November 1997, Merck, Germany, at a temperature of 20°C. The value of Δn is determined at 589 nm, and the value of Δε is determined at 1 kHz. In each case, ne and no are the refractive indices of the extraordinary and ordinary rays under the conditions shown above.

[0525] The degree of anisotropy R is determined at the maximum wavelength of the absorption band of the dye under consideration in each case, using the values ​​of the extinction coefficient E(p) (extinction coefficient of the mixture when the molecular orientation is parallel to the polarization direction of light) and the extinction coefficient E(s) (extinction coefficient of the mixture when the molecular orientation is perpendicular to the polarization direction of light). If there are multiple absorption bands for the dye, typically the strongest absorption band is selected. The molecular orientation of the mixture is achieved with an alignment film as known in the prior art. To eliminate the influence of the liquid crystal medium and other absorption or reflections, measurements are performed on the same mixture without each dye, and the obtained values ​​are subtracted.

[0526] Measurements are performed using linearly polarized light, where the vibration direction is either parallel to the orientation direction (definition of E(p)) or perpendicular to it (definition of E(s)). This can be achieved by rotating the polarizer relative to the device to achieve two different polarization directions using a linear polarizer. Therefore, the polarization direction of the incident polarization is rotated to measure E(p) and E(s).

[0527] From the values ​​obtained for E(p) and E(s), the anisotropy R is calculated according to the following formula, particularly as shown in "Polarized Light in Optics and Spectroscopy" by DSKliger et al., published by Academic Press in 1990. A detailed explanation of the method for determining the anisotropy of liquid crystal media containing dichroic dyes is also given in Chapter 11.4.2 of Liquid Crystals—Applications and Uses, Vol. 3, 1992, World Scientific Publishing.

[0528]

number

[0529] Isotropic absorbance E iso It is calculated from the values ​​obtained as a result of E(s) and E(p) according to the following formula.

[0530]

number

[0531] Isotropic absorption coefficient (here, ε iso It is denoted as follows. ) is calculated according to the following formula.

[0532]

number

[0533] In the formula, c is the dye concentration (in particular, given in weight %), and d is the measured thickness of the guest-host medium layer (in particular, given in cm).

[0534] The following examples are illustrative of the present invention and do not limit its scope in any way. These examples and their modifications, or other equivalents, will be obvious to those skilled in the art in view of this disclosure. [Examples]

[0535] In the example, V0 represents the capacitance threshold voltage [V] at 20°C. n e This represents the anomalous refractive index at 20°C and 589nm. n o This represents the normal refractive index at 20°C and 589nm. Δn represents the optical anisotropy at 20°C and 589 nm. ε ∥ This represents the dielectric constant parallel to the director at 20°C and 1kHz. ε ⊥ This represents the dielectric constant perpendicular 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°C, and is determined by the rotational method in a magnetic field. K1 is the elastic constant at 20°C, the "spray" deformation [pN], K2 is the elastic constant at 20°C, the "twist" deformation [pN], K3 is the elastic constant at 20°C, and the "bend" deformation [pN].

[0536] In this invention, the term "threshold voltage" refers to the capacitance threshold (V0) unless otherwise specified. In the example, as is commonly done, the optical threshold is 10% relative contrast (V0). 10 ) will also be shown.

[0537] <Example of synthesis>

[0538] <Synthesis Example 1> Preparation of Compound 1

[0539] [ka]

[0540] <Process 1>

[0541] [ka]

[0542] 4,5-bis(2-ethylhexyl)-dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dipyrrole can be obtained by the method described by Chung, Chin-Lung et al., Organic Electronics 2018, Vol. 18, pp. 6-16. At room temperature, 0.60 g, 1.20 mmol of 4,5-bis(2-ethylhexyl)-dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dipyrrole is added with stirring to a solution of 0.36 g, 2.40 mmol of heptanoyl chloride in 6 mL of dichloromethane. After stirring at this temperature for 18 hours, the resulting red solution is carefully added to a cooled 2N HCl solution and extracted with dichloromethane. The combined organic phase is dried over sodium sulfate. Finally, it is purified by column chromatography (silica gel; heptane / DCM: 9 / 1) to obtain the ketone body as a red oily substance. EI-MS: m / z: 610.3.

[0543] <Process 2>

[0544] [ka]

[0545] A 10 mL solution of N-bromosuccinimide (0.28 g, 1.57 mmol) in THF is added dropwise to a 10 mL solution of the ketone (1.00 g, 1.64 mmol) obtained in step 1 in THF, under light-shielding conditions at 0°C. The resulting solution is heated to room temperature and stirred at this temperature for a further 2 hours. The solution is purified by column chromatography (silica gel; heptane / DCM: 9 / 1) to obtain the bromide ketone product as a red solid. This compound is used directly in the next step without further purification.

[0546] <Process 3>

[0547] [ka]

[0548] N,N,-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboran-2-yl)aniline is available according to Chung, Bures et al., Sci. Pap. Univ. Pardubice, Series A 2014, Vol. 20, pp. 247-259. Pd(OAc)2 (18.4 mg, 0.08 mmol), Sphos (69.4 mg, 0.16 mmol), the bromine ketone body obtained in step 2 (1.13 g, 1.64 mmol), K3PO4 (1.05 g, 4.94 mmol), and N,N,-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboran-2-yl)aniline (1.03 g, 2.46 mmol) are dissolved in THF (10 mL) and water (2 mL). The resulting mixture is heated to 65 °C and stirred at this temperature for 18 hours. The reaction mixture is extracted with dichloromethane. The combined organic phase is dried over MgSO4 and filtered. Finally, the mixture is purified by column chromatography (reverse phase; acetonitrile / THF) to obtain compound 1 as a red oily substance.

[0549] [Table 55]

[0550] APCI-MS:m / z:870.5.

[0551] Compound 1 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 750 (weight %·cm) -1 So, λ max It shows an absorption maximum at 470 nm.

[0552] <Synthesis Example 2> Preparation of Compound 2

[0553] [ka]

[0554] <Process 1>

[0555] [ka]

[0556] 4,5-Bis(2-ethylhexyl)-dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dipyrrole (1.00 g, 2.00 mmol) and 2-ethylhexyanoyl chloride (1.30 g, 7.99 mmol) are mixed in dichloromethane (10 mL), to which aluminum chloride (1.60 g, 12.03 mmol) is added with stirring at room temperature. After stirring at this temperature for 18 hours, the resulting red solution is carefully added to a cooled HCl (6N) solution and extracted with dichloromethane. The combined organic phase is dried over sodium sulfate. The ketone product is finally purified by column chromatography (silica gel; DCM) and recrystallization from DCM / MeOH:2 / 5 to obtain a red oily substance. APCI-MS: m / z: 625.3.

[0557] <Process 2>

[0558] [ka]

[0559] A 3 mL THF solution of N-bromosuccinimide (0.19 g, 1.12 mmol) is added dropwise to a 3 mL THF solution of the ketone body (0.70 g, 0.64 mmol) obtained in step 1, under light protection at 0°C. The resulting solution is heated to room temperature and stirred for a further 2 hours. The solution is purified by column chromatography (silica gel; DCM) to obtain the bromide ketone body as a red solid. This compound is used directly in the next step without further purification.

[0560] <Process 3>

[0561] [ka]

[0562] Pd(OAc)2 (11.5 mg, 0.05 mmol), SPhos (43.4 mg, 0.10 mmol), the bromide ketone body obtained in step 2 (0.85 g, 1.21 mmol, HPLC: 85%), K3PO4 (0.65 g, 3.09 mmol), and N,N,-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboran-2-yl)aniline (0.60 g, 1.55 mmol) are dissolved in THF (7 mL) and water (2 mL). The resulting mixture is heated to 65°C and stirred at this temperature for 3 days. The reaction mixture is extracted with dichloromethane. The combined organic phase is dried over MgSO4 and filtered. Compound 2 is obtained as a red oil by final purification by column chromatography (reverse phase, acetonitrile / THF).

[0563] [Table 56]

[0564] APCI-MS:m / z:884.5.

[0565] Compound 2 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 715 (weight %·cm) -1 So, λ max It shows an absorption maximum at 470 nm.

[0566] <Synthesis Example 3> Preparation of Compound 3

[0567] [ka]

[0568] Compound 1 (100 mg, 0.11 mmol) prepared in Synthesis Example 1, malononitrile (2.28 g, 34.45 mmol), and lithium bis(trimethyl)azanide (0.96 g, 5.58 mmol) are dissolved in 1,2-dichloroethane (3 mL) and stirred at 80°C for 18 hours. Water (100 mL) and DCM (100 mL) are added to the cooled reaction mixture. The mixture is separated, and the organic phase is washed several times with water. The solvent is removed, and the resulting solid is dissolved in DCM and precipitated by adding MeOH. Finally, the mixture is purified by column chromatography (silica gel; heptane / toluene: 1 / 1) to obtain compound 3 as a blue solid.

[0569] [Table 57]

[0570] APCI-MS:m / z:918.5.

[0571] Compound 3 has an isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 880 (weight %·cm) -1 So, λ max It shows an absorption maximum at 602 nm.

[0572] <Synthesis Example 4> Preparation of Compound 4

[0573] [ka]

[0574] <Process 1>

[0575] [ka]

[0576] To a solution of 4,5-bis(2-ethylhexyl)-dithieno[2,3-d:2',3'-d']thieno[3,2-b:4,5-b']dipyrrole (1.09 g, 2.18 mmol) in THF (15 mL), N-BuLi (1.38 mL, 2.21 mmol, 1.6 M hexane solution) is added dropwise while stirring at -78 °C. After stirring at this temperature for 1 hour, the resulting red solution is raised to room temperature and CO2 gas is passed through for 1 hour. HCl (2 M) and ethyl acetate are added. The organic phase is separated and dried over sodium sulfate. Finally, the solution is purified by recrystallization from n-heptane to obtain a red solid carboxylic acid product.

[0577] [Table 58]

[0578] EI-MS:m / z:542.4.

[0579] <Process 2>

[0580] [ka]

[0581] A solution of ({[3-(dimethylamino)propyl]imino}methylidene)(ethyl)amine (0.38 g, 2.45 mmol) in toluene (1 mL) is added dropwise at 0°C to a solution of the carboxylic acid product obtained in step 1 (1.10 g, 2.02 mmol) in toluene (5.5 mL). The resulting solution is warmed to room temperature and stirred at this temperature for a further 16 hours. Oxalic acid (53 mg, 0.40 mmol) is added and the mixture is stirred for 1 hour. Purification by column chromatography (silica gel; toluene) yields the carboxylate product as a red oily substance. This compound is used directly in the next step without further purification.

[0582] <Process 3>

[0583] [ka]

[0584] A 21 mL THF solution of N-bromosuccinimide (275 mg, 1.54 mmol) is added to a 72 mL THF solution of the carboxylate salt (1.00 g, 1.47 mmol) obtained in step 2, under light-shielding conditions at 0°C. The solution is stirred at this temperature for a further 30 minutes, and then heated to room temperature overnight. The solution is purified by column chromatography (silica gel; THF) to obtain the bromide carboxylate as a red solid (APCI-MS: m / z: 758.1). This compound is used directly in the next step without further purification.

[0585] <Step 4>

[0586] [ka]

[0587] A solution of N,N,-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxoboran-2-yl)aniline (0.68 g, 1.65 mmol) in toluene (6 mL) is slowly added to a mixture of toluene (11 mL), Pd2dba3 (5.1 mg, 0.01 mmol), P(o-tol)3 (6.8 mg, 0.02 mmol) in aqueous Na2CO3 solution (2.2 mL, 2 M), and the bromine carboxylate product obtained in step 3 (0.53 g, 0.56 mmol, HPLC: 80%). The resulting mixture was stirred at 100°C for 18 hours, then a mixture of Pd2dba3 (3.6 mg, 0.01 mmol), P(o-tol)3 (6.6 mg, 0.02 mmol), toluene (3 ml), and Na2CO3 aqueous solution (1.2 mL, 2 M) was added, and the resulting mixture was stirred further at 100°C for 18 hours. Water (30 mL) and MTBE (30 mL) were added to the cooled reaction mixture. The phases were separated, and the aqueous phase was extracted several times with MTBE. The combined organic phase was dried over sodium sulfate and filtered. Compound 4 was obtained as an orange solid by final purification by column chromatography (reverse phase; acetonitrile / THF) and recrystallization from heptane / toluene:2 / 1.

[0588] [Table 59]

[0589] APCI-MS:m / z:939.5.

[0590] Compound 4 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 695 (weight %·cm) -1 So, λ max An absorption maximum is observed at 485 nm. As shown below, the anisotropy R measured for host mixture H-1 is 0.70.

[0591] <Synthesis Examples 5, 6, 7, 8 and 9> Compounds 5, 6, 7, 8, and 9 were prepared in the same manner as in the above synthesis examples 1 to 4, and their physical properties were investigated.

[0592] <Compound 5>

[0593] [ka]

[0594] Compound 5 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 840 (weight %·cm) -1 So, λ max It shows an absorption maximum at 721 nm.

[0595] <Compound 6>

[0596] [ka]

[0597] Compound 6 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 675 (weight %·cm) -1 So, λ maxIt exhibits an absorption maximum at 473 nm. As shown below, the anisotropy R measured for host mixture H-1 is 0.71.

[0598] <Compound 7>

[0599] [ka]

[0600] Compound 7 has the isotropic extinction coefficient ε measured in host mixture H-1, as shown below. iso 685 (weight %·cm) -1 So, λ max It shows an absorption maximum at 598 nm.

[0601] <Compound 8>

[0602] [ka]

[0603] <Compound 9>

[0604] [ka]

[0605] <Examples of mixed mixtures and comparative mixed mixtures>

[0606] <Comparative mixture example 1> Liquid crystal host mixture H-1 has the composition and properties shown in the following table, and is prepared and characterized with respect to its general physical properties.

[0607] [Table 60]

[0608] Comparative mixture CM-1 is prepared by mixing 96.621% of mixture H-1 with the compound of the following formula:

[0609] 0.100% of the compound shown below (hereinafter referred to as ST-1),

[0610] [ka]

[0611] 0.100% of the compound shown below (hereinafter referred to as ST-2),

[0612] [ka]

[0613] 0.127% of the compound of formula R-5011 as listed in Table F above,

[0614] 0.476% of the following compound (hereinafter referred to as D-A1),

[0615] [ka]

[0616] 1.246% of the compound shown below (hereinafter referred to as D-A2), and

[0617] [ka]

[0618] The following compound (hereinafter referred to as D-A3) is present in a concentration of 1.330%.

[0619] [ka]

[0620] <Comparative mixture example 2> A liquid crystal host mixture H-2 was prepared, and its general physical properties were evaluated. Its composition and properties are shown in the table below.

[0621] [Table 61]

[0622] Comparative mixture CM-2 is prepared by mixing 90.68% of mixture H-2 with the compound of the following formula:

[0623] 0.10% of compound ST-1,

[0624] 1.05% of the following compound (hereinafter referred to as D-B1),

[0625] [ka]

[0626] 1.63% of the following compound (hereinafter referred to as D-B2),

[0627] [ka]

[0628] 2.10% of the following compound (hereinafter referred to as D-B3),

[0629] [ka]

[0630] 1.64% of the following compound (hereinafter referred to as D-B4),

[0631] [ka]

[0632] 0.60% of the compound shown below (hereinafter referred to as D-B5), and

[0633] [ka]

[0634] 2.20% of the following compound (hereinafter referred to as D-B6).

[0635] [ka]

[0636] Comparative mixture CM-2.1 is prepared by mixing 99.847% of mixture CM-2 and 0.153% of compound R-5011, as shown in Table F above.

[0637] Comparative mixture CM-2.2 is prepared by mixing 99.673% of mixture CM-2 and 0.327% of compound R-5011, as shown in Table F above.

[0638] <Comparative mixture example 3> Comparative mixture CM-3 is prepared by mixing 94.22% of mixture H-2, 0.10% of compound ST-1, 0.10% of compound ST-2, 0.83% of compound D-A1, 1.00% of compound D-A2, 1.57% of compound D-A3, and 2.18% of compound S-811 as described in Table F above.

[0639] <Comparative mixture example 4> Liquid crystal host mixture H-3 has the composition and properties shown in the following table, and is prepared and characterized with respect to its general physical properties.

[0640] [Table 62]

[0641] Liquid crystal reference mixture H-3.1 is prepared by mixing 99.97% of mixture H-3 and 0.03% of compound ST-1.

[0642] Comparative mixture CM-4 is prepared by mixing 90.128% of mixture H-3.1 with 1.160% of compound D-B1, 1.919% of compound D-B2, 1.800% of compound D-B3, 1.300% of compound DB-4, 0.730% of compound DB-5, 2.110% of compound DB-6, and 0.853% of the compound shown below.

[0643] [ka]

[0644] Comparative mixture CM-4.1 is prepared by mixing 99.236% of mixture CM-4 and 0.764% of compound S-811, as shown in Table F above.

[0645] Comparative mixture CM-4.2 is prepared by mixing 98.980% of mixture CM-4 and 1.020% of compound S-811, as shown in Table F above.

[0646] <Mixture example> The suitability of the dyes prepared in Synthesis Examples 1-7 for use in LC media and devices that control energy transfer was investigated.

[0647] <Mixture example 1> Mixture M-1 is prepared by adding 0.030% of compound ST-1, 0.050% of the compound of formula S-811 listed in Table F above, 0.213% of compound 1, 0.233% of compound 3, and 0.120% of compound 4 to the host mixture H-1 described above.

[0648] Mixture M-1 is packed into TN double cells. Each cell has a thickness of 25 μm and is equipped with a polyimide orientation film with a pre-tilt angle of 1°. Despite the relatively small amount of dichroic dye used, this electro-optic cell exhibits good contrast between the dark and light states.

[0649] <Mixture example 2> Mixture M-2 is prepared by adding 0.030% of compound ST-1, 0.050% of the compound of formula S-811 listed in Table F above, 1.122% of compound 2, 0.600% of compound 4, and 1.500% of compound 7 to the host mixture H-2 described above.

[0650] The mixture M-2 is packed into a 5 μm thick TN double cell, which is fitted with a polyimide orientation film with a pre-tilt angle of 1°. Despite the relatively thin cell thickness, this device exhibits good contrast between the dark and light states.

[0651] <Mixture example 3> Mixture M-3 is prepared by adding 0.030% of compound ST-1, 0.420% of compound 3, 0.097% of compound 4, 0.081% of compound 5, and 0.432% of compound 6 to the host mixture H-3 shown above.

[0652] Mixture M-3 is packed into a VA double cell. This cell has a crossed shape and each cell has a polyimide orientation film with a thickness of 15 μm and a pre-tilt angle of 89°. This electro-optic device exhibits good contrast between the dark and light states.

[0653] <Mixture example 4> Mixture M-4 is prepared by adding 0.030% of compound ST-1, 1.010% of the compound of formula S-811 listed in Table F, 1.070% of compound 1, 1.165% of compound 3, 0.299% of compound 4, and 0.250% of compound 5 to the host mixture H-3.

[0654] Mixture M-4 is packed into a VA single cell having a polyimide orientation layer with a twist angle of 240°, a thickness of 8 μm, and a pre-tilt angle of 85°. Despite being a single cell with a relatively thin switching layer, this device exhibits good contrast between the dark and light states.

[0655] <Mixture example 5> Mixture M-5 is prepared by adding 0.03% of compound ST-1, 2.50% of compound 1, 2.10% of compound 3, 0.57% of compound 4, and 0.48% of compound 5 to the host mixture H-3.

[0656] Mixture M-5 was packed into a single VA cell. This cell is non-twisted and features a 6 μm thick polyimide-oriented film with a pre-tilt angle of 89°. Despite being a single cell with a relatively thin switching layer, the device exhibits adequate contrast between the dark and light states.

[0657] <Mixture example 6> Mixture M-6 is prepared by adding 0.03% of compound ST-1, 1.34% of the compound of formula S-811 listed in Table F above, 2.50% of compound 1, 2.10% of compound 3, 0.57% of compound 4, and 0.48% of compound 5 to the host mixture H-3.

[0658] The mixture M-6 is packed into a VA single cell having a polyimide orientation film with a twist angle of 240°, a thickness of 6 μm, and a pre-tilt angle of 85°. Despite being a single cell with a relatively thin switching layer, this device exhibits good contrast between the dark and light states.

[0659] <Mixture example 7> Mixture M-7 is prepared by adding 0.76% of the compound of formula S-811, 2.05% of compound 1, 1.80% of compound 3, and 1.02% of compound 4 to the host mixture H-1 described above.

[0660] Mixture M-7 was packed into an STN cell having a polyimide orientation layer with a twist angle of 240°, a thickness of 6 μm, and a pre-tilt angle of 5°. Despite being a single cell with a relatively thin switching layer, this device exhibits good contrast between the dark and light states.

[0661] <Mixture example 8> Mixture M-8 is prepared by adding 0.38% of the compound of formula R-5011, 2.05% of compound 1, 1.80% of compound 3, and 1.02% of compound 4 to the host mixture H-1 described above.

[0662] Mixture M-8 was packed into a planar high-twist HTN cell having a polyimide orientation layer with a twist angle of 1080°, a thickness of 6 μm, and a pre-tilt angle of 1°. Despite being a single cell with a relatively thin switching layer, this device exhibits good contrast between the dark and light states.

[0663] <Mixture example 9> Mixture M-9 is prepared by adding 0.10% of compound ST-1, 0.10% of compound ST-2, 0.23% of the compound of formula R5011 listed in Table F, 0.90% of compound 2, 0.31% of compound 4, 0.27% of compound 5, 0.95% of compound 6, and 2.50% of compound 7 to the host mixture H-1.

[0664] Mixture M-9 was packed into a planar, highly twisted HTN cell having a polyimide-oriented film with a twist angle of 1080°, a thickness of 10 μm, and a pre-tilt angle of 1°. This device exhibits good contrast between the dark and light states.

[0665] <Mixture example 10> Mixture M-10 is prepared by adding 0.10% of compound ST-1, 0.90% of compound 1, 1.35% of compound 3, and 1.04% of compound 4 to the host mixture H-2 shown above.

[0666] Mixture M-10 was packed into a Heilmeyer cell (5 μm cell thickness, 1° pre-tilt polyimide oriented film) equipped with a linear polarizer. This device exhibits appropriate contrast between the dark and light states.

[0667] Compounds 1-9 and mixtures M-1-M-10 are very suitable for use in devices that regulate the passage of energy from an external space to an internal space, such as a window.

Claims

1. Compound of formula I. 【Chemistry 1】 (In the formula, R １ and R ２ They are the same or different, H, F, CN, N(R ｚ ) ２ , represents a linear alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, in addition to one or more non-adjacent CH groups. ２ The groups are arranged such that the O and / or S atoms are not directly bonded to each other, independently of each other, -C(R) ｚ ) = C(R ｚ )-, -C≡C-, 【Chemistry 2】 -N(R) ｚ ) may be replaced with -, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-, provided that one or more H atoms are also replaced with F, Cl, Br, I or CN. R ｚ represents, independently at each occurrence, H, halogen, a straight-chain alkyl having 1 to 12 C atoms, or a branched or cyclic alkyl having 3 to 12 C atoms, provided that in addition, one or more non-adjacent CH ２ groups may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- such that O and / or S atoms are not directly linked to each other, provided that in addition, one or more H atoms may be replaced by F or Cl, Q １ and Q ２ They are the same or different, single bond, -O-, -S-, -CF ２ O-, -OCF ２ -, -CF ２ -, -CF ２ CF ２ -, -CO-, -CR ｘ１ =CR ｘ２ -, -C≡C-, -NR ｘ１ -, -N=N-, or preferably an alicyclic or heterocyclic group having 4 to 25 ring atoms, which may include a fused ring, which is unsubstituted, monosubstituted or polysubstituted with L, Z １ and Z ２ They are the same or different, single bond, -O-, -S-, -C(O)-, -CR ｙ１ R ｙ２ -, -CF ２ O-, -OCF ２ -, -C(O)-O-, -OC(O)-, -OC(O)-O-, -OCH ２ -ien-CH ２ O-, -SCH ２ -ien-CH ２ S-, -CF ２ S-, -SCF ２ -, - (CH ２ ) ｎ１ -, -CF ２ CH ２ -ien-CH ２ CF ２ -, - (CF ２ ) ｎ１ -, -CR ｘ１ =CR ｘ２ -, -C≡C-, -CR ｘ１ =CR ｘ２ -CO-, -CO-CR ｘ１ =CR ｘ２ -, -CR ｘ１ =CR ｘ２ -COO-, -OCO-CR ｘ１ =CR ｘ２ - or -N=N- represents, R ｘ１ , R ｘ２ Each of these independently represents an alkyl group having H, F, Cl, CN, or 1 to 12 C atoms. R ｙ１ This represents an alkyl group having H or 1 to 12 C atoms. R ｙ２ This represents an alkyl group having 1 to 12 carbon atoms. n1 represents 1, 2, 3, or 4. A １ and A ２ represents an aromatic, heteroaromatic, alicyclic, or heterocyclic group having the same or different ring atoms, preferably 4 to 25 ring atoms, which may include a fused ring, which is unsubstituted, monosubstituted, or polysubstituted with L. L represents F, Cl, -CN, or a linear alkyl group having 1 to 25 carbon atoms, or a branched or cyclic alkyl group having 3 to 25 carbon atoms, provided that one or more non-adjacent CH groups are present. ２ The group may be replaced with -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- such that the O atoms and / or S atoms are not directly bonded to each other, provided that one or more H atoms are each replaced with F or Cl. D represents a donor group selected from heteroaromatic groups containing at least four fused rings, where each ring may be unsubstituted, monosubstituted, or polysubstituted with L. A represents an acceptor group, n represents 0, 1, 2 or 3, and o represents 0 or 1, However, the compound contains at least five rings.

2. The compound according to claim 1, wherein the acceptor group A is an electron-withdrawing group, and preferably an electron-deficient substructure lacking π electrons.

3. The compound according to claim 1 or 2, wherein the donor group D is a heteroacene having linearly condensed rings, wherein each ring may be unsubstituted, monosubstituted, or polysubstituted with L, where L is defined as described in claim 1.

4. A １ is an aryl or heteroaryl group, preferably 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene, thiazole-2,5-diyl, thiophene-2,5-diyl, thienothiophene-2,5-diyl, selenofen-2,5-diyl, thienopyrrole-2,5-diyl, dithienopyrrolediyl, dithienosilodiyl, cyclopentadithiophenediyl, pyridine-2,5-diyl, pyrimidinediyl, or pyridazinediyl, wherein one or more H atoms may be replaced by a group L as defined in claim 1, and / or Q １ and Z １ represents a single bond, and / or n represents 1 or 2, preferably 1, and / or o represents 0. The compound according to any one of claims 1 to 3.

5. The compound contains at least 500 (weight %·cm) －１ A compound according to any one of claims 1 to 4, having an isotropic extinction coefficient.

6. A mixture comprising two or more compounds as described in any one of claims 1 to 5.

7. Use of the compound according to any one of claims 1 to 5 in a liquid crystal medium.

8. A liquid crystal medium comprising one or more compounds according to any one of claims 1 to 5, and at least one additional mesogenic compound.

9. The liquid crystal medium according to claim 8, wherein the medium comprises one or more compounds selected from the group of compounds of formula II-1 and II-2. 【Transformation 3】 (In the formula, R ２ This represents an alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms, or an alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 carbon atoms, provided that one or more CH ２ The foundations are independent of each other, 【Chemistry 4】 It can be replaced with, 【Transformation 5】 And, L ２１ , L ２２ , L ２３ and L ２４ Each of these independently represents either H or F. L ２５ is H or CH ３ Represents, and X ２ (This represents a halogen, alkyl or alkoxy halogen having 1 to 3 carbon atoms, or an alkenyl or alkenyloxy halogen having 2 or 3 carbon atoms.)

10. The liquid crystal medium according to claim 8 or 9, wherein the medium comprises one or more compounds selected from the group of compounds of formula III and IV. 【Transformation 6】 (In the formula, R ３ , R ４ , R ５ and R ６ F and CF are independent of each other. ３ OCF ３ , represents a group selected from CN and a linear or branched alkyl or alkoxy having 1 to 15 carbon atoms or a linear or branched alkenyl having 2 to 15 carbon atoms, which is unsubstituted, CN or CF ３ It is monosubstituted or monosubstituted or polysubstituted with halogen, provided that there is one or more CH3s. ２ The groups can be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -OCOO- or -C≡C-, in each case independently of each other, so that the oxygen atoms are not directly bonded to one another. L １ , L ２ , L ３ , L ４ and L ５ (Each of these independently represents either H or F.)

11. The liquid crystal medium according to any one of claims 8 to 10, wherein the medium comprises one or more compounds selected from the group of compounds of formula CY, PY, and AC. 【Transformation 7】 (In the formula, a represents 0, 1, or 2, preferably 1 or 2. b represents 0 or 1, c represents 0, 1, or 2. d represents 0 or 1, 【Transformation 8】 This represents, 【Chemistry 9】 This represents, 【Chemistry 10】 This represents, R １ , R ２ , R ＡＣ１ , R ＡＣ２ Each of these is an alkyl group having 1 to 12 carbon atoms (with the addition that the oxygen atoms are not directly bonded to each other, and one or two non-adjacent CH groups). ２ The basis is, 【Chemistry 11】 -O-, -CH=CH-, -CO-, -OCO-, or -COO- may be substituted.), preferably representing an alkyl or alkoxy having 1 to 6 C atoms. Z ｘ 、Z ｙ and Z ＡＣ are each independently of the others, -CH ２ CH ２ -, -CH=CH-, -CF ２ O-, -OCF ２ -, -CH ２ O-, -OCH ２ -, -CO-O-, -O-CO-, -C ２ F ４ -, -CF=CF-, -CH=CH-CH ２ O- or a single bond, preferably a single bond, and L １～４ These are F, Cl, CN, and OCF, each independent of the others. ３ CF ３ ,CH ３ ,CH ２ F, CHF ２ (Preferably, it represents F.)

12. The liquid crystal medium according to any one of claims 8 to 11, further comprising one or more dichroic dyes different from the compound of formula I described in any one of claims 1 to 5.

13. The medium is, - One or more chiral compounds, preferably chiral compounds represented by the following formula, 【Chemistry 12】 More preferably, the R-stereoisomer of the chiral compound, and / or - One or more types of stabilizers, and / or - One or more polymerizable compounds, preferably one or more polymerizable mesogenic compounds A liquid crystal medium according to any one of claims 8 to 12, further comprising:

14. Use of a compound according to any one of claims 1 to 5 or a liquid crystal medium according to any one of claims 8 to 13 in an electro-optical display, a device for controlling the passage of energy from an external space to an internal space, an electrical semiconductor, an organic field-effect transistor, a printed circuit, a radio frequency identification element, an organic light-emitting diode, an illumination element, a photovoltaic device, a light sensor, an effect pigment, a decorative element, or a polymer coloring dye.

15. A device for regulating the passage of energy from an external space to an internal space, comprising a switching layer containing a liquid crystal medium as described in any one of claims 8 to 13.

16. A window including the device described in claim 15.

17. A method for preparing the compound of formula I described in claim 1, - A step of providing a compound of formula I-Br, 【Chemistry 13】 (In the formula, D, A, Z ２ A ２ Q ２ , R ２ (and o have the meanings described in claim 1.) and - A step of subjecting a compound of formula I-Br to a chemical reaction, preferably a cross-coupling reaction. A method that includes this.

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