Dichroic dye compound, liquid crystal composition, liquid crystal cell, and liquid crystal display device

Abstract

The present application relates to a dichroic dye compound represented by chemical formula 1, a liquid crystal composition, a liquid crystal cell, and a liquid crystal display device. Specifically, the dichroic dye compound includes a structure in which a thiophene ring and an X ring are condensed at a core and contains a non-aromatic functional group at a terminal, and the liquid crystal composition includes the dichroic dye compound and a liquid crystal material. In addition, the liquid crystal cell includes a first substrate, a liquid crystal layer, and a second substrate, wherein the liquid crystal layer contains the liquid crystal composition. The liquid crystal display device includes the liquid crystal cell.

Description

Dichroic dye compound, liquid crystal composition, liquid crystal cell and liquid crystal display device

[0001] The present application relates to a dichroic dye compound, a liquid crystal composition, a liquid crystal cell, and a liquid crystal display device.

[0002] This application claims the benefit of the filing date of Korean Patent Application No. 10-2024-0155273 filed with the Korean Intellectual Property Office on November 5, 2024, the contents of which are incorporated herein in their entirety.

[0003] Liquid crystals are used as dielectrics, particularly in display devices, whereby the optical properties of the material may be affected by the applied voltage. In a guest-host system, the liquid crystal medium comprises one or more dichroic dyes in addition to the liquid crystal. Due to a direct dependence on light absorption by the dye molecules, the transmittance of the dye-doped liquid crystal to light can be controlled when the dyes change their alignment with the liquid crystal.

[0004] In addition to use in liquid crystal displays, the above-described type of device is also used as a switching element to control the passage of light or energy. In devices for controlling the passage of energy from an external space to an internal space, a number of different technical solutions have been proposed. In one possible mode for the device, a liquid crystal medium combined with one or more of the aforementioned dichroic dyes can generally be used in the switching layers. By applying voltage, a change in the orientational alignment of the dichroic dye molecules can be achieved in these switching layers. Thus, a change in the transmittance of the switching layer can be obtained due to direction-dependent absorption.

[0005] Research is needed on dichroic dye compounds that offer advantages in terms of device performance and reliability, as well as compositions and media containing them.

[0006] The present application aims to provide a dichroic dye compound, a liquid crystal composition, a liquid crystal cell, and a liquid crystal display device.

[0007] One embodiment of the present application provides a dichroic dye compound represented by the following chemical formula 1.

[0008] [Chemical Formula 1]

[0009]

[0010] In the above chemical formula 1,

[0011] X is a substituted or unsubstituted pyrazine ring; a substituted or unsubstituted quinoxaline ring; or a substituted or unsubstituted pyrrolidine-2,5-dione ring, and

[0012] H1 and H2 are identical or different from each other and are each independently substituted or unsubstituted divalent heterocyclic rings, and

[0013] L1 and L2 are equal to or different from each other and are each independently directly coupled; -O-; -S-; -C(=O)-; -C(RR')-; -C(F2)O-; -OC(F2)-; -C(=O)O-; -OC(=O)-; -OC(H2)-; -C(H2)O-; -C(R)=C(R')-; -C≡C-; -C(R)=C(R')-C(=O)-; -C(=O)-C(R)=C(R')-; -C(R)=C(R')-C(=O)O-; or -OC(=O)-C(R)=C(R')- and,

[0014] R and R' are the same or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0015] Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkyl carbonyl group; a substituted or unsubstituted alkoxycarbonyl group; a substituted or unsubstituted alkylcarbonyloxy group; a substituted or unsubstituted alkoxycarbonyloxy group; a substituted or unsubstituted heterocycloalkyl group; or a combination thereof,

[0016] Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted alkoxy group, and Ra and Rb of -N(Ra)(Rb) combine with A1 or A2 to form a substituted or unsubstituted N-containing ring, and

[0017] A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent aryl groups; or are substituted or unsubstituted divalent heteroaryl groups, or each combine with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0018] In addition, another embodiment of the present application provides a liquid crystal composition comprising the dichroic dye compound and the liquid crystal material.

[0019] In addition, another embodiment of the present application provides a liquid crystal cell comprising a first substrate; a liquid crystal layer; and a second substrate, wherein the liquid crystal layer comprises the liquid crystal composition.

[0020] In addition, another embodiment of the present application provides a liquid crystal display device including the liquid crystal cell.

[0021] When a dichroic dye compound according to one embodiment of the present application is used in a liquid crystal composition, a liquid crystal composition with excellent performance, appearance, stability, and reliability can be provided even under demanding operating conditions such as increased temperature or direct and extended sunlight irradiation.

[0022] In addition, the composition containing the dichroic dye compound exhibits excellent solubility in a liquid crystal medium and can achieve a meaningful and effective dye concentration within the liquid crystal medium, which can favorably contribute to the contrast ratio and switching performance obtainable in a switchable device.

[0023] FIG. 1 is a diagram illustrating the structure of a liquid crystal cell according to one embodiment of the present application.

[0024] [Explanation of the symbol]

[0025] 10: First substrate

[0026] 20: Liquid crystal layer

[0027] 30: Second substrate

[0028] The present application will be described in more detail below.

[0029] In this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0030] Examples of substituents in this specification are described below, but are not limited thereto.

[0031] The term "substitution" above means that a hydrogen atom bonded to a carbon or nitrogen atom of a compound is replaced with another substituent, and the substitution site is not limited to the site where the hydrogen atom is substituted, that is, any site where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0032] In this specification, the term “substituted or unsubstituted” means one or more substituents selected from the group consisting of halogen groups; cyano groups; hydroxyl groups; oxygen (=O); amine groups; nitro groups; silyl groups; ester groups; -ORs; -SRs; alkyl groups; haloalkyl groups; alkenyl groups; alkynyl groups; cycloalkyl groups; aryl groups; and heterocyclic groups, or is substituted with a substituent in which two or more of the exemplified substituents are connected, or has no substituents, wherein Rs is an alkyl group, haloalkyl group, cycloalkyl group, aryl group, or heterocyclic group. In this specification, hydrogen includes all of hydrogen; deuterium; and tritium.

[0033] In this specification, the halogen group is fluorine, chlorine, bromine, or iodine.

[0034] In this specification, the amine group is -NR 101 R 102 It can be represented as, and R 101 and R 102 Each is independently hydrogen, deuterium, alkyl group, alkenyl group, aryl group, or heterocyclic group. The number of carbon atoms in the amine group is not particularly limited, but is preferably 0 to 30.

[0035] In this specification, the silyl group is -SiR 103 R 104 R 105 It can be represented as, and R 103 , R 104 and R 105 Each is independently hydrogen, deuterium, alkyl group, alkenyl group, aryl group, or heterocyclic group. Specific examples include, but are not limited to, trimethylsilyl group, triethylsilyl group, triphenylsilyl group, diphenylsilyl group.

[0036] In this specification, the ester group is -C(=O)OR 106 , or -OC(=O)R 106 Indicated as, and the above R 106is a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heterocyclic group. The number of carbon atoms in the ester group is not particularly limited, but is preferably 2 to 30. R 106 In the case of this substituted or unsubstituted alkyl group, the ester group may be referred to as an alkoxycarbonyl group.

[0037] In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc., but are not limited thereto.

[0038] In the present specification, the haloalkyl group is an alkyl group substituted with a halogen group, and may be a straight chain or a branched chain. The number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include CF3, C2F5, etc., but are not limited thereto.

[0039] In the present specification, the alkenyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30.

[0040] In the present specification, the alkynyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30.

[0041] In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 30 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, b(cyclohexyl), cycloheptyl, cyclooctyl, etc., but is not limited thereto.

[0042] In the present specification, the alkoxy group may be a straight chain, a branched chain, or a cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but it is preferred to have 1 to 30 carbon atoms. Specifically, it may be methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, etc., but is not limited thereto.

[0043] In the present specification, the aryl group is not particularly limited, but is preferably 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

[0044] When the above aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 6 to 30. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

[0045] When the above aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms be 10 to 30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, terphenyl group, pyrenyl group, fluorenyl group, etc., but is not limited thereto.

[0046] In this specification, the aryl group among the aryloxy groups is the same as the examples of aryl groups described above. Specifically, aryloxy groups include phenoxy groups, 1-biphenyloxy groups, etc., but are not limited thereto.

[0047] In the present specification, the heterocyclic group comprises one or more atoms that are not carbon, i.e., heteroatoms, and specifically, the heteroatoms may comprise one or more atoms selected from the group consisting of O, N, Se, S, etc. The number of carbon atoms is not particularly limited, but it is preferable that the number of carbon atoms is 2 to 30, and the heterocyclic group may be monocyclic or polycyclic. The heterocyclic group comprises a heterocycloalkyl group and a heteroaryl group, and the heterocycloalkyl group and the heteroaryl group may condense with additional rings such as cycloalkyl and aryl.

[0048] The above heterocycloalkyl group is one in which one or more carbon atoms of a cycloalkyl group are substituted with heteroatoms, examples of which include pyrrolidine, piperidine, oxirane, and oxetane groups, but are not limited thereto, and examples of heterocycloalkyl groups in which additional rings are condensed include indolin and tetrahydroquinoline groups, but are not limited thereto.

[0049] The above heteroaryl group is one in which one or more carbon atoms of an aryl group are substituted with heteroatoms, examples of which include, but are not limited to, thiophene groups, furan groups, pyrrole groups, imidazole groups, thiazole groups, oxazole groups, pyridine groups, pyrimidine groups, triazine groups, quinoline groups, indole groups, carbazole groups, selenophene groups, dihydrothienodioxine groups, thienopyrrole groups, thienothiazole groups, thienothiophene groups, benzodithiophene groups, etc.

[0050] In this specification, the alkyl carbonyl group is -C(=O)R 108 Indicated as, and R 108 is an alkyl group, and the description of the aforementioned alkyl group may apply.

[0051] In this specification, the alkoxycarbonyl group is -C(=O)R 109 Indicated as, and R 109 is an alkoxy group, and the description of the alkoxy group described above can be applied.

[0052] In this specification, the alkyl carbonyloxy group is -OC(=O)R 110 Indicated as, and R 110 is an alkyl group, and the description of the aforementioned alkyl group may apply.

[0053] In this specification, the alkoxycarbonyloxy group is -OC(=O)R 111 Indicated as, and R 111 is an alkoxy group, and the description of the alkoxy group described above can be applied.

[0054] In this specification, the examples of the aforementioned aryl group or heteroaryl group apply, except that the divalent aryl group or divalent heteroaryl group is a divalent group.

[0055] In this specification, the ring comprises a hydrocarbon ring, a heteroring, or a condensed ring thereof, and specifically comprises an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic heteroring, an aromatic heteroring, or a condensed ring thereof.

[0056] Except that the aliphatic hydrocarbon ring and the aromatic hydrocarbon ring are not monovalent, the examples of the aforementioned cycloalkyl group and aryl group apply.

[0057] The examples of the aforementioned heterocyclic rings apply to the aliphatic heterocyclic rings and aromatic heterocyclic rings, except that each is not monovalent.

[0058] In this specification, "adjacent" groups may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the atom on which the substituent is substituted, or another substituent substituted on the atom on which the substituent is substituted. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted on the same carbon in an aliphatic ring may be interpreted as adjacent groups.

[0059] In this specification, Cn (where n is an integer of 1 or more) means the number of carbon atoms. For example, it means 1 to 60 carbon atoms in C1 to C60.

[0060] dichroic dye compounds

[0061] One embodiment of the present application provides a dichroic dye compound represented by the following chemical formula 1.

[0062] [Chemical Formula 1]

[0063]

[0064] In the above chemical formula 1, the definition of each substituent is as described above.

[0065] The dichroic dye compound of the present application is characterized by being represented by the above chemical formula 1, specifically having a structure in which a thiophene ring and an X ring are condensed in the compound core portion, having non-aromatic functional groups in the terminal Q1 and Q2 structures, and having a structure of -A1(A2)-L1(L2)-H1(H2)- between the core and the terminals.

[0066] With such structural features, it is possible to synthesize a dichroic dye with a high absorption coefficient, thereby reducing the amount of dichroic dye used. Additionally, by forming a conjugation system centered on the core structure, compatibility and reliability in the liquid crystal structure can be enhanced, while simultaneously increasing the dichroic ratio, thus providing advantages in terms of performance, appearance, stability, and reliability even when used under demanding conditions.

[0067] To look more specifically, the function of the electron acceptor is maximized by including a ring condensed from a thiophene ring, a pyrazine ring, a quinoxaline ring, or a pyrrolidine-2,5-dione ring as a core structure.

[0068] Furthermore, heterocyclic groups (heteroaryls) are formed on both sides of the core structure as H1 and H2, acting as electron donors; this maximizes the ability to sufficiently transfer electrons to the electron acceptor in the core structure.

[0069] L1 and L2, which are structures connected to the above H1 and H2, are non-aromatic linkers, and through appropriate linkers, the degree of formation of a conjugated system centered on the core structure can be controlled, thereby determining the absorption wavelength of the dichroic dye and controlling the liquid crystal solubility and compatibility.

[0070] Finally, by including non-aromatic functional groups at the ends (Q1 and Q2), solubility in the liquid crystal medium can be increased. When the planarity of the dye itself increases due to the core structure and conjugated system, solubility in the liquid crystal medium decreases, and consequently, a problem of reduced compatibility may occur. However, as in the present invention, by introducing various alkyl chains as non-aromatic functional groups at the ends, solubility can be increased and a dye concentration with a significant effect can be achieved.

[0071] In one embodiment of the present application, X is a substituted or unsubstituted pyrazine ring; a substituted or unsubstituted quinoxaline ring; or a substituted or unsubstituted pyrrolidine-2,5-dione ring.

[0072] In one embodiment of the present application, X may be a substituted or unsubstituted pyrazine ring.

[0073] In one embodiment of the present application, X may be a substituted or unsubstituted quinoxaline ring. In this case, the position condensed with the thiophene ring may be a pyrazine ring among the quinoxaline rings.

[0074] In one embodiment of the present application, X may be a substituted or unsubstituted pyrrolidine-2,5-dione ring.

[0075] In one embodiment of the present application, the formula 1 may be represented by any one of the following formulas 1-1 to 1-3.

[0076] [Chemical Formula 1-1]

[0077]

[0078] [Chemical Formula 1-2]

[0079]

[0080] [Chemical Formula 1-3]

[0081]

[0082] In the above chemical formulas 1-1 to 1-3,

[0083] R1 to R4 are the same or different from one another and are each independently hydrogen; deuterium; halogen group; cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); haloalkyl group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; substituted or unsubstituted heteroaryl group; or a combination thereof,

[0084] Rd, Re and Rf are the same or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0085] R5 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0086] The definitions of the remaining substituents are the same as the definitions in Chemical Formula 1 above.

[0087] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; or a combination thereof.

[0088] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; or a combination thereof.

[0089] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C2 to C30 heteroaryl group; or a combination thereof.

[0090] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a combination thereof.

[0091] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a combination thereof.

[0092] In one embodiment of the present application, R1 to R4 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C6 to C30 aryl group; or a combination thereof.

[0093] In one embodiment of the present application, the R5 may be hydrogen; deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.

[0094] In one embodiment of the present application, the R5 may be hydrogen; deuterium; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C6 to C40 aryl group; or a substituted or unsubstituted C2 to C40 heteroaryl group.

[0095] In one embodiment of the present application, the R5 may be hydrogen; deuterium; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.

[0096] In one embodiment of the present application, the R5 may be hydrogen; deuterium; or a substituted or unsubstituted C1 to C60 alkyl group.

[0097] In one embodiment of the present application, the R5 may be hydrogen; deuterium; or a substituted or unsubstituted C1 to C30 alkyl group.

[0098] In one embodiment of the present application, the R5 may be hydrogen; deuterium; or a substituted or unsubstituted C1 to C20 alkyl group.

[0099] In one embodiment of the present application, H1 and H2 are the same or different from each other and are each independently substituted or unsubstituted divalent heterocyclic rings.

[0100] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently substituted or unsubstituted divalent heteroaryl groups.

[0101] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently substituted or unsubstituted divalent C2 to C60 heteroaryl groups.

[0102] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently substituted or unsubstituted divalent C2 to C40 heteroaryl groups.

[0103] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently substituted or unsubstituted divalent C2 to C30 heteroaryl groups.

[0104] In one embodiment of the present application, H1 and H2 are the same or different from each other and may each independently be a substituted or unsubstituted divalent thiophene group; a substituted or unsubstituted divalent furan group; a substituted or unsubstituted divalent pyrrole group; a substituted or unsubstituted divalent selenophene group; a substituted or unsubstituted dihydrothienodioxine group; a substituted or unsubstituted divalent thiazole group; a substituted or unsubstituted divalent thienopyrrole group; a substituted or unsubstituted divalent thienothiazole group; a substituted or unsubstituted divalent thienothiophene group; or a substituted or unsubstituted divalent benzodithiophene group.

[0105] In one embodiment of the present application, H1 and H2 are the same or different from each other and each independently comprises: a divalent thiophene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent furan group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent pyrrole group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent selenophene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent dihydrothienodioxine group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; and a divalent thiazole group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group. It may be a divalent thienopyrrole group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent thienothiazole group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; a divalent thienothiophene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; or a divalent benzodithiophene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group.

[0106] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently represented by any one of the following chemical formulas H-1 to H-4.

[0107] [Chemical Formula H-1]

[0108]

[0109] [Chemical Formula H-2]

[0110]

[0111] [Chemical Formula H-3]

[0112]

[0113] [Chemical Formula H-4]

[0114]

[0115] In the above chemical formulas H-1 to H-4,

[0116] Y1 and Y2 are the same or different from each other, and each is independently O; S; Se; or N(H19), and

[0117] W1 is N or C(H2O), and

[0118] H11 to H20 are the same or different from one another and are each independently hydrogen; deuterium; a halogen group; a cyano group; an ester group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,

[0119] * is the site that combines with another structure in the above chemical formula 1.

[0120] In one embodiment of the present application, Y1 and Y2 are the same or different from each other and are each independently O; S; Se; or N(H19), and H19 may be a substituted or unsubstituted alkyl group.

[0121] In one embodiment of the present application, W1 is N or C(H2O), and H2O may be hydrogen; a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

[0122] In one embodiment of the present application, H11 to H18 may be the same or different from one another and may each independently be hydrogen; a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

[0123] In one embodiment of the present application, H1 and H2 may be the same or different from each other and may each be independently selected from the following structures.

[0124]

[0125] In the above structure, H21 to H24 are the same or different from each other and each independently hydrogen; a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group, and * is a site that bonds with another structure in the above chemical formula 1.

[0126] In one embodiment of the present application, L1 and L2 are the same or different from each other and are each independently directly coupled; -O-; -S-; -C(=O)-; -C(RR')-; -C(F2)O-; -OC(F2)-; -C(=O)O-; -OC(=O)-; -OC(H2)-; -C(H2)O-; -C(R)=C(R')-; -C≡C-; -C(R)=C(R')-C(=O)-; -C(=O)-C(R)=C(R')-; -C(R)=C(R')-C(=O)O-; or -OC(=O)-C(R)=C(R')-.

[0127] In one embodiment of the present application, L1 and L2 may be the same or different from each other and may each independently be -O-; -S-; -C(=O)-; -C(=O)O-; -OC(=O)-; -OC(H2)-; -C(H2)O-; -C(R)=C(R')-; -C≡C-; -C(R)=C(R')-C(=O)-; or -C(=O)-C(R)=C(R')-.

[0128] In one embodiment of the present application, L1 and L2 may be directly coupled.

[0129] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkyl carbonyl group; a substituted or unsubstituted alkoxycarbonyl group; a substituted or unsubstituted alkylcarbonyloxy group; a substituted or unsubstituted alkoxycarbonyloxy group; a substituted or unsubstituted heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; Alternatively, it is a substituted or unsubstituted alkoxy group, or Ra and Rb of -N(Ra)(Rb) combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0130] In one embodiment of the present application, Ra and Rb of the -N(Ra)(Rb) may be one of the listed substituents, or may combine with A1 or A2 of Formula 1 to form a substituted or unsubstituted N-containing ring. When both Q1 and Q2 of Formula 1 are -N(Ra)(Rb), Q1 and Q2 may each independently combine with or not combine with A1 and A2.

[0131] In one embodiment of the present application, Q1 and Q2 do not include an aromatic structure. By not including an aromatic structure in Q1 and Q2, which are terminal structures in Formula 1, the effect of increasing solubility can be expected.

[0132] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; a substituted or unsubstituted C2 to C60 alkenyl group; a substituted or unsubstituted C2 to C60 alkynyl group; a substituted or unsubstituted C1 to C60 alkoxy group; a substituted or unsubstituted C1 to C60 alkyl carbonyl group; a substituted or unsubstituted C1 to C60 alkoxycarbonyl group; a substituted or unsubstituted C1 to C60 alkylcarbonyloxy group; a substituted or unsubstituted C1 to C60 alkoxycarbonyloxy group; a substituted or unsubstituted C2 to C60 heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; Deuterium; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C3 to C60 cycloalkyl group; or a substituted or unsubstituted C1 to C60 alkoxy group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0133] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; a substituted or unsubstituted C2 to C40 alkenyl group; a substituted or unsubstituted C2 to C40 alkynyl group; a substituted or unsubstituted C1 to C40 alkoxy group; a substituted or unsubstituted C1 to C40 alkyl carbonyl group; a substituted or unsubstituted C1 to C40 alkoxycarbonyl group; a substituted or unsubstituted C1 to C40 alkylcarbonyloxy group; a substituted or unsubstituted C1 to C40 alkoxycarbonyloxy group; a substituted or unsubstituted C2 to C40 heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; Deuterium; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C3 to C40 cycloalkyl group; or a substituted or unsubstituted C1 to C40 alkoxy group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0134] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C1 to C30 alkyl carbonyl group; a substituted or unsubstituted C1 to C30 alkoxycarbonyl group; a substituted or unsubstituted C1 to C30 alkylcarbonyloxy group; a substituted or unsubstituted C1 to C30 alkoxycarbonyloxy group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; Deuterium; a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; or a substituted or unsubstituted C1 to C30 alkoxy group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0135] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted C1 to C30 alkyl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C2 to C30 alkenyl group; a substituted or unsubstituted C2 to C30 alkynyl group; a substituted or unsubstituted C1 to C30 alkoxy group; a substituted or unsubstituted C1 to C30 alkyl carbonyl group; a substituted or unsubstituted C1 to C30 alkoxycarbonyl group; a substituted or unsubstituted C1 to C30 alkylcarbonyloxy group; a substituted or unsubstituted C1 to C30 alkoxycarbonyloxy group; a substituted or unsubstituted C2 to C30 heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; Deuterium; or a substituted or unsubstituted C1 to C30 alkyl group, or Ra and Rb of -N(Ra)(Rb) can combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0136] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); an alkyl group substituted or unsubstituted with a halogen group; a cycloalkyl group; an alkenyl group; an alkynyl group; an alkoxy group substituted or unsubstituted with a halogen group; an alkyl carbonyl group; an alkoxycarbonyl group; an alkyl carbonyloxy group; an alkoxycarbonyloxy group; a heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; an alkyl group substituted or unsubstituted with a halogen group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0137] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a C1 to C30 alkyl group substituted or unsubstituted with a halogen group; a C3 to C30 cycloalkyl group; a C2 to C30 alkenyl group; a C2 to C30 alkynyl group; a C1 to C30 alkoxy group substituted or unsubstituted with a halogen group; a C1 to C30 alkyl carbonyl group; a C1 to C30 alkoxycarbonyl group; a C1 to C30 alkylcarbonyloxy group; a C1 to C30 alkoxycarbonyloxy group; a C2 to C30 heterocycloalkyl group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; The alkyl group may be substituted or unsubstituted with a halogen group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0138] In one embodiment of the present application, Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a C1 to C30 alkyl group substituted or unsubstituted with a halogen group; a cyclohexyl group; an ethenyl group; an ethinyl group; a C1 to C30 alkoxy group substituted or unsubstituted with a halogen group; a C1 to C30 alkyl carbonyl group; a C1 to C30 alkoxycarbonyl group; a C1 to C30 alkylcarbonyloxy group; a C1 to C30 alkoxycarbonyloxy group; a morpholine group; a tetrahydropyran group; a dioxane group; a piperidine group; a piperazine group; or a combination thereof, and Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; The alkyl group may be substituted or unsubstituted with a halogen group, or Ra and Rb of -N(Ra)(Rb) may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0139] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent aryl groups; or substituted or unsubstituted divalent heteroaryl groups, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0140] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent C6 to C60 aryl groups; or substituted or unsubstituted divalent C2 to C60 heteroaryl groups, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0141] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent C6 to C40 aryl groups; or substituted or unsubstituted divalent C2 to C40 heteroaryl groups, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0142] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent C6 to C30 aryl groups; or substituted or unsubstituted divalent C2 to C30 heteroaryl groups, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0143] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently a substituted or unsubstituted divalent phenyl group; a substituted or unsubstituted divalent naphthyl group; a substituted or unsubstituted divalent fluorene group; a substituted or unsubstituted divalent thiophene group; or a substituted or unsubstituted divalent thienothiazole group, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0144] In one embodiment of the present application, A1 and A2 are the same or different from each other and are each independently a divalent phenyl group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, a haloalkyl group, a haloalkoxy group, and an alkoxy group; a divalent naphthyl group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, a haloalkyl group, and an alkoxy group; a divalent fluorene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, a haloalkyl group, and an alkoxy group; a divalent thiophene group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group; or a divalent thienothiazole group substituted or unsubstituted with a substituent selected from a halogen group, an alkyl group, and an alkoxy group, or are combined with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

[0145] In one embodiment of the present application, when Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form a substituted or unsubstituted N-containing ring.

[0146] In one embodiment of the present application, when Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form a substituted or unsubstituted N-containing C2 to C60 ring.

[0147] In one embodiment of the present application, when Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form a substituted or unsubstituted N-containing C2 to C40 ring.

[0148] In one embodiment of the present application, when Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form a substituted or unsubstituted N-containing C2 to C30 ring.

[0149] In one embodiment of the present application, where Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form a substituted or unsubstituted N-containing heterocycloalkyl and aryl condensation ring.

[0150] In one embodiment of the present application, when Q1 or Q2 is -N(Ra)(Rb), Ra and Rb may combine with A1 or A2 to form an N-containing heterocycloalkyl and aryl condensation ring that is substituted or unsubstituted with a substituent selected from a halogen group and an alkyl group.

[0151] For example, A1-Q1 and A2-Q2 of the above chemical formula 1 may include the following structures, and the following structures may be further substituted according to the definition above.

[0152]

[0153] In one embodiment of the present application, the formula 1 may be represented by any one of the following formulas 2 to 4.

[0154] [Chemical Formula 2]

[0155]

[0156] [Chemical Formula 3]

[0157]

[0158] [Chemical Formula 4]

[0159]

[0160] In the above chemical formulas 2 to 4,

[0161] Y3 and Y4 are equal to or different from each other, and each is independently O; S; Se; or N(R27), and

[0162] R1 to R4 are the same or different from one another and are each independently hydrogen; deuterium; halogen group; cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); haloalkyl group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; substituted or unsubstituted heteroaryl group; or a combination thereof,

[0163] Rd, Re and Rf are the same or different from each other, and each is independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0164] R5 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and

[0165] R21 to R27 are the same or different from one another, and each is independently hydrogen; deuterium; a halogen group; a cyano group; an ester group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted alkoxy group, and

[0166] a and b are each integers from 1 to 4, and when a and b are each 2 or greater, the substituents inside the parentheses are the same or different, and

[0167] The definitions of the remaining substituents are the same as the definitions in Chemical Formula 1 above.

[0168] In one embodiment of the present application, R21 to R27 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

[0169] In one embodiment of the present application, R21 to R27 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a substituted or unsubstituted C1 to C60 alkyl group; or a substituted or unsubstituted C1 to C60 alkoxy group.

[0170] In one embodiment of the present application, R21 to R27 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a substituted or unsubstituted C1 to C30 alkyl group; or a substituted or unsubstituted C1 to C30 alkoxy group.

[0171] In one embodiment of the present application, R21 to R27 may be the same or different from one another and may each independently be hydrogen; deuterium; a halogen group; a substituted or unsubstituted C1 to C15 alkyl group; or a substituted or unsubstituted C1 to C15 alkoxy group.

[0172] In one embodiment of the present application, the dichroic dye compound may be any one of the following compounds.

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189] The solubility of a dichroic dye compound in a liquid crystal according to one embodiment of the present application is 50 wt% or more. The upper limit of the solubility is not limited, but is, for example, 100 wt% or less.

[0190] A dichroic dye compound according to one embodiment of the present application has a maximum absorption wavelength within a wavelength range of 550 nm to 750 nm.

[0191] A dichroic dye compound according to one embodiment of the present application has a dichroic ratio (DR) of 8.0 or higher.

[0192] In the present application, the dichroic ratio (DR) is a factor capable of confirming anisotropy, wherein the peak absorbance (A) in the case parallel to the polarization direction with respect to polarized light, e.g., polarized UV. par Absorption (A) when ) is perpendicular to the polarization direction per Value divided by ) (A par / A per It means ).

[0193] A dichroic dye compound according to one embodiment of the present application can be used in a liquid crystal display device by dissolving it in a liquid crystal material.

[0194] Liquid crystal composition

[0195] One embodiment of the present application provides a liquid crystal composition comprising the aforementioned dichroic dye compound and liquid crystal material.

[0196] In one embodiment of the present application, the liquid crystal material is JNC 5011XX, etc., but is not limited thereto.

[0197] In one embodiment of the present application, the liquid crystal composition may additionally include additives commonly used in the art.

[0198] In one embodiment of the present application, the liquid crystal composition may further include a chiral agent.

[0199] In one embodiment of the present application, the chiral agent may enable the liquid crystal layer to achieve a twisted orientation state. The chiral agent is not particularly limited as long as it can induce the desired twisting without impairing liquid crystal properties (e.g., nematic regularity). The chiral agent for inducing twisting in a liquid crystal material includes chirality in its molecular structure.

[0200] In one embodiment of the present application, the chiral agent may be a compound having one or more asymmetric carbons; a compound having an asymmetric point on a heteroatom, such as a chiral amine or chiral sulfoxide; or a compound having an axially asymmetric, optically active site, such as a cumulene or binaphthol, but is not limited thereto.

[0201] In one embodiment of the present application, the chiral agent may be, for example, a low molecular weight compound with a molecular weight of 1,500 or less. As the chiral agent, commercially available chiral nematic liquid crystals may be used, for example, the chiral dopant liquid crystal S-811 commercially available from Merck or LC756 from BASF.

[0202] The application ratio of the chiral agent is selected to achieve a desired d / p ratio in the liquid crystal layer. Generally, the content (weight%) of the chiral agent can be calculated using the formula 100 / HTP (Helixcal Twisting Power) × Pitch (p) (nm). The HTP represents the twisting strength of the chiral agent. Referring to the above method, the content of the chiral agent can be determined by considering the desired pitch. In one example, the content of the chiral agent may be 0.5 to 10 parts by weight per 100 parts by weight of the liquid crystal material. Specifically, the content of the chiral agent may be 1 to 7 parts by weight, or 1 to 5 parts by weight, per 100 parts by weight of the liquid crystal material.

[0203] liquid crystal cell

[0204] Another embodiment of the present application provides a liquid crystal cell comprising a first substrate; a liquid crystal layer; and a second substrate, wherein the liquid crystal layer comprises the liquid crystal composition described above.

[0205] In one embodiment of the present application, the liquid crystal cell comprises a first substrate, a liquid crystal layer on one surface of the first substrate, and a second substrate on the surface opposite to the surface of the liquid crystal layer facing the first substrate.

[0206] Referring to FIG. 1, a liquid crystal cell according to one embodiment of the present application may include a structure stacked in the order of a first substrate (10); a liquid crystal layer (20); and a second substrate (30).

[0207] A liquid crystal cell according to one embodiment of the present application may include additional structures as needed in addition to the first substrate, the liquid crystal layer, and the second substrate. For example, the liquid crystal cell may further include an adhesive layer.

[0208] A liquid crystal cell according to one embodiment of the present application may utilize known techniques in addition to comprising a liquid crystal layer containing the liquid crystal composition described above.

[0209] In one embodiment of the present application, the first substrate and the second substrate are not particularly limited, but, for example, a glass film, a crystalline or amorphous silicon film, an inorganic film such as quartz or ITO (Indium Tin Oxide) film, or a polymer film may be used.

[0210] In one embodiment of the present application, the first substrate and the second substrate may be polymer films.

[0211] In one embodiment of the present application, the polymer film may be TAC (triacetyl cellulose); COP (cyclo olefin copolymer) such as norbornene derivatives; PMMA (poly(methyl methacrylate); PC (polycarbonate); PE (polyethylene); PP (polypropylene); PVA (polyvinyl alcohol); DAC (diacetyl cellulose); Pac (Polyacrylate); PES (poly ether sulfone); PEEK (polyetheretherketon); PEI (polyetherimide); PPS (polyphenylsulfone); PEN (polyethylenemaphthatlate); PET (polyethyleneterephtalate); PI (polyimide); PSF (polysulfone); PAR (polyarylate) or amorphous fluoropolymer, but is not limited thereto.

[0212] In one embodiment of the present application, the first substrate and the second substrate may, if necessary, include a coating layer of a silicon compound such as gold, silver, silicon dioxide or silicon monoxide, or a coating layer such as an anti-reflective layer.

[0213] In one embodiment of the present application, the thickness of the first substrate and the second substrate may each be about 10 μm to about 1,000 μm.

[0214] In one embodiment of the present application, the thickness of the first substrate and the second substrate may each be 20 μm or more, 40 μm or more, 60 μm or more, 80 μm or more, 100 μm or more, 120 μm or more, 140 μm or more, 160 μm or more, or 180 μm or more, and may be 900 μm or less, 800 μm or less, 700 μm or less, 600 μm or less, 500 μm or less, or 400 μm or less. When the thickness of the first substrate and the second substrate satisfies the above range, when manufacturing a transmittance variable device by bonding a liquid crystal cell with an outer substrate, appearance defects such as wrinkles can be reduced.

[0215] In one embodiment of the present application, the liquid crystal layer may be a GHLC layer (Guest host liquid crystal layer), but is not limited thereto.

[0216] In one embodiment of the present application, the thickness of the liquid crystal layer may be 0.01 μm to 30 μm, but is not particularly limited.

[0217] In one embodiment of the present application, the thickness of the liquid crystal layer may be 0.05 μm or more, 0.1 μm or more, 0.5 μm or more, 1 μm or more, 1.5 μm or more, 2 μm or more, 2.5 μm or more, 3 μm or more, 3.5 μm or more, 4 μm or more, 4.5 μm or more, 5 μm or more, 5.5 μm or more, 6 μm or more, 6.5 μm or more, 7 μm or more, 7.5 μm or more, or 8 μm or more, and may be 25 μm or less, 20 μm or less, or 15 μm or less.

[0218] In one embodiment of the present application, the liquid crystal layer may change its orientation state depending on the voltage applied to the liquid crystal cell. For example, when no voltage is applied to the liquid crystal cell, the liquid crystal layer may have a first orientation state, and when voltage is applied to the liquid crystal cell, the liquid crystal layer may have a second orientation state different from the first orientation state. The first orientation state and the second orientation state may each be selected from a horizontal orientation state, a vertical orientation state, a twist orientation state, an inclined orientation state, a hybrid orientation state, etc.

[0219] The above horizontal orientation state refers to a state in which the directors of the liquid crystal material within the liquid crystal layer are arranged approximately parallel to the plane of the liquid crystal layer. For example, the angle formed by the directors with respect to the plane of the liquid crystal layer may be approximately -10° to 10°, or -5° to 5°, or approximately 0°.

[0220] The above vertical orientation state is a state in which the directors of the liquid crystal material within the liquid crystal layer are arranged approximately perpendicularly to the plane of the liquid crystal layer, and for example, the angle formed by the directors with respect to the plane of the liquid crystal layer may be about 80° to 100°, or 85° to 95°, or about 90°.

[0221] The above twisted orientation state may refer to a helical structure in which the directioners of the liquid crystal material within the liquid crystal layer are twisted along a virtual helical axis to form layers. The above twisted orientation state can be implemented in a vertical, horizontal, or oblique orientation state; that is, the vertical twisted orientation mode is a state in which individual liquid crystal materials are vertically oriented and twisted along a helical axis to form layers, the horizontal twisted orientation mode is a state in which individual liquid crystal materials are horizontally oriented and twisted along a helical axis to form layers, and the oblique twisted orientation mode is a state in which individual liquid crystal compounds are obliquely oriented and twisted along a helical axis to form layers.

[0222] The above hybrid orientation state may refer to an orientation state in which the tilt angle, which is the angle formed by the directioner of the liquid crystal material within the liquid crystal layer with respect to the plane of the liquid crystal layer, gradually increases or decreases along the thickness direction of the liquid crystal layer.

[0223] Liquid crystal display

[0224] Another embodiment of the present application provides a liquid crystal display device comprising the liquid crystal cell described above.

[0225] In one embodiment of the present application, the liquid crystal display device may be applied to a lens, a vehicle sunroof, a smart window, etc.

[0226] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0227] <Core 중간체의 제조>

[0228] 1. Manufacture of Core 1

[0229] Core 1, a dichroic dye intermediate, was synthesized through the following reaction.

[0230] (1) Manufacture of Core 1-1

[0231]

[0232] 2,5-dibromo-3,4-dinitrothiophene (30.0 g, 90.0 mmol), potassium carbonate (125.0 g, 540.0 mmol), tetrahydrofuran (300 mL), and water (100 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclostriphenylphosphine palladium (0) (5.2 g, 4.50 mmol) was added. 2-thiophenvoronic acid (35.0 g, 270.0 mmol) was dissolved in tetrahydrofuran (15 mL) and slowly added dropwise to the reaction mixture, followed by stirring at 80°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, the tetrahydrofuran was removed, and the resulting solid was washed with water and filtered. The obtained solid was recrystallized with dichloromethane and ethanol to obtain Core 1-1 (30.0 g, yield 99%).

[0233] (2) Manufacture of Core 1-2

[0234]

[0235] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. To the obtained solid, a 39% glyoxal aqueous solution (4 mL, 35.5 mmol) and ethanol (50 mL) were added and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 1-2 (7.6 g, yield 85%).

[0236] (3) Manufacture of Core 1

[0237]

[0238] Core 1-2 (7.6 g, 25.3 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, then maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (9.0 g, 50.6 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 1 (9.9 g, yield 85%).

[0239] 2. Manufacture of Core 2

[0240] Core 2, a dichroic dye intermediate, was synthesized through the following reaction.

[0241] (1) Manufacture of Core 2-1

[0242]

[0243] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. 2,3-butenedione (3.1 g, 35.46 mmol) and ethanol (50 mL) were added to the obtained solid and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 2-1 (7.8 g, yield 80%).

[0244] (2) Manufacture of Core 2

[0245]

[0246] Core 2-1 (7.8 g, 23.7 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (8.4 g, 47.4 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 2 (9.2 g, yield 80%).

[0247] 3. Manufacturing of Core 3

[0248] Core 3, a dichroic dye intermediate, was synthesized through the following reaction.

[0249] (1) Manufacture of Core 3-1

[0250]

[0251] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. Hexenedione (4.0 g, 35.46 mmol) and ethanol (50 mL) were added to the obtained solid and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 3-1 (8.4 g, yield 80%).

[0252] (2) Manufacture of Core 3

[0253]

[0254] Core 3-1 (8.4 g, 23.6 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (8.4 g, 47.1 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 3 (9.1 g, yield 75%).

[0255] 4. Manufacturing of Core 4

[0256] Core 4, a dichroic dye intermediate, was synthesized through the following reaction.

[0257] (1) Manufacture of Core 4-1

[0258]

[0259] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. Glyoxylic acid (2.6 g, 35.46 mmol) and ethanol (50 mL) were added to the obtained solid and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 4-1 (7.1 g, yield 76%).

[0260] (2) Manufacture of Core 4-2

[0261]

[0262] Core 4-1 (7.1 g, 22.4 mmol), methyl iodide (3.8 g, 26.9 mmol), potassium carbonate (4.6 g, 33.7 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and hexane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Core 4-2 (6.1 g, yield 82%).

[0263] (3) Manufacture of Core 4

[0264]

[0265] Core 4-2 (6.1 g, 18.5 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, then maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (6.6 g, 36.9 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 4 (5.8 g, yield 64%).

[0266] 5. Manufacturing of Core 5

[0267] Core 5, a dichroic dye intermediate, was synthesized through the following reaction.

[0268] (1) Manufacture of Core 5-1

[0269]

[0270] Core 4-1 (7.1 g, 22.4 mmol), 2-bromobutane (9.2 g, 67.2 mmol), potassium carbonate (9.3 g, 67.2 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and hexane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Core 5-1 (5.8 g, yield 69%).

[0271] (2) Manufacture of Core 5

[0272]

[0273] Core 5-1 (5.8 g, 15.6 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (5.5 g, 31.1 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 5 (5.9 g, yield 71%).

[0274] 6. Manufacturing of Core 6

[0275] Core 6, a dichroic dye intermediate, was synthesized through the following reaction.

[0276] (1) Manufacture of Core 6-1

[0277]

[0278] Core 4-1 (10.0 g, 31.6 mmol), diisoprolyl ethylamine (6.1 g, 47.4 mmol), and chloroform (400 mL) were added to a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, then maintained at 0°C. While maintaining 0°C, trifluoromethanesulfonic anhydride (10.7 g, 37.9 mmol) was slowly added dropwise. After the dropwise addition was complete, the reaction was carried out at room temperature. Once the reaction was finished, the temperature was lowered to 0°C, water was added, and the mixture was stirred thoroughly at room temperature. After stirring, the substance was extracted using water and chloroform, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained product, Core 6-1 (14.0 g, yield 99%), was used in the next reaction immediately.

[0279] (2) Manufacture of Core 6-2

[0280]

[0281] Core 6-1 (14.0 g, 31.2 mmol), potassium carbonate (8.6 g, 62.4 mmol), tetrahydrofuran (30 mL), and acetonitrile (90 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred thoroughly. Phenol (3.5 g, 37.5 mmol) was added, and the reaction was carried out under reflux with increasing temperature and stirring. After the reaction was complete, the mixture was cooled to room temperature, and the resulting solid was washed with acetonitrile and filtered. The obtained solid was extracted using water and toluene, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was dissolved in tetrahydrofuran, acetonitrile was added to form a solid, and the resulting solution was filtered. The obtained solid was dried in an 80°C oven to obtain Core 6-2 (11.8 g, yield 96%).

[0282] (3) Manufacture of Core 6

[0283]

[0284] Core 6-2 (11.8 g, 30.1 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (10.7 g, 60.1 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 6 (13.9 g, yield 84%).

[0285] 7. Manufacturing of Core 7

[0286] Core 7, a dichroic dye intermediate, was synthesized through the following reaction.

[0287] (1) Manufacture of Core 7-1

[0288]

[0289] Core 6-1 (10.0 g, 22.3 mmol), potassium carbonate (6.2 g, 44.6 mmol), tetrahydrofuran (30 mL), and acetonitrile (90 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred thoroughly. Cyclohexylthiol (3.1 g, 26.8 mmol) was added, and the reaction was carried out under increasing reflux and stirring. After the reaction was complete, the mixture was cooled to room temperature, and the resulting solid was washed with acetonitrile and filtered. The obtained solid was extracted using water and toluene, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was dissolved in tetrahydrofuran, acetonitrile was added to form a solid, and the resulting solution was filtered. The obtained solid was dried in an 80°C oven to obtain Core 7-1 (8.8 g, yield 95%).

[0290] (2) Manufacture of Core 7

[0291]

[0292] Core 7-1 (8.8 g, 21.2 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (7.6 g, 42.4 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 7 (9.8 g, yield 81%).

[0293] 8. Manufacturing of Core 8

[0294] Core 8, a dichroic dye intermediate, was synthesized through the following reaction.

[0295] (1) Manufacture of Core 8-1

[0296]

[0297] Core 6-1 (10.0 g, 22.3 mmol), potassium carbonate (6.2 g, 44.6 mmol), tetrahydrofuran (30 mL), and acetonitrile (90 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred thoroughly. 4-methylbenzenethiol (3.3 g, 26.8 mmol) was added, and the reaction was carried out under increasing reflux and stirring. After the reaction was complete, the mixture was cooled to room temperature, and the resulting solid was washed with acetonitrile and filtered. The obtained solid was extracted using water and toluene, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was dissolved in tetrahydrofuran, acetonitrile was added to form a solid, and the resulting solution was filtered. The obtained solid was dried in an 80°C oven to obtain Core 8-1 (8.8 g, yield 93%).

[0298] (2) Manufacture of Core 8

[0299]

[0300] Core 8-1 (8.8 g, 20.8 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, then maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (7.4 g, 41.6 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 8 (10.0 g, yield 83%).

[0301] 9. Manufacturing of Core 9

[0302] Core 9, a dichroic dye intermediate, was synthesized through the following reaction.

[0303] (1) Manufacture of Core 9-1

[0304]

[0305] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. Benzyl (7.5 g, 35.46 mmol) and ethanol (50 mL) were added to the obtained solid and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 9-1 (11.7 g, yield 87%).

[0306] (2) Manufacture of Core 9

[0307]

[0308] Core 9-1 (11.7 g, 25.9 mmol) and tetrahydrofuran (400 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (9.2 g, 51.7 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (200 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 9 (14.1 g, yield 89%).

[0309] 10. Manufacture of Core 10

[0310] Core 10, a dichroic dye intermediate, was synthesized through the following reaction.

[0311] (1) Manufacture of Core 10-1

[0312]

[0313] Core 1-1 (10 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. To the obtained solid, o-quinone (3.8 g, 35.46 mmol) and dichloromethane (50 mL) were added, followed by the addition of 2 mL of acetic acid as a catalyst, and the mixture was stirred under reflux for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, ethanol (80 mL) was added, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 10-1 (3.6 g, yield 35%).

[0314] (2) Manufacture of Core 10

[0315]

[0316] Core 10-1 (3.6 g, 10.4 mmol) and tetrahydrofuran (200 mL) were placed in a 500 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (3.7 g, 20.7 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (100 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 10 (4.2 g, yield 80%).

[0317] 11. Manufacture of Core 11

[0318] Core 11, a dichroic dye intermediate, was synthesized through the following reaction.

[0319] (1) Manufacture of Core 11-1

[0320]

[0321] Under a nitrogen atmosphere, 4-thiophenedicarboxylic anhydride (10.0 g, 64.9 mmol) and tetrahydrofuran (50 mL) were placed in a 250 mL flask and stirred at 0°C. 2-normal methylamine tetrahydrofuran solution (65 mL, 130.0 mmol) was slowly added dropwise at 0°C. After the addition was complete, the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was washed with tetrahydrofuran and filtered, and the next reaction was immediately carried out. Potassium acetate (0.64 g, 6.5 mmol), acetic anhydride (20 mL), and acetic acid (60 mL) were added, and the mixture was heated under reflux and stirred for 12 hours. After the reaction was complete, the reaction mixture was placed in ice water and stirred. The resulting solid was washed with water and filtered. The obtained solid was dried in an 80℃ oven to obtain Core 11-1 (5.4 g, yield 50%).

[0322] (2) Manufacture of Core 11-2

[0323]

[0324] Under a nitrogen atmosphere, Core 11-1 (5.4 g, 32.3 mmol) was placed in a 250 mL flask containing a 1 / 3 volume ratio solution of sulfuric acid and trifluoroacetic acid (50 mL). After stirring until well dissolved, the mixture was maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (12.1 g, 67.8 mmol) was slowly added dropwise. Once the reaction was complete, the reaction mixture was placed in ice water to form a solid; the resulting solid was washed with water and filtered. The obtained solid was dried in an 80°C oven to obtain Core 11-2 (9.4 g, yield 90%).

[0325] (3) Manufacture of Core 11-3

[0326]

[0327] Core 11-2 (9.4 g, 28.9 mmol), potassium carbonate (24.0 g, 173.6 mmol), tetrahydrofuran (60 mL), and water (20 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (1.7 g, 1.4 mmol) was added. 2-Thiophenvoronic acid (11.1 g, 86.8 mmol) was dissolved in tetrahydrofuran (20 mL) and slowly added dropwise to the reaction mixture, followed by stirring at 80°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, the tetrahydrofuran was removed, and the resulting solid was washed with water and filtered. The obtained solid was recrystallized with dichloromethane and ethanol to obtain Core 11-3 (6.2 g, yield 65%).

[0328] (4) Manufacture of Core 11

[0329]

[0330] Core 11-3 (6.2 g, 18.8 mmol) and tetrahydrofuran (300 mL) were placed in a 500 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (6.7 g, 37.6 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (150 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 11 (6.9 g, yield 75%).

[0331] 12. Manufacture of Core 12

[0332] Core 12, a dichroic dye intermediate, was synthesized through the following reaction.

[0333] (1) Manufacture of Core 12-1

[0334]

[0335] Under a nitrogen atmosphere, 4-thiophenedicarboxylic anhydride (10.0 g, 64.9 mmol) and tetrahydrofuran (50 mL) were placed in a 250 mL flask and stirred at 0°C. 2,2,2-trifluoroethylamine (12.9 g, 130.0 mmol) was added to the tetrahydrofuran (50 mL) and slowly added dropwise at 0°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the mixture was washed with tetrahydrofuran and filtered, and the next reaction was immediately carried out. Potassium acetate (0.64 g, 6.5 mmol), acetic anhydride (20 mL), and acetic acid (60 mL) were added, and the mixture was heated under reflux and stirred for 12 hours. After the reaction was complete, the reaction mixture was placed in ice water and stirred. The resulting solid was washed with water and filtered. The obtained solid was dried in an 80℃ oven to obtain Core 12-1 (6.9 g, yield 45%).

[0336] (2) Manufacture of Core 12-2

[0337]

[0338] Under a nitrogen atmosphere, Core 12-1 (6.9 g, 29.3 mmol) was placed in a 250 mL flask containing a 1 / 3 volume ratio solution of sulfuric acid and trifluoroacetic acid (50 mL). After stirring until well dissolved, the mixture was maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (11.0 g, 61.6 mmol) was slowly added dropwise. Once the reaction was complete, the reaction mixture was placed in ice water to form a solid; the resulting solid was washed with water and filtered. The obtained solid was dried in an 80°C oven to obtain Core 12-2 (10.5 g, yield 91%).

[0339] (3) Manufacture of Core 12-3

[0340]

[0341] Core 12-2 (10.5 g, 26.7 mmol), potassium carbonate (22.2 g, 160.3 mmol), tetrahydrofuran (60 mL), and water (20 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (1.5 g, 1.3 mmol) was added. 2-thiophenvoronic acid (10.3 g, 80.2 mmol) was dissolved in tetrahydrofuran (20 mL) and slowly added dropwise to the reaction mixture, followed by stirring at 80°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature, the tetrahydrofuran was removed, and the resulting solid was washed with water and filtered. The obtained solid was recrystallized with dichloromethane and ethanol to obtain Core 12-3 (7.5 g, yield 70%).

[0342] (4) Manufacture of Core 12

[0343]

[0344] Core 12-3 (7.5 g, 18.8 mmol) and tetrahydrofuran (300 mL) were placed in a 500 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining the temperature at 0°C, N-bromosuccinimide (6.7 g, 37.6 mmol) was slowly added dropwise. Once the reaction was complete, the temperature was raised to room temperature, and ethanol (150 mL) was added to form a solid. The resulting solid was washed with ethanol and filtered. The obtained solid was dried in an 80°C oven to obtain Core 12 (7.6 g, yield 73%).

[0345] 13. Manufacture of Core 13

[0346] Core 13, a dichroic dye intermediate, was synthesized through the following reaction.

[0347] (1) Manufacture of Core 13

[0348]

[0349] Under a nitrogen atmosphere, 2,5-dibromo-3,4-dinitrothiophene (9.8 g, 29.6 mmol), tin(II) chloride dihydrate (46.7 g, 206.9 mmol), and ethanol (150 mL) were added to a 250 mL flask and stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature and stirred while adding a 15% sodium hydroxide solution to form a solid. The resulting solid was washed with water and filtered. Dimethyl oxalate (4.2 g, 35.5 mmol) and ethanol (50 mL) were added to the obtained solid and stirred under reflux for 1 hour. After the reaction was complete, the mixture was cooled to room temperature, the resulting solid was washed with ethanol, filtered, and dried in an 80°C oven to obtain Core 13 (4.4 g, yield 42%).

[0350] <Boronate 중간체의 제조>

[0351] 1. Preparation of Boronate 1

[0352] Boronate 1, a dichroic dye intermediate, was synthesized through the following reaction.

[0353] (1) Preparation of Boronate 1-1

[0354]

[0355] 4-bromo-3-methylphenol (10.0 g, 53.5 mmol), 1-bromo-2-ethylhexene (11.1 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with water and hexane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 1-1 (12.7 g, yield 79%).

[0356] (2) Preparation of Boronate 1

[0357]

[0358] Boronate 1-1 (12.7 g, 42.4 mmol), potassium acetate (12.3 g, 125.7 mmol), bis(pinacolato)diborone (11.7 g, 46.1 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 1 (14.5 g, yield 99%), was used in the next reaction.

[0359] 2. Preparation of Boronate 2

[0360] Boronate 2, a dichroic dye intermediate, was synthesized through the following reaction.

[0361] (1) Preparation of Boronate 2-1

[0362]

[0363] 4-bromo-3-fluorophenol (10.0 g, 52.4 mmol), 2-bromobutane (7.9 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and hexane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 2-1 (9.8 g, yield 76%).

[0364] (2) Preparation of Boronate 2

[0365]

[0366] Boronate 2-1 (9.8 g, 39.7 mmol), potassium acetate (11.7 g, 119.0 mmol), bis(pinacolato)diborone (11.1 g, 43.6 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 2 (10.9 g, yield 93%), was used in the next reaction.

[0367] 3. Preparation of Boronate 3

[0368] Boronate 3, a dichroic dye intermediate, was synthesized through the following reaction.

[0369] (1) Preparation of Boronate 3-1

[0370]

[0371] 4-bromo-3-fluorophenol (10.0 g, 52.4 mmol), 3-bromoheptane (10.3 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with water and hexane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 3-1 (7.9 g, yield 52%).

[0372] (2) Preparation of Boronate 3

[0373]

[0374] Boronate 3-1 (7.9 g, 27.3 mmol), potassium acetate (8.0 g, 82.0 mmol), bis(pinacolato)diborone (7.6 g, 30.0 mmol), and dioxene (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.60 g, 0.82 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 3 (8.8 g, yield 96%), was used in the next reaction.

[0375] 4. Preparation of Boronate 4

[0376] Boronate 4, a dichroic dye intermediate, was synthesized through the following reaction.

[0377] (1) Preparation of Boronate 4-1

[0378]

[0379] 4-bromo-3-fluoroaniline (13.3 g, 70 mmol), sodium triacetoxyborohydride (16.3 g, 77 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. 2-ethylhexanal (9.9 g, 77 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 4-1 (16.9 g, yield 80%).

[0380] (2) Preparation of Boronate 4

[0381]

[0382] Boronate 4-1 (16.9 g, 56 mmol), potassium acetate (16.5 g, 168 mmol), bis(pinacolato)diborone (15.6 g, 61.6 mmol), and dioxene (80 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.4 g, 1.9 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 4 (19.4 g, yield 99%), was used in the next reaction.

[0383] 5. Preparation of Boronate 5

[0384] Boronate 5, a dichroic dye intermediate, was synthesized through the following reaction.

[0385] (1) Preparation of Boronate 5

[0386]

[0387] Under a nitrogen atmosphere, 4-bromo-N,N-dibutylaniline (11.9 g, 41.9 mmol), potassium acetate (12.3 g, 125.7 mmol), bis(pinacolato)diborone (11.7 g, 46.1 mmol), and dioxene (50 mL) were placed in a 250 mL flask and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 5 (13.7 g, yield 99%), was used in the next reaction.

[0388] 6. Preparation of Boronate 6

[0389] Boronate 6, a dichroic dye intermediate, was synthesized through the following reaction.

[0390] (1) Preparation of Boronate 6-1

[0391]

[0392] m-toluidine (50 g, 466.6 mmol), sodium triacetoxyborohydride (217.6 g, 1026.5 mmol), and dichloromethane (1000 mL) were placed in a 2000 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Butanal (74.0 g, 1026.5 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained product, Boronate 6-1 (92.1 g, yield 99%), was used in the next reaction.

[0393] (2) Preparation of Boronate 6-2

[0394]

[0395] Boronate 6-1 (92.1 g, 419.8 mmol) and dichloromethane (600 mL) were added to a 2000 mL flask under a nitrogen atmosphere and stirred until well dissolved, after which the temperature was maintained at 0°C. While maintaining 0°C, N-bromosucciniamide (74.7 g, 419.8 mmol) dissolved in dimethylformamide (150 mL) was slowly added dropwise. The mixture was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water at least three times, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 6-2 (112.7 g, yield 90%).

[0396] (3) Preparation of Boronate 6

[0397]

[0398] Boronate 6-2 (112.7 g, 377.8 mmol), potassium acetate (111.2 g, 1133.5 mmol), bis(pinacolato)diborone (105.5 g, 415.6 mmol), and dioxene (550 mL) were placed in a 1000 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (8.3 g, 11.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 6 (129.2 g, yield 99%), was used in the next reaction.

[0399] 7. Preparation of Boronate 7

[0400] Boronate 7, a dichroic dye intermediate, was synthesized through the following reaction.

[0401] (1) Preparation of Boronate 7-1

[0402]

[0403] 4-bromo-3-fluoroaniline (13.3 g, 70 mmol), sodium triacetoxyborohydride (32.6 g, 154 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Butanal (11.1 g, 154 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 7-1 (16.9 g, yield 80%).

[0404] (2) Preparation of Boronate 7

[0405]

[0406] Boronate 7-1 (16.9 g, 56 mmol), potassium acetate (16.5 g, 168 mmol), bis(pinacolato)diborone (15.6 g, 61.6 mmol), and dioxene (80 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.4 g, 1.9 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 7 (19.4 g, yield 99%), was used in the next reaction.

[0407] 8. Preparation of Boronate 8

[0408] Boronate 8, a dichroic dye intermediate, was synthesized through the following reaction.

[0409] (1) Preparation of Boronate 8-1

[0410]

[0411] 4-bromo-3-fluoroaniline (13.3 g, 70.0 mmol), sodium triacetoxyborohydride (32.6 g, 154.0 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Pentanal (13.3 g, 154.0 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 8-1 (19.0 g, yield 82%).

[0412] (2) Preparation of Boronate 8

[0413]

[0414] Boronate 8-1 (19.0 g, 57.5 mmol), potassium acetate (16.9 g, 173 mmol), bis(pinacolato)diborone (16.1 g, 63.3 mmol), and dioxene (80 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.4 g, 1.9 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 8 (21.5 g, yield 99%), was used in the next reaction.

[0415] 9. Preparation of Boronate 9

[0416] Boronate 9, a dichroic dye intermediate, was synthesized through the following reaction.

[0417] (1) Preparation of Boronate 9-1

[0418]

[0419] 4-bromo-3-fluoroaniline (13.3 g, 70.0 mmol), sodium triacetoxyborohydride (16.3 g, 77.0 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Butanal (5.6 g, 77.0 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 9-1 (13.3 g, yield 77%).

[0420] (2) Preparation of Boronate 9-2

[0421]

[0422] Boronate 9-1 (13.3 g, 54 mmol), sodium triacetoxyborohydride (12.6 g, 59.4 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. 2-ethylhexanal (7.6 g, 59.4 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 9-2 (15.0 g, yield 78%).

[0423] (3) Preparation of Boronate 9

[0424]

[0425] Boronate 9-2 (15.0 g, 41.9 mmol), potassium acetate (12.3 g, 125.7 mmol), bis(pinacolato)diborone (11.7 g, 46.1 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 9 (16.8 g, yield 99%), was used in the next reaction.

[0426] 10. Preparation of Boronate 10

[0427] Boronate 10, a dichroic dye intermediate, was synthesized through the following reaction.

[0428] (1) Preparation of Boronate 10-1

[0429]

[0430] 4-bromoaniline (12.0 g, 70.0 mmol), sodium triacetoxyborohydride (16.3 g, 77.0 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Acetaldehydride (3.4 g, 77.0 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 10-1 (10.5 g, yield 75%).

[0431] (2) Preparation of Boronate 10-2

[0432]

[0433] Boronate 10-1 (10.5 g, 52.4 mmol), 2-bromobutane (7.9 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and hexane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 10-2 (7.7 g, yield 57%).

[0434] (3) Preparation of Boronate 10

[0435]

[0436] Boronate 10-2 (7.7 g, 30.1 / 41.9 mmol), potassium acetate (8.8 g, 90.2 mmol), bis(pinacolato)diborone (8.4 g, 33.1 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 10 (8.8 g, yield 97%), was used in the next reaction.

[0437] 11. Preparation of Boronate 11

[0438] Boronate 11, a dichroic dye intermediate, was synthesized through the following reaction.

[0439] (1) Preparation of Boronate 11-1

[0440]

[0441] 4-bromo-3-methylphenol (10.0 g, 53.5 mmol), 2-methoxyethyl chloroformate (8.9 g, 64.2 mmol), triethylamine (5.4 g, 53.5 mmol), 4-dimethylaminopyridine (0.33 g, 2.7 mmol), and dichloromethane (40 mL) were added to a 250 mL flask under a nitrogen atmosphere and stirred at room temperature for 4 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 11-1 (12.3 g, yield 79%).

[0442] (2) Preparation of Boronate 11

[0443]

[0444] Boronate 11-1 (12.3 g, 42.4 mmol), potassium acetate (12.3 g, 125.7 mmol), bis(pinacolato)diborone (11.7 g, 46.1 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 11 (14.1 g, yield 99%), was used in the next reaction.

[0445] 12. Preparation of Boronate 12

[0446] Boronate 12, a dichroic dye intermediate, was synthesized through the following reaction.

[0447] (1) Preparation of Boronate 12-1

[0448]

[0449] 4-bromo-3,5-difluoroaniline (14.6 g, 70.0 mmol), sodium triacetoxyborohydride (32.6 g, 154.0 mmol), and dichloroethane (100 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Pentanal (13.3 g, 154 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 12-1 (17.9 g, yield 73%).

[0450] (2) Preparation of Boronate 12

[0451]

[0452] Boronate 12-1 (10.0 g, 28.8 mmol), potassium acetate (8.5 g, 86.3 mmol), bis(pinacolato)diborone (8.1 g, 31.6 mmol), and dioxene (60 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.7 g, 1.0 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 12 (9.9 g, yield 87%), was used in the next reaction.

[0453] 13. Preparation of Boronate 13

[0454] Boronate 13, a dichroic dye intermediate, was synthesized through the following reaction.

[0455]

[0456] Under a nitrogen atmosphere, 1-bromo-4-(2-ethylhexyl)-2-fluorobenzene (7.8 g, 27.3 mmol), potassium acetate (8.0 g, 82.0 mmol), bis(pinacolato)diborone (7.6 g, 30.0 mmol), and dioxene (40 mL) were placed in a 250 mL flask and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.60 g, 0.82 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 13 (7.5 g, yield 82%), was used in the next reaction.

[0457] 14. Preparation of Boronate 14

[0458] Boronate 14, a dichroic dye intermediate, was synthesized through the following reaction.

[0459] (1) Preparation of Boronate 14-1

[0460]

[0461] 4-bromo-3-fluorophenol (10.0 g, 52.4 mmol), 1-bromo-2-ethylhexane (11.1 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and hexane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 14-1 (13.5 g, yield 85%).

[0462] (2) Preparation of Boronate 14

[0463]

[0464] Boronate 14-1 (13.5 g, 44.5 mmol), potassium acetate (13.0 g, 133.6 mmol), bis(pinacolato)diborone (12.4 g, 49.0 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.91 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 14 (14.9 g, yield 96%), was used in the next reaction.

[0465] 15. Preparation of Boronate 15

[0466] Boronate 15, a dichroic dye intermediate, was synthesized through the following reaction.

[0467] (1) Preparation of Boronate 15-1

[0468]

[0469] 4'-hydroxyacetophenone (7.1 g, 52.4 mmol), 2-bromobutane (7.9 g, 57.6 mmol), potassium carbonate (8.7 g, 62.8 mmol), and dimethylformamide (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted with water and hexane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane and tetrahydrofuran, and the solvent was removed to obtain Boronate 15-1 (8.8 g, yield 87%).

[0470] (2) Preparation of Boronate 15-2

[0471]

[0472] Boronate 15-1 (8.8 g, 45.8 mmol) and ethanol (90 mL) were placed in a 500 mL flask under a nitrogen atmosphere and stirred thoroughly. Sodium hydroxide (9.2 g, 229.0 mmol) was dissolved in water (90 mL) and added to the reaction vessel. While maintaining the reaction vessel at 0°C, 5-bromothiophene-2-carboxyldehyde (8.7 g, 45.8 mmol) was thoroughly mixed with ethanol (30 mL) and slowly added dropwise. The reaction vessel was slowly raised to room temperature while stirring for 12 hours. Upon completion of the reaction, ice water (100 mL) was added, and the pH was adjusted to neutral using hydrochloric acid. The resulting solid was then washed with water and filtered. The filtered solid was recrystallized from ethanol to obtain Boronate 15-2 (14.5 g, yield 87%).

[0473] (3) Preparation of Boronate 15

[0474]

[0475] Boronate 15-2 (14.5 g, 39.7 mmol), potassium acetate (11.7 g, 119.0 mmol), bis(pinacolato)diborone (11.1 g, 43.6 mmol), and dioxene (50 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.92 g, 1.3 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 15 (11.4 g, yield 70%), was used in the next reaction.

[0476] 16. Preparation of Boronate 16

[0477] Boronate 16, a dichroic dye intermediate, was synthesized through the following reaction.

[0478] (1) Preparation of Boronate 16-1

[0479]

[0480] 3-(trifluoromethoxy)aniline (5.0 g, 28.2 mmol), sodium triacetoxyborohydride (13.2 g, 62.1 mmol), and dichloromethane (40 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 0°C for 0.5 hours. Pentanal (5.3 g, 62.1 mmol) was slowly added dropwise at 0°C. The reaction was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water and dichloromethane, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The obtained product, Boronate 16-1 (8.9 g, yield 99%), was used in the next reaction.

[0481] (2) Preparation of Boronate 16-2

[0482]

[0483] Boronate 16-1 (8.9 g, 28.0 mmol) and dichloromethane (40 mL) were added to a 250 mL flask under a nitrogen atmosphere and stirred until well dissolved, then maintained at 0°C. While maintaining 0°C, N-bromosuccinimide (5.0 g, 28.0 mmol) dissolved in dimethylformamide (10 mL) was slowly added dropwise. The mixture was stirred at room temperature for 12 hours. After the reaction was complete, the substance was extracted using water at least three times, treated with anhydrous magnesium sulfate to remove water, filtered, and concentrated under reduced pressure. The product was purified by column chromatography using hexane, and the solvent was removed to obtain Boronate 16-2 (10.1 g, yield 91%).

[0484] (3) Preparation of Boronate 16

[0485]

[0486] Boronate 16-2 (10.1 g, 25.5 mmol), potassium acetate (7.5 g, 76.5 mmol), bis(pinacolato)diborone (7.1 g, 28.0 mmol), and dioxene (550 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 100°C for 0.5 hours, after which [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.56 g, 0.76 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filtrate concentrated under reduced pressure. The obtained product, Boronate 16 (10.9 g, yield 96%), was used in the next reaction.

[0487] Preparation of Dichroic Dye Compounds

[0488] 1. Example 1: Preparation of Compound 1

[0489] Compound 1, a dichroic dye, was synthesized through the following reaction.

[0490]

[0491] Core 1 (3.5 g, 7.7 mmol), Boronate 1 (8.0 g, 23.1 mmol), potassium carbonate (6.4 g, 46.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.44 g, 0.38 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 1 (4.8 g, yield 85%).

[0492] MS: [M+H]+ = 736.33

[0493] 2. Example 2: Preparation of Compound 2

[0494] Compound 2, a dichroic dye, was synthesized through the following reaction.

[0495]

[0496] Core 2 (3.7 g, 7.7 mmol), Boronate 10 (7.0 g, 23.1 mmol), potassium carbonate (6.4 g, 46.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.44 g, 0.38 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 2 (4.0 g, yield 77%).

[0497] MS: [M+H]+ = 678.27

[0498] 3. Example 3: Preparation of Compound 3

[0499] Compound 3, a dichroic dye, was synthesized through the following reaction.

[0500]

[0501] Core 3 (4.1 g, 8.0 mmol), Boronate 3 (8.1 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 3 (4.7 g, yield 76%).

[0502] MS: [M+H]+ = 772.31

[0503] 4. Example 4: Preparation of Compound 4

[0504] Compound 4, a dichroic dye, was synthesized through the following reaction.

[0505]

[0506] Core 3 (5.0 g, 9.7 mmol), Boronate 8 (11.0 g, 29.2 mmol), potassium carbonate (8.1 g, 58.3 mmol), tetrahydrofuran (60 mL), and water (20 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.56 g, 0.49 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 4 (7.1 g, yield 85%).

[0507] MS: [M+H]+ = 854.43

[0508] 5. Example 5: Preparation of Compound 5

[0509] Compound 5, a dichroic dye, was synthesized through the following reaction.

[0510]

[0511] Core 3 (4.0 g, 7.8 mmol), Boronate 9 (9.5 g, 23.3 mmol), potassium carbonate (6.5 g, 46.7 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.45 g, 0.39 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 5 (6.0 g, yield 85%).

[0512] MS: [M+H]+ = 910.51

[0513] 6. Example 6: Preparation of Compound 6

[0514] Compound 6, a dichroic dye, was synthesized through the following reaction.

[0515]

[0516] Core 4 (3.8 g, 7.8 mmol), Boronate 9 (9.5 g, 23.3 mmol), potassium carbonate (6.5 g, 46.7 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.45 g, 0.39 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 6 (5.6 g, yield 81%).

[0517] MS: [M+H]+ = 884.41

[0518] 7. Example 7: Preparation of Compound 7

[0519] Compound 7, a dichroic dye, was synthesized through the following reaction.

[0520]

[0521] Core 5 (4.2 g, 8.0 mmol), Boronate 7 (8.4 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 7 (5.2 g, yield 80%).

[0522] MS: [M+H]+ = 814.37

[0523] 8. Example 8: Preparation of Compound 8

[0524] Compound 8, a dichroic dye, was synthesized through the following reaction.

[0525]

[0526] Core 6 (4.3 g, 7.8 mmol), Boronate 5 (7.7 g, 23.3 mmol), potassium carbonate (6.5 g, 46.7 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.45 g, 0.39 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 8 (4.9 g, yield 79%).

[0527] MS: [M+H]+ = 798.37

[0528] 9. Example 9: Preparation of Compound 9

[0529] Compound 9, a dichroic dye, was synthesized through the following reaction.

[0530]

[0531] Core 7 (4.6 g, 8.0 mmol), Boronate 2 (7.1 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 9 (4.8 g, yield 80%).

[0532] MS: [M+H]+ = 746.20

[0533] 10. Example 10: Preparation of Compound 10

[0534] Compound 10, a dichroic dye, was synthesized through the following reaction.

[0535]

[0536] Core 7 (4.4 g, 7.7 mmol), Boronate 3 (7.8 g, 23.1 mmol), potassium carbonate (6.4 g, 46.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.44 g, 0.38 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 10 (5.5 g, yield 86%).

[0537] MS: [M+H]+ = 830.29

[0538] 11. Example 11: Preparation of Compound 11

[0539] Compound 11, a dichroic dye, was synthesized through the following reaction.

[0540]

[0541] Core 7 (4.6 g, 8.0 mmol), Boronate 7 (8.4 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 11 (5.4 g, yield 79%).

[0542] MS: [M+H]+ = 856.38

[0543] 12. Example 12: Preparation of Compound 12

[0544] Compound 12, a dichroic dye, was synthesized through the following reaction.

[0545]

[0546] Core 7 (5.6 g, 9.7 mmol), Boronate 8 (11.0 g, 29.2 mmol), potassium carbonate (8.1 g, 58.3 mmol), tetrahydrofuran (60 mL), and water (20 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.56 g, 0.49 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 12 (7.0 g, yield 79%).

[0547] MS: [M+H]+ = 912.43

[0548] 13. Example 13: Preparation of Compound 13

[0549] Compound 13, a dichroic dye, was synthesized through the following reaction.

[0550]

[0551] Core 7 (4.6 g, 8.0 mmol), Boronate 9 (9.7 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 13 (6.9 g, yield 89%).

[0552] MS: [M+H]+ = 968.44

[0553] 14. Example 14: Preparation of Compound 14

[0554] Compound 14, a dichroic dye, was synthesized through the following reaction.

[0555]

[0556] Core 8 (4.9 g, 8.5 mmol), Boronate 2 (7.5 g, 25.5 mmol), potassium carbonate (7.0 g, 51.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.49 g, 0.43 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 14 (4.8 g, yield 75%).

[0557] MS: [M+H]+ = 754.19

[0558] 15. Example 15: Preparation of Compound 15

[0559] Compound 15, a dichroic dye, was synthesized through the following reaction.

[0560]

[0561] Core 8 (4.8 g, 8.2 mmol), Boronate 3 (8.3 g, 24.6 mmol), potassium carbonate (6.8 g, 49.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.47 g, 0.41 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 15 (5.6 g, yield 81%).

[0562] MS: [M+H]+ = 839.15

[0563] 16. Example 16: Preparation of Compound 16

[0564] Compound 16, a dichroic dye, was synthesized through the following reaction.

[0565]

[0566] Core 8 (4.6 g, 8.0 mmol), Boronate 7 (8.4 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 16 (5.9 g, yield 85%).

[0567] MS: [M+H]+ = 864.34

[0568] 17. Example 17: Preparation of Compound 17

[0569] Compound 17, a dichroic dye, was synthesized through the following reaction.

[0570]

[0571] Core 8 (4.6 g, 8.0 mmol), Boronate 8 (9.1 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 17 (6.1 g, yield 83%).

[0572] MS: [M+H]+ = 920.37

[0573] 18. Example 18: Preparation of Compound 18

[0574] Compound 18, a dichroic dye, was synthesized through the following reaction.

[0575]

[0576] Core 8 (4.6 g, 8.0 mmol), Boronate 9 (9.7 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 18 (6.0 g, yield 77%).

[0577] MS: [M+H]+ = 976.42

[0578] 19. Example 19: Preparation of Compound 19

[0579] Compound 19, a dichroic dye, was synthesized through the following reaction.

[0580]

[0581] Core 9 (4.9 g, 8.0 mmol), Boronate 3 (8.1 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 19 (5.8 g, yield 83%).

[0582] MS: [M+H]+ = 868.33

[0583] 20. Example 20: Preparation of Compound 20

[0584] Compound 20, a dichroic dye, was synthesized through the following reaction.

[0585]

[0586] Core 9 (4.7 g, 7.7 mmol), Boronate 6 (8.0 g, 23.1 mmol), potassium carbonate (6.4 g, 46.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.44 g, 0.38 mmol) was added. The mixture was stirred for 12 hours under increasing reflux. After the reaction was complete, the mixture was cooled to room temperature, and the substance was extracted using water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, followed by filtration and concentration under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to yield Compound 20 (5.9 g, yield 86%).

[0587] MS: [M+H]+ = 886.41

[0588] 21. Example 21: Preparation of Compound 21

[0589] Compound 21, a dichroic dye, was synthesized through the following reaction.

[0590]

[0591] Core 10 (4.1 g, 8.1 mmol), Boronate 1 (8.4 g, 24.3 mmol), potassium carbonate (6.7 g, 48.6 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.47 g, 0.41 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 21 (5.1 g, yield 80%).

[0592] MS: [M+H]+ = 786.35

[0593] 22. Example 22: Preparation of Compound 22

[0594] Compound 22, a dichroic dye, was synthesized through the following reaction.

[0595]

[0596] Core 11 (3.9 g, 7.9 mmol), Boronate 1 (8.2 g, 23.7 mmol), potassium carbonate (6.6 g, 47.4 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 22 (4.4 g, yield 73%).

[0597] MS: [M+H]+ = 767.33

[0598] 23. Example 23: Preparation of Compound 23

[0599] Compound 23, a dichroic dye, was synthesized through the following reaction.

[0600]

[0601] Core 11 (3.9 g, 7.9 mmol), Boronate 4 (8.3 g, 23.7 mmol), potassium carbonate (6.6 g, 47.4 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 23 (4.0 g, yield 65%).

[0602] MS: [M+H]+ = 773.33

[0603] 24. Example 24: Preparation of Compound 24

[0604] Compound 24, a dichroic dye, was synthesized through the following reaction.

[0605]

[0606] Core 12 (4.5 g, 8.0 mmol), Boronate 11 (8.1 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 24 (5.4 g, yield 83%).

[0607] MS: [M+H]+ = 815.11

[0608] 25. Example 25: Preparation of Compound 25

[0609] Compound 25, a dichroic dye, was synthesized through the following reaction.

[0610]

[0611] Core 3 (4.1 g, 8.0 mmol), Boronate 12 (9.5 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 25 (5.1 g, yield 72%).

[0612] MS: [M+H]+ = 890.42

[0613] 26. Example 26: Preparation of Compound 26

[0614] Compound 26, a dichroic dye, was synthesized through the following reaction.

[0615]

[0616] Core 10 (4.1 g, 8.1 mmol), Boronate 13 (8.1 g, 24.3 mmol), potassium carbonate (6.7 g, 48.6 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.47 g, 0.41 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 26 (5.4 g, yield 87%).

[0617] MS: [M+H]+ = 762.31

[0618] 27. Example 27: Preparation of Compound 27

[0619] Compound 27, a dichroic dye, was synthesized through the following reaction.

[0620] (1) Preparation of Compound 27-1

[0621]

[0622] Core 10 (4.1 g, 8.1 mmol), Boronate 14 (8.5 g, 24.3 mmol), potassium carbonate (6.7 g, 48.6 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.47 g, 0.41 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 27-1 (3.4 g, yield 64%).

[0623] (2) Preparation of Compound 27

[0624]

[0625] Compound 27-1 (3.4 g, 5.2 mmol), Boronate 1 (5.4 g, 15.7 mmol), potassium carbonate (4.3 g, 31.2 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.30 g, 0.26 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain Compound 27 (3.8 g, yield 92%).

[0626] MS: [M+H]+ = 793.30

[0627] 28. Example 28: Preparation of Compound 28

[0628] Compound 28, a dichroic dye, was synthesized through the following reaction.

[0629]

[0630] Core 13 (4.1 g, 8.0 mmol), Boronate 15 (9.5 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then the substance was extracted using water and dichloromethane. After removing the water by treatment with anhydrous magnesium sulfate, the mixture was filtered and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 28 (5.1 g, yield 72%).

[0631] MS: [M+H]+ = 890.42

[0632] 29. Example 29: Preparation of Compound 29

[0633] Compound 29, a dichroic dye, was synthesized through the following reaction.

[0634]

[0635] Core 3 (4.1 g, 8.0 mmol), Boronate 16 (10.6 g, 24.0 mmol), potassium carbonate (6.6 g, 48.0 mmol), tetrahydrofuran (45 mL), and water (15 mL) were placed in a 250 mL flask under a nitrogen atmosphere and stirred at 80°C for 0.5 hours, after which tetracyclophenylphosphine palladium (0) (0.46 g, 0.40 mmol) was added. The mixture was stirred at 80°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, then extracted with water and dichloromethane. The water was removed by treatment with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained product was recrystallized with dichloromethane and ethanol to obtain compound 29 (5.6 g, yield 71%).

[0636] MS: [M+H]+ = 890.42

[0637] 30. Comparative Example 1

[0638] A compound with the following structure was prepared as a dichroic dye.

[0639]

[0640] 31. Comparative Example 2

[0641] A compound with the following structure was prepared as a dichroic dye.

[0642]

[0643] 32. Comparative Example 3

[0644] A compound with the following structure was prepared as a dichroic dye.

[0645]

[0646] <Experimental Example>

[0647] The physical properties of the dichroic dyes obtained in the above examples and comparative examples were measured by the following method, and the results are shown in Tables 1 and 2.

[0648] 1. Solubility Evaluation

[0649] The solubility in a liquid crystal film cell was observed as follows. The dichroic dyes obtained in the above examples and comparative examples were mixed with the liquid crystal at a concentration of 1 wt% to 5 wt%, up to a maximum of 8 wt%, then a magnetic bar was added and stirred at 60°C for about 2 hours, then left in an orbital shaker for about 12 hours or more, and the liquid crystal mixture was filtered through a 0.2 µm PP filter to fabricate a liquid crystal film cell, and the solubility of the dye was analyzed through this.

[0650] Specifically, transmittance according to each dye concentration was measured to examine the range of dye concentrations where transmittance increases despite the increase in concentration, and the minimum dye concentration within that range was measured and listed in Table 1 below. In addition, to verify this, a UV-Vis spectrum was taken to observe changes in the spectrum shape. Furthermore, the liquid crystal film cell was observed under a microscope to see if dye clumping occurred depending on the angle of the dye.

[0651] The greater the minimum dye concentration value listed in Table 1 below, the better the solubility can be evaluated.

[0652] 2. Evaluation of Contrast and Transmittance Variability Characteristics

[0653] A liquid crystal + dye mixture was prepared using the dichroic dyes obtained in the above examples and comparative examples, and a liquid crystal film cell was fabricated after filtering the mixture through a 0.2 µm PP filter. An electrode tape was connected to the upper and lower PET-ITO plates of the liquid crystal film cell to obtain a liquid crystal film cell capable of voltage application. The liquid crystal film cell was mounted on a Nippon-Denshoku NHD7000 (haze meter), and the total transmittance was measured at 0 V and 50 V. △TT (%, variable transmittance) = TT 50V (%)-TT 0V Defined as (%), CR = TT 50V (%) / TT 0VThe contrast ratio value was calculated using a mathematical formula defined as (%) and recorded in Table 2 below. Voltage was applied to the liquid crystal film cell using a function generator to check the transmittance level, and then the contrast ratio was measured.

[0654] As the contrast ratio (CR) value listed in Table 2 below increases, the absorption anisotropy increases, and it can be evaluated that the transmittance variability characteristic is excellent.

[0655] 3. Reliability Evaluation

[0656] A liquid crystal + dye mixture was prepared using the dichroic dyes obtained in the above examples and comparative examples, and the mixture was filtered through a 0.2 µm PP filter. Then, the resulting single dye liquid crystal mixture was injected into a glass cell and the injection port was sealed to produce an evaluation liquid crystal film cell.

[0657] L* at 0V and 48V after mounting the sample on the HunterLAB customized VISTA 초기 , a* 초기 , b* 초기 Measure the value, and after exposing to an Atlas Ci5000 weathering tester under PV3929 conditions for 500 hours, L* 신뢰성후 , a* 신뢰성후 , b* 신뢰성후 By measuring the value, △E*=((L* 신뢰성후 -L* 초기 )^2+(a* 신뢰성후 -a* 초기 )^2+(b* 신뢰성후 -b* 초기 The value of △E* was calculated using the mathematical formula defined as )^2)^(1 / 2).

[0658] The smaller the △E* value listed in Table 2 below, the less the color change, and the better the reliability can be evaluated.

[0659] In addition, the sample was placed in the JASCO V770, a wavelength range including the absorption range of the dye was set, and the initial Abs was measured. After being exposed to the Atlas Ci5000 weathering tester under PV3929 conditions for 500 hours, the sample was placed in the V770 to measure the reliability-post-reliability Abs. The △ Abs(%) value is the calculated difference (%) between the initial Abs and the reliability-post-reliability Abs at the maximum absorption wavelength, and the smaller the absolute value of the △ Abs(%) value listed in Table 2 below, the less the change in absorbance, so the reliability can be evaluated as excellent.

[0660] UV solution (Toluene 10 -5 M) Solubility Evaluation Abs(nm)ελ max,f(nm)Solubility(wt%) Example 15800.176005.0 or more Example 26000.276213.4 Example 35500.215727.0 or more Example 45810.296045.0 or more Example 55870.306113.4 Example 65760.286015.0 or more Example 75780.306065.0 or more Example 86120.266465.0 or more Example 95770.175897.0 or more Example 105790.185915.0 or more Example 116100.246375.0 or more Example 126160.276507.0 or more Example 136210.256445.0 Example 145870.185895.0 Example 155890.195995.0 Example 166220.226545.0 Example 176310.246427.0 Example 186470.266565.0 Example 196290.216404.3 Example 206340.176655.0 Example 216800.177253.5 Example 224260.414365.0 Example 234690.494754.0 Example 244200.394405.0 Example 255680.255895.0 or higher Example 266750.157202.3 Example 277300.247802.8 Example 285890.196332.6 Example 295720.275947.0 or higher Comparative Example 15310.175451.1 Comparative Example 26600.286821.4 Comparative Example 34980.485101.3

[0661] △TT(%)CR△E*(0V)△E*(48V)△Abs(%) Example 1 31.00 3.13 46.40 13.65 -47.30 Example 2 29.00 2.95 24.12 7.78 -37.13 Example 3 32.00 3.25 5.112 10 -6.63 Example 4 29.90 3.016.12 5.28 -11.90 Example 5 31.00 3.028 035.73 -14.04 Example 6 30.50 3.11 45.84 26.62 -37.24 Example 7 31.50 2.85 16.16 10.94 -15.27 Example 834.703.0332.3815.58-24.69 Example 931.202.9914.728.18-1.73 Example 1031.003.0114.787.28-3.56 Example 1128.902.6214.997.22-12.70 Example 1227.802.7016.849.08-14.13 Example 1327.702.6617.888.98-16.78 Example 1431.202.209.114.68-6.54 Example 1530.502.3010.915.99-7.79 Example 1634.702.5114.127.72-12.01 Example 1733.502.4911.445.55-11.25 Example 1833.402.5012.125.48-11.31 Example 1928.202.037.014.53-14.49 Example 2034.703.0222.577.89-41.58 Example 2128.202.6728.878.63-17.86 Example 2216.204.1814.347.87-13.05 Example 2315.803.8616.688.87-16.56 Example 2416.504.0221.249.09-20.45 Example 2530.303.227.085.62-8.75 Example 2625.202.2038.919.67-24.74 Example 2726.702.5033.709.11-21.56 Example 2828.802.7834.658.98-22.48 Example 2932.102.9313.159.63-21.58 Comparative Example 127.762.8777.4525.67-69.76 Comparative Example 231.352.4547.2828.45-45.43 Comparative Example 330.052.3457.3527.89-51.34

[0662] As shown in Table 2 above, the dichroic dye compounds obtained in Examples 1 to 29 had a solubility of 2.3 wt% to 7.0 wt% or higher, and it was confirmed that they exhibited stable solubility performance in the medium due to their high solubility, while also possessing generally excellent transmittance variability characteristics with a single dye contrast ratio. On the other hand, the dichroic dye compounds obtained in Comparative Examples 1 to 3 had a solubility of less than 1.5 wt%, which was insufficient compared to the examples, and it was confirmed that they generally lacked light resistance reliability compared to the examples.

Claims

1. Dichroic dye compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X is a substituted or unsubstituted pyrazine ring; a substituted or unsubstituted quinoxaline ring; or a substituted or unsubstituted pyrrolidine-2,5-dione ring, and H1 and H2 are identical or different from each other and are each independently substituted or unsubstituted divalent heterocyclic rings, and L1 and L2 are equal to or different from each other and are each independently directly coupled; -O-; -S-; -C(=O)-; -C(RR')-; -C(F2)O-; -OC(F2)-; -C(=O)O-; -OC(=O)-; -OC(H2)-; -C(H2)O-; -C(R)=C(R')-; -C≡C-; -C(R)=C(R')-C(=O)-; -C(=O)-C(R)=C(R')-; -C(R)=C(R')-C(=O)O-; or -OC(=O)-C(R)=C(R')- and, R and R' are the same or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and Q1 and Q2 are the same or different from each other and are each independently a halogen group; -N(Ra)(Rb); -Si(Ra)(Rb)(Rc); a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkyl carbonyl group; a substituted or unsubstituted alkoxycarbonyl group; a substituted or unsubstituted alkylcarbonyloxy group; a substituted or unsubstituted alkoxycarbonyloxy group; a substituted or unsubstituted heterocycloalkyl group; or a combination thereof, Ra to Rc are the same or different from each other and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted alkoxy group, and Ra and Rb of -N(Ra)(Rb) combine with A1 or A2 to form a substituted or unsubstituted N-containing ring, and A1 and A2 are the same or different from each other and are each independently substituted or unsubstituted divalent aryl groups; or are substituted or unsubstituted divalent heteroaryl groups, or each combine with Ra and Rb of -N(Ra)(Rb) to form a substituted or unsubstituted N-containing ring.

2. A dichroic dye compound according to Claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1 to 1-3, R1 to R4 are the same or different from one another, and each independently is hydrogen; deuterium; a halogen group; a cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); a haloalkyl group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; or a combination thereof, Rd, Re and Rf are the same or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and R5 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and The definitions of the remaining substituents are the same as the definitions in Chemical Formula 1 above.

3. A dichroic dye compound according to Claim 1, wherein H1 and H2 are the same or different from each other and each independently represented by any one of the following chemical formulas H-1 to H-4: [Chemical Formula H-1] [Chemical Formula H-2] [Chemical Formula H-3] [Chemical Formula H-4] In the above chemical formulas H-1 to H-4, Y1 and Y2 are the same or different from each other, and each is independently O; S; Se; or N(H19), and W1 is N or C(H2O), and H11 to H20 are the same or different from one another and are each independently hydrogen; deuterium; a halogen group; a cyano group; an ester group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, * is the site that combines with another structure in the above chemical formula 1.

4. A dichroic dye compound according to Claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 2 to 4: [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 2 to 4, Y3 and Y4 are equal to or different from each other, and each is independently O; S; Se; or N(R27), and R1 to R4 are the same or different from one another and are each independently hydrogen; deuterium; halogen group; cyano group; -O(Rd); -S(Re); -C(=O)O(Rf); haloalkyl group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; substituted or unsubstituted aryl group; substituted or unsubstituted heteroaryl group; or a combination thereof, Rd, Re and Rf are the same or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and R5 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, and R21 to R27 are the same or different from one another, and each is independently hydrogen; deuterium; a halogen group; a cyano group; an ester group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted alkoxy group, and a and b are each integers from 1 to 4, and when a and b are each 2 or greater, the substituents inside the parentheses are the same or different, and The definitions of the remaining substituents are the same as the definitions in Chemical Formula 1 above.

5. A dichroic dye compound according to claim 1, wherein "substituted or unsubstituted" means one or more substituents selected from the group consisting of a halogen group; a cyano group; a hydroxyl group; oxygen (=O); an amine group; a nitro group; a silyl group; an ester group; -ORs; -SRs; a sulfide group; an alkyl group; a haloalkyl group; an alkenyl group; an alkynyl group; a cycloalkyl group; an alkoxy group; an aryloxy group; an aryl group; and a heterocyclic group, or a substituent in which two or more of the said substituents are connected, or not having any substituents, wherein Rs is an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

6. The dichroic dye compound of Claim 1, wherein the dichroic dye compound is any one of the following compounds:

7. A liquid crystal composition comprising a dichroic dye compound according to any one of claims 1 to 6; and a liquid crystal material.

8. A liquid crystal composition according to claim 7, further comprising a chiral agent.

9. A liquid crystal cell comprising a first substrate; a liquid crystal layer; and a second substrate, The liquid crystal layer is a liquid crystal cell comprising a liquid crystal composition according to claim 7.

10. A liquid crystal display device comprising a liquid crystal cell according to claim 9.

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