Total anthraquinone type black dichroic dye, guest-host liquid crystal composition and application

Abstract

The invention relates to the technical field of dichroic dyes, and particularly provides a total anthraquinone type black dichroic dye, a guest-host liquid crystal composition containing the total anthraquinone type black dichroic dye and application of the total anthraquinone type black dichroic dye. The total anthraquinone type black dichroic dye provided by the invention comprises an anthraquinone type orange dye, an anthraquinone type red dye and an anthraquinone type blue dye, each of the anthraquinone orange dye, the anthraquinone red dye and the anthraquinone blue dye comprises a structural formula as shown in a formula (1). The total anthraquinone type black dichroic dye provided by the invention shows remarkable absorption in a visible light broadband range of 400-650nm, not only covers a main interval from purple light to red light, but also keeps relatively stable absorbance in the broadband, and shows broadband absorption characteristics; meanwhile, the average dichroic ratio can reach 11.28, and the optical performance is excellent; and the material also has excellent switching performance between a black opaque state and a transparent state, and can realize rapid reversible switching between the two states under the action of an electric field.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of dichroic dyes, in particular to a full anthraquinone type black dichroic dye, and also relates to a guest-host liquid crystal composition comprising the same and application. BACKGROUND

[0002] Black dichroic dye is a kind of functional dye which shows significant anisotropy in the absorption of light in the direction of the long axis and the short axis of the molecule, and can achieve balanced absorption in the full wave band of visible light, which has important value in the field of intelligent light modulation devices. With the development of emerging technologies such as intelligent glass, flexible display and automobile light modulation glass, the market demand for high-performance black dichroic dye is increasing.

[0003] At present, the commercial black dichroic dye is mainly an azo type dye system. This kind of dye has the advantages of strong designability of molecular structure, mature synthesis process, etc., and has good dichroism in liquid crystal medium. However, the azo bond in its molecular structure is extremely easy to undergo cis-trans isomerization under light conditions, which causes the dye to fade or discolor, which seriously limits its reliability for long-term outdoor use. Anthraquinone type dye has better light stability and thermal stability than azo type dye due to its unique conjugated system and rigid structure, but the discotic molecular structure of anthraquinone dye is quite different from the high aspect ratio structure of commonly used liquid crystal molecules, resulting in low orientation order and unsatisfactory dichroic ratio, which cannot meet the requirements of high-end optoelectronic devices. Therefore, it is a technical problem to be solved in the field to develop a full anthraquinone type black dichroic dye with high dichroic ratio and high stability. SUMMARY

[0004] In view of the above problems, the present application provides a full anthraquinone type black dichroic dye, which has excellent optical performance and can be used for a long time without fading or discoloration in ultraviolet light environment. The present application also provides a guest-host liquid crystal light modulation device comprising the dye, which has excellent colorless-black state switching performance.

[0005] To solve the above technical problems, in a first aspect, the present application provides a full anthraquinone type black dichroic dye, which comprises an anthraquinone type orange dye, an anthraquinone type red dye and an anthraquinone type blue dye.

[0006] The anthraquinone type orange dye, the anthraquinone type red dye and the anthraquinone type blue dye all comprise a structural formula shown in formula (1):

[0007]

[0008] When formula (1) represents the anthraquinone orange dye, substituents R1, R4, R5, R8 in the structural formula are each independently selected from a hydrogen atom, a hydroxyl group or a halogen, and R2, R3, R6, R7 are each independently selected from substituent A or a hydrogen atom; the structural formula of the substituent A is shown in formula (2):

[0009]

[0010] In formula (2), j is 0 or 1; k is an integer, and 0≤k≤25;

[0011] When formula (1) represents the anthraquinone red dye, substituents R1, R4, R5, R8 in the structural formula are each independently selected from a hydrogen atom, a hydroxyl group or a halogen, and R2, R3, R6, R7 are each independently selected from the substituent A or a hydrogen atom;

[0012] When formula (1) represents the anthraquinone blue dye, substituents R1, R5 in the structural formula are each independently selected from a hydrogen atom, a hydroxyl group, an amino group, a nitro group or a halogen; R4, R8 are each independently selected from a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a halogen or a substituent B; R2, R3, R6, R7 are each independently selected from substituent C or a hydrogen atom; the structural formula of the substituent B is shown in formula (3):

[0013]

[0014] In formula (3), m is 0 or 1; n is an integer, and 0≤n≤25;

[0015] The structural formula of the substituent C is shown in formula (4):

[0016]

[0017] In formula (4), x is 0 or 1; y is 0 or 1; z is an integer, and 0≤z≤25.

[0018] The present application optimizes the substituent structure of anthraquinone dyes, introduces specific functional groups, maintains the inherent photo-thermal stability of the rigid conjugated skeleton of anthraquinone molecules, improves the solubility and orientation order of the molecules in the liquid crystal medium, enables the dye molecules to better cooperate with the liquid crystal molecules, and thus obtains a higher dichroic ratio. Meanwhile, the present application adopts a red, orange and blue three-primary-color complex system, realizes balanced absorption in a wide band range (400-650nm, covering the core visible spectrum in the field of display or dimming), avoids color deviation caused by multi-component complexing, ensures pure black state performance, and is particularly suitable for scenes requiring long-term outdoor use.

[0019] Preferably, the full anthraquinone type black dichroic dye comprises the following components in mass percentage: anthraquinone type orange dye 20-60%, anthraquinone type red dye 20-60%, and anthraquinone type blue dye 20-60%.

[0020] Preferably, the anthraquinone type orange dye has the formula (5):

[0021]

[0022] In formula (5), k is an integer, and 0≤k≤25.

[0023] Preferably, the anthraquinone type red dye has the formula (6):

[0024]

[0025] In formula (6), k is an integer, and 0≤k≤25.

[0026] Preferably, the anthraquinone type blue dye has the formula (7):

[0027]

[0028] In formula (7), z is an integer, and 0≤z≤25; m is 0 or 1; and n is an integer, and 0≤n≤25.

[0029] Further preferably, the anthraquinone type orange dye has the formula (8):

[0030]

[0031] Further preferably, the anthraquinone type red dye has the formula (9):

[0032]

[0033] Further preferably, the anthraquinone type blue dye has the formula (10):

[0034]

[0035] The further preferred anthraquinone dye molecular structure of the present application realizes synergistic stabilization, the hydroxyl group introduced by the red dye enhances the hydrogen bonding with the liquid crystal, the moderate length alkoxy chain in the orange dye balances the solubility and orientation, and the rigid structure of the blue dye maintains the ordered arrangement of molecules, the difference in dipole moment of the three forms a dynamic electrostatic balance network, which prevents molecular aggregation and does not interfere with the orientation of the liquid crystal, realizes the uniform dispersion state of the dye in the liquid crystal system, and does not cause phase separation due to long-term use, and improves the durability and stability of the dye.

[0036] In a second aspect, the present application provides a guest-host liquid crystal composition, comprising the full anthraquinone type black dichroic dye.

[0037] Preferably, the guest-host liquid crystal composition comprises the following components by weight fraction: liquid crystal material 80-99 parts, full anthraquinone type black dichroic dye 1-10 parts, chiral agent 0.1-5 parts.

[0038] Preferably, the liquid crystal material is at least one of cyano-containing liquid crystal and fluorine-containing liquid crystal.

[0039] Preferably, the chiral agent comprises at least one of R811 chiral agent, S811 chiral agent, R1011 chiral agent, S1011 chiral agent, R5011 chiral agent, and S5011 chiral agent.

[0040] In a third aspect, the present application provides use of the full anthraquinone type black dichroic dye or the guest-host liquid crystal composition in preparation of a liquid crystal light-adjusting device.

[0041] In a fourth aspect, the present application provides a guest-host liquid crystal light-adjusting device, wherein the raw material for preparing the guest-host liquid crystal light-adjusting device comprises the guest-host liquid crystal composition provided by the present application. The guest-host liquid crystal light-adjusting device can reversibly switch between a black opaque state and a transparent state under the action of an electric field.

[0042] In a fourth aspect, the present application provides a preparation method of a guest-host liquid crystal light-adjusting device, comprising the following steps: injecting the guest-host liquid crystal composition into a liquid crystal cell to obtain the guest-host liquid crystal light-adjusting device.

[0043] Preferably, the liquid crystal cell is also sprayed with spacer particles; the spacer particles comprise at least one of glass microspheres, polystyrene microspheres, and polymethyl methacrylate microspheres, and the spraying density is 100-800 pieces / cm 2 .

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] (1) The full anthraquinone type black dichroic dye provided by the application shows significant absorption in the wide band range of 400-650nm visible light by compounding anthraquinone type orange, red and blue dyes in a specific ratio, not only covers the main interval from purple light to red light, but also keeps the absorbance relatively stable in the wave band, presents the wide band absorption characteristics, can meet the demand of black vision in most daily light scenes, and can adapt to the technical requirements of related optical devices for wide range of visible light absorption. The average dichroic ratio of the full anthraquinone type black dichroic dye can reach 11.28, and the optical performance is excellent; at the same time, it adopts full anthraquinone type structure and does not contain light unstable groups, and has excellent light stability, which can be used for a long time in the ultraviolet light environment without fading or discoloration.

[0046] (2) The guest-host liquid crystal dimming device prepared based on the full anthraquinone type black dichroic dye provided by the application has excellent black opaque state and transparent state switching performance, can realize rapid reversible conversion of the two states under the action of an electric field, and is suitable for multiple fields such as intelligent dimming glass and display. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 The dichroic absorption spectrum diagram of the anthraquinone type orange dye prepared for the embodiment 1 of the application;

[0048] Figure 2 The dichroic absorption spectrum diagram of the anthraquinone type red dye prepared for the embodiment 2 of the application;

[0049] Figure 3 The dichroic absorption spectrum diagram of the anthraquinone type blue dye prepared for the embodiment 3 of the application;

[0050] Figure 4 The actual picture of the full anthraquinone type black dichroic dye prepared for the embodiment 4 of the application;

[0051] Figure 5 The absorption spectrum diagram of the full anthraquinone type black dye prepared for the embodiment 4 of the application;

[0052] Figure 6 The actual picture of the guest-host liquid crystal dimming device prepared for the embodiment 5 of the application. DETAILED DESCRIPTION

[0053] In order to more clearly illustrate the specific embodiments of the application or the technical solutions in the prior art, the specific embodiments will be briefly introduced below, and obviously, the embodiments described below are some embodiments of the application, and other embodiments can also be obtained by those skilled in the art without creative labor on the basis of these embodiments.

[0054] The specific experimental steps or conditions are not indicated in the examples, and the operation or conditions can be carried out according to the conventional experimental steps described in the literature in the art. The raw materials or instruments used are conventional products that can be obtained by purchase, including but not limited to the raw materials or instruments used in the examples of the present application.

[0055] Example 1

[0056] The present example provides an orange anthraquinone dye, the structural formula of which is shown in formula (8):

[0057]

[0058] The present example provides a preparation method of an orange anthraquinone dye, the reaction formula of which is:

[0059]

[0060] The preparation process includes the following steps:

[0061] Under the protection of argon, 2.73 equivalents of 2,6-dibromoanthraquinone were dissolved in anhydrous toluene, and oxygen was removed to obtain an anhydrous toluene mixed solution; another anhydrous triethylamine was used as a solvent, and 0.546 equivalents of cuprous iodide, 0.164 equivalents of triphenylphosphine and 0.164 equivalents of bis(triphenylphosphine)palladium chloride were sequentially added, and after oxygen removal, it was transferred to the anhydrous toluene mixed solution; 6.01 equivalents of 4-n-pentyloxyphenylacetylene were added to the reaction system at a constant pressure, the reactor was sealed, heated to 90°C, and refluxed in the dark for 12 hours (the reaction progress was monitored by TLC). After the reaction was completed, the reaction liquid was poured into ice water for quenching, then extracted with dichloromethane, and the organic phases were combined; the organic phase was washed with saturated NaCl solution and dried with anhydrous Na2SO4, filtered and concentrated to obtain the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 2:1), the fractions were collected, and vacuum dried to obtain the orange anthraquinone dye 2,6-di(4-pentyloxyphenylacetylene) anthraquinone.

[0062] Figure 1 The dichroic absorption spectrum of the anthraquinone orange dye prepared in the present example is shown in Figure 1 It can be seen that the dye has strong absorption in the direction of the long axis of the molecule, and the absorption is significantly reduced along the short axis of the molecule, showing a significant dichroism characteristic. The dichroic ratio of the dye was tested by ultraviolet-visible spectrophotometer at room temperature, and the dichroic ratio was 12.83.

[0063] Example 2

[0064] The present example provides a red anthraquinone dye, the structural formula of which is shown in formula (9):

[0065]

[0066] The embodiment provides a preparation method of a red anthraquinone type dye, and a reaction formula is as follows:

[0067]

[0068]

[0069] The preparation process comprises the following steps:

[0070] (1) Preparation of intermediate product 1: 11.8 equivalents of iodine, 7.75 equivalents of iodic acid and 12.9 equivalents of 1,5-dihydroxyanthraquinone are sequentially added in glacial acetic acid, and the mixture is fully stirred under a nitrogen protection atmosphere; the mixture is heated to 115 DEG C to perform a reflux reaction, and the reaction lasts for 5 hours; when the reaction solution is cooled to 25 DEG C, deionized water is slowly added dropwise, at this time, orange-yellow solid is precipitated; the solid product is collected by suction filtration, washed to be neutral by cold water and dried, to obtain the intermediate product 1 (1,5-dihydroxy-2,6-diiodoanthraquinone) for subsequent reaction;

[0071] (2) Preparation of intermediate product 2: 2.03 equivalents of 1,5-dihydroxy-2,6-diiodoanthraquinone are dissolved in anhydrous dichloromethane, 5.08 equivalents of triethylamine are added, and the reaction system is cooled to 0 DEG C under nitrogen protection, and constant temperature stirring is performed for 10 minutes; then 5.08 equivalents of acetyl chloride are slowly added dropwise, and the system temperature is strictly controlled to be less than or equal to 5 DEG C during the dropwise addition; after the dropwise addition is completed, the cold bath is removed, and the system is slowly warmed to 25 DEG C, and stirring reaction is continued for 5 hours; after the reaction is completed, the solvent in the reaction solution is removed by reduced pressure distillation, and the residue is purified by a silica gel column chromatography (eluent is petroleum ether: ethyl acetate = 4:1), and after drying, the intermediate product 2 (1,5-diethoxyl-2,6-diiodoanthraquinone) is obtained;

[0072] (3) Preparation of intermediate product 3: 1.74 equivalents of 1,5-diethoxyl-2,6-diiodoanthraquinone are dissolved in a toluene / triethylamine mixed solvent, and the system is replaced by argon three times to remove oxygen; 0.5 equivalents of palladium dichloride triphenylphosphine, 0.5 equivalents of cuprous iodide and 0.15 equivalents of triphenylphosphine are sequentially added, and stirring activation is performed at 25 DEG C for 15 minutes; then 6.0 equivalents of 4-pentyloxyphenylacetylene are added dropwise at constant pressure, the reaction temperature is maintained at 25 DEG C, and the reaction lasts for 14 hours; after the reaction is completed, the solvent in the reaction solution is removed by reduced pressure distillation, and the residue is purified by a silica gel column chromatography (eluent is petroleum ether: ethyl acetate = 4:1), and after vacuum drying, the intermediate product 3 (1,5-diethoxyl-2,6-di(4-pentyloxyphenylacetylene) anthraquinone) is obtained;

[0073] (4) Preparation of red anthraquinone type dye: 0.215 equivalent of 1,5-diethyl ester-2,6-di(4-pentyloxy phenyl acetylene) anthraquinone was dissolved in anhydrous ethanol, and the system was stirred under argon protection to disperse uniformly; 5 equivalent of sodium hydroxide aqueous solution was added dropwise, and the temperature of the system was controlled to be ≤30°C during the dropwise addition; after the dropwise addition was completed, the temperature program was started, and the temperature was increased to 50°C at a rate of 2°C / min, and the reaction was carried out for 7 hours under light-proof conditions; after the reaction was completed, the reaction liquid was cooled to 10°C, and the precipitate was collected by suction filtration; after washing with cold ethanol for three times, the precipitate was dissolved in dichloromethane, and washed with dilute hydrochloric acid for three times to remove residual alkali; the organic phase was dried over anhydrous sodium sulfate, and concentrated under reduced pressure; the concentrate was purified by silica gel column chromatography (eluent: ethyl acetate: petroleum ether = 1:4), the target fraction was collected and vacuum dried to obtain a red anthraquinone type dye (1,5-di-carboxyl-2,6-di(4-pentyloxy phenyl acetylene) anthraquinone).

[0074] Figure 2 The dichroic absorption spectrum of the anthraquinone red dye prepared in this example is shown in FIG. 1. It can be seen that the dye has strong absorption in the direction of the long axis of the molecule, and the absorption is significantly reduced in the direction of the short axis of the molecule, showing a significant dichroism characteristic. The dichroic ratio of the dye was tested by a UV-Vis spectrophotometer at room temperature, and the dichroic ratio was 11.62. Figure 2

[0075] Example 3

[0076] This example provides a blue anthraquinone type dye, and the structural formula is shown as formula (10):

[0077]

[0078] This example provides a preparation method of a blue anthraquinone type dye, and the reaction formula is as follows:

[0079]

[0080]

[0081] The preparation process includes the following steps:

[0082] (1) Preparation of intermediate product 1: 2 equivalent of 1,5-dihydroxy-4,8-dinitro anthraquinone was dissolved in anhydrous dimethylformamide, and the raw material was fully dispersed under argon protection; 6 equivalent of N-bromosuccinimide was added for light-proof reaction for 10 h, and the reaction temperature was maintained at 25°C; after the reaction was completed, the reaction liquid was slowly poured into ice water, and stirring was performed to promote the precipitation; the solid was collected by suction filtration, and then washed with deionized water for three times, washed with 5% sodium thiosulfate aqueous solution until the filtrate was colorless, and finally washed with cold methanol once; the product was dried to obtain a brown red target product 1 (2,6-dibromo-1,5-dihydroxy-4,8-dinitro anthraquinone).​

[0083] (2) Preparation of intermediate 2: 1 equivalent of 2,6-dibromo-1,5-dihydroxy-4,8-dinitroanthraquinone and 2 equivalents of n-butyl aniline were dissolved in anhydrous dimethylformamide, and the reaction was carried out under argon protection with a temperature increase of 2°C / min to 130°C, stirring in the dark; after the reaction was completed, the reaction solution was cooled to 25°C, and 10% NaOH aqueous solution was slowly added dropwise to adjust the pH of the system to 12, and stirring was continued for 30 minutes; petroleum ether was added to the system, and after standing and layering, the upper organic phase was discarded; the aqueous phase was adjusted to pH 1 with dilute hydrochloric acid, and then extracted with dichloromethane, and the combined organic phases were concentrated under reduced pressure; the crude product was treated with petroleum ether, and after suction filtration and drying, intermediate 2 (2,6-dibromo-4-(4-butyl anilino)-1,5-dihydroxy-8-nitroanthraquinone) was obtained;

[0084] (3) Preparation of intermediate 3: 1.03 equivalents of 2,6-dibromo-4-(4-butyl anilino)-1,5-dihydroxy-8-nitroanthraquinone and 5.15 equivalents of zinc powder were suspended in anhydrous tetrahydrofuran, and the mixture was stirred under argon protection; 10% dilute hydrochloric acid aqueous solution was added dropwise to the system, and the temperature was controlled ≤30°C during the addition, and then a temperature increase program was started, with a heating rate of 2°C / min to 66°C for reflux reaction, and the reaction was carried out in the dark for 4 hours (TLC monitoring, with complete disappearance of the raw material point as the reaction endpoint). After the reaction solution was cooled to 5°C, it was suction filtered using a sand core funnel preloaded with diatomite; the filter cake was washed with pre-cooled tetrahydrofuran, and the combined filtrates were concentrated under reduced pressure; ethanol was added to the concentrate (volume ratio of concentrate to ethanol 1:5) for slurry treatment, and suction filtration was performed to obtain the crude product; the crude product was further slurry treated with a dichloromethane / petroleum ether mixed solvent, and after vacuum drying, intermediate 3 (4-amino-2,6-dibromo-8-(4-butyl anilino)-1,5-dihydroxyanthraquinone) was obtained;

[0085] (4) Preparation of blue anthraquinone dye: 1.35 equivalents of p-pentyloxyphenol were dissolved in anhydrous N-methylpyrrolidone under argon protection, and the system was cooled to 0°C by ice bath; 1.33 equivalents of sodium hydride were added in batches, and the addition rate was strictly controlled ≤0.1 g / min, and after addition, the system was stirred at 0°C for 30 minutes; then 0.27 equivalents of 4-amino-2,6-dibromo-8-(4-butyl anilino)-1,5-dihydroxyanthraquinone were added, and argon was bubbled for 10 minutes to completely remove oxygen; then the temperature was increased to 100°C at a rate of 3°C / min, and the reaction was carried out in the dark for 10 hours (TLC monitoring, with complete disappearance of the raw material point as the reaction endpoint), to obtain a blue anthraquinone dye.

[0086] Figure 3 The dichroic absorption spectrum of the anthraquinone blue dye prepared in this example. From the Figure 3It can be seen that the dye has strong absorption in the direction of the long axis of the molecule, and the absorption is significantly reduced in the direction of the short axis of the molecule, showing a significant dichroism feature. The dichroic ratio of the dye is 10.92 at room temperature tested by a UV-Vis spectrophotometer.

[0087] Example 4

[0088] The embodiment provides a preparation method of a full anthraquinone type black dichroic dye, comprising the following steps:

[0089] The orange anthraquinone dye prepared in Example 1, the red anthraquinone dye prepared in Example 2 and the blue anthraquinone dye prepared in Example 3 are mixed by a solution calibration method, a certain mass of dye molecules is dissolved in a fixed volume of weak volatile solvent, and the mixing of the dyes is realized by transferring a quantitative solvent, to obtain a full anthraquinone type black dichroic dye, and a physical diagram is as shown in Figure 4 The mass percentage of the orange dye, the red dye and the blue dye in the full anthraquinone type black dichroic dye obtained by mixing is 22%:22%:56% after calculation.

[0090] Figure 5 An absorption spectrum curve of the full anthraquinone type black dichroic dye prepared in the embodiment is shown in Figure 5 It can be seen that the dye shows significant absorption in a wide band of visible light (400-650 nm), covering the main interval from purple light to red light, and the absorbance remains relatively stable in the band, showing the characteristics of wide band absorption, which can meet the black visual demand in most daily light scenes, and is suitable for application fields such as smart dimming glass, display and the like which require wide range absorption of visible light.

[0091] The full anthraquinone type black dichroic dye prepared in the embodiment is put into liquid crystal SLC1717 and mixed fully, and then a dichroic ratio of the dye is tested at room temperature by a UV-Vis spectrophotometer, and the data is shown in Table 1. The full anthraquinone type black dichroic dye provided in the application achieves the highest dichroic ratio near the core band of human eye vision (about 555 nm), which can reach 13.29. In the wide band range of visible light (400-650 nm), after weighted average by CIE 1931 standard visual function, the average dichroic ratio is 11.28, and the dye has excellent optical performance.

[0092] Table 1 Dichroic performance of the guest-host liquid crystal system doped with the black dichroic dye

[0093]

[0094] Example 5

[0095] The embodiment provides a guest-host liquid crystal composition, which comprises the following components in parts by weight: 94.53 parts of a liquid crystal material, 4.72 parts of the all-anthraquinone type black dichroic dye prepared in the embodiment 4, and 0.75 parts of a chiral agent; wherein the liquid crystal material is liquid crystal E7, and the chiral agent is R811 chiral agent.

[0096] The embodiment also provides a guest-host liquid crystal light modulation device, and the preparation raw material comprises the guest-host liquid crystal composition provided in the embodiment.

[0097] The preparation method of the guest-host liquid crystal light modulation device provided in the embodiment comprises the following steps:

[0098] The liquid crystal material, the all-anthraquinone type black dichroic dye and the chiral agent are mixed to obtain a guest-host liquid crystal composition; the guest-host liquid crystal composition is filled into a glass liquid crystal box by capillary action, and the liquid crystal box is sprayed with spacing particles (glass microspheres) at a spraying density of 200 / cm 2 , to obtain a guest-host liquid crystal light modulation device, and a physical diagram is shown in Figure 6 . The guest-host liquid crystal light modulation device provided in the embodiment can realize switching performance of on-off states by controlling the application or disconnection of an electric field.

[0099] Obviously, the above embodiment is only an example for clearly illustrating, and does not limit the embodiments. For ordinary skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, all the embodiments need not and cannot be exhausted. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A black bipolar dye of all-anthraquinone type, characterized in that, The all-anthraquinone black bidirectional dye includes an anthraquinone orange dye, an anthraquinone red dye, and an anthraquinone blue dye; The anthraquinone orange dye, the anthraquinone red dye, and the anthraquinone blue dye all include the structural formula shown in formula (1): When formula (1) represents the anthraquinone-type orange dye, the substituents R1, R4, R5, and R8 in the structural formula are each independently selected from hydrogen atoms, hydroxyl groups, or halogens, and R2, R3, R6, and R7 are each independently selected from substituent A or hydrogen atoms; the structural formula of substituent A is shown in formula (2): In equation (2), j is 0 or 1; k is an integer, and 0 ≤ k ≤ 25; When formula (1) represents the anthraquinone-type red dye, the substituents R1, R4, R5, and R8 in the structural formula are each independently selected from hydrogen atoms, hydroxyl groups, or halogens, and R2, R3, R6, and R7 are each independently selected from the substituent A or hydrogen atoms. When formula (1) represents the anthraquinone-type blue dye, the substituents R1 and R5 in the structural formula are each independently selected from hydrogen atom, hydroxyl, amino, nitro or halogen; R4 and R8 are each independently selected from hydrogen atom, hydroxyl, amino, nitro, halogen or substituent B; R2, R3, R6 and R7 are each independently selected from substituent C or hydrogen atom; the structural formula of substituent B is shown in formula (3): In equation (3), m is 0 or 1; n is an integer, and 0 ≤ n ≤ 25; The substituent C has the structural formula shown in formula (4): In equation (4), x is 0 or 1; y is 0 or 1; z is an integer, and 0 ≤ z ≤ 25.

2. The all-anthraquinone type black bidirectional dye as described in claim 1, characterized in that, The all-anthraquinone black bipolar dye comprises the following components by mass percentage: 20-60% anthraquinone orange dye, 20-60% anthraquinone red dye, and 20-60% anthraquinone blue dye.

3. The all-anthraquinone type black bidirectional dye as described in claim 1 or 2, characterized in that, The structural formula of the anthraquinone orange dye is shown in formula (5): In equation (5), k is an integer, and 0 ≤ k ≤ 25; The structural formula of the anthraquinone-type red dye is shown in formula (6): In equation (6), k is an integer, and 0 ≤ k ≤ 25; The structural formula of the anthraquinone-type blue dye is shown in formula (7): In equation (7), z is an integer and 0 ≤ z ≤ 25; m is 0 or 1; n is an integer and 0 ≤ n ≤ 25.

4. The all-anthraquinone type black bidirectional dye as described in claim 1 or 2, characterized in that, The structural formula of the anthraquinone orange dye is shown in formula (8): The structural formula of the anthraquinone-type red dye is shown in formula (9): The structural formula of the anthraquinone-type blue dye is shown in formula (10):

5. A guest-host liquid crystal composition, characterized in that, Includes the all-anthraquinone type black bidirectional dye as described in any one of claims 1-4.

6. The guest-host liquid crystal composition as described in claim 5, characterized in that, The host-guest liquid crystal composition comprises the following components by weight: 80-99 parts of liquid crystal material, 1-10 parts of anthraquinone-type black dihedral dye, and 0.1-5 parts of chiral agent.

7. The guest-host liquid crystal composition as described in claim 6, characterized in that, The liquid crystal material is selected from at least one of cyano-containing liquid crystals and fluorine-containing liquid crystals; and / or The chiral agent is selected from at least one of R811 chiral agent, S811 chiral agent, R1011 chiral agent, S1011 chiral agent, R5011 chiral agent, and S5011 chiral agent.

8. The use of the all-anthraquinone black dihedral dye according to any one of claims 1-4 or the guest-host liquid crystal composition according to any one of claims 5-7 in the preparation of liquid crystal dimming devices.

9. A guest-host liquid crystal dimming device, characterized in that, The raw materials used in the preparation of the guest-host liquid crystal dimming device include the guest-host liquid crystal composition as described in any one of claims 5-7.

10. A method for preparing the guest-host liquid crystal dimming device according to claim 9, characterized in that, The process includes the following steps: injecting the guest-host liquid crystal composition into a liquid crystal cell to obtain the guest-host liquid crystal dimming device.

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