Gray dye composition and application of dye liquid crystal composition containing gray dye composition

Abstract

The invention relates to a gray dye composition, which consists of at least one yellow dichroic dye, at least one red dichroic dye, at least one purple dichroic dye and at least one blue dichroic dye, and has uniform total absorption in a visible light region when being mixed with a parent liquid crystal composition for use. The liquid crystal composition has high contrast when applied to light valves, switchable windows, switchable mirrors and guest-host displays.

Description

Technical Field

[0001] The present invention relates to a grey dye composition, a dye liquid crystal composition containing the same, and their applications in light valves, switchable windows, switchable mirrors and guest-host displays. Background Art

[0002] Dye liquid crystal is a guest-host liquid crystal material composed of doping a small amount of guest dichroic dye in a host liquid crystal. Due to the interaction between the host and the guest, the dichroic dye molecules will be arranged orderly following the host liquid crystal molecules. Therefore, the arrangement mode of the host liquid crystal can be changed by changing the applied external electric field, and then the arrangement direction of the dye molecules can be driven to change. Among them, dichroic dye refers to a dye compound with different light absorption intensities along different axes. Therefore, when its direction changes following the rotation of the host liquid crystal molecules, its light absorption ability also changes accordingly, so as to achieve the effect of adjusting the light transmittance. By adding dichroic dyes of different colors, the liquid crystal device can present different colors, and the adjustment of visible light in different bands can be realized.

[0003] Compared with traditional liquid crystal devices, this kind of technology does not need to use a polarizing plate, so it has higher light utilization rate. In recent years, with people's continuous pursuit of a higher quality of life, the application fields of dye liquid crystal have been continuously expanded. Such as the color-changing sunroof of cars, the color-changing glass inside and outside buildings, the color-changing side windows on large public transport vehicles, and smart glasses that change color with the intensity of external light, etc., are all emerging application scenarios of dye liquid crystal. Compared with the application scenarios of traditional liquid crystal materials, dye liquid crystal has a wider range of use in large-size devices, and many of them are emerging fields, so its demand is greater and the application prospect is broader. In most application scenarios, it is required that the dye liquid crystal presents a dark color close to black in the dark state to achieve a more comprehensive absorption of visible light. However, due to the molecular structure limitation of the dye compound, it is difficult for a single dye to achieve a black or grey effect with full absorption in the visible light range. Therefore, dyes with different absorption bands need to be combined together to achieve a more comprehensive absorption of visible light. A dye composition in which multiple dyes are combined to achieve a black or grey effect is what we need. Summary of the Invention

[0004] Object of the Invention: The main object of the present invention is to provide a grey dye composition and a dye liquid crystal composition containing the composition. The dye liquid crystal composition has uniform full absorption in the visible light region and has a high contrast when applied to light valves, switchable windows, switchable mirrors and guest-host displays.

[0005] Technical solution: To achieve the above object, the present invention provides a gray dye composition, characterized in that the dye composition comprises at least one yellow dichroic dye, at least one red dichroic dye, at least one purple dichroic dye and at least one blue dichroic dye;

[0006] The yellow dichroic dye is selected from the formulas A1 to A5, and the formulas A1 to A5 are as follows:

[0007] A1,

[0008] A2,

[0009] A3,

[0010] A4,

[0011] A5,

[0012] Wherein, R1 and R1' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups;

[0013] The red dichroic dye is selected from the formulas B1 to B7, and the formulas B1 to B7 are as follows:

[0014] B1,

[0015] B2,

[0016] B3,

[0017] B4,

[0018] B5,

[0019] B6,

[0020] B7,

[0021] Wherein, R2 and R2' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups;

[0022] The purple dichroic dye is selected from Formulas C1 to C6, and Formulas C1 to C6 are as follows:

[0023] C1,

[0024] C2,

[0025] C3,

[0026] C4,

[0027] C5,

[0028] C6,

[0029] Wherein, R3 and R3' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups;

[0030] The blue dichroic dye is selected from Formulas D1 to D4, and Formulas D1 to D4 are as follows:

[0031] D1,

[0032] D2,

[0033] D3,

[0034] D4,

[0035] Wherein, R4 and R4' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups.

[0036] In one embodiment of the present invention, there is also provided a gray dye liquid crystal composition, characterized in that the gray dye liquid crystal composition contains the above-mentioned gray dye composition, and the mass fraction of the gray dye composition in the gray dye liquid crystal composition is 0.5% to 30%.

[0037] In one embodiment of the present invention, the gray dye liquid crystal composition further includes at least one liquid crystal compound of component II, at least one liquid crystal compound of component III, at least one liquid crystal compound of component IV, at least one liquid crystal compound of component V, a chiral agent with a mass fraction of 0 to 20%, and a stabilizer with a mass fraction of 0 to 20%.

[0038] Component II is a liquid crystal compound having the general formula II, and the general formula II is as follows:

[0039]

[0040] n is 1 or 2;

[0041] When n is 1, Selected from

[0042] When n is 2, the component includes two That is Appearing twice in the component,

[0043] Each independently when appearing each time is

[0044] Y1 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups;

[0045] Component III is a liquid crystal compound having the general formula III as follows:

[0046]

[0047] Y2 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups;

[0048] X1 and X2 are each independently selected from H or F, and at least one of X1 and X2 is F;

[0049] Component IV is a liquid crystal compound having the general formula IV as follows:

[0050]

[0051] Y3 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups,

[0052] Component V is a liquid crystal compound having general formulas V1 to V3, and the general formulas V1 to V3 are as follows:

[0053] V1, V2, V3,

[0054] wherein Y4 and Y4' are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups. Detailed implementation mode

[0055] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0056] The following further describes the present application in detail with reference to specific embodiments, and these embodiments should not be construed as limiting the scope claimed by the present application.

[0057] In order to solve the above problems, in a typical implementation mode of the present invention, a gray dye composition is provided, which is characterized in that the dye composition contains at least one yellow dichroic dye, at least one red dichroic dye, at least one purple dichroic dye and at least one blue dichroic dye;

[0058] The yellow dichroic dye is selected from formulas A1 to A5, and the formulas A1 to A5 are as follows:

[0059] A1,

[0060] A2,

[0061] A3,

[0062] A4,

[0063] A5,

[0064] Wherein, R1 and R1' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups.

[0065] The red dichroic dye is selected from the formulas B1 to B7, and the formulas B1 to B7 are as follows:

[0066] B1,

[0067] B2,

[0068] B3,

[0069] B4,

[0070] B5,

[0071] B6,

[0072] B7,

[0073] Among them, R2 and R2' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups.

[0074] The purple dichroic dye is selected from Formulas C1 to C6, and Formulas C1 to C6 are as follows:

[0075] C1,

[0076] C2,

[0077] C3,

[0078] C4,

[0079] C5,

[0080] C6,

[0081] Among them, R3 and R3' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups.

[0082] The blue dichroic dye is selected from Formulas D1 to D4, and Formulas D1 to D4 are as follows:

[0083] D1,

[0084] D2,

[0085] D3,

[0086] D4,

[0087] wherein, R4 and R4' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups.

[0088] In one embodiment of the present invention, in the yellow dichroic dye, R1 and R1' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl and alkoxy groups.

[0089] In one embodiment of the present invention, in the red dichroic dye, R2 and R2' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl and alkoxy groups.

[0090] In one embodiment of the present invention, in the purple dichroic dye, R3 and R3' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl and alkoxy groups.

[0091] In one embodiment of the present invention, in the blue dichroic dye, R4 and R4' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl and alkoxy groups.

[0092] In one embodiment of the present invention, there is also provided a gray dye liquid crystal composition, characterized in that the gray dye liquid crystal composition contains the above-mentioned gray dye composition, and the mass fraction of the gray dye composition in the gray dye liquid crystal composition is 0.5% to 30%.

[0093] The dichroic dyes mentioned in the embodiments of the present invention are all synthesized independently, and the raw materials used for synthesis can all be obtained through commercial channels.

[0094] When the yellow, red, purple, and blue dichroic dyes are used in combination, they can achieve full absorption in the visible light range (400 - 700 nm); by adjusting the ratio of each dye, the absorption curve can be made uniform, thereby achieving a black or gray effect.

[0095] In one embodiment of the present invention, the gray dye liquid crystal composition further includes at least one liquid crystal compound of component II, at least one liquid crystal compound of component III, at least one liquid crystal compound of component IV, at least one liquid crystal compound of component V, a chiral agent with a mass fraction of 0 - 20%, and a stabilizer with a mass fraction of 0 - 20%.

[0096] Component II is a liquid crystal compound with the general formula II, and the general formula II is as follows:

[0097]

[0098] n is 1 or 2;

[0099] When n is 1, Selected from

[0100] When n is 2, the component includes two That is Appears twice in the component,

[0101] Each time it appears, it is independently

[0102] Y1 is selected from an alkyl group with 1 - 7 carbon atoms, an alkoxy group with 1 - 7 carbon atoms, an alkenyl group with 2 - 7 carbon atoms, an alkenyloxy group with 2 - 7 carbon atoms, a halogenated alkyl group with 1 - 7 carbon atoms, a halogenated alkoxy group with 1 - 7 carbon atoms, a halogenated alkenyl group with 2 - 7 carbon atoms, a halogenated alkenyloxy group with 2 - 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group with 1 - 7 carbon atoms, an alkoxy group with 1 - 7 carbon atoms, an alkenyl group with 2 - 7 carbon atoms, or an alkenyloxy group with 2 - 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups, and alkenyloxy groups.

[0103] Component III is a liquid crystal compound with the general formula III, and the general formula III is as follows:

[0104]

[0105] Y2 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups;

[0106] X1 and X2 are each independently selected from H or F, and at least one of X1 and X2 is F;

[0107] The component IV is a liquid crystal compound having the general formula IV as follows:

[0108]

[0109] Y3 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups,

[0110] The component V is a liquid crystal compound having the general formulas V1 to V3 as follows:

[0111] V1, V2, V3,

[0112] Wherein, Y4 and Y4' are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups.

[0113] In one embodiment of the present invention, the chiral agent is selected from one or more of the following chiral agents, and the chiral agents are as follows:

[0114]

[0115]

[0116] In one embodiment of the present invention, the stabilizer is selected from one or more of the following stabilizers, and the stabilizers are as follows:

[0117] S1, S2, S3, S4,

[0118] Wherein, Y5 is selected from H, F, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups.

[0119] In another typical embodiment of the present application, an application of the above liquid crystal composition in a light valve, a switchable window, a switchable mirror and a guest-host display is provided.

[0120] The gray dye liquid crystal composition provided by the present invention can be prepared according to a conventional method. Generally, at a high temperature, the required amount of components is dissolved in a lower amount in the components constituting the main component; the solutions of each component can also be mixed into an organic solvent, such as mixed into acetone, chloroform or methanol, and after sufficient mixing, the solvent is removed again, for example, the solvent is removed by distillation.

[0121] The preparation method of the gray dye liquid crystal composition provided by the present invention is as follows: first, the color dyes constituting the gray dye composition are mixed evenly, and then the obtained gray dye composition is dissolved in the liquid crystal composition, and heated to 110 °C and stirred for more than 24 h to obtain a uniformly mixed gray dye liquid crystal composition.

[0122] The preparation method of the test cell of the gray dye liquid crystal composition provided by the present invention is as follows: the above-prepared dissolved gray dye liquid crystal composition is sucked into a horizontally aligned liquid crystal cell by capillary action. The thickness of the liquid crystal cell is 3 - 20 μm.

[0123] In a typical embodiment of the present invention, the thickness of the gray dye liquid crystal composition layer is 9 μm.

[0124] In another typical embodiment of the present application, an application of the above gray dye liquid crystal composition in a light valve, a switchable window, a switchable mirror, and a guest - host display is provided.

[0125] Hereinafter, the beneficial effects of the present invention will be further described in conjunction with embodiments.

[0126] The following examples are used to explain the present invention rather than limit it. The percentages involved in the examples are all mass percentages, and the temperature is expressed in degrees Celsius. The measured physical and chemical parameters are represented as follows: T NI represents the clearing point; △n represents the optical anisotropy (△n = n e -n o , 589 nm, measurement temperature 25 °C); △ε represents the dielectric anisotropy (△ε = ε ∥ -ε ⊥ , 25 °C); K 11 represents the splay elastic coefficient (measurement temperature 25 °C); K 33 represents the bend elastic coefficient (measurement temperature 25 °C); τ 亮 represents the light state transmittance (the light state is when the driving voltage is 0 V); τ 暗 represents the dark state transmittance (the dark state is when the driving voltage is 48 V); CR represents the contrast ratio, and the contrast ratio CR = τ 亮 / τ 暗 ; CIE x,y represents the color coordinates, and the color coordinates use the CIE1931 standard colorimetric system. And T NI is measured by DSC; △n is measured by an Abbe refractometer; △ε, K11 and K 33 ; A test cell of the dye liquid crystal composition is driven by a digital synthesizing function signal generator, the driving voltage is 0 - 48V, the waveform is a square wave, and the thickness of the dye liquid crystal composition layer of the test cell is 9μm; τ is measured by a haze meter 亮 and τ 暗 ; The color coordinates are measured by a color analyzer.

[0127] In each embodiment of the present invention, the main chain of the liquid crystal molecule is named: cyclohexyl is represented by the letter C; phenyl is represented by the letter P; phenyl with a single fluorine substitution on the left is represented by the letter H2, and phenyl with a single fluorine substitution on the right is represented by the letter H1; The corresponding codes for the specific group structures are shown in Table 1:

[0128] Table 1

[0129]

[0130]

[0131] The side chains of each compound are converted into chemical formulas according to Table 2 below. The left side chain is represented by R1, and the right side chain is represented by R2. Among them, the group C n H 2n+1 and C m H 2m+1 are straight-chain alkyl groups with n and m carbon atoms respectively. Cp represents cyclopentyl C n H 2n+1 Cp represents cyclopentyl with a straight-chain alkyl group having n carbon atoms. The main chain and the side chain, as well as the side chains, are separated by "-". When naming, the main chain is in front and the side chain is behind. For example, is represented by CMPP - 2 - N; is represented by CPP - 3 - N, is represented by PH1P - 3 - N; is represented by CC - 3 - V.

[0132] Table 2

[0133]

[0134]

[0135] Examples of dye compositions

[0136] Example G1

[0137] The dye composition of Example G1 is shown in Table 3

[0138] Table 3

[0139]

[0140] Example G2

[0141] The dye composition of Example G2 is shown in Table 4

[0142] Table 4

[0143]

[0144]

[0145] Example G3

[0146] The dye composition of Example G3 is shown in Table 5

[0147] Table 5

[0148]

[0149] Example G4

[0150] The dye composition of Example G4 is shown in Table 6

[0151] Table 6

[0152]

[0153] Example G5

[0154] The dye composition of Example G5 is shown in Table 7

[0155] Table 7

[0156]

[0157] Example G6

[0158] The dye composition of Example G6 is shown in Table 8

[0159] Table 8

[0160]

[0161] Example G7

[0162] The dye composition of Example G7 is shown in Table 9

[0163] Table 9

[0164]

[0165]

[0166] Examples of host liquid crystal compositions

[0167] Example H1

[0168] The composition and measurement parameters of the liquid crystal composition of Example H1 are shown in Table 10.

[0169] Table 10

[0170]

[0171] Examples of dye-doped liquid crystal compositions

[0172] Mixed dye liquid crystal compositions GH1 - GH8 were prepared by mixing dye composition examples G1 - G7 with the parent liquid crystal composition of Example H1, and were filled into a horizontally aligned liquid crystal cell with a cell thickness of 9 μm to test their performance. The compositions and performance parameters of the dye liquid crystal compositions GH1 - GH8 are shown in Tables 11 - 18.

[0173] Table 11

[0174]

[0175]

[0176] Table 12

[0177]

[0178] Table 13

[0179]

[0180] Table 14

[0181]

[0182] Table 15

[0183]

[0184] Table 16

[0185]

[0186] Table 17

[0187]

[0188] Table 18

[0189]

[0190] As can be seen from Examples GH1 to GH8 of the dye liquid crystal composition, in accordance with the guidance of the present invention, a gray dye liquid crystal composition with color coordinates close to standard black (0.33, 0.33) can be obtained by using the dye liquid crystal composition described in the present invention; as can be seen from Examples GH1 and GH2, GH7 and GH8 of the dye liquid crystal composition, when the components and total mass ratio of the used dye composition remain unchanged, introducing a chiral agent can effectively reduce the dark state transmittance to obtain a higher contrast ratio.

[0191] Although the present invention does not exhaust all dyes and dye liquid crystal compositions claimed for protection, it can be foreseen by those skilled in the art that, based on the above-mentioned disclosed embodiments, other similar materials can be obtained in a similar manner by simply combining their own professional attempts without creative efforts. Due to limited space here, only representative embodiments are listed.

[0192] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A gray dye composition, characterized in that, The dye composition contains at least one yellow dichroic dye, at least one red dichroic dye, at least one purple dichroic dye, and at least one blue dichroic dye; The yellow dichroic dye is selected from Formulae A1 to A5, and Formulae A1 to A5 are as follows: A1、 A2、 A3、 A4、 A5、 Wherein, R1 and R1' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups, and alkenyloxy groups; The red dichroic dye is selected from Formulae B1 to B7, and Formulae B1 to B7 are as follows: B1、 B2、 B3、 B4、 B5、 B6、 B7、 Wherein, R2 and R2' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups, and alkenyloxy groups; The purple dichroic dye is selected from Formulae C1 to C6, and Formulae C1 to C6 are as follows: C1、 C2、 C3、 C4、 C5、 C6、 Wherein, R3 and R3' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group, and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups, and alkenyloxy groups; The blue dichroic dye is selected from Formulae D1 to D4, and Formulae D1 to D4 are as follows: D1、 D2、 D3、 D4、 Among them, R4 and R4' are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups.

2. The gray dye composition according to claim 1, wherein In the yellow dichroic dye, R1 and R1' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl groups and alkoxy groups.

3. A gray dye composition according to claim 1, wherein In the red dichroic dye, R2 and R2' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl groups and alkoxy groups.

4. A gray dye composition according to claim 1, wherein In the purple dichroic dye, R3 and R3' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl groups and alkoxy groups.

5. A gray dye composition according to claim 1, wherein In the blue dichroic dye, R4 and R4' are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 5 carbon atoms; the alkyl group and the alkoxy group are straight-chain or branched-chain alkyl groups and alkoxy groups.

6. A gray dye liquid crystal composition, characterized in that, The gray dye liquid crystal composition contains the gray dye composition according to claim 1, and the mass fraction of the gray dye composition in the gray dye liquid crystal composition is 0.5% to 30%.

7. The gray dye liquid crystal composition according to claim 6, characterized in that, The liquid crystal composition further includes at least one liquid crystal compound of component II, at least one liquid crystal compound of component III, at least one liquid crystal compound of component IV, at least one liquid crystal compound of component V, a chiral agent with a mass fraction of 0 to 20% and a stabilizer with a mass fraction of 0 to 20%. Component II is a liquid crystal compound having the general formula II, and the general formula II is as follows: n is 1 or 2; When n is 1, selected from When n is 2, the component includes two That is appears twice in the component, and each independently is Y1 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups; Component III is a liquid crystal compound having the general formula III as follows: Y2 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups; X1 and X2 are each independently selected from H or F, and at least one of X1 and X2 is F; Component IV is a liquid crystal compound having the general formula IV as follows: Y3 is selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups, Component V is a liquid crystal compound having the general formulas V1 to V3 as follows: V1, V2, V3, Wherein, Y4 and Y4' are each independently selected from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl groups, alkoxy groups, alkenyl groups and alkenyloxy groups.

8. A gray dye liquid crystal composition according to claim 7, characterized in that The chiral agent is selected from one or more of the following chiral agents, and the chiral agents are as follows:

9. A gray dye liquid crystal composition according to claim 7, wherein The stabilizer is selected from one or more of the following stabilizers, and the stabilizers are as follows: S1, S2, S3, S4, wherein Y5 is selected from H, F, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, a halogenated alkyl group having 1 to 7 carbon atoms, a halogenated alkoxy group having 1 to 7 carbon atoms, a halogenated alkenyl group having 2 to 7 carbon atoms, a halogenated alkenyloxy group having 2 to 7 carbon atoms, cyclopentyl, or cyclopentyl substituted by an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group, the alkenyl group and the alkenyloxy group are straight-chain or branched-chain alkyl, alkoxy, alkenyl and alkenyloxy groups.

10. Use of the composition according to any one of claims 1 to 9 in a light valve, a switchable window, a switchable mirror and a guest-host type display.

Images