Dye liquid crystal composition and application thereof

Abstract

The invention discloses a dye liquid crystal composition and application thereof, and belongs to the technical field of liquid crystal materials. The liquid crystal liquid is composed of a liquid crystal main body and dichroic dye, wherein the liquid crystal main body is composed of at least one compound represented by a general formula I, a general formula II-A, a general formula II-B and a general formula III: I, II-A, II-B and III. The dye liquid crystal composition provided by the invention has relatively low power consumption and good color and photo-thermal stability, and can be used in a normally black display liquid crystal device formed by glass or a flexible substrate.

Description

TECHNICAL FIELD

[0001] The present application relates to compositions and applications thereof, in particular to a dye liquid crystal composition composed of a liquid crystal host and a dichroic dye, and the application of the dye liquid crystal composition in a normally black display liquid crystal device composed of a glass substrate or a flexible substrate, and belongs to the technical field of liquid crystal materials. BACKGROUND

[0002] How to improve the quality of liquid crystal display and better realize the colorization of liquid crystal is the main research direction of liquid crystal display application. Among them, dye liquid crystal based on guest-host effect has been widely concerned due to its unique advantages. Dye liquid crystal can realize color display of different gray scales by doping a certain amount of dichroic dye (guest) in the liquid crystal host (host), because the arrangement of liquid crystal molecules is controlled by electric field, and then the orientation of dye molecules changes. The device prepared based on dye liquid crystal has the advantages of bright color and display color tone not affected by viewing angle, and has great potential in practical application.

[0003] However, in the actual application process, we found that the existing dye liquid crystal based on guest-host effect often has the problems of high power consumption and significant color shift after long-term aging under ultraviolet or high temperature.

[0004] The above two problems are the key bottlenecks hindering the practical application of high-performance dye liquid crystal display devices. Therefore, there is an urgent need in the art to develop new dye liquid crystal material systems to overcome the above defects. SUMMARY

[0005] In order to solve the problems of the prior art, the purpose of the present application is to provide a dye liquid crystal composition with low power consumption and low high-temperature and ultraviolet color difference, and the application of the dye liquid crystal composition.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: A dye liquid crystal composition composed of a liquid crystal host and a dichroic dye, wherein: The liquid crystal host is composed of at least one compound represented by general formula I, at least one compound represented by general formula II-A, at least one compound represented by general formula II-B, and at least one compound represented by general formula III: I; II-A; II-B; III; R1, R2, R3, R4 each independently represent halogenated or unhalogenated alkyl having 1 to 10 carbon atoms, one or more CH2 groups in the alkyl group can be replaced independently of one another by -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O- or -S-, the O and S atoms are not directly connected; 、 、 、 、 、 each independently represent or wherein one or more H atoms can be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5, halogenated or unhalogenated alkyl having 1 to 10 carbon atoms, halogenated or unhalogenated alkoxy having 1 to 10 carbon atoms, halogenated or unhalogenated alkenyl having 2 to 10 carbon atoms, halogenated or unhalogenated alkenyloxy having 2 to 10 carbon atoms, C6 or lower cycloalkyl or C6 or lower cycloalkenyl; wherein, when 、 、 、 、 、 represents phenylene, one or more CH on the phenyl ring can be replaced by N; when 、 、 、 、 、 represents cyclohexylene, one or more CH2 in the ring can be replaced by O; The dichroic dye consists of at least one compound represented by the general formula D-AI, at least one compound represented by the general formula D-BI, at least one compound represented by the general formula D-II and at least one compound represented by the general formula D-III: D-AI; D-BI; D-II; D-III; DR1, DR2, DR3, DR4, DR5 each independently represents halogenated or non-halogenated alkyl group having 1 to 10 carbon atoms, one or more CH2 groups in the alkyl group can be replaced by -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O- or -S- independently from each other, O and S atoms are not directly connected; C1, C2 each independently represents hydrogen atom, halogen atom, hydroxyl group, amino group or halogenated or non-halogenated alkyl group having 1 to 10 carbon atoms, one or more CH2 groups in the alkyl group can be replaced by -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O- or -S- independently from each other, O and S atoms are not directly connected; L1 represents substituted or non-substituted arylene group having 6 to 50 carbon atoms, substituted or non-substituted heteroarylene group having 2 to 50 carbon atoms, the substituents are alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or halogen; L2 represents hydrogen atom, substituted or non-substituted C1-C12 alkyl group, substituted or non-substituted C2-C6 alkenyl group, substituted or non-substituted alkoxy group having 1 to 18 carbon atoms, substituted or non-substituted alkylamino group having 1 to 18 carbon atoms, substituted or non-substituted cycloalkoxy group having 5 to 12 carbon atoms, substituted or non-substituted alkenyloxy group having 2 to 18 carbon atoms, -C=N, halogenated alkyl group having 1 to 4 carbon atoms, sulfo group, acyl group, acylamino group having 2 to 18 carbon atoms, acyloxy group having 2 to 18 carbon atoms, substituted or non-substituted aryl group having 6 to 50 carbon atoms, substituted or non-substituted heteroaryl group having 2 to 50 carbon atoms, the substituents are alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or halogen; 、 、 , amino group or halogenated or non-halogenated alkyl group having 1 to 10 carbon atoms, one or more CH2 groups in the alkyl group can be replaced by -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O- or -S- independently from each other, O and S atoms are not directly connected; L1 represents substituted or non-substituted arylene group having 6 to 50 carbon atoms, substituted or non-substituted heteroarylene group having 2 to 50 carbon atoms, the substituents are alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or halogen; L2 represents hydrogen atom, substituted or non-substituted C1-C12 alkyl group, substituted or non-substituted C2-C6 alkenyl group, substituted or non-substituted alkoxy group having 1 to 18 carbon atoms, substituted or non-substituted alkylamino group having 1 to 18 carbon atoms, substituted or non-substituted cycloalkoxy group having 5 to 12 carbon atoms, substituted or non-substituted alkenyloxy group having 2 to 18 carbon atoms, -C=N, halogenated alkyl group having 1 to 4 carbon atoms, sulfo group, acyl group, acylamino group having 2 to 18 carbon atoms, acyloxy group having 2 to 18 carbon atoms, substituted or non-substituted aryl group having 6 to 50 carbon atoms, substituted or non-substituted heteroaryl group having 2 to 50 carbon atoms, the substituents are alkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms or halogen; The compounds represented by general formula I, general formula II-A, general formula II-B and general formula III are respectively 20-30%, 20-30%, 10-30%, 15-40% of the total weight of the liquid crystal main body, the compounds represented by general formula D-AI, general formula D-BI, general formula D-II and general formula D-III are respectively 0.23-1.29%, 0.1-0.56%, 0.12-0.67% and 0.55-3.08% of the weight of the liquid crystal main body.

[0007] The application of the aforementioned dye liquid crystal composition in the normally black display liquid crystal device composed of glass substrate or flexible substrate.

[0008] The application has the advantages of: (1) By optimizing the type and ratio of the liquid crystal host, the power consumption of the dye liquid crystal composition is significantly reduced, the quality of the dye liquid crystal composition is improved, and the ultraviolet discoloration of the dye liquid crystal composition is effectively improved; (2) By optimizing the type and ratio of the liquid crystal host, the clearing point of the liquid crystal host is improved, and the high-temperature discoloration of the dye liquid crystal composition is effectively alleviated; (3) The dye liquid crystal composition prepared based on the host-guest effect has low power consumption, good color and light-heat stability, and can be applied to a normally black display liquid crystal device composed of a glass substrate or a flexible substrate. DETAILED DESCRIPTION

[0009] The components used in the examples, the preparation of the dye liquid crystal composition, and the performance parameters of the dye liquid crystal composition are obtained by conventional methods.

[0010] The percentages in the examples represent weight percentages unless otherwise specified.

[0011] T （N，I） (℃) represents the clearing point.

[0012] △n represents the optical anisotropy at 20°C, 589 nm.

[0013] △ε represents the dielectric anisotropy at 25°C, 1 kHz.

[0014] I0(μA) represents the initial power consumption current of the crystal.

[0015] I 180 (μA) represents the power consumption current after irradiation for 180 s by a UV lamp with an irradiation intensity of 4 mW / cm 2 .

[0016] L* represents the lightness in the CIE Lab color space, indicating the lightness and darkness of the color, with a value of 0-100.

[0017] a* represents the red-green axis in the CIE Lab color space, with a negative value being green and a positive value being red.

[0018] b* represents the yellow-blue axis in the CIE Lab color space, with a negative value being blue and a positive value being yellow.

[0019] △E UV represents the degree of deviation of the color from the initial color after irradiation for 12 h by a UV lamp with an irradiation intensity of 4 mW / cm 2 .

[0020] △E 150 represents the degree of deviation of the color from the initial color after baking at a high temperature of 150°C for 12 h.

[0021] When △EUV and the value of ΔE 150 When the value of ΔE is less than or equal to 0.5, it means that there is a slight color difference; when the value of ΔE is greater than 0.5 and less than or equal to 1.5, it means that there is a light color difference; when the value of ΔE is greater than 1.5 and less than or equal to 3.0, it means that there is an obvious color difference; when the value of ΔE is greater than 3.0 and less than or equal to 6.0, it means that there is a very obvious color difference; and when the value of ΔE is greater than 6.0, it means that there is a strong color difference.

[0022] I. Composition of the dye liquid crystal composition The dye liquid crystal composition provided by the present application is composed of a liquid crystal main body and a dichroic dye.

[0023] 1. Liquid crystal main body The liquid crystal main body is composed of at least one compound represented by general formula I, at least one compound represented by general formula II-A, at least one compound represented by general formula II-B, and at least one compound represented by general formula III.

[0024] I; II-A; II-B; III; R1, R2, R3, R4 each independently represent halogenated or unhalogenated alkyl containing 1 to 10 carbon atoms, one or more CH2 groups in the alkyl group can be replaced by -C≡C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O- or -S- independently of one another, and the O atom and the S atom are not directly connected.

[0025] , , , , , each independently represent or wherein one or more H atoms can be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5, halogenated or unhalogenated alkyl containing 1 to 10 carbon atoms, halogenated or unhalogenated alkoxy containing 1 to 10 carbon atoms, halogenated or unhalogenated alkenyl containing 2 to 10 carbon atoms, halogenated or unhalogenated alkenyloxy containing 2 to 10 carbon atoms, C6 or less cycloalkyl or C6 or less cycloalkenyl; wherein, when , , , , , In the case of phenylene, one or more CH on the phenyl ring can be replaced by N; when , , , , , In the case of cyclohexylene, one or more CH2 in the ring can be replaced by O.

[0026] wherein the compounds represented by general formula I are selected from the group consisting of: I-1 ; I-2; I-3; I-4; I-5; I-6; I-7; I-8; I-9; I-10; I-11 ; I-12; I-13; I-14; I-15; and I-16.

[0027] wherein the compounds represented by general formula II-A are selected from the group consisting of: II-A-1 ; II-A-2; II-A-3; II-A-4; II-A-5; II-A-6; II-A-7; II-A-8; II-A-9; II-A-10; II-A-11; II-A-12; II-A-13; II-A-14; II-A-15; II-A-16; II-A-17; II-A-18; II-A-19; II-A-20; II-A-21; II-A-22; II-A-23; and II-A-24.

[0028] The compounds represented by the general formula II-B are selected from the group consisting of: II-B-1; II-B-2; II-B-3; II-B-4; II-B-5; II-B-6; II-B-7; II-B-8; II-B-9; II-B-10; II-B-11; II-B-12; II-B-13; II-B-14; II-B-15; II-B-16; II-B-17; II-B-18; II-B-19; and II-B-20.

[0029] The compounds represented by general formula III are selected from: III-1; III-2; III-3; III-4; III-5; III-6; III-7; III-8; III-9; III-10; III-11; III-12; III-13; III-14; III-15; and III-16.

[0030] In the liquid crystal host, the compound represented by general formula I accounts for 20-30% of the total weight of the liquid crystal host, the compound represented by general formula II-A accounts for 20-30% of the total weight of the liquid crystal host, the compound represented by general formula II-B accounts for 10-30% of the total weight of the liquid crystal host, and the compound represented by general formula III accounts for 15-40% of the total weight of the liquid crystal host. The liquid crystal host with the above-mentioned ratio has a high clearing point, a low power consumption current, and a low ultraviolet and high-temperature aging color difference, and has good solubility for the following dichromatic dyes as the host in the guest-host effect.

[0031] 2. Dichromatic dye The dichromatic dye consists of at least one compound represented by general formula D-AI, at least one compound represented by general formula D-BI, at least one compound represented by general formula D-II, and at least one compound represented by general formula D-III, and is black.

[0032] D-AI; D-BI; D-II; D-III.

[0033] DR1, DR2, DR3, DR4, and DR5 each independently represent a halogenated or non-halogenated alkyl group containing 1 to 10 carbon atoms, and one or more CH2 groups in the alkyl group can be replaced with -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O-, or -S- independently of each other, and the O atom and the S atom are not directly connected.

[0034] C1 and C2 each independently represent , , , an amino group, or a halogenated or non-halogenated alkyl group containing 1 to 10 carbon atoms, and one or more CH2 groups in the alkyl group can be replaced with -C=C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O-, or -S- independently of each other, and the O atom and the S atom are not directly connected.

[0035] L1represents a substituted or unsubstituted arylene group containing 6 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group containing 2 to 50 carbon atoms, the substituents being an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 18 carbon atoms or a halogen; L2represents a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted alkoxy group containing 1 to 18 carbon atoms, a substituted or unsubstituted alkylamino group containing 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkoxy group containing 5 to 12 carbon atoms, a substituted or unsubstituted alkenyloxy group containing 2 to 18 carbon atoms, -C≡N, a haloalkyl group containing 1 to 4 carbon atoms, a sulfo group, an acyl group, an acylamino group containing 2 to 18 carbon atoms, an acyloxy group containing 2 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group containing 2 to 50 carbon atoms, the substituents being an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 18 carbon atoms or a halogen.

[0036] The compounds of general formula D-AI are selected from: D-AI-1 ; D-AI-2; D-AI-3; and D-AI-4.

[0037] The compounds of general formula D-BI are selected from: D-BI-1 ; D-BI-2; D-BI-3; and D-BI-4.

[0038] The compounds of general formula D-II are selected from: D-II-1 ; D-II-2; D-II-3; and D-II-4.

[0039] The compounds of general formula D-III are selected from: D-III-1 ; D-III-2; D-III-3; D-III-4; and D-III-5.

[0040] In the dichroic dye, the compound represented by general formula D-AI is used in an amount of 0.23-1.29% by weight of the liquid crystal host, the compound represented by general formula D-BI is used in an amount of 0.1-0.56% by weight of the liquid crystal host, the compound represented by general formula D-II is used in an amount of 0.12-0.67% by weight of the liquid crystal host, and the compound represented by general formula D-III is used in an amount of 0.55-3.08% by weight of the liquid crystal host. The dichroic dye in the above ratio has high contrast and good color and light-thermal stability, and as a guest in the above-mentioned liquid crystal host, it has high solubility in the guest-host effect.

[0041] II. Performance of the dye liquid crystal composition For the convenience of expression, the structure of the dye molecule and the liquid crystal molecule is represented by code combination. Among them, the code of the ring structure is shown in Table 1, the code of the connecting group is shown in Table 2, and the code of the terminal group is shown in Table 3.

[0042] Table 1 Code of ring structure

[0043] Table 2 Code of connecting group

[0044] Table 3 Code of terminal group

[0045] Code combination rule: code of middle ring structure and connecting group from left to right-code of left terminal group-code of right terminal group.

[0046] Examples: Molecular structure: Code combination: CC-a-V.

[0047] Molecular structure: Code combination: CU-a-N.

[0048] Molecular structure: Code combination: CPU-a-F.

[0049] Molecular structure: Code combination: PGP-a-c.

[0050] The present application mainly studies the changes of power consumption current, color before and after high temperature and ultraviolet aging of the dye liquid crystal composition. The power consumption current (including initial power consumption current I0, power consumption current I 180 after ultraviolet lamp aging for 180s) of the dye liquid crystal composition is tested, the quality of the reactive dye liquid crystal composition, the lower the power consumption current, the better the quality of the product; the CIE Lab color space coordinates L*, a*, b* (including the color coordinates in the initial state, the color coordinates after ultraviolet lamp irradiation for 12h under the light intensity of 4mW / cm 2 , and the color coordinates after high temperature 150℃ baking for 12h) are tested, the stability of the dye liquid crystal composition is measured by the changes △E UV and △E 150 of the color coordinates in the initial state and after ultraviolet or high temperature aging, the smaller the △E UV and △E 150 , the smaller the color change of the dye liquid crystal composition, that is, the more stable the dye liquid crystal composition.

[0051] Comparative Example 1 The composition of the liquid crystal composition CR is as follows in mass percentage: PZP-4-N 10%, PZG-5-N 10%, CZG-2-N 8%, CZG-3-N 9%, CPZG-4-N 7%, CPZG-5-N 7%, CPP-3-N 8%, CPP-5-B 8%, PZPG-2-F 7%, PZPG-4-F 8%, PZPC-2-3 6%, PZGP-3-5 6%, PZGP-4-2 6%.

[0052] The performance parameter test results of the liquid crystal composition CR are as follows: T （N，I） =102.9℃, △n=0.178, △ε=16.5, I0=0.10μA, I 180 =0.32μA.

[0053] The liquid crystal monomers used in the liquid crystal composition CR are all conventional liquid crystal monomers for positive display mode, which have the characteristics of simple preparation, easy to obtain materials and low cost, and are widely used in liquid crystal positive display mode, and are a relatively common liquid crystal composition in the industry.

[0054] Comparative Example 2 The dye liquid crystal composition A is composed of the liquid crystal composition CR and a dichroic dye.

[0055] The composition of the dye liquid crystal composition A is as follows in mass percentage: Liquid crystal composition CR 100%, Formula D-AI-2 0.23%, Formula D-BI-4 0.10%, Formula D-II-3 0.30%. 0.12%, Formula D-III-2 0.25%, Formula D-III-3 0.30%.

[0056] The performance parameter test results of the dye liquid crystal composition A are as follows: L* = 63.86, a* = -0.0445, b* = -0.9163, I0= 0.33 μA, I 180 = 0.75 μA, ΔΕ UV = 1.63, ΔΕ 150 = 3.31.

[0057] The dye liquid crystal composition A presents black as a whole, and the absorption wavelengths uniformly cover the visible light and ultraviolet regions. After high-temperature aging or ultraviolet aging, the color difference is greater than 0.5, and the color change before and after aging can be more obviously observed by naked eye.

[0058] Example 1

[0059] The composition of the liquid crystal host LC1 is as follows in mass percentage: General Formula I: PP-4-N 27%; General Formula II-A: CPP-5-N 8%, PGU-4-N 12%, CCU-5-N 6%; General Formula II-B: CPG-5-F 6%, CPP-3-F 9%; General Formula III: CCP-3-1 8%, CCP-3-2 8%, PGP-2-3 5%, PGP-3-5 5%, PGP-4-2 6%.

[0060] The performance parameter test results of the liquid crystal host LC1 are as follows: T （N，I） = 122.3℃, Δn = 0.208, Δε = 8.5, I0= 0.06 μA, I 180 = 0.12 μA.

[0061] Example 2

[0062] The composition of the liquid crystal host LC2 is as follows in mass percentage: General Formula I: PP-3O-N 16%, DP-2-N 5%, MP-2-N 8%; General Formula II-A: CCU-3-N 6%, CPP-3-N 6%, CPP-5-N 5%, CGP-5-N 4%, PPP-3-N 9%; Formula II-B: CCP-3-F 3%, CCP-5-F 3%, PPP-3-F 7%, PGU-3-F 6%, PGU-2-F 8%; Formula III: PGP-2-5 8%, PGP-3-5 8%, PGP-4-2 8%.

[0063] The performance parameters of the liquid crystal host LC3 were tested as follows: T （N，I） = 126.9°C, Δn = 0.241, Δε = 10.2, I0= 0.07 μA, I 180 = 0.11 μA.

[0064] Example 3

[0065] The composition of the liquid crystal host LC3 is as follows in mass percentage: Formula I: CP-5-N 8%, PP-4-N 5%, PP-3O-N 8%; Formula II-A: CGP-5-N 4%, CGP-3-N 3%, CGIP-3-N 4%, PPU-4-N 9%; Formula II-B: CCP-3-F 3%, CCP-5-F 3%, PPP-3-F 7%, PGU-3-F 6%, PGU-2-F 8%; Formula III: PGP-2-5 8%, PGP-3-5 8%, PGP-4-2 8%.

[0066] The performance parameters of the liquid crystal host LC3 were tested as follows: T （N，I） = 113.2°C, Δn = 0.268, Δε = 15.4, I0= 0.05 μA, I 180 = 0.09 μA.

[0067] Example 4

[0068] The composition of the liquid crystal host LC4 is as follows in mass percentage: Formula I: CP-5-N 9%, PP-3O-N 8%, PP-4-N 13%; Formula II-A: CGP-5-N 4%, PPU-4-N 6%, PPP-3-N 4%, PGU-4-N 5%, PGU-5-N 5%; Formula II-B: CCG-2-F 4%, CCG-5-F 6%, CCU-3-F 7%, CCU-5-F 7%, PGU-2-F 6%; Formula III: CPP-4-3 6%, CPP-3-5 4%, PGP-4-2 6%.

[0069] The performance parameter test results of the liquid crystal host LC4 are as follows: T （N，I） = 119.7°C, Δn = 0.205, Δε = 19.0, I0= 0.10 μA, I 180 = 0.19 μA.

[0070] Example 5

[0071] The composition of the liquid crystal host LC5 is as follows in mass percentage: Formula I: CP-5-N 11%, PP-4-N 5%, PP-3O-N 6%, DP-2-N 3%; Formula II-A: CPP-3-N 4%, CPP-5-N 3%, PPU-4-N 4%, CGP-3-N 5%, CGIP-3-N 4%; Formula II-B: PPP-3-F 6%, PGU-5-F 3%, PGU-2-F 6%; Formula III: CPP-4-3 6%, CPP-3-5 6%, PPP-3-2 7%, PGP-2-5 5%, PGP-3-5 8%, PGP-4-2 8%.

[0072] The performance parameter test results of the liquid crystal host LC5 are as follows: T （N，I） = 130.5°C, Δn = 0.198, Δε = 8.7, I0= 0.08 μA, I 180 = 0.13 μA.

[0073] Example 6

[0074] The dye liquid crystal composition B1 is composed of the liquid crystal host LC1 and dichroic dyes.

[0075] The composition of the dye liquid crystal composition B1 is as follows in mass percentage: Liquid crystal host LC1 100%, Formula D-AI-2 0.23%, Formula D-BI-4 0.10%, Formula D-II-3 0.12%, Formula D-III-2 0.25%, Formula D-III-3 0.30%.

[0076] The performance parameter test results of the dye liquid crystal composition B1 are as follows: L* = 60.46, a* = -0.0241, b* = -0.8830, I0= 0.20 μA, I 180 = 0.25 μA, ΔEUV = 0.26, ΔΕ 150 = 0.31.

[0077] The dye liquid crystal composition B1 presents black as a whole, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔΕ UV , ΔΕ 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak to the naked eye. The dichroic dye has high solubility in the liquid crystal host LC1. Compared with the dye liquid crystal composition A, the dye liquid crystal composition B1 has high weather resistance, and is suitable for various application scenarios.

[0078] Example 7

[0079] The dye liquid crystal composition B2 is composed of the liquid crystal host LC1 and the dichroic dye.

[0080] The composition of the dye liquid crystal composition B2 is as follows in terms of mass percentage: The liquid crystal host LC1 100%, the formula D-AI-2 0.46%, the formula D-BI-4 0.20%, the formula D-II-3 0.25%, the formula D-III-2 0.50%, and the formula D-III-3 0.60%.

[0081] The performance parameter test results of the dye liquid crystal composition B2 are as follows: L* = 54.12, a* = -0.7741, b* = -1.1089, I0= 0.22 μA, I 180 = 0.27 μA, ΔΕ UV = 0.20, ΔΕ 150 = 0.37.

[0082] The dye liquid crystal composition B2 presents black as a whole, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔΕ UV , ΔΕ 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak to the naked eye. The dichroic dye has high solubility in the liquid crystal host LC1. Compared with the dye liquid crystal composition A, the dye liquid crystal composition B2 has high weather resistance, and is suitable for various application scenarios.

[0083] Example 8

[0084] The dye liquid crystal composition B3 is composed of the liquid crystal host LC2 and the dichroic dye.

[0085] The composition of the dye liquid crystal composition B3 is as follows in terms of mass percentage: Liquid crystal host LC2 100%, Formula D-AI-2 0.78%, Formula D-BI-4 0.34%, Formula D-II-3 0.41%, Formula D-III-2 0.85%, Formula D-III-3 1.02%.

[0086] The performance parameter test results of the dye liquid crystal composition B3 are as follows: L* = 44.07, a* = -0.5475, b* = -1.4328, I0= 0.18 μA, I 180 = 0.22 μA, ΔE UV = 0.33, ΔE 150 = 0.42.

[0087] The dye liquid crystal composition B3 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔE UV , ΔE 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak to the naked eye. The dichroic dye has a high solubility in the liquid crystal host LC2. Compared with in the liquid crystal host LC1, the dichroic dye has a higher solubility in the liquid crystal host LC2, which can provide better dark state shielding.

[0088] Example 9

[0089] The dye liquid crystal composition B4 is composed of the liquid crystal host LC2 and the dichroic dye.

[0090] The composition of the dye liquid crystal composition B4 in mass percentage is as follows: Liquid crystal host LC2 100%, Formula D-AI-2 1.29%, Formula D-BI-4 0.56%, Formula D-II-3 0.67%, Formula D-III-2 1.40%, Formula D-III-3 1.68%.

[0091] The performance parameter test results of the dye liquid crystal composition B4 are as follows: L* = 32.47, a* = -1.3005, b* = -1.8457, I0= 0.15 μA, I 180 = 0.32 μA, ΔE UV = 0.29, ΔE 150 = 0.44.

[0092] The dye liquid crystal composition B4 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔE UV , ΔE 150less than 0.5, and the naked eye feels that the change is weak. The dichroic dye has a higher solubility in the liquid crystal host LC2. Compared with in the liquid crystal host LC1, the dichroic dye has a higher solubility in the liquid crystal host LC2, which can provide better dark state shielding.

[0093] Example 10

[0094] The dye liquid crystal composition B5 is composed of the liquid crystal host LC3 and the dichroic dye.

[0095] The composition of the dye liquid crystal composition B5 is as follows in mass percentage: The liquid crystal host LC3 100%, the formula D-AI-2 0.78%, the formula D-BI-4 0.34%, the formula D-II-3 0.41%, the formula D-III-2 0.85%, and the formula D-III-3 1.02%.

[0096] The performance parameter test results of the dye liquid crystal composition B5 are as follows: L*=43.12, a*=-0.6352, b*=-1.0784, I0=0.16μA, I 180 =0.19μA, △E UV =0.13, △E 150 =0.38.

[0097] The dye liquid crystal composition B5 presents black as a whole, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (△E UV , △E 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the naked eye feels that the change is weak. The dichroic dye has a higher solubility in the liquid crystal host LC3. Compared with in the liquid crystal host LC2, the dichroic dye has better UV resistance in the liquid crystal host LC3, and the color difference before and after UV aging is lower.

[0098] Example 11

[0099] The dye liquid crystal composition B6 is composed of the liquid crystal host LC3 and the dichroic dye.

[0100] The composition of the dye liquid crystal composition B6 is as follows in mass percentage: The liquid crystal host LC3 100%, the formula D-AI-2 1.29%, the formula D-BI-4 0.56%, the formula D-II-3 0.67%, the formula D-III-2 1.40%, and the formula D-III-3 1.68%.

[0101] The performance parameter test results of the dye liquid crystal composition B6 are as follows: L* = 30.25, a* = -1.2158, b* = -1.3571, I0= 0.13 μΑ, I 180 = 0.28 μΑ, ΔΕ UV = 0.12, ΔΕ 150 = 0.40.

[0102] The dye liquid crystal composition B6 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔΕ UV , ΔΕ 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak in the sense of naked eye. The dichroic dye has high solubility in the liquid crystal host LC3. Compared with in the liquid crystal host LC2, the dichroic dye has better UV resistance in the liquid crystal host LC3, and the color difference before and after UV aging is lower.

[0103] Example 12

[0104] The dye liquid crystal composition B7 is composed of the liquid crystal host LC4 and the dichroic dye.

[0105] The composition of the dye liquid crystal composition B7 in mass percentage is as follows: Liquid crystal host LC4 100%, formula D-AI-2 0.23%, formula D-BI-4 0.10%, formula D-II-3 0.12%, formula D-III-2 0.25%, formula D-III-3 0.30%.

[0106] The performance parameter test results of the dye liquid crystal composition B7 are as follows: L* = 53.74, a* = -0.4107, b* = -1.2089, I0= 0.28 μΑ, I 180 = 0.36 μΑ, ΔΕ UV = 0.19, ΔΕ 150 = 0.33.

[0107] The dye liquid crystal composition B7 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔΕ UV , ΔΕ 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak in the sense of naked eye. The dichroic dye has high solubility in the liquid crystal host LC4. Compared with in the liquid crystal host LC1, the dichroic dye has stronger absorption of light in the liquid crystal host LC4 under the same addition amount, which is reflected in the deeper color in the naked eye observation.

[0108] Example 13

[0109] Dye liquid crystal composition B8 is composed of liquid crystal host LC4 and dichroic dye.

[0110] The composition of dye liquid crystal composition B8 is as follows in mass percentage: Liquid crystal host LC4 100%, formula D-AI-2 0.46%, formula D-BI-4 0.20%, formula D-II-3 0.25%, formula D-III-2 0.50%, formula D-III-3 0.60%.

[0111] The performance parameter test results of dye liquid crystal composition B8 are as follows: L*=47.33, a*=-0.9410, b*=-1.3263, I0=0.31μA, I 180 =0.42μA, ΔE UV =0.26, ΔE 150 =0.45.

[0112] Dye liquid crystal composition B8 presents black as a whole, and the uniform absorption wavelength covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (ΔE UV , ΔE 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak to the naked eye. The dichroic dye has high solubility in liquid crystal host LC4. Compared with in liquid crystal host LC1, the dichroic dye has stronger absorption of light in liquid crystal host LC4 under the same addition amount, which is reflected in the deeper color in the naked eye observation.

[0113] Example 14

[0114] Dye liquid crystal composition B9 is composed of liquid crystal host LC5 and dichroic dye.

[0115] The composition of dye liquid crystal composition B9 is as follows in mass percentage: Liquid crystal host LC5 100%, formula D-AI-2 0.53%, formula D-BI-4 0.23%, formula D-II-3 0.28%, formula D-III-2 0.58%, formula D-III-3 0.69%.

[0116] The performance parameter test results of dye liquid crystal composition B9 are as follows: L*=49.27, a*=-0.8573, b*=-0.9215, I0=0.11μA, I 180 =0.27μA, ΔE UV =0.26, ΔE 150 =0.11.

[0117] The dye liquid crystal composition B9 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (△E UV , △E 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak in the naked eye feeling. The dichroic dye has high solubility in the liquid crystal main body LC5. Compared with in the liquid crystal main body LC1, the dichroic dye has better high-temperature resistance in the liquid crystal main body LC4 under the same addition amount, and the color difference before and after high-temperature aging is lower.

[0118] Example 15

[0119] The dye liquid crystal composition B10 is composed of the liquid crystal main body LC5 and the dichroic dye.

[0120] The composition of the dye liquid crystal composition B10 in mass percentage is as follows: The liquid crystal main body LC5 is 100%, the formula D-AI-2 is 1.03%, the formula D-BI-4 is 0.45%, the formula D-II-3 is 0.54%, the formula D-III-2 is 1.13%, and the formula D-III-3 is 1.35%.

[0121] The performance parameter test results of the dye liquid crystal composition B10 are as follows: L* is 36.38, a* is -1.1456, b* is -1.5134, I0 is 0.13 mu A, I 180 is 0.29 mu A, △E UV is 0.33, and △E 150 is 0.13.

[0122] The dye liquid crystal composition B10 as a whole presents black color, and the absorption wavelength uniformly covers the visible light and ultraviolet region. The power consumption (I0, I 180 ) is low, and the color difference (△E UV , △E 150 ) is less than 0.5 after high-temperature aging or ultraviolet aging, and the change is weak in the naked eye feeling. The dichroic dye has high solubility in the liquid crystal main body LC5. Compared with in the liquid crystal main body LC1, the dichroic dye has better high-temperature resistance in the liquid crystal main body LC4 under the same addition amount, and the color difference before and after high-temperature aging is lower.

[0123] In summary, the dye liquid crystal composition provided by the application has low driving power consumption, good color and light-heat stability, and can be applied in a normally black display liquid crystal device composed of a glass substrate or a flexible substrate.

[0124] It should be noted that the above examples do not limit the present application in any form, and any technical solutions obtained by equivalent replacement or equivalent transformation fall within the protection scope of the present application.

Claims

1. A dye-based liquid crystal composition, characterized in that, The dye-liquid crystal composition comprises a liquid crystal matrix and a dichroic dye, wherein: The liquid crystal matrix is ​​composed of at least one compound represented by general formula I, at least one compound represented by general formula II-A, at least one compound represented by general formula II-B, and at least one compound represented by general formula III. I； II-A: II-B; III; R1, R2, R3, and R4 each independently represent a haloalkyl or non-haloalkyl group containing 1 to 10 carbon atoms. One or more CH2 groups in the alkyl group can be independently replaced by -C≡C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O-, or -S-. The O and S atoms are not directly connected. , , , , , Each independent expression or One or more H atoms may be replaced by Br, Cl, F, CN, -NCS, -SCN, SF5, a haloalkyl or non-haloalkyl group containing 1 to 10 carbon atoms, a haloalkoxy group containing 1 to 10 carbon atoms, a haloalkenyl or non-haloalkenyl group containing 2 to 10 carbon atoms, a haloalkoxy group containing 2 to 10 carbon atoms, or a cycloalkyl or cycloalkenyl group with fewer than 6 carbon atoms; wherein, when , , , , , When representing a phenylene ring, one or more CH atoms on the benzene ring can be substituted with N atoms; when , , , , , When representing a cyclohexyl group, one or more CH2 groups on the ring can be replaced by O; Dichroic dyes are composed of at least one compound represented by general formula D-AI, at least one compound represented by general formula D-BI, at least one compound represented by general formula D-II, and at least one compound represented by general formula D-III. D-AI; D-BI; D-II: D-III; DR1, DR2, DR3, DR4, and DR5 each independently represent haloalkyl or non-haloalkyl groups containing 1 to 10 carbon atoms. One or more CH2 groups in the alkyl group can be independently replaced by -C≡C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O-, or -S-, with the O and S atoms not directly bonded; C1 and C2 each independently represent... , , The alkyl group is an amino group or a halogenated or unhalogenated alkyl group containing 1 to 10 carbon atoms, wherein one or more CH2 groups in the alkyl group may be independently replaced by -C≡C-, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -(CO)O-, -O(CO)-, -(CO)-, -O-, or -S-, and the O and S atoms are not directly connected; L1 represents a substituted or unsubstituted aryl group containing 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group containing 2 to 50 carbon atoms, and the substituent is an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 18 carbon atoms, or a halogen; L2 represents a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, or a substituted or unsubstituted alkyl group. The alkoxy group containing 1 to 18 carbon atoms, the substituted or unsubstituted alkylamino group containing 1 to 18 carbon atoms, the substituted or unsubstituted cycloalkoxy group containing 5 to 12 carbon atoms, the substituted or unsubstituted alkenoxy group containing 2 to 18 carbon atoms, -C≡N, the haloalkyl group containing 1 to 4 carbon atoms, the sulfonyl group, the acyl group, the amide group containing 2 to 18 carbon atoms, the acyloxy group containing 2 to 18 carbon atoms, the substituted or unsubstituted aryl group containing 6 to 50 carbon atoms, the substituted or unsubstituted heteroaryl group containing 2 to 50 carbon atoms, wherein the substituent is an alkyl group containing 1 to 18 carbon atoms, an alkoxy group containing 1 to 18 carbon atoms, or a halogen; The compounds represented by general formulas I, II-A, II-B, and III account for 20-30%, 20-30%, 10-30%, and 15-40% of the total weight of the liquid crystal substrate, respectively. The compounds represented by general formulas D-AI, D-BI, D-II, and D-III account for 0.23-1.29%, 0.1-0.56%, 0.12-0.67%, and 0.55-3.08% of the weight of the liquid crystal substrate, respectively.

2. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula I are selected from: I-1； I-2； I-3； I-4； I-5； I-6； I-7； I-8； I-9； I-10； I-11； I-12； I-13； I-14； I-15； sum I-16.

3. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula II-A are selected from: II-A-1; II-A-2; II-A-3; II-A-4; II-A-5; II-A-6; II-A-7; II-A-8; II-A-9; II-A-10; II-A-11; II-A-12; II-A-13; II-A-14; II-A-15; II-A-16; II-A-17; II-A-18; II-A-19; II-A-20; II-A-21; II-A-22; II-A-23; sum II-A-24.

4. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula II-B are selected from: II-B-1; II-B-2; II-B-3; II-B-4; II-B-5; II-B-6; II-B-7; II-B-8; II-B-9; II-B-10; II-B-11; II-B-12; II-B-13; II-B-14; II-B-15; II-B-16; II-B-17; II-B-18; II-B-19; and II-B-20.

5. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula III are selected from: III-1; III-2; III-3; III-4; III-5; III-6; III-7; III-8; III-9; III-10; III-11; III-12; III-13; III-14; III-15; and III-16.

6. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by the general formula D-AI are selected from: D-AI-1; D-AI-2; D-AI-3; and D-AI-4。 7. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by the general formula D-BI are selected from: D-BI-1; D-BI-2; D-BI-3; and D-BI-4.

8. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula D-II are selected from: D-II-1: D-II-2; D-II-3; and D-II-4.

9. The dye-liquid crystal composition according to claim 1, characterized in that, The compounds represented by general formula D-III are selected from: D-III-1; D-III-2; D-III-3; D-III-4; and D-III-5.

10. The use of the dye liquid crystal composition of claim 1 in a normally black liquid crystal display device made of a glass substrate or a flexible substrate.

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