A dichroic dye composition and a dye liquid crystal mixture containing the same

Abstract

The present invention belongs to the field of liquid crystal material technology, and specifically relates to a dichroic dye composition and a dye-liquid crystal mixture containing the same. The dichroic dye composition comprises at least one dichroic dye represented by general formula I, at least one dichroic dye represented by general formula II, at least one dichroic dye represented by general formula III, and at least one dichroic dye represented by general formula IV. The dichroic dye composition can absorb wavelengths covering the entire visible light region and portions of the ultraviolet and near-infrared regions. The dye-liquid crystal mixture comprises the dichroic dye composition as a guest and a liquid crystal composition as a host, wherein the liquid crystal composition has a low Abbe number and relatively low viscosity, and has high solubility in the dichroic dye composition. The resulting dye-liquid crystal mixture exhibits excellent light and heat stability and exhibits high light-dark contrast when used in VA-type liquid crystal devices. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the technical field of liquid crystal materials, and in particular relates to a dichroic dye composition and a dye liquid crystal mixture containing the same. Background Art

[0002] Liquid crystals are used, in particular, as dielectrics in display devices, taking advantage of the fact that the optical properties of such substances can be influenced by the electric field they experience. Electro-optical devices based on liquid crystals are well known to those skilled in the art and can be based on a variety of effects. Devices of this type are, for example, cells with dynamic scattering, DAP (Deformation of Alignment Phase) cells, TN cells with twisted nematic structures, STN ("Super Twisted Nematic") cells, SBE ("Super Birefringence Effect") cells, OMI ("Optical Mode Interference") cells, and guest-host cells.

[0003] Devices based on the guest-host effect were first described by Heilmeier and Zanoni (GH Heilmeier et al., Appl. Phys. Lett., 1968, 13, 91f) and have been widely used since then, primarily in liquid crystal display elements.

[0004] The prior art discloses liquid crystal media for guest-host display devices, comprising cyanobiphenyl derivatives and one or more dichroic dyes (WO2009 / 141295 and WO2010 / 118422). For similar applications, the prior art discloses liquid crystal mixtures containing one or more tricyclic compounds having two or more fluorine substituents and one or more dichroic dyes. These compounds are used in guest-host LC devices (US Pat. No. 6,033,598 and US Pat. No. 5,762,824).

[0005] However, there continues to be interest in new liquid crystal mixtures containing one or more dichroic dyes. Specifically, there is a need for mixtures in which the dichroic dyes readily dissolve and remain in solution for long periods of time. In particular, there continues to be a need for mixtures that are stable to light and electric fields over long periods of time. There also continues to be a need for mixtures in which the dichroic dyes exhibit high anisotropy, meaning good molecular alignment with the liquid crystal mixture. There also continues to be a need for mixtures that exhibit high-definition bright spots and high and low-temperature stability. Summary of the Invention

[0006] The present invention is directed to a novel dichroic dye composition having at least one, and preferably several, of the following desirable properties: good solubility of the dye in liquid crystal media, good photothermal stability, and high absorption anisotropy, i.e., a high ability of the dye to align with the liquid crystal. Furthermore, the dye should exhibit strong absorption in both the VIS and NIR regions of light.

[0007] Surprisingly, it has been found that the dichroic dye compositions according to the invention and dye-liquid crystal mixtures comprising at least one bicyclic cyano compound, at least one tricyclic cyano compound, at least one tetracyclic or polycyclic compound achieve the current technical goals.

[0008] The terms bicyclic, tricyclic and polycyclic refer to compounds having two, three or more rings. The rings may be aromatic, heteroaromatic, aliphatic or heteroaliphatic.

[0009] Specifically, the dichroic dye composition of the present invention comprises at least one dichroic dye represented by general formula I, at least one dichroic dye represented by general formula II, at least one dichroic dye represented by general formula III, and at least one dichroic dye represented by general formula IV:

[0010] The general formula I is specifically:

[0011]

[0012] The general formula II is specifically:

[0013]

[0014] The general formula III is specifically:

[0015]

[0016] The general formula IV is specifically:

[0017]

[0018] Among them, R1-R 10 Each independently represents a straight-chain or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group of 1 to 7 carbon atoms;

[0019] a1-a3, b1-b3 each independently represent 0, 1 or 2;

[0020] Z1 to Z6 each independently represent an ester group, a cyclohexyl group, a phenyl group, an esterphenyl group or a phenylcyclohexyl group.

[0021] In the present invention, dichroic dyes are light-absorbing compounds whose absorption properties depend on the alignment of the compound with respect to the polarization direction of light. The dichroic dye compounds of the present invention typically have an elongated shape, similar to the shape of liquid crystal compounds, with one spatial direction (the longitudinal axis) being significantly longer than the other two spatial directions.

[0022] Preferably, R4, R5, R7, R8 and R 10represents other substituents except methyl; more preferably, one or more of R4, R5, R7, and R8 represent ethyl, and R10 represents isobutyl or isopentyl.

[0023] Preferably, a1-a3, b1-b3 independently represent 0 or 1.

[0024] Preferably, one or more of Z1, Z4, and Z6 represent a phenyl group.

[0025] Preferably, the general formula I is one or more compounds selected from the group consisting of the compounds of formulas I-A-1 to I-B-3:

[0026]

[0027] Preferably, the general formula Ⅰ is selected from one or more compounds of formula II-A-1 to II-B-3:

[0028]

[0029] Preferably, the general formula III is selected from one or more compounds selected from formula III-A-1 to III-B-3:

[0030]

[0031]

[0032] Preferably, the general formula IV is selected from one or more compounds of formulas IV-1 to IV-6:

[0033]

[0034] The present invention also provides a dye-liquid crystal mixture with negative dielectric anisotropy, wherein the dye-liquid crystal mixture comprises the above-mentioned dichroic dye composition as a guest and a liquid crystal composition as a host. The liquid crystal composition as the host is preferably a nematic liquid crystal composition.

[0035] Specifically, the nematic liquid crystal composition includes at least one of the compounds represented by formula V and at least one of the compounds represented by formula VI;

[0036]

[0037] Among them, in the general formula V, R 11 、R 12 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 Straight-chain alkenyl;

[0038] In the general formula VI, R13 、R 14 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 Straight-chain alkenyl;

[0039] Z7 represents -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O- or a single bond.

[0040] The liquid crystal composition provided by the present invention has a low Abbe number, relatively low viscosity, and high dye solubility. The dichroic dye composition provided by the present invention has excellent solubility in the liquid crystal composition. The resulting dye-liquid crystal mixture exhibits excellent light and heat stability, and exhibits high light-dark contrast when used in VA-type liquid crystal devices.

[0041] As a preferred embodiment of the above technical solution, the compound represented by general formula V is selected from one or more of formulas VA1 to VA16:

[0042]

[0043] Further preferably, the compound represented by general formula V is selected from one or more of VA8, VA16, VIB14, and VIB16;

[0044] As a preferred embodiment of the above technical solution, the compound represented by general formula VI is selected from one or more of formulas VIA to VIB:

[0045]

[0046] Among them, R 13 、R 14 Each independently represents a C1-C7 straight-chain alkyl group, a C1-C7 straight-chain alkoxy group or a C2-C7 straight-chain alkenyl group.

[0047] Further preferably, the compound represented by general formula VI is selected from one or more of formulas VIA1 to VIB16:

[0048]

[0049]

[0050] Most preferably, the compound represented by formula VI is selected from one or more of VIA8, VIA16, VIB6, and VIB14;

[0051] Furthermore, the nematic liquid crystal composition comprises one or more compounds represented by formula VII;

[0052]

[0053] Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

[0054] Preferably, the compound represented by general formula VII is selected from one or more of formula VIIA to formula VIIC:

[0055]

[0056] Among them, R 15 、R 16 Each independently represents a straight-chain alkyl group of C1 to C7, a straight-chain alkoxy group of C1 to C7 or a straight-chain alkenyl group of C2 to C7, Z8 can represent -CH2CH2-, -CH2O-, -CO-O-, -O-CO-, -CF=CF-, -CH=CH-CH2O- or a single bond, A1 represents trans-1,4-cyclohexyl or 1,4-phenylene, and a4 is 0 or 1.

[0057] Further preferably, the compound represented by general formula VII is selected from one or more of formula VIIA1 to formula VIIC16:

[0058]

[0059]

[0060]

[0061] Most preferably, the compound represented by general formula VII is selected from one or more of VIIA5 to VIIA8, VIIA12 to VIIA16, VIIB2, VIIB6, VIIB14, and VIIC5 to VIIC8.

[0062] Furthermore, the nematic liquid crystal composition comprises one or more compounds represented by formula VIII;

[0063]

[0064] In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

[0065] Preferably, the compound represented by general formula VIII is selected from one or more of formulas VIIIA to VIIIB:

[0066]

[0067] Among them, R 17 、R 18 Each independently represents a C1-C7 straight-chain alkyl group, a C1-C7 straight-chain alkoxy group or a C2-C7 straight-chain alkenyl group.

[0068] More preferably, the compound represented by general formula VIII is selected from one or more of formula VIIIA1 to formula VIIIB24:

[0069]

[0070]

[0071]

[0072] Most preferably, the compound represented by general formula VIII is selected from one or more of VIIIA7, VIIIA11, VIIIA12, VIIIA21, VIIIB18, and VIIIB22.

[0073] Furthermore, the nematic liquid crystal composition comprises the following components in percentage by mass:

[0074] (1) 22 to 58% of the compound represented by formula V;

[0075] (2) 0-22% of the compound represented by formula VI;

[0076] (3) 10-30% of the compound represented by formula VII;

[0077] (4) 10-40% of the compound represented by formula VIII;

[0078] Preferably, the nematic liquid crystal composition comprises the following components in percentage by mass:

[0079] (1) 25-55% of the compound represented by formula V;

[0080] (2) 0-20% of the compound represented by formula VI;

[0081] (3) 12 to 28% of the compound represented by formula VII;

[0082] (4) 13 to 38% of the compound represented by formula VIII;

[0083] More preferably, the nematic liquid crystal composition comprises the following components in percentage by mass:

[0084] (1) 25-50% of the compound represented by formula V;

[0085] (2) 0 to 18% of the compound represented by formula VI;

[0086] (3) 15-25% of the compound represented by formula VII;

[0087] (4) 16 to 35% of the compound represented by formula VIII;

[0088] Further preferably, the nematic liquid crystal composition comprises the following components in percentage by mass:

[0089] (1) 30-46% of the compound represented by formula V;

[0090] (2) 0-15% of the compound represented by formula VI;

[0091] (3) 18 to 24% of the compound represented by formula VII;

[0092] (4) 19-32% of the compound represented by the general formula VIII.

[0093] The dye liquid crystal mixture provided by the present invention further comprises a chiral dopant. Table 1 shows chiral compounds that can preferably be used as the chiral dopant in the dye liquid crystal mixture of the present invention.

[0094] Table 1: Chiral compounds

[0095]

[0096] Preferably, based on the weight of the liquid crystal composition, the dye liquid crystal mixture contains 0.01 to 2% of the chiral compound, preferably 0.5 to 1.8%, more preferably 0.6 to 1.5%, and even more preferably 0.66 to 1.5%.

[0097] In a preferred embodiment, based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass:

[0098] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0％～1.8％ 3 Dye Formula II 0％～3.0％ 4 Dye Formula III 0％～3.0％ 5 Dye Formula IV 0％～4.0％ 6 R / S811 0.01％～2.0％

[0099] As a preferred embodiment of the above technical solution, the dye liquid crystal mixture comprises the following components in the following mass percentages:

[0100] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0.2％～1.2％ 3 Dye Formula II 0.3％～2.0％ 4 Dye Formula III 0.2％～2.5％ 5 Dye Formula IV 1.3％～2.7％ 6 R / S811 1.0％～1.8％

[0101] Further preferably, the dye liquid crystal mixture comprises the following components in percentage by mass:

[0102]

[0103]

[0104] More preferably, the dye liquid crystal mixture comprises the following components in percentage by mass:

[0105] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0.5％～0.9％ 3 Dye Formula II 0.44％～0.8％ 4 Dye Formula III 0.27％～0.5％ 5 Dye Formula IV 1.39％～2.5％ 6 R / S811 1.25％～1.5％。

[0106] In another preferred embodiment, the dye liquid crystal mixture may further comprise the following components in percentage by weight based on the weight of the liquid crystal composition:

[0107] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0％～1.8％ 3 Dye Formula II 0％～3.0％ 4 Dye Formula III 0％～3.0％ 5 Dye Formula IV 0％～4.0％ 6 R / S2011 0.01％～2.0％

[0108] As a preferred embodiment of the above technical solution, the dye liquid crystal mixture comprises the following components in the following mass percentages:

[0109] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0.2％～1.2％ 3 Dye Formula II 0.3％～2.0％ 4 Dye Formula III 0.2％～2.5％ 5 Dye Formula IV 1.3％～2.7％ 6 R / S2011 0.5％～1.8％

[0110] Further preferably, the dye liquid crystal mixture comprises the following components in percentage by mass:

[0111]

[0112]

[0113] More preferably, the dye liquid crystal mixture comprises the following components in percentage by mass:

[0114] Serial number Components Weight percentage (%) 1 Liquid crystal composition 100 2 Dye Formula I 0.5％～0.9％ 3 Dye Formula II 0.44％～0.8％ 4 Dye Formula III 0.27％～0.5％ 5 Dye Formula IV 1.39％～2.5％ 6 R / S2011 0.66％～1.41％

[0115] The preparation method of the dye liquid crystal mixture of the present invention is not particularly limited and can be produced by mixing two or more compounds using conventional methods, such as by mixing different components at high temperature and dissolving them in each other.

[0116] The present invention also provides a device comprising the dye liquid crystal mixture, which can regulate the energy radiated by the sun from an external space (preferably an environment directly exposed to sunlight) to an internal space (a building or a vehicle) or another unit substantially isolated from the environment.

[0117] Preferably, the device directly or indirectly modulates the energy of solar radiation, specifically electromagnetic radiation in the UV-A, VIS, and NIR regions. The UV-A region refers to the wavelength range of 320 nm to 380 nm, the VIS region refers to the wavelength range of 380 nm to 780 nm, and the NIR region refers to the wavelength range of 780 nm to 2000 nm.

[0118] Among the various technical solutions for regulating the passage of energy from the exterior to the interior, the use of switching layers containing dye-liquid crystal mixtures is advantageous. Due to their direction-dependent absorption, the spatial orientation of the dichroic compound molecules in these switching layers can be altered by applying a voltage.

[0119] Preferably, the device is a VA liquid crystal box with a twisted-supertwisted nematic phase structure (twist angle 180°-360°), which utilizes the omnidirectional arrangement of liquid crystals in a plane to achieve light absorption in all directions of natural light without the use of polarizers, thereby realizing high brightness-dark contrast in applications. DETAILED DESCRIPTION

[0120] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0121] Unless otherwise indicated, percentages in the present invention are percentages by weight; temperatures are in degrees Celsius; Δn represents optical anisotropy (25°C); Δε represents dielectric anisotropy (25°C, 1000 Hz); γ1 represents rotational viscosity (mPa.s, 25°C); and Cp represents the clearing point of the liquid crystal composition (°C).

[0122] In the following liquid crystal mixtures, the group structures in the liquid crystal compounds are represented by the codes shown in Table 2.

[0123] Table 2: Group structure codes of liquid crystal compounds

[0124]

[0125] Take the following compound structure as an example:

[0126]

[0127] Expressed as: 5CCEC2

[0128] Preparation of liquid crystal dye mixtures

[0129] Nematic LC host mixtures N-1 to N-4 were prepared as follows:

[0130] The weight percentages of the components in the liquid crystal compositions of the following nematic LC host mixtures and the performance parameters of the liquid crystal compositions are shown in the following table.

[0131] Mixture N-1

[0132] Table 3: Weight percentage and performance parameters of each component in the liquid crystal composition

[0133]

[0134]

[0135] Mixture N-2

[0136] Table 4: Weight percentage and performance parameters of each component in the liquid crystal composition

[0137]

[0138] Mixture N-3

[0139] Table 5: Weight percentage and performance parameters of each component in the liquid crystal composition

[0140]

[0141]

[0142] Mixture N-4

[0143] Table 6: Weight percentage and performance parameters of each component in the liquid crystal composition

[0144]

[0145]

[0146] In the following examples, the weight percentages of the dye monomer, chiral agent, antioxidant, and anti-UV additive are based on the weight of the nematic liquid crystal composition and are added separately in addition to the mass percentage of the nematic liquid crystal composition. The structural formula of the antioxidant is:

[0147]

[0148] The structural formula of the anti-UV additive is:

[0149]

[0150] Example 1

[0151] Table 7 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0152] Mixture Code Weight percentage (%) N-1 100 Dye Ⅰ-A-1 0.9 Dye Ⅱ-B-3 0.8 Dye III-A-2 0.5 Dye IV-1 1.2 Dye IV-3 1.3 R / S811 1.5 antioxidants 0.03 Anti-UV additives 0.3

[0153] The dye-liquid crystal mixture described in Example 1 is black overall and absorbs wavelengths covering the entire visible light range and portions of the ultraviolet and near-infrared regions. In a liquid crystal cell with a cell thickness of 6-9 μm, the dark-state transmittance can reach a minimum of less than 8%. This dye-liquid crystal mixture has a low Abbe number, exhibiting high light-dark contrast in VA-type liquid crystal devices. It also has low viscosity, excellent solubility in liquid crystal medium N-1, and good photothermal stability. The glass transition temperature of this dye-liquid crystal mixture is below 0°C.

[0154]

[0155] Example 2

[0156] Table 8 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0157] Mixture Code Weight percentage (%) N-2 100 Dye Ⅰ-A-1 0.64 Dye Ⅱ-B-3 0.57 Dye III-A-2 0.35 Dye IV-1 0.86 Dye IV-3 0.93 R / S811 1.25 antioxidants 0.03 Anti-UV additives 0.3

[0158] The dye-liquid crystal mixture described in Example 2 is black overall and absorbs wavelengths covering the entire visible light range and portions of the ultraviolet and near-infrared regions. In a liquid crystal cell with a cell thickness of 6-9 μm, the dark-state transmittance can reach a minimum of less than 10%. This dye-liquid crystal mixture has a low Abbe number, exhibiting high light-dark contrast and high-definition bright spots in VA-type liquid crystal devices. The dye has excellent solubility in liquid crystal medium N-2 and good photothermal stability. The glass transition temperature of this dye-liquid crystal mixture is below -20°C, and the clearing point can reach 109°C.

[0159]

[0160] Example 3

[0161] Table 9 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0162]

[0163]

[0164] The dye-liquid crystal mixture described in Example 3 is black overall and absorbs wavelengths covering all visible light and portions of the ultraviolet and near-infrared regions. In a liquid crystal cell with a cell thickness of 6-9 μm, the dark-state transmittance can reach a minimum of less than 10%. This dye-liquid crystal mixture has a low dispersion coefficient. Compared to the liquid crystal mixture described in Example 2, this liquid crystal mixture exhibits higher light-dark contrast in VA-type liquid crystal device applications. The dye has better solubility in liquid crystal medium N-3 and good photothermal stability. The glass transition temperature of this dye-liquid crystal mixture is below -20°C.

[0165]

[0166] Example 4

[0167] Table 10 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0168] Mixture Code Weight percentage (%) N-4 100 Dye Ⅰ-A-1 0.50 Dye Ⅱ-B-3 0.44 Dye III-A-2 0.27 Dye IV-1 0.67 Dye IV-3 0.72 R / S811 1.33 antioxidants 0.03 Anti-UV additives 0.3

[0169] The dye liquid crystal mixture mentioned in Example 4 is black as a whole and can absorb wavelengths covering all visible light and part of the ultraviolet and near-infrared regions. In a liquid crystal cell with a cell thickness of 6-9 μm, the dark state transmittance can reach a minimum of less than 16%. This dye liquid crystal mixture has a low dispersion coefficient. Compared with the liquid crystal mixture mentioned in Example 3, this dye liquid crystal mixture shows a higher light-dark contrast in VA-type liquid crystal device applications. The solubility of the dye in liquid crystal medium N-4 is not as good as N-3, and the light and heat stability is good. The glass transition temperature of this dye liquid crystal mixture is below -20°, and the clearing point can reach 110°.

[0170]

[0171] Example 5

[0172] Table 11 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0173]

[0174] Example 6

[0175] Table 12 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0176]

[0177] Example 7

[0178] Table 13 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0179]

[0180]

[0181] Example 8

[0182] Table 14 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0183]

[0184] Example 9

[0185] Table 15 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0186]

[0187]

[0188] Example 10

[0189] Table 16 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0190]

[0191] Example 11

[0192] Table 17 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0193]

[0194] Example 12

[0195] Table 18 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0196]

[0197] Example 13

[0198] Table 19 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0199]

[0200] Example 14

[0201] Table 20 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0202]

[0203] Example 15

[0204] Table 21 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0205]

[0206] Example 16

[0207] Table 22 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0208]

[0209]

[0210] Example 17

[0211] Table 23 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0212]

[0213] Example 18

[0214] Table 24 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0215]

[0216]

[0217] Example 19

[0218] Table 25 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0219]

[0220] Example 20

[0221] Table 26 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0222]

[0223]

[0224] Example 21

[0225] Table 27 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0226]

[0227] Example 22

[0228] Table 28 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0229]

[0230] Example 23

[0231] Table 29 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0232]

[0233]

[0234] Example 24

[0235] Table 30 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0236]

[0237] Example 25

[0238] Table 31 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0239]

[0240]

[0241] Example 26

[0242] Table 32 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0243]

[0244] Example 27

[0245] Table 33 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0246]

[0247]

[0248] Example 28

[0249] Table 34 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0250]

[0251] Example 29

[0252] Table 35 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0253]

[0254]

[0255] Example 30

[0256] Table 36 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0257]

[0258] Example 31

[0259] Table 37 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0260]

[0261]

[0262] Implementation 32

[0263] Table 38 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0264]

[0265] Example 33

[0266] Table 39 Weight percentage and performance parameters of each component in the dye liquid crystal mixture

[0267]

[0268] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made thereto. Therefore, such modifications and improvements, without departing from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A dye liquid crystal mixture, characterized in that: A dichroic dye composition is included as a guest and a liquid crystal composition is included as a host; the dichroic dye composition includes at least one dichroic dye represented by general formula I, at least one dichroic dye represented by general formula II, at least one dichroic dye represented by general formula III, and at least one dichroic dye represented by general formula IV: The general formula I is specifically: ； The general formula II is specifically: ； The general formula III is specifically: ； The general formula IV is specifically: ； Among them, R1-R 10 Each independently represents a straight-chain or branched alkyl group, alkenyl group, alkoxy group, alkenyloxy group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkoxycarbonyloxy group of 1 to 7 carbon atoms; a1-a3, b1-b3 each independently represent 0, 1 or 2; Z1-Z6 each independently represent an ester group, a cyclohexyl group, a phenyl group, an ester phenyl group or a phenylcyclohexyl group; Based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass: ； The main liquid crystal composition is a nematic liquid crystal composition; the liquid crystal composition includes at least one of the compounds represented by general formula V and at least one of the compounds represented by general formula VI; ； Among them, in the general formula V, R 11 、R 12 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A straight-chain alkenyl group; In the general formula VI, R 13 、R 14 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 Straight-chain alkenyl; Z7 represents -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C2F4-, -CF=CF-, -CH=CH-CH2O- or a single bond.

2. The dye liquid crystal mixture according to claim 1, characterized in that R4, R5, R7, R8 and R 10 represents other substituents except methyl; and / or, a1-a3, b1-b3 independently represent 0 or 1; And / or, one or more of Z1, Z4, and Z6 represent a phenyl group.

3. The dye liquid crystal mixture according to claim 2, characterized in that One or more of R4, R5, R7, and R8 represent an ethyl group, R 10 represents isobutyl or isopentyl.

4. The dye liquid crystal mixture according to claim 1, characterized in that General formula I is one or more compounds selected from formulas Ⅰ-A-1 to Ⅰ-B-3: 。 5. The dye liquid crystal mixture according to claim 2, characterized in that General formula I is one or more compounds selected from formulas Ⅰ-A-1 to Ⅰ-B-3: 。 6. The dye liquid crystal mixture according to claim 3, characterized in that General formula I is one or more compounds selected from formulas Ⅰ-A-1 to Ⅰ-B-3: 。 7. The dye liquid crystal mixture according to any one of claims 1 to 6, characterized in that: The general formula ⅠI is one or more compounds selected from formulas Ⅱ-A-1 to Ⅱ-B-3: 。 8. The dye liquid crystal mixture according to any one of claims 1 to 6, characterized in that: The general formula III is selected from one or more compounds selected from formula III-A-1 to III-B-3: 。 9. The dye liquid crystal mixture according to claim 7, characterized in that The general formula III is selected from one or more compounds selected from formula III-A-1 to III-B-3: 。 10. The dye liquid crystal mixture according to any one of claims 1 to 6 and 9, characterized in that: The general formula IV is one or more compounds selected from formulas IV-1 to IV-6: 。 11. The dye liquid crystal mixture according to claim 7, characterized in that The general formula IV is one or more compounds selected from formulas IV-1 to IV-6: 。 12. The dye liquid crystal mixture according to claim 8, characterized in that The general formula IV is one or more compounds selected from formulas IV-1 to IV-6: 。 13. The dye liquid crystal mixture according to claim 1, characterized in that The compound represented by general formula V is selected from one or more of formulas VA1 to VA16: 。 14. The dye liquid crystal mixture according to claim 13, characterized in that The compound represented by general formula V is selected from one or more of VA8 and VA16.

15. The dye liquid crystal mixture according to claim 1 or 13, characterized in that The compound represented by general formula VI is selected from one or more of formulas VIA to VIB: ； Among them, R 13 、R 14 Each independently represents a C1-C7 straight-chain alkyl group, a C1-C7 straight-chain alkoxy group or a C2-C7 straight-chain alkenyl group.

16. The dye liquid crystal mixture according to claim 15, characterized in that The compound represented by general formula VI is selected from one or more of formulas VIA1 to VIB16: 。 17. The dye liquid crystal mixture according to claim 16, characterized in that The compound represented by general formula VI is selected from one or more of VIA8, VIA16, VIB6, and VIB14.

18. The dye liquid crystal mixture according to any one of claims 1 to 6, 9, 11 to 14, 16, and 17, characterized in that: The nematic liquid crystal composition comprises one or more compounds represented by formula VII; ； Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

19. The dye liquid crystal mixture according to claim 7, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VII; ； Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

20. The dye liquid crystal mixture according to claim 8, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VII; ； Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

21. The dye liquid crystal mixture according to claim 10, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VII; ； Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

22. The dye liquid crystal mixture according to claim 15, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VII; ； Among them, R 15 、R 16 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A1 represents a trans-1,4-cyclohexyl group or a 1,4-phenylene group, and a4 is 0 or 1.

23. The dye liquid crystal mixture according to claim 18, characterized in that The compound represented by general formula VII is selected from one or more of formulas VIIA to VIIC: ； Among them, R 15 、R 16 Each independently represents a C1~C7 straight-chain alkyl, a C1~C7 straight-chain alkoxy or a C2~C7 straight-chain alkenyl, Z8 can represent -CH2CH2-, -CH2O-, -CO-O-, -O-CO-, -CF=CF-, -CH=CH-CH2O- or a single bond, A1 represents trans-1,4-cyclohexyl or 1,4-phenylene, and a4 is 0 or 1.

24. The dye liquid crystal mixture according to any one of claims 19 to 22, characterized in that The compound represented by general formula VII is selected from one or more of formulas VIIA to VIIC: ； Among them, R 15 、R 16 Each independently represents a C1~C7 straight-chain alkyl, a C1~C7 straight-chain alkoxy or a C2~C7 straight-chain alkenyl, Z8 can represent -CH2CH2-, -CH2O-, -CO-O-, -O-CO-, -CF=CF-, -CH=CH-CH2O- or a single bond, A1 represents trans-1,4-cyclohexyl or 1,4-phenylene, and a4 is 0 or 1.

25. The dye liquid crystal mixture according to claim 23, characterized in that The compound represented by general formula VII is selected from one or more of formula VIIA1 to formula VIIC16: 。 26. The dye liquid crystal mixture according to claim 24, characterized in that The compound represented by general formula VII is selected from one or more of formula VIIA1 to formula VIIC16: 。 27. The dye liquid crystal mixture according to claim 25 or 26, characterized in that The compound represented by general formula VII is selected from one or more of VIIA5 to VIIA8, VIIA12 to VIIA16, VIIB2, VIIB6, VIIB14, and VIIC5 to VIIC8.

28. The dye liquid crystal mixture according to any one of claims 1-6, 9, 11-14, 16, 17, 19-23, 25, and 26, characterized in that: The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

29. The dye liquid crystal mixture according to claim 7, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

30. The dye liquid crystal mixture according to claim 8, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

31. The dye liquid crystal mixture according to claim 10, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

32. The dye liquid crystal mixture according to claim 15, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

33. The dye liquid crystal mixture according to claim 18, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

34. The dye liquid crystal mixture according to claim 24, characterized in that The nematic liquid crystal composition comprises one or more compounds represented by formula VIII; ； In the general formula VIII, R 17 、R 18 Each independently represents C1~C 12 Straight chain alkyl, C1~C 12 Straight chain alkoxy or C2~C 12 A2 and A3 each independently represent a trans-1,4-cyclohexyl group or a 1,4-phenylene group.

35. The dye liquid crystal mixture according to claim 28, characterized in that The compound represented by general formula VIII is selected from one or more of formulas VIIIA to VIIIB: ； Among them, R 17 、R 18 Each independently represents a C1-C7 straight-chain alkyl group, a C1-C7 straight-chain alkoxy group or a C2-C7 straight-chain alkenyl group.

36. The dye liquid crystal mixture according to claims 29 to 34, characterized in that The compound represented by general formula VIII is selected from one or more of formulas VIIIA to VIIIB: ； Among them, R 17 、R 18 Each independently represents a C1-C7 straight-chain alkyl group, a C1-C7 straight-chain alkoxy group or a C2-C7 straight-chain alkenyl group.

37. The dye liquid crystal mixture according to claim 35, characterized in that The compound represented by general formula VIII is selected from one or more of formula VIIIA1 to formula VIIIB24: 。 38. The dye liquid crystal mixture according to claim 36, characterized in that The compound represented by general formula VIII is selected from one or more of formula VIIIA1 to formula VIIIB24: 。 39. The dye liquid crystal mixture according to claim 37 or 38, characterized in that The compound represented by general formula VIII is selected from one or more of VIIIA7, VIIIA11, VIIIA12, VIIIA21, VIIIB18, and VIIIB22.

40. The dye liquid crystal mixture according to any one of claims 1-6, 9, 11-14, 16, 17, 19-23, 25, 26, 29-35, 37, and 38, wherein: The nematic liquid crystal composition comprises the following components in percentage by mass: (1), 22 to 58% of the compound represented by formula V; (2) 0-22% of the compound represented by Formula VI; (3) 10-30% of the compound represented by Formula VII; (4) 10-40% of the compound represented by formula VIII.

41. The dye liquid crystal mixture according to claim 40, characterized in that The nematic liquid crystal composition comprises the following components in percentage by mass: (1) 25-55% of the compound represented by formula V; (2) 0-20% of the compound represented by Formula VI; (3), 12 to 28% of the compound represented by formula VII; (4) 13 to 38% of the compound represented by formula VIII.

42. The dye liquid crystal mixture according to claim 41, characterized in that The nematic liquid crystal composition comprises the following components in percentage by mass: (1) 25-50% of the compound represented by formula V; (2) 0-18% of the compound represented by Formula VI; (3) 15-25% of the compound represented by Formula VII; (4) 16 to 35% of the compound represented by formula VIII.

43. The dye liquid crystal mixture according to claim 42, characterized in that The nematic liquid crystal composition comprises the following components in percentage by mass: (1), 30-46% of the compound represented by formula V; (2) 0-15% of the compound represented by Formula VI; (3), 18 to 24% of the compound represented by formula VII; (4) 19-32% of the compound represented by general formula VIII.

44. The dye liquid crystal mixture according to any one of claims 1-6, 9, 11-14, 16, 17, 19-23, 25, 26, 29-35, 37, 38, 41-43, characterized in that The dye liquid crystal mixture further comprises a chiral compound.

45. The dye liquid crystal mixture according to claim 40, characterized in that The dye liquid crystal mixture further comprises a chiral compound.

46. ​​The dye liquid crystal mixture according to claim 45, characterized in that The chiral compound is R / S811 and / or R / S2011: 。 47. The dye liquid crystal mixture according to claim 46, characterized in that The dye liquid crystal mixture contains 0.01-2% of the chiral compound based on the weight of the liquid crystal composition.

48. The dye liquid crystal mixture according to claim 47, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture contains 0.5-1.8% of the chiral compound.

49. The dye liquid crystal mixture according to claim 48, characterized in that The dye liquid crystal mixture contains 0.6-1.5% of the chiral compound based on the weight of the liquid crystal composition.

50. The dye liquid crystal mixture according to claim 49, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture contains 0.66-1.5% of the chiral compound.

51. The dye liquid crystal mixture according to claim 44, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass: 。 52. The dye liquid crystal mixture according to claim 51, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 53. The dye liquid crystal mixture according to any one of claims 45 to 50, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass: 。 54. The dye liquid crystal mixture according to claim 53, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 55. The dye liquid crystal mixture according to claim 52 or 54, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 56. The dye liquid crystal mixture according to claim 44, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass: 。 57. The dye liquid crystal mixture according to claim 56, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 58. The dye liquid crystal mixture according to claim 57, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 59. The dye liquid crystal mixture according to any one of claims 45 to 50, characterized in that Based on the weight of the liquid crystal composition, the dye liquid crystal mixture comprises the following components in percentage by mass: 。 60. The dye liquid crystal mixture according to claim 59, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。 61. The dye liquid crystal mixture according to claim 60, characterized in that The dye liquid crystal mixture comprises the following components in percentage by mass: 。

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