Liquid crystal composition having negative dielectric anisotropy and liquid crystal display device containing same

Abstract

The present application provides a liquid crystal composition having negative dielectric anisotropy and a liquid crystal display device containing same. The liquid crystal composition comprises at least one stabilizer, at least one compound represented by formula II, and at least one compound represented by formula F and / or formula N. By means of the design of the stabilizer and liquid crystal components as well as the compounding synergy thereof, under the condition of having a high clearing point, excellent optical anisotropy, and excellent dielectric anisotropy Δε, the liquid crystal composition also has high elastic constants K11, K33, a small rotational viscosity γ1, a smaller ratio of rotational viscosity to elastic constant γ1 / K11, a smaller ratio of elastic constant to dielectric anisotropy K11 / |Δε|, a low response time, a fast response speed, low operating voltage and power consumption, and low LC scattering. At the same time, said composition exhibits excellent photoelectrical stability and a high voltage holding ratio (VHR), which can eliminate image sticking or accelerate the dissipation of image sticking.

Description

Liquid crystal composition with negative dielectric anisotropy and liquid crystal display device containing the same Technical Field

[0001] The present application belongs to the technical field of liquid crystal materials, and specifically relates to a liquid crystal composition with negative dielectric anisotropy and a liquid crystal display device containing the same. Background Art

[0002] A liquid crystal display (LCD) is a device that relies on the electro-optical properties of liquid crystals to achieve display performance. Based on the arrangement of the liquid crystal molecules, it can be categorized into the following types: PC (phase change), TN (twist nematic), STN (super twisted nematic), DS (dynamic scattering), FLC (ferroelectric liquid crystal), GH (guest-host), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). Key display performance indicators include color reproduction, brightness, contrast, viewing angle, resolution, and power consumption. TFT-IPS / FFS combined with TFT control matrix has become the main application type due to its advantages such as high resolution, high contrast, high color reproduction and large viewing angle.

[0003] In IPS / FFS display mode, achieving high-contrast display effects requires reducing light leakage in the dark state. Besides the device manufacturing process, the main light leakage factor of the device is optical scattering caused by the liquid crystal layer. The degree of LC scattering can be measured using the following formula:

[0004] Where, d represents the thickness of the liquid crystal cell, n e represents the extraordinary refractive index, n o represents the ordinary refractive index, K ave is the average elastic constant. Under the designed liquid crystal refractive index and cell thickness, increasing Kave It can effectively improve the contrast of the display, and increasing the nematic phase transition temperature Cp of the liquid crystal can often obtain a larger K ave However, at the same time, the rotational viscosity of the liquid crystal will also increase, causing the liquid crystal response speed to slow down. An effective solution is to use monomers with a larger K value (such as cyclohexene monomers); K ave After the increase, in order to maintain a lower operating voltage and reduce power consumption, it is necessary to increase the dielectric constant ε of the liquid crystal. The large-scale use of liquid crystal monomers with small dielectric constants will significantly increase the rotational viscosity γ1 of the liquid crystal. An effective solution is to use a smaller content of liquid crystal monomers with large dielectric constants.

[0005] However, Big K ave Cyclohexene monomers with high dielectric constants and liquid crystal monomers with large dielectric constants often have low optical and electrical stability due to their structural factors. Under prolonged and extreme operating conditions, they aggregate ions or directly decompose, resulting in a decrease in voltage holding ratio (VHR) and image sticking. Therefore, how to make liquid crystal materials with high elastic constants and low viscosity, maintain high contrast, low operating voltage, low power consumption, low response time, and low LC scattering, while improving optical and electrical stability, achieving high VHR, and reducing image sticking, is an urgent problem to be solved in this field. Summary of the Invention

[0006] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0007] The present application provides a liquid crystal composition with negative dielectric anisotropy and a liquid crystal display device containing the same, wherein the liquid crystal composition has a high elastic constant K while having suitable clearing point, optical anisotropy and dielectric anisotropy. 11 and K 33 , lower rotational viscosity γ1, reducing γ1 / K 11 , shorten response time, reduce power consumption, reduce LC Scattering, and have excellent photoelectric stability, with high VHR, can eliminate image persistence or accelerate the dissipation of image persistence.

[0008] In a first aspect, the present application provides a liquid crystal composition with negative dielectric anisotropy, the liquid crystal composition comprising:

[0009] At least one stabilizer selected from the group consisting of:

[0010] At least one compound of formula II:

[0011] as well as

[0012] At least one compound of formula F and / or formula N:

[0013] Wherein, X represents -H, -OH, -O*, or a linear or branched alkyl group containing 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms; one or at least two non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 5 carbon atoms may be independently replaced by -O- or -CO-; -O* represents an oxygen free radical;

[0014] R1 and R2 each independently represent a linear or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms, One or at least two non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0015] R3 and R4 each independently represent -H, halogen, a linear or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms, The straight or branched alkyl group containing 1 to 12 carbon atoms, One or at least two non-adjacent -CH2- in the group may be independently replaced by -CH=CH-, -C≡C-, -O-, -S-, -CO-, -CO-O- or -O-CO-, and one or at least two -H in the group may be independently replaced by -F or -Cl;

[0016] R N1 and R N2 Each independently represents a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms, One or at least two non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0017] ring and Ring Each independently expresses described One or at least two -CH2- in the ring may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds; At most one -H in the ring may be substituted by halogen, and at least one ring or ring Each independently expresses

[0018] ring and Ring Each independently expresses described One or at least two -CH2- in the ring may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds; One or at least two -H in the ring may be replaced by -F, -Cl, -CN, -CH3 or -OCH3, and one or at least two -CH= in the ring may be replaced by -N=;

[0019] ring and Ring Each independently expresses in One or at least two -CH2- in the ring may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds, wherein One or at least two -H in the ring may be independently replaced by -F, -Cl or -CN, and one or at least two -CH= in the ring may be replaced by -N=;

[0020] G represents -O-, -S-, -CO-, -CF2-, -NH- or -NF-;

[0021] L1 and L2 each independently represent -H, halogen, a halogenated or unhalogenated alkyl group containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms, or a halogenated or unhalogenated alkoxy group containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms;

[0022] L N1 and L N2 Each independently represents -H, halogen, a linear or branched alkyl group containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms, or a linear or branched alkoxy group containing 1 to 3 (e.g., 1, 2, or 3) carbon atoms;

[0023] Z1, Z2, Z N1 and Z N2Each independently represents a single bond, -O-, -S-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)4-, -CF2O- or -OCF2-;

[0024] Z3 represents a single bond, -O(CH2) a -or-S(CH2) a -; a represents an integer from 0 to 5, for example, 0, 1, 2, 3, 4 or 5;

[0025] n represents an integer of 1-20, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

[0026] n1 represents 1 or 2; when n1=2, the ring Same or different;

[0027] n F1 and n F2 Each independently represents 0, 1 or 2; when n F1 =2, the ring Same or different, Z1 same or different; when n F2 =2, the ring Same or different, Z2 same or different;

[0028] n N1 Indicates 0, 1, 2, or 3, n N2 Represents 0 or 1, and 0≤n N1 +n N2 ≤3;

[0029] When n N1 When it means 2 or 3, the ring Same or different, Z N1 Same or different.

[0030] The present application has found that in the process of applying an oversaturation voltage, the ions in the liquid crystal and the device continue to gather near the electrode under the action of the DC bias, and the internal electric field formed by the ions that are not easy to dissipate after the power is removed causes the liquid crystal to still deflect, and the brightness slowly decreases, forming image residue. The liquid crystal composition with negative dielectric anisotropy provided by the present application contains at least one stabilizer, and the stabilizer is selected from the group consisting of the compound of formula I-1, the compound of formula I-2, the compound of formula I-3, and the compound of formula I-4, which is a hindered amine light stabilizer that can adsorb ions / free radicals, eliminate the internal electric field, and promote the rapid dissipation of residual images. In the present application, a stabilizer of a specific structure is compounded with a compound of formula II, formula F and / or formula N comprising a cyclohexene structure. Through the design of each component and mutual coordination, the liquid crystal composition has a higher elastic constant (K under the condition of having excellent optical anisotropy, clearing point and dielectric anisotropy Δε. 11 and K 33 ), smaller rotational viscosity γ1, smaller ratio of rotational viscosity to elastic constant γ1 / K 11 , smaller ratio of elastic constant to dielectric anisotropy K 11 / △ε, resulting in a shorter response time and faster response speed, lower operating voltage and power consumption, and lower light scattering LC Scattering, and exhibiting excellent photoelectric stability, resulting in a high voltage holding ratio VHR, which can eliminate image sticking or accelerate the dissipation of image sticking.

[0031] The following are preferred technical solutions of this application, but are not intended to limit the technical solutions provided in this application. Through the following preferred technical solutions, the objectives and beneficial effects of this application can be better achieved and realized.

[0032] In the present application, the 1-5 carbon atoms can be 2, 3, 4 or 5 carbon atoms; the 1-12 carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms; the 1-3 carbon atoms can be 1, 2 or 3 carbon atoms; in the present application, when n2=2, there are 2 rings in the compound. These two They may have the same structure or different structures. For example, one may be Another one is The expressions "same or different" in this application have the same meaning; "can be replaced by..." in this application means that it can be replaced or not replaced, that is, replacement or non-replacement falls within the scope of protection of this application. The same applies to "can be replaced by...", and the positions of "replacement" and "replacement" can be arbitrary; in this application, the short straight lines on one or both sides of the group structure represent access bonds, not methyl groups, for example The short straight line on the left, Short straight lines on both sides; the halogen includes F, Cl, Br or I; when the same description is referred to below, it has the same meaning; the "halogenated" means that at least one -H in the group is replaced by a halogen (-F, -Cl, -Br or -I); when the same description is referred to below, it has the same meaning.

[0033] In some embodiments of the present application, X represents -H, -OH, -O*, a linear or branched alkyl group containing 1-5 carbon atoms, a linear or branched alkoxy group containing 1-5 carbon atoms, or a linear or branched acyl group containing 1-5 carbon atoms.

[0034] In some embodiments of the present application, X represents -H, -OH, -O*, -CH3, -OCH3 or -CO-CH3.

[0035] In some embodiments of the present application, n represents an integer of 2-16, and more preferably an integer of 2-14.

[0036] In some embodiments of the present application, the stabilizer comprises at least one selected from the group consisting of a compound of Formula I-3 or a compound of Formula I-4.

[0037] In some embodiments of the present application, the stabilizer comprises at least one selected from the group consisting of a compound of Formula I-1 or a compound of Formula I-3.

[0038] In some embodiments of the present application, the stabilizer comprises at least one compound selected from the group consisting of a compound of formula I-1, a compound of formula I-2, a compound of formula I-3, or a compound of formula I-4, wherein X represents -O*.

[0039] In some embodiments of the present application, the mass percentage of the stabilizer in the liquid crystal composition is 0.001%-0.1%, for example, it can be 0.002%, 0.003%, 0.005%, 0.008%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%, etc., preferably 0.002%-0.05%, and further preferably 0.002%-0.01%.

[0040] In some embodiments of the present application, the compound of formula II is selected from the group consisting of the following compounds:

[0041] as well as

[0042] Wherein, R1 and R2 have the same defined ranges as those in Formula II.

[0043] In some embodiments of the present application, R1 and R2 represent a straight-chain alkyl group containing 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, a straight-chain alkoxy group containing 1-9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms, or a straight-chain alkenyl group containing 2-9 (e.g., 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms, and further preferably a straight-chain alkyl group containing 1-10 carbon atoms or a straight-chain alkenyl group containing 2-9 carbon atoms.

[0044] In some embodiments of the present application, the compound of formula II comprises at least one (e.g., 1, 2, 3 or 4, etc.) compound selected from the group consisting of compounds of formula II-1, compounds of formula II-2, compounds of formula II-5, and compounds of formula II-6.

[0045] In some embodiments of the present application, the compound of formula II comprises at least one (eg, 1, 2, 3, or 4, etc.) compound selected from the group consisting of compounds of formula II-2 and compounds of formula II-6.

[0046] In some embodiments of the present application, the compound of formula II is selected from the group consisting of the following compounds:

[0047] as well as

[0048] wherein R1 and R2 each independently represent a straight-chain alkyl group containing 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms, or a straight-chain alkoxy group containing 1 to 9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms;

[0049] R 11 and R 21 Each independently represents a straight-chain alkenyl group containing 2 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms.

[0050] In some embodiments of the present application, the compound of formula II comprises at least one (for example, 1, 2, 3 or 4, etc.) compound selected from the group consisting of compounds of formula II-2-1, compounds of formula II-2-2, compounds of formula II-2-3, compounds of formula II-6-1, and compounds of formula II-6-3.

[0051] In some embodiments of the present application, the mass percentage of the compound of formula II in the liquid crystal composition is 1%-30%, for example, it can be 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, etc., and more preferably 2%-20%.

[0052] In some embodiments of the present application, the mass percentage of at least one (for example, 1, 2, 3 or 4, etc.) compound of formula II selected from the group consisting of compounds of formula II-2 and compounds of formula II-6 is 1%-30%, for example, it can be 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, etc., and more preferably 2%-20%.

[0053] In some embodiments of the present application, the mass percentage of at least one (for example, 1, 2, 3 or 4, etc.) compound of formula II selected from the group consisting of compounds of formula II-2-1, compounds of formula II-2-2, compounds of formula II-2-3, compounds of formula II-6-1, and compounds of formula II-6-3 is 1%-28%, for example, it can be 2%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, etc., and further preferably 2%-20%.

[0054] In some embodiments of the present application, the G represents -O- or -S-.

[0055] In some embodiments of the present application, L1 and L2 represent -F.

[0056] In some embodiments of the present application, the compound of formula F is selected from the group consisting of the following compounds:

[0057] as well as

[0058] wherein said R3, R4 and Z3 have the same defined ranges as in formula F;

[0059] Y1 and Y2 each independently represent -O- or -CH2-.

[0060] In some embodiments of the present application, the compound of formula F is selected from at least one (eg, 1, 2, 3, 4, or 5, etc.) group consisting of compounds of formula F-1 and compounds of formula F-2:

[0061] as well as

[0062] In some embodiments of the present application, R3 represents a straight-chain alkyl group containing 1-8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms or a straight-chain alkoxy group containing 1-6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, and a straight-chain alkoxy group containing 1-6 carbon atoms is further preferred.

[0063] In some embodiments of the present application, Z3 represents a single bond, -O-, -OCH2- or -OCH2CH2-.

[0064] In some embodiments of the present application, the R4 represents a straight-chain alkyl group containing 1-8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8) carbon atoms, a straight-chain alkoxy group containing 1-6 (e.g., 1, 2, 3, 4, 5, or 6) carbon atoms, More preferably, the straight chain alkyl group contains 1 to 8 carbon atoms, the straight chain alkoxy group contains 1 to 6 carbon atoms,

[0065] In some embodiments of the present application, the compound of formula F is selected from the group consisting of the following compounds:

[0066] as well as

[0067] wherein R4′ represents a straight-chain alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7 or 8) carbon atoms;

[0068] ring express Further optimization

[0069] In some embodiments of the present application, the compound of formula N is selected from the group consisting of the following compounds:

[0070] as well as

[0071] Among them, R N1 and R N2 Has the same definition as in Formula N.

[0072] In some embodiments of the present application, the RN1 and R N2 Each independently represents a straight-chain alkyl group containing 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, a straight-chain alkoxy group containing 1 to 9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms, or a straight-chain alkenyl group containing 2 to 9 (e.g., 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms.

[0073] In some embodiments of the present application, the R N2 Each independently represents a straight-chain alkoxy group containing 1 to 9 carbon atoms.

[0074] In some embodiments of the present application, the compound of formula N comprises at least one (for example, 1, 2, 3, 4, 5, 6, 7 or 8, etc.) compound selected from the group consisting of a compound of formula N-2, a compound of formula N-3, a compound of formula N-5, a compound of formula N-6, a compound of formula N-7, a compound of formula N-10, a compound of formula N-11, a compound of formula N-12, a compound of formula N-13, a compound of formula N-23, a compound of formula N-25, a compound of formula N-29 or a compound of formula N-30.

[0075] In some embodiments of the present application, the liquid crystal composition comprises at least one compound of Formula F and at least one compound of Formula N.

[0076] In some embodiments of the present application, the mass percentage of the compound of formula F in the liquid crystal composition is 1%-30%, for example, it can be 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, etc., preferably 2%-25%.

[0077] In some embodiments of the present application, the mass percentage of at least one (for example, 1, 2, 3 or 4, etc.) compound of formula F selected from the group consisting of compounds of formula F-1 or compounds of formula F-2 is 1%-28%, for example, it can be 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, etc., preferably 2%-25%.

[0078] In some embodiments of the present application, the mass percentage of the compound of formula N in the liquid crystal composition is 1%-70%, for example, it can be 5%, 8%, 10%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 34.5%, 35%, 38%, 40%, 43%, 44%, 45%, 46%, 48.5%, 50%, 52.6%, 53%, 55%, 58%, 60%, 65% or 70%, etc., and more preferably 20%-55%.

[0079] In some embodiments of the present application, at least one (e.g., 1, 2, 3, 4, 5, 6, 7, or 8, etc.) compound is selected from the group consisting of compounds of formula N-2, compounds of formula N-3, compounds of formula N-5, compounds of formula N-6, compounds of formula N-7, compounds of formula N-10, compounds of formula N-11, compounds of formula N-12, compounds of formula N-13, compounds of formula N-23, compounds of formula N-25, compounds of formula N-29, compounds of formula N-30, compounds of formula N-31, compounds of formula N-32, compounds of formula N-33, compounds of formula N-34, compounds of formula N-35, compounds of formula N-36, compounds of formula N-37, compounds of formula N-38, compounds of formula N-39, compounds of formula N-40, compounds of formula N-41, compounds of formula N-42, compounds of formula N-43, compounds of formula N-44, compounds of formula N-45, compounds of formula N-46, compounds of formula N-47, compounds of formula N-48, compounds of formula N-49, compounds of formula N-50, compounds of formula N-51, compounds of formula N-52, compounds of formula N-53, compounds of formula N-54, compounds of formula N-56, compounds of formula N-57, compounds of formula N-58, compounds of formula N-59, compounds of formula N-60, compounds of formula N-61, compounds of formula N-62, compounds of formula N-63, compounds of formula N-64, compounds of formula N-65 The mass percentage of the compound of formula N in the group consisting of the compound of formula N-30 is 1%-65%, for example, it can be 5%, 8%, 10%, 15%, 18%, 20%, 25%, 28%, 30%, 34.5%, 35%, 38%, 40%, 43%, 44%, 45%, 46%, 48.5%, 50%, 52.6%, 53%, 55%, 58%, 60% or 65%, etc., and more preferably 20%-55%.

[0080] In some embodiments of the present application, the liquid crystal composition further comprises at least one compound of formula M:

[0081] Among them, R M1 and R M2 Each independently represents a straight or branched alkyl group containing 1 to 12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12) carbon atoms, One or at least two non-adjacent -CH2- in the linear or branched alkyl group containing 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0082] ring ring and Ring Each independently expresses described One or at least two -CH2- in the can be replaced by -O-; At most one -H in may be replaced by halogen;

[0083] Z M1 and Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CH2CH2- or -(CH2)4-;

[0084] n M1 represents 0, 1, 2, or 3, where n M1 =2 or 3, the ring Same or different, Z M2 Same or different.

[0085] In some embodiments of the present application, the compound of formula M is selected from the group consisting of the following compounds:

[0086] as well as

[0087] Among them, R M1 and R M2 Each independently represents a straight-chain or branched alkyl group containing 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, and one or two or more non-adjacent -CH2- in the straight-chain or branched alkyl group containing 1 to 10 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-.

[0088] In some embodiments of the present application, the R M1 and R M2 Each independently represents a straight-chain alkyl group containing 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) carbon atoms, a straight-chain alkoxy group containing 1 to 9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms, or a straight-chain alkenyl group containing 2 to 9 (e.g., 2, 3, 4, 5, 6, 7, 8 or 9) carbon atoms.

[0089] In some embodiments of the present application, the compound of formula M comprises at least one (e.g., 1, 2, 3, 4, 5 or 6, etc.) compound selected from the group consisting of compounds of formula M-1, compounds of formula M-18, compounds of formula M-23 or compounds of formula M-34.

[0090] In some embodiments of the present application, the liquid crystal composition comprises at least one (eg, 1, 2, 3 or 4, etc.) R M1 and / or R M2 A compound of formula M which is a compound of formula M-1, a compound of formula M-18 or a compound of formula M-23 containing a linear alkenyl group of 2 to 6 (eg, 2, 3, 4, 5 or 6) carbon atoms.

[0091] In some embodiments of the present application, the liquid crystal composition comprises at least one (eg, 1, 2, 3 or 4, etc.) R M1 and / or R M2 The compound of formula M-1 is a straight chain alkenyl group containing 2 to 6 (eg, 2, 3, 4, 5 or 6) carbon atoms.

[0092] The alkenyl group in the present application is preferably a group represented by any one of formulas (V1) to (V9), and is particularly preferably represented by formula (V1), formula (V2), formula (V8), or formula (V9). The groups represented by formulas (V1) to (V9) are as follows: Here, * represents the carbon atom in the ring structure to which it is bonded.

[0093] In some embodiments of the present application, the mass percentage of the compound of formula M in the liquid crystal composition is 1%-55%, for example, it can be 2%, 5%, 8%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 23.5%, 25%, 27.5%, 28%, 29%, 30%, 32%, 34%, 35%, 35.4%, 36%, 38%, 40%, 45%, 46%, 48% or 50%, 52%, 54%, or 55%, etc., and more preferably 5%-50%.

[0094] In some embodiments of the present application, the mass percentage of at least one (for example, 1, 2, 3, 4, 5 or 6, etc.) compound of formula M selected from the group consisting of compounds of formula M-1, compounds of formula M-18, compounds of formula M-23 or compounds of formula M-34 is 1%-54%, for example, it can be 2%, 5%, 8%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 23.5%, 25%, 27.5%, 28%, 29%, 30%, 32%, 34%, 35%, 35.4%, 36%, 38%, 40%, 45%, 46%, 48%, 50%, 52% or 54%, etc., and further preferably 5%-55%.

[0095] In addition to the above compounds, the liquid crystal composition of the present application may also include any one or a combination of at least two of common nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, polymerizable monomers, and additives.

[0096] In a preferred embodiment, the liquid crystal composition further comprises at least one additive.

[0097] In a preferred embodiment, the additive includes any one or a combination of at least two of a dopant, an antioxidant, an ultraviolet absorber, an infrared absorber or other light stabilizers.

[0098] It should be noted that the other light stabilizers refer to light stabilizers different from the compound of formula I-1, the compound of formula I-2, the compound of formula I-3, and the compound of formula I-4.

[0099] Possible dopants that are preferably added to the liquid crystal composition of the present application are shown below:

[0100] as well as

[0101] Here, “+” indicates a chiral site.

[0102] In some embodiments of the present application, the mass percentage of the dopant in the liquid crystal composition is 0%-5%; preferably, the mass percentage of the dopant in the liquid crystal composition is 0.01%-1%.

[0103] In addition, the antioxidants, other light stabilizers and other additives used in the liquid crystal composition of the present application are preferably the following:

[0104] Here, x represents a positive integer from 1 to 12.

[0105] Exemplarily, the other light stabilizers are selected from the light stabilizers shown below:

[0106] In some embodiments of the present application, the mass percentage of other light stabilizers in the liquid crystal composition is 0%-5%; preferably, the mass percentage of other light stabilizers in the liquid crystal composition is 0.01%-1%, and more preferably 0.01%-0.1%.

[0107] In a second aspect, the present application provides a liquid crystal display device, comprising the liquid crystal composition as described in the first aspect.

[0108] In a preferred embodiment, the liquid crystal display device is any one of a VA display mode, a PSVA display mode, an IPS display mode, and a NFFS display mode.

[0109] Compared with the related art, this application has the following beneficial effects:

[0110] The negative dielectric anisotropy liquid crystal composition provided in the present application has a high elastic constant K while having excellent clearing point, optical anisotropy and dielectric anisotropy Δε through the design and compounding of the stabilizer and liquid crystal components. 11 and K 33 , smaller rotational viscosity γ1, smaller ratio of rotational viscosity to elastic constant γ1 / K 11 , smaller ratio of elastic constant to dielectric anisotropy K 11 / △ε, has a shorter response time, faster response speed, lower operating voltage and power consumption, and lower light scattering LC Scattering, while showing excellent photoelectric stability and a higher voltage holding rate VHR, which can eliminate image persistence or accelerate the dissipation of image persistence.

[0111] Still other aspects will become apparent upon reading and understanding the detailed description. DETAILED DESCRIPTION

[0112] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations of the present application.

[0113] For ease of expression, in the following examples and comparative examples, the group structures of the components in the liquid crystal composition are represented by the codes listed in Table 1:

[0114] Table 1

[0115] Take the following compound as an example:

[0116] The structure is represented by the codes listed in Table 1 as follows: nCLWO2; wherein C represents 1,4-cyclohexylene, L represents 1,4-cyclohexenylene, W represents 2,3-difluoro-1,4-phenylene, n represents the number of carbon atoms of the left-end alkyl group, for example, if n is "3", it means that the alkyl group is n-propyl, and OC2H5 represents ethoxy.

[0117] The abbreviated codes for the test items in the following examples and comparative examples are as follows:

[0118] Cp clearing point (nematic-isotropic phase transition temperature, °C)

[0119] Δn optical anisotropy (589nm, 25℃)

[0120] Δε dielectric anisotropy (1kHz, 25℃)

[0121] K 11 Splay elastic constant (25℃)

[0122] K 33 Bending elastic constant (25℃)

[0123] γ1 Rotational viscosity (mPa·s, 25°C)

[0124] γ1 / K 11 Ratio of rotational viscosity to splay elastic constant

[0125] K 11 / Δε Ratio of splay elastic constant to dielectric anisotropy

[0126] n o Refractive index of ordinary light (589nm, 25℃)

[0127] n e Refractive index of extraordinary light (589nm, 25℃)

[0128] LC Scattering

[0129] IS disappearance time The disappearance time of image persistence (min)

[0130] Wherein, Cp: measured by MP70 melting point apparatus;

[0131] Δn: Δn=n e -n o , measured using an Abbe refractometer under a sodium lamp (589nm) at 25°C;

[0132] Δε: Δε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥is the dielectric constant perpendicular to the molecular axis. Test conditions: 25°C, 1 kHz, VA-type test cell with a cell thickness of 6 μm.

[0133] K 11 and K 33 : Calculated using an LCR meter and a VA test cell to test the CV curve of the liquid crystal. Test conditions: 6μm VA test cell, V = 0.1-20V;

[0134] γ1: measured using the LCM-2 liquid crystal property evaluation system; test conditions: 25°C, 160-240V, test cell thickness 20μm;

[0135] LC Scattering:LC in, (K 11 +K 22 +K 33 ), K 11 , K 22 , K 33 The test method is as shown above;

[0136] IS dissipation time: Use DMS 505 photoelectric comprehensive tester to apply supersaturation voltage (13V) to a FFS box for 2 hours and then apply L 64 Grayscale voltage, at this time, read and record the brightness value at regular intervals, time-brightness curve L-t1, apply a low voltage (0.1V) for 2h to another FFS box, and then apply L 64 Grayscale voltage, at this time, read and record the brightness value at regular intervals to obtain the time-brightness curve L-t2, and then take the difference between the L-t1 and L-t2 curves to obtain the relative afterimage dissipation curve △Lt; when △L is zero, the afterimage is considered to have completely disappeared, and the time t at this time is recorded as the IS dissipation time, where the box thickness of the FFS box is 3μm.

[0137] The compounds used in the following examples and comparative examples can be synthesized by known methods or obtained through commercial channels. These synthesis techniques are conventional, and the resulting liquid crystal compositions have been tested to meet the standards for electronic compounds.

[0138] Liquid crystal compositions were prepared according to the proportions of the liquid crystal compositions in the following examples and comparative examples. The liquid crystal compositions were prepared according to conventional methods in the art, such as mixing in a prescribed proportion by heating, ultrasonication, suspension, etc.

[0139] Comparative Example 1

[0140] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0141] Comparative Example 2

[0142] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0143] Comparative Example 3

[0144] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0145] The amount of the stabilizer is calculated based on the amount of other liquid crystal components as 100%. Taking Comparative Example 3 as an example, the total amount of other liquid crystal components is 100%, and the added amount of the stabilizer is 0.01%. The following embodiments / comparative examples involving stabilizers have the same description and are not repeated here.

[0146] Example 1

[0147] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0148] Example 2

[0149] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0150] Example 3

[0151] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0152] Example 4

[0153] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0154] Example 5

[0155] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0156] Example 6

[0157] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0158] Example 7

[0159] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0160] Example 8

[0161] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0162] Example 9

[0163] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0164] Example 10

[0165] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0166] Example 11

[0167] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0168] Example 12

[0169] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0170] Example 13

[0171] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0172] Example 14

[0173] A liquid crystal composition comprises the components in the following mass percentages, and the performance test results thereof are listed in the following table:

[0174] Comparative Example 2 contains the compound of Formula N of the present application, but does not contain the compound of Formula II. Comparative Example 1 contains the compound of Formula F and Formula N of the present application, but does not contain the compound of Formula II of the present application. Compared with Comparative Example 2, it has a smaller γ1 / K 11 and smaller K 11 / △ε, but it has a considerable dissipation time IS. Comparative Example 3 is based on Comparative Example 1 and further includes the compound of Formula I of the present application. Although the dissipation time IS is improved, γ1 / K is sacrificed. 11 and K 11 / △ε. Comparison of Example 1 of the present application with Comparative Examples 1-3 shows that the present application, through the design and compounding of a stabilizer of a specific structure with a compound of Formula II, Formula F and / or Formula N containing a cyclohexenyl group, has a higher elastic constant K while having excellent clearing point, optical anisotropy and dielectric anisotropy △ε. 11 and K 33 , smaller rotational viscosity γ1, smaller ratio of rotational viscosity to elastic constant γ1 / K 11 , smaller ratio of elastic constant to dielectric anisotropy K 11 / △ε, has lower response time and faster response speed, lower operating voltage and power consumption, lower LC Scattering, and shorter IS dissipation time, which can eliminate image persistence or accelerate the dissipation of image persistence.

[0175] Furthermore, according to Examples 2, 3, and 4, it can be seen that, compared to the difunctional stabilizers of Formula I-1 and Formula I-2, the liquid crystal composition containing the trifunctional stabilizer of Formula I-3 has a shorter IS dissipation time and has better performance in eliminating image sticking and accelerating the dissipation of image sticking. According to Examples 6, 7, and 8, it can be seen that the stabilizer whose terminal group X is an oxygen free radical can more effectively eliminate the internal electric field and promote the rapid dissipation of residual images. According to Examples 9, 10, and 11, it can be seen that in the liquid crystal composition of the present application, the stabilizer with a specific structure can achieve excellent results even at a low content. Based on cost considerations, the content of the stabilizer is preferably 0.001%-0.1%, and more preferably 0.001%-0.01%.

[0176] In summary, the present invention introduces a stabilizer with a specific structure and compounds it with a specific liquid crystal component, so that the liquid crystal composition has a larger elastic constant K value, K, on ​​the basis of having excellent clearing point, optical anisotropy and dielectric anisotropy Δε.11 15.5-21.2, K 33 The rotational viscosity is 17.6-22, the lower rotational viscosity, γ1 is 86-125mPa·s, and the ratio of rotational viscosity to elastic constant, γ1 / K 11 is 5.2-6.5, indicating a shorter response time and faster response speed, a smaller ratio of elastic constant to dielectric anisotropy, K 11 / △ε is -3.76 to -7.1, indicating that it has low driving voltage and power consumption, low light scattering degree, LC Scattering is 0.019-0.028, IS dissipation time is 17.1-19.9min, which can quickly eliminate image retention and has excellent photoelectric stability.

[0177] The applicant declares that this application uses the above-mentioned embodiments to illustrate the liquid crystal composition with negative dielectric anisotropy and the liquid crystal display device containing the same, but this application is not limited to the above-mentioned embodiments, that is, it does not mean that this application must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent replacement of various raw materials of the product of this application, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of this application.

Claims

1. A liquid crystal composition having negative dielectric anisotropy, comprising: At least one stabilizer, the stabilizer being selected from the group consisting of the following compounds: At least one compound of formula II: and At least one compound of formula F and / or formula N: Among them, X represents -H, -OH, -O*, a linear or branched alkyl group having 1 to 5 carbon atoms; one or at least two non-adjacent -CH2- in the linear or branched alkyl group having 1 to 5 carbon atoms may be independently replaced by -O- or -CO- respectively; -O* represents an oxygen radical; R1 and R2 each independently represent a straight-chain or branched alkyl group containing 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in the linear or branched alkyl group having 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively; R3 and R4 each independently represent -H, halogen, a straight-chain or branched alkyl group having 1 to 12 carbon atoms, The straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in may be independently replaced by -CH=CH-, -C≡C-, -O-, -S-, -CO-, -CO-O- or -O-CO- respectively, and one or at least two -H in the foregoing groups may be independently replaced by -F or -Cl; R N1 and R N2 each independently represents a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in the linear or branched alkyl group having 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively; Ring Sum ring Each independently represents The said One or at least two of the -CH2- therein may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds; the At most one - H in it may be substituted by a halogen, and at least one ring Or a ring Each independently represents Ring Sum ring Each independently represents The said One or at least two of the -CH2- in it can be replaced by -O-, and one or at most two of the single bonds in the ring can be replaced by double bonds; the one or at least two -H may be replaced by -F, -Cl, -CN, -CH3 or -OCH3, and one or at least two -CH= in one or more rings may be replaced by -N=; Ring Sum ring Each independently represents Among them One or at least two of the -CH2- therein may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds, wherein one or at least two -H may be independently replaced by -F, -Cl or -CN, and one or at least two -CH= in one or more rings may be replaced by -N=; G represents -O-, -S-, -CO-, -CF2-, -NH- or -NF-; L1 and L2 each independently represent -H, a halogen, a halogenated or unhalogenated alkyl group having 1 to 3 carbon atoms, or a halogenated or unhalogenated alkoxy group having 1 to 3 carbon atoms; L N1 and L N2 each independently represents -H, a halogen, a straight-chain or branched alkyl group having 1 to 3 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 3 carbon atoms; Z1, Z2, Z N1 and Z N2 each independently represents a single bond, -O-, -S-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)4-, -CF2O- or -OCF2-; Z3 represents a single bond, -O(CH2) a - or -S(CH2) a -; a represents an integer from 0 to 5; n represents an integer from 1 to 20; n1 represents 1 or 2; when n1 = 2, the ring are the same or different; n F1 and n F2 each independently represents 0, 1 or 2; when n F1 = 2, the ring identical or different, Z1 is identical or different; when n F2 = 2, the ring are the same or different, and Z2 are the same or different; n N1 represents 0, 1, 2, or 3, where n N2 represents 0 or 1, and 0 ≤ n N1 + n N2 ≤ 3; When n N1 represents 2 or 3, the ring Same or different, Z N1 Same or different.

2. The liquid crystal composition according to claim 1, characterized in that, the X represents -H, -OH, -O*, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, or a linear or branched acyl group having 1 to 5 carbon atoms.

3. The liquid crystal composition according to claim 1, wherein The mass percentage content of the stabilizer in the liquid crystal composition is 0.001% - 0.1%.

4. The liquid crystal composition according to claim 1, wherein, The compound of formula II is selected from the group consisting of the following compounds: and Wherein, R1 and R2 have the same defined range as in formula II.

5. The liquid crystal composition according to claim 1, wherein The compound of formula F is selected from the group consisting of the following compounds: and Wherein, R3, R4 and Z3 have the same defined range as in formula F; Y1 and Y2 each independently represent -O- or -CH2-.

6. The liquid crystal composition according to claim 1, wherein The compound of formula N is selected from the group consisting of the following compounds: and wherein, R N1 and R N2 have the same defined scope as in formula N.

7. The liquid crystal composition according to claim 1, wherein The liquid crystal composition contains at least one compound of formula F and at least one compound of formula N; Preferably, the mass percentage content of the compound of formula F in the liquid crystal composition is 1% - 30%; Preferably, the mass percentage content of the compound of formula N in the liquid crystal composition is 1% - 70%.

8. The liquid crystal composition according to claim 1, wherein, The liquid crystal composition further comprises at least one compound of formula M: wherein, R M1 and R M2 each independently represents a straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in the linear or branched alkyl group having 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively; Ring Ring Sum ring Each independently represents The One or at least two of the -CH2- groups therein may be replaced by -O-; the At most one - H therein may be substituted by a halogen; Z M1 and Z M2 each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH═CH-, -CH2CH2- or -(CH2)4-; n M1 represents 0, 1, 2, or 3, where when n M1 = 2 or 3, the ring Same or different, Z M2 Same or different.

9. The liquid crystal composition according to claim 8, wherein, The compound of formula M is selected from the group consisting of the following compounds: and wherein, R M1 and R M2 each independently represents a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and one or more than two non-adjacent -CH2- in the straight-chain or branched alkyl group having 1 to 10 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively.

10. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 - 9.

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