Liquid crystal composition with negative dielectric anisotropy and liquid crystal display device containing liquid crystal composition

Abstract

The invention provides a liquid crystal composition with negative dielectric anisotropy and a liquid crystal display device comprising the liquid crystal composition. The liquid crystal composition comprises at least one stabilizer, at least one compound as shown in a formula II and at least one compound as shown in a formula F and / or a formula N. Through the design and compounding synergism of the stabilizer and the liquid crystal component, the liquid crystal composition has excellent clearing point, optical anisotropy and dielectric anisotropy epsilon; the liquid crystal composition has high elastic constants K11 and K33, low rotary viscosity gamma1, a low ratio gamma1 / K11 of the rotary viscosity to the elastic constant, a low ratio K11 / epsilon of the elastic constant to dielectric anisotropy, low response time, high response speed, low working voltage and power consumption, low LC Scattering, excellent photoelectric stability, and good application prospects. The high voltage holding ratio VHR is achieved, and image residue can be eliminated or dissipation of the image residue can be accelerated.

Description

Technical Field

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

[0002] A liquid crystal display (LCD) is a device that realizes display relying on the electro-optical properties of liquid crystals. According to the arrangement configuration of liquid crystal molecules, it can be divided into: 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), FPA (field-induced photo-reactive alignment), etc. The performance indicators of the display mainly include color reproducibility, brightness, contrast ratio, viewing angle, resolution, power consumption, etc. TFT-IPS / FFS combined with a TFT control matrix has become the main application type due to its advantages such as high resolution, high contrast ratio, high color reproducibility, and a large viewing angle.

[0003] In the IPS / FFS display mode, to obtain a high-contrast display effect, it is necessary to reduce the light leakage in the dark state. Except for the device manufacturing process, the main light leakage factor of the device is the optical scattering caused by the liquid crystal layer. The scattering degree of the liquid crystal (LC Scattering) can be measured according to the following formula:

[0004]

[0005] where d represents the thickness of the liquid crystal cell, n e represents the extraordinary light refractive index, n o represents the ordinary light refractive index, K ave is the average elastic constant. When the liquid crystal refractive index and cell thickness are designed, increasing K avecan effectively improve the contrast ratio of the display. Increasing the nematic phase transition temperature Cp of the liquid crystal often results in a larger K ave , but at the same time, the rotational viscosity of the liquid crystal also increases, leading to a slower liquid crystal response speed. 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. However, using a large amount of liquid crystal monomers with a small dielectric constant will significantly increase the rotational viscosity γ1 of the liquid crystal. An effective method is to use a small amount of liquid crystal monomers with a large dielectric constant.

[0006] However, cyclohexene monomers with a large K ave value and liquid crystal monomers with a large dielectric constant often have low photo - and electro - stability due to their structural factors. They aggregate ions or directly decompose under extreme working environments for a long time, resulting in a decrease in the voltage holding ratio VHR, image retention, etc. Therefore, how to make the liquid crystal material have a high elastic constant and low viscosity, maintain high contrast, low operating voltage, low power consumption, low response time and low LC Scattering, while improving photo - and electro - stability, having a high VHR and reducing image retention, is an urgent problem to be solved in this field. SUMMARY OF THE INVENTION

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a liquid crystal composition with negative dielectric anisotropy and a liquid crystal display device containing the same. The liquid crystal composition has a suitable clearing point, optical anisotropy and dielectric anisotropy, while having a high elastic constant K 11 and K 33 , a low rotational viscosity γ1, reducing γ1 / K 11 , shortening the response time, reducing power consumption, reducing LC Scattering, and having excellent photo - and electro - stability, having a high VHR, and being able to eliminate image retention or accelerate the dissipation of image retention.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In the first aspect, the present invention provides a liquid crystal composition with negative dielectric anisotropy, the liquid crystal composition comprising:

[0010] At least one stabilizer, the stabilizer being selected from the group consisting of the following compounds:

[0011]

[0012] At least one compound of formula II:

[0013] And at least one compound of formula F and / or formula N:

[0014]

[0015]

[0016] Among them, X represents -H, -OH, -O*, a linear or branched alkyl group containing 1 to 5 (such as 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 can be independently replaced by -O- or -CO- respectively; -O* represents an oxygen radical;

[0017] R1 and R2 each independently represent a linear or branched alkyl group containing 1 to 12 (such as 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 can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively;

[0018] R3 and R4 each independently represent -H, a halogen, a linear or branched alkyl group containing 1 to 12 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, the linear or branched alkyl group containing 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in it can 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 can be independently replaced by -F or -Cl;

[0019] R N1 and R N2 each independently represent a linear or branched alkyl group containing 1 to 12 (such as 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 can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO- respectively;

[0020] Ring and Ring each independently represent the One or at least two of the -CH2- therein can be replaced by -O-, and one or at most two single bonds in the rings can be replaced by double bonds; the At most one -H therein can be replaced by a halogen, and at least one of the rings Or the ring Each independently represents

[0021] Ring And the ring Each independently represents The One or at least two of the -CH2- therein can be replaced by -O-, and one or at most two single bonds in the rings can be replaced by double bonds; the One or at least two of the -H therein can be replaced by -F, -Cl, -CN, -CH3 or -OCH3, and one or at least two of the -CH= in the rings can be replaced by -N=;

[0022] Ring And the ring Each independently represents Wherein One or at least two of the -CH2- therein can be replaced by -O-, and one or at most two single bonds in the rings can be replaced by double bonds, wherein One or at least two of the -H therein can be independently replaced by -F, -Cl or -CN respectively, and one or at least two of the -CH= in the rings can be replaced by -N=;

[0023] G represents -O-, -S-, -CO-, -CF2-, -NH- or -NF-;

[0024] L1 and L2 each independently represent -H, a halogen, a halogenated or unhalogenated alkyl group containing 1 - 3 (e.g., 1, 2, 3) carbon atoms, or a halogenated or unhalogenated alkoxy group containing 1 - 3 (e.g., 1, 2, 3) carbon atoms;

[0025] L N1 And L N2 Each independently represent -H, a halogen, a straight-chain or branched-chain alkyl group containing 1 - 3 (e.g., 1, 2, 3) carbon atoms, or a straight-chain or branched-chain alkoxy group containing 1 - 3 (e.g., 1, 2, 3) carbon atoms;

[0026] 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-;

[0027] Z3 represents a single bond, -O(CH2) a - or -S(CH2) a -; a represents an integer from 0 to 5, for example, it can be 0, 1, 2, 3, 4 or 5;

[0028] n represents an integer from 1 to 20, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

[0029] n1 represents 1 or 2; when n1 = 2, the ring are the same or different;

[0030] n F1 and n F2 each independently represents 0, 1 or 2; when n F1 = 2, the ring are the same or different, Z1 are the same or different; when n F2 = 2, the ring are the same or different, Z2 are the same or different

[0031] n N1 represents 0, 1, 2 or 3, n N2 represents 0 or 1, and 0 ≤ n N1 + n N2 ≤ 3;

[0032] When n N1 represents 2 or 3, the ring are the same or different, Z N1 are the same or different.

[0033] It has been found in the research of the present invention that during the application of an oversaturated voltage, ions in the liquid crystal and the device continuously accumulate near the electrodes under the action of a DC bias voltage. After the power is removed, the internal electric field formed due to the difficulty of ion dissipation causes the liquid crystal to still deflect, and the brightness slowly decreases, resulting in image retention. The liquid crystal composition with negative dielectric anisotropy provided by the present invention contains at least one stabilizer, and the stabilizer is selected from the group consisting of compounds of formula I-1, compounds of formula I-2, compounds of formula I-3, and compounds of formula I-4. It is a hindered amine light stabilizer that can adsorb ions / free radicals, eliminate the internal electric field, and promote the rapid dissipation of afterimages. In the present invention, a stabilizer with a specific structure is compounded with a compound of formula II containing a cyclohexene structure, a compound of formula F, and / or a compound of formula N. Through the design and mutual cooperation of each component, the liquid crystal composition has excellent optical anisotropy, clearing point, and dielectric anisotropy △ε, and has a relatively high elastic constant (K 11 and K 33 ), a smaller rotational viscosity γ1, a smaller ratio of rotational viscosity to elastic constant γ1 / K 11 , a smaller ratio of elastic constant to dielectric anisotropy K 11 / △ε. Therefore, it has a lower response time and a faster response speed, a lower operating voltage and power consumption, a lower degree of light scattering LC Scattering, and exhibits excellent optoelectronic stability, with a high voltage holding ratio VHR, and can eliminate image retention or accelerate the dissipation of image retention.

[0034] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the purpose and beneficial effects of the present invention can be better achieved and realized.

[0035] In the present invention, the 1-5 carbon atoms can all be 2, 3, 4, or 5 carbon atoms; the 1-12 carbon atoms can all be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms; the 1-3 carbon atoms can all be 1, 2, or 3 carbon atoms; in the present invention, when n2 = 2, there are 2 rings in the compound These two can have the same structure or different structures. Exemplarily, one can be and the other can be When the present invention involves the expression of "the same or different", it has the same meaning; in the present invention, "can be independently replaced by..." means that it can be replaced or not replaced, that is, whether it is replaced or not replaced belongs to the protection scope of the present invention. The same applies to "can be independently substituted by...", and the positions of "substitute" and "substitute" can be arbitrary; in the present invention, the short straight lines on one side or both sides of the group structure represent the access bond, not the methyl group. For example The short straight line on the left, The short straight lines on both sides; the halogen includes F, Cl, Br or I; when the same description is involved below, it has the same meaning; the "halogenated" means that at least 1 -H in the group is replaced by a halogen (-F, -Cl, -Br or -I); when the same description is involved below, it has the same meaning.

[0036] In some embodiments of the present invention, X represents -H, -OH, -O*, a straight-chain or branched alkyl group containing 1 - 5 carbon atoms, a straight-chain or branched alkoxy group containing 1 - 5 carbon atoms, or a straight-chain or branched acyl group containing 1 - 5 carbon atoms.

[0037] In some embodiments of the present invention, X represents -H, -OH, -O*, -CH3, -OCH3 or -CO-CH3.

[0038] In some embodiments of the present invention, n represents an integer from 2 to 16, more preferably an integer from 2 to 14.

[0039] In some embodiments of the present invention, the stabilizer comprises at least one selected from the group consisting of compounds of Formula I-3 and compounds of Formula I-4.

[0040] In some embodiments of the present invention, the stabilizer comprises at least one selected from the group consisting of compounds of Formula I-1 and compounds of Formula I-3.

[0041] In some embodiments of the present invention, the stabilizer comprises at least one selected from the group consisting of compounds of Formula I-1, compounds of Formula I-2, compounds of Formula I-3, and compounds of Formula I-4, where X represents -O*.

[0042] In some embodiments of the present invention, the mass percentage content 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%, more preferably 0.002% - 0.01%.

[0043] In some embodiments of the present invention, the compounds of Formula II are selected from the group consisting of the following compounds:

[0044]

[0045] And

[0046]

[0047] Among them, R1 and R2 have the same defined ranges as in Formula II.

[0048] In some embodiments of the present invention, R1 and R2 represent a straight-chain alkyl group containing 1 to 10 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, a straight-chain alkoxy group containing 1 to 9 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms, or a straight-chain alkenyl group containing 2 to 9 (such as 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms, and further preferably a straight-chain alkyl group containing 1 to 10 carbon atoms or a straight-chain alkenyl group containing 2 to 9 carbon atoms.

[0049] In some embodiments of the present invention, the compound of Formula II comprises at least one (such as 1, 2, 3, or 4, etc.) selected from the group consisting of the compound of Formula II-1, the compound of Formula II-2, the compound of Formula II-5, and the compound of Formula II-6.

[0050] In some embodiments of the present invention, the compound of Formula II comprises at least one (such as 1, 2, 3, or 4, etc.) selected from the group consisting of the compound of Formula II-2 and the compound of Formula II-6.

[0051] In some embodiments of the present invention, the compound of Formula II is selected from the group consisting of the following compounds:

[0052]

[0053]

[0054] and

[0055]

[0056] Among them, R1 and R2 each independently represent a straight-chain alkyl group containing 1 to 10 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms or a straight-chain alkoxy group containing 1 to 9 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms;

[0057] R 11 and R 21 each independently represent a straight-chain alkenyl group containing 2 to 10 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms.

[0058] In some embodiments of the present invention, the compound of Formula II comprises at least one (e.g., 1, 2, 3, or 4, etc.) selected from the group consisting of the compound of Formula II-2-1, the compound of Formula II-2-2, the compound of Formula II-2-3, the compound of Formula II-6-1, and the compound of Formula II-6-3.

[0059] In some embodiments of the present invention, the mass percentage content 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 further preferably 2% - 20%.

[0060] In some embodiments of the present invention, the mass percentage content of at least one (e.g., 1, 2, 3, or 4, etc.) compound of Formula II selected from the group consisting of the compound of Formula II-2 and the compound 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 further preferably 2% - 20%.

[0061] In some embodiments of the present invention, the mass percentage content of at least one (e.g., 1, 2, 3, or 4, etc.) compound of Formula II selected from the group consisting of the compound of Formula II-2-1, the compound of Formula II-2-2, the compound of Formula II-2-3, the compound of Formula II-6-1, and the compound 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%.

[0062] In some embodiments of the present invention, G represents -O- or -S-.

[0063] In some embodiments of the present invention, L1 and L2 represent -F.

[0064] In some embodiments of the present invention, the compound of Formula F is selected from the group consisting of the following compounds:

[0065]

[0066]

[0067] and

[0068]

[0069] Among them, R3, R4 and Z3 have the same defined ranges as in formula F;

[0070] Y1 and Y2 each independently represent -O- or -CH2-.

[0071] In some embodiments of the present invention, the compound of formula F is selected from at least one (e.g., 1, 2, 3, 4, 5, etc.) group consisting of compounds of formula F-1 and compounds of formula F-2:

[0072] and

[0073]

[0074] In some embodiments of the present invention, R3 represents a straight-chain alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, 8) carbon atoms or a straight-chain alkoxy group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, 6) carbon atoms, and more preferably a straight-chain alkoxy group containing 1 to 6 carbon atoms.

[0075] In some embodiments of the present invention, Z3 represents a single bond, -O-, -OCH2- or -OCH2CH2-.

[0076] In some embodiments of the present invention, R4 represents a straight-chain alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, 8) carbon atoms, a straight-chain alkoxy group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, 6) carbon atoms, more preferably a straight-chain alkyl group containing 1 to 8 carbon atoms, a straight-chain alkoxy group containing 1 to 6 carbon atoms,

[0077] In some embodiments of the present invention, the compound of formula F is selected from the group consisting of the following compounds:

[0078]

[0079] and

[0080]

[0081] wherein R4' represents a straight-chain alkyl group containing 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, 8) carbon atoms;

[0082] ring represents more preferably In some embodiments of the present invention, the compound of formula N is selected from the group consisting of the following compounds:

[0083]

[0084]

[0085]

[0086] and

[0087]

[0088] wherein, R N1 and R N2 have the same defined ranges as in formula N.

[0089] In some embodiments of the present invention, said R N1 and R N2 each independently represent a straight-chain alkyl group containing 1 - 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, a straight-chain alkoxy group containing 1 - 9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms, or a straight-chain alkenyl group containing 2 - 9 (e.g., 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms.

[0090] In some embodiments of the present invention, said R N2 each independently represent a straight-chain alkoxy group containing 1 - 9 carbon atoms.

[0091] In some embodiments of the present invention, the compound of formula N comprises at least one (e.g., 1, 2, 3, 4, 5, 6, 7, 8, etc.) selected from the group consisting of the compound of formula N-2, the compound of formula N-3, the compound of formula N-5, the compound of formula N-6, the compound of formula N-7, the compound of formula N-10, the compound of formula N-11, the compound of formula N-12, the compound of formula N-13, the compound of formula N-23, the compound of formula N-25, the compound of formula N-29, the compound of formula N-30.

[0092] In some embodiments of the present invention, the liquid crystal composition comprises at least one compound of formula F and at least one compound of formula N.

[0093] In some embodiments of the present invention, the mass percentage content 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., and preferably 2% - 25%.

[0094] In some embodiments of the present invention, the mass percentage content of at least one (such as 1, 2, 3 or 4, etc.) compound of formula F selected from the group consisting of the compound of formula F-1 and the compound 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., and preferably 2% - 25%.

[0095] In some embodiments of the present invention, the mass percentage content 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%.

[0096] In some embodiments of the present invention, the mass percentage content of at least one (such as 1, 2, 3, 4, 5, 6, 7, 8, etc.) compound of formula N selected from the group consisting of the compound of formula N-2, the compound of formula N-3, the compound of formula N-5, the compound of formula N-6, the compound of formula N-7, the compound of formula N-10, the compound of formula N-11, the compound of formula N-12, the compound of formula N-13, the compound of formula N-23, the compound of formula N-25, the compound of formula N-29 and 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%.

[0097] In some embodiments of the present invention, the liquid crystal composition further comprises at least one compound of formula M:

[0098]

[0099] Wherein, R M1 and R M2Each independently represents a straight-chain or branched-chain alkyl group having 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 straight-chain or branched-chain alkyl group having 1 to 12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-;

[0100] Ring Ring And ring Each independently represents The One or at least two -CH2- in it may be replaced by -O-; the At most one -H in it may be substituted by a halogen;

[0101] Z M1 And Z M2 Each independently represents a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CH2CH2-, or -(CH2)4-;

[0102] n M1 Represents 0, 1, 2, or 3, where when n M1 = 2 or 3, the rings Are the same or different, and Z M2 Are the same or different.

[0103] In some embodiments of the present invention, the compound of formula M is selected from the group consisting of the following compounds:

[0104]

[0105]

[0106]

[0107] And

[0108]

[0109] Wherein, R M1 And R M2Each independently represents a straight-chain or branched alkyl group having 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, and one or two or more non-adjacent -CH2- in the straight-chain or branched alkyl group having 1 to 10 carbon atoms can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-.

[0110] In some embodiments of the present invention, the R M1 and R M2 Each independently represents a straight-chain alkyl group having 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, a straight-chain alkoxy group having 1 to 9 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms, or a straight-chain alkenyl group having 2 to 9 (e.g., 2, 3, 4, 5, 6, 7, 8, 9) carbon atoms.

[0111] In some embodiments of the present invention, the compound of formula M comprises at least one (e.g., 1, 2, 3, 4, 5, 6, etc.) selected from the group consisting of the compound of formula M-1, the compound of formula M-18, the compound of formula M-23, and the compound of formula M-34.

[0112] In some embodiments of the present invention, the liquid crystal composition comprises at least one (e.g., 1, 2, 3, 4, etc.) R M1 and / or R M2 A compound of formula M selected from the group consisting of the compound of formula M-1, the compound of formula M-18, and the compound of formula M-23, wherein R and / or R is a straight-chain alkenyl group having 2 to 6 (e.g., 2, 3, 4, 5, 6) carbon atoms.

[0113] In some embodiments of the present invention, the liquid crystal composition comprises at least one (e.g., 1, 2, 3, 4, etc.) R M1 and / or R M2 A compound of formula M-1, wherein R and / or R is a straight-chain alkenyl group having 2 to 6 (e.g., 2, 3, 4, 5, 6) carbon atoms.

[0114] The alkenyl group in the present invention is preferably any one of the groups represented by formula (V1) to formula (V9), and particularly preferably formula (V1), formula (V2), formula (V8) or (V9). The groups represented by formula (V1) to formula (V9) are as follows:

[0115] Wherein, * represents a carbon atom in the ring structure to which it is bonded.

[0116] In some embodiments of the present invention, the mass percentage content 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 further preferably 5% - 50%.

[0117] In some embodiments of the present invention, the mass percentage content of at least one (such as 1, 2, 3, 4, 5, 6, etc.) compound of formula M selected from the group consisting of the compound of formula M-1, the compound of formula M-18, the compound of formula M-23, and the compound 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% or 50%, 52%, 54%, etc., and further preferably 5% - 55%.

[0118] In addition to the above compounds, the liquid crystal composition of the present invention may also contain any one or at least two combinations of conventional nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, polymerizable monomers, and additives.

[0119] In a preferred technical solution, the liquid crystal composition further includes at least one additive.

[0120] In a preferred technical solution, the additive includes any one or at least two combinations of a dopant, an antioxidant, an ultraviolet absorber, an infrared absorber, and other light stabilizers.

[0121] 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.

[0122] The following shows the possible dopants preferably added to the liquid crystal composition of the present invention:

[0123]

[0124]

[0125] And

[0126]

[0127] Among them, + represents a chiral site.

[0128] In some embodiments of the present invention, the mass percentage content of the dopant in the liquid crystal composition is 0% - 5%; preferably, the mass percentage content of the dopant in the liquid crystal composition is 0.01% - 1%.

[0129] In addition, antioxidants, other light stabilizers and other additives used in the liquid crystal composition of the present invention are preferably the following substances:

[0130]

[0131]

[0132]

[0133] Among them, x represents a positive integer from 1 to 12.

[0134] Exemplarily, other light stabilizers are selected from the light stabilizers shown below:

[0135]

[0136] In some embodiments of the present invention, the mass percentage content of other light stabilizers in the liquid crystal composition is 0% - 5%; preferably, the mass percentage content of other light stabilizers in the liquid crystal composition is 0.01% - 1%, and more preferably 0.01% - 0.1%.

[0137] In a second aspect, the present invention provides a liquid crystal display device, and the liquid crystal display device includes the liquid crystal composition as described in the first aspect.

[0138] In a preferred technical solution, the liquid crystal display device is any one of VA display mode, PSVA display mode, IPS display mode, and NFFS display mode.

[0139] Compared with the prior art, the present invention has the following beneficial effects:

[0140] In the negative dielectric anisotropy liquid crystal composition provided by the present invention, through the design and compounding synergy of stabilizers and liquid crystal components, it has a high elastic constant K while having excellent clearing point, optical anisotropy and dielectric anisotropy △ε 11 and K 33 、a smaller rotational viscosity γ1, a smaller ratio of rotational viscosity to elastic constant γ1 / K 11 、a smaller ratio of elastic constant to dielectric anisotropy K 11 / Δε, having a low response time, a fast response speed, a low operating voltage and power consumption, a low degree of LC Scattering, and at the same time exhibiting excellent optoelectronic stability, having a high voltage holding ratio VHR, capable of eliminating image retention or accelerating the dissipation of image retention. Detailed implementation mode

[0141] The technical solution of the present invention will be further described below through specific implementation modes. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0142] For the convenience 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:

[0143] Table 1

[0144]

[0145] Taking the compound with the following structural formula as an example:

[0146] If this structure is represented by the codes listed in Table 1, it can be expressed as: nCLWO2; where 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 alkyl group at the left end. For example, when n is "3", it means that the alkyl group is n-propyl, and OC2H5 represents ethoxy.

[0147] The abbreviated codes for the test items in the following examples and comparative examples are as follows:

[0148]

[0149]

[0150] Among them, Cp: measured by an MP70 melting point instrument;

[0151] Δn: Δn = n e -n o , measured using an Abbe refractometer under a sodium lamp (589 nm) light source at 25 °C;

[0152] Δε: Δε = ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, and ε ⊥ is the dielectric constant perpendicular to the molecular axis. Test conditions: a VA-type test cell at 25 °C, 1 kHz, and a cell thickness of 6 μm;

[0153] K 11 and K33 : Measured using an LCR meter and a VA test kit, calculated from the C-V curve of the liquid crystal. Test conditions: a 6-μm VA-type test kit, V = 0.1 - 20 V;

[0154] γ1: Measured using an LCM-2 type liquid crystal physical property evaluation system; Test conditions: 25 °C, 160 - 240 V, cell thickness 20 μm;

[0155] LC Scattering: Among them, K 11 、K 22 、K 33 The test methods are as shown above;

[0156] IS decay time: Using a DMS 505 optoelectronic comprehensive tester, apply a supersaturated voltage (13 V) to an FFS cell for 2 h, then apply an L 64 gray-scale voltage. At this time, start reading and recording the brightness value at regular intervals, and obtain the time-brightness curve L-t1. Apply a low voltage (0.1 V) to another FFS cell for 2 h, then apply an L 64 gray-scale voltage. At this time, start reading and recording the brightness value at regular intervals to obtain the time-brightness curve L-t2. Then, take the difference between the two curves L-t1 and L-t2 to obtain the relative afterimage decay curve △L-t; When △L is zero, it is regarded as the complete disappearance of the afterimage, and the time t at this time is recorded as the IS decay time, where the cell thickness of the FFS cell is 3 μm.

[0157] The compounds used in the following examples and comparative examples can all be synthesized by known methods or obtained through commercial channels. These synthetic technologies are conventional, and each liquid crystal composition obtained meets the standards of electronic compounds after testing.

[0158] Prepare the liquid crystal composition according to the ratio of each liquid crystal composition in the following examples and comparative examples. The preparation of the liquid crystal composition is carried out according to the conventional methods in the art, such as mixing in a specified ratio by heating, ultrasonic, suspension, etc.

[0159] Comparative Example 1

[0160] A liquid crystal composition contains the components with the mass percentage shown in the following table, and its performance test results are listed in the following table:

[0161]

[0162]

[0163] Comparative Example 2

[0164] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0165]

[0166] Comparative Example 3

[0167] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0168]

[0169]

[0170] Among them, the dosage of the stabilizer is calculated based on the dosage of other liquid crystal components being 100%. Taking Comparative Example 3 as an example, the total amount of other liquid crystal components is 100%, and the addition amount of the stabilizer is 0.01%. The following examples / comparative examples involving the stabilizer have the same expression and will not be elaborated further.

[0171] Example 1

[0172] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0173]

[0174] Example 2

[0175] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0176]

[0177]

[0178] Example 3

[0179] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0180]

[0181] Example 4

[0182] A liquid crystal composition, comprising components with mass percentages as shown in the following table, and listing the performance test results in the following table:

[0183]

[0184]

[0185] Example 5

[0186] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0187]

[0188]

[0189] Example 6

[0190] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0191]

[0192] Example 7

[0193] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0194]

[0195]

[0196] Example 8

[0197] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0198]

[0199] Example 9

[0200] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0201]

[0202] Example 10

[0203] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0204]

[0205]

[0206] Example 11

[0207] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0208]

[0209] Example 12

[0210] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0211]

[0212]

[0213] Example 13

[0214] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0215]

[0216]

[0217] Example 14

[0218] A liquid crystal composition comprising components in the mass percentages shown in the following table, and listing the performance test results in the following table:

[0219]

[0220] 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 the compound of 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 a smaller K 11 / △ε, but it has a comparable decay time IS. On the basis of Comparative Example 1, Comparative Example 3 further contains the compound of formula I of the present application. Although the decay time IS is improved, it sacrifices γ1 / K 11 and K 11 / △ε. Comparing Example 1 of the present invention with Comparative Examples 1-3, it can be seen that through the design and compounding of a stabilizer with a specific structure and the compounds of formula II containing cyclohexenyl, formula F and / or formula N of the present invention, it has a high elastic constant K while having excellent clearing point, optical anisotropy and dielectric anisotropy △ε 11 and K 33 , a smaller rotational viscosity γ1, and a smaller ratio of rotational viscosity to elastic constant γ1 / K 11, a smaller ratio K of elastic constant to dielectric anisotropy 11 / Δε, having a lower response time, faster response speed, lower operating voltage and power consumption, lower LC Scattering, and a shorter IS decay time, capable of eliminating image retention or accelerating the dissipation of image retention.

[0221] Furthermore, according to Examples 2, 3, and 4, compared with the stabilizers of bifunctional Formula I-1 and Formula I-2, the liquid crystal composition containing the trifunctional stabilizer of Formula I-3 has a shorter IS decay time and has a better performance in eliminating image retention and accelerating the dissipation of image retention. According to Examples 6, 7, and 8, the stabilizer with the end group X being an oxygen radical can more effectively eliminate the internal electric field and promote the rapid dissipation of afterimages. According to Examples 9, 10, and 11, in the liquid crystal composition of the present invention, the stabilizer with a specific structure can also achieve excellent effects at a low content. Considering cost, the content of the stabilizer is preferably 0.001%-0.1%, and more preferably 0.001%-0.01%.

[0222] In summary, the present invention introduces a stabilizer with a specific structure and combines it with specific liquid crystal components, so that the liquid crystal composition has a larger elastic constant K value on the basis of excellent clearing point, optical anisotropy, and dielectric anisotropy Δε. K 11 is 15.5 - 21.2, K 33 is 17.6 - 22, lower rotational viscosity, γ1 is 86 - 125 mPa·s, a smaller 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 / Δε is -3.76 to -7.1, indicating a lower driving voltage and power consumption, a lower degree of light scattering, LC Scattering is 0.019 - 0.028, the IS decay time is 17.1 - 19.9 min, capable of quickly eliminating image retention, and having excellent optoelectronic stability.

[0223] The applicant declares that the present invention uses the above examples to illustrate the negative dielectric anisotropy liquid crystal composition of the present invention and the liquid crystal display device containing the same, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the products of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A liquid crystal composition having negative dielectric anisotropy, characterized in that, The liquid crystal composition comprises: At least one stabilizer 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: Wherein, X represents -H, -OH, -O*, a straight-chain or branched alkyl group having 1 to 5 carbon atoms; one or at least two non-adjacent -CH2- in the straight-chain or branched alkyl group having 1 to 5 carbon atoms can be independently replaced by -O- or -CO- respectively; -O* represents an oxygen radical; R1 and R2 each independently represent a straight-chain or branched-chain alkyl group containing 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in the straight-chain or branched-chain alkyl group containing 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 alkyl group having 1 to 12 carbon atoms, one or at least two non-adjacent -CH2- in which 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 straight-chain or branched-chain 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 and the ring each independently represents the one or at least two -CH2- in the above 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 the above may be replaced by a halogen, and at least one ring or the ring each independently represents Ring and the ring each independently represents the one or at least two -CH2- in the above may be replaced by -O-, and one or at most two single bonds in the ring may be replaced by double bonds; the one or at least two -H in the above 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=; Ring and the ring each independently represents wherein one or at least two of the -CH2- therein can be replaced by -O-, and one or at most two single bonds in the ring can be replaced by double bonds, wherein one or at least two of the -H therein can be independently replaced by -F, -Cl or -CN respectively, and -CH= in one or at least two rings can 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, 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 rings are the same or different, and Z1 are the same or different; when n F2 = 2, the rings are the same or different, and Z2 are the same or different; n N1 represents 0, 1, 2, or 3, n N2 represents 0 or 1, and 0 ≤ n N1 + n N2 ≤ 3; When n N1 represents 2 or 3, the rings are the same or different, and Z N1 are the same or different.

2. The liquid crystal composition according to claim 1, wherein The X represents -H, -OH, -O*, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, a straight-chain or branched acyl group having 1 to 5 carbon atoms.

3. The liquid crystal composition according to claim 1, characterized in that, 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 compounds of formula II are selected from the group consisting of the following compounds: and Wherein, R1 and R2 have the same defined ranges as in formula II.

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

6. The liquid crystal composition according to claim 1, characterized in that, The compounds of formula N are 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, characterized in that, The liquid crystal composition comprises 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, characterized in that, 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 straight-chain or branched-chain 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 and the ring each independently represents the one or at least two -CH2- in can be replaced by -O-; the at most one -H in can 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 rings are the same or different, and Z M2 are the same or different.

9. The liquid crystal composition according to claim 8, wherein The compounds of formula M are selected from the group consisting of the following compounds: and Among them, R M1 and R M2 each independently represents a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, and one or more than two non-adjacent -CH2- in the straight-chain or branched-chain 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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