Liquid crystal composition, liquid crystal display device comprising the liquid crystal composition

Abstract

This invention discloses a liquid crystal composition and its applications. The liquid crystal composition contains at least one or more compounds represented by Formula I and one or more compounds represented by Formula II. The liquid crystal composition exhibits excellent vibration resistance and minimal power consumption change after aging under extreme conditions of high temperature and high humidity (85°C-85%). It solves the problems of flickering and black spots in VA mode displays after vibration, and poor reliability after aging under extreme conditions, demonstrating promising application prospects.

Description

Technical Field

[0001] This invention relates to the field of liquid crystal display technology. More specifically, it relates to a liquid crystal composition and a liquid crystal display device comprising the liquid crystal composition. Prior Technology

[0002] VA (Vertical Alignment) mode is an important mode in liquid crystal display (LCD) technology. Its basic principle is that in VA mode LCDs, liquid crystal molecules are aligned perpendicular to the substrate when no voltage is applied. This vertical alignment results in low light transmittance initially. When a voltage is applied, the liquid crystal molecules tilt, thereby changing the light transmittance. By precisely controlling the voltage, the degree of tilt of the liquid crystal molecules can be adjusted, thus controlling the brightness of each pixel. Compared to other LCD modes (such as TN mode), the vertically aligned liquid crystal molecules in VA mode have certain advantages in viewing angle characteristics and contrast ratio.

[0003] VA mode monitors typically have a high static contrast ratio. This is because, when off, the vertical alignment of liquid crystal molecules effectively blocks light, resulting in deeper blacks. When on, they can achieve high brightness output, thus improving the contrast between bright and dark areas of the image. For example, some high-end VA monitors can achieve a contrast ratio of 3000:1, presenting more vivid and realistic images, and performing exceptionally well in displaying night scenes and dark-toned movie scenes. The high contrast of VA mode, due to its precise control over liquid crystal molecules, allows for better reproduction of various details and colors in images.

[0004] VA mode offers a wide viewing angle both horizontally and vertically. When viewed from the side, the color and brightness of the image show relatively little attenuation. This is because the vertical alignment of the liquid crystal molecules and their control over light at different viewing angles allow the observer to still see a clear and accurate image within a certain range of angles. Compared to TN mode, VA mode monitors are more advantageous in scenarios where multiple people are viewing the screen simultaneously or where it is necessary to view the screen content from different angles (such as using a monitor to display content in a conference room).

[0005] With the rapid development of electrification and intelligentization of transportation, automotive displays are experiencing rapid growth. LCD displays, currently the dominant technology, hold approximately 95% of the automotive market share; newer display technologies like OLED and MiniLED have smaller market shares due to price and power consumption considerations. Negative VA mode LCDs dominate automotive displays due to their numerous advantages. Compared to conventional positive VA mode LCDs, negative VA mode LCDs offer higher contrast, with a very clear contrast between black and white, resulting in a clearer and more vivid display for instruments, videos, and images. Negative VA mode LCD panels consume less power; unlike other full-mode LCD panels, the molecular alignment process of negative VA mode LCDs does not involve a complex process that consumes a lot of electricity. Negative VA LCDs offer good stability and reliability, maintaining good display quality even after prolonged use; furthermore, negative VA mode LCD panels have a wider viewing angle, providing clear images even when viewed from the side or at an angle.

[0006] VA (Polymer Network Liquid Crystal) displays differ significantly from PNLC (Polymer Network Liquid Crystal) displays. VA displays require a polarizer, utilizing the tilt of the liquid crystal in an electric field to change the direction of polarized light. The electric field controls whether polarized light passes through the polarizer, thus creating white and black. Even if a small amount of polymer is added to the negative liquid crystal, the resulting polymer does not change the display mode. PNLC, unlike VA displays, incorporates a larger amount of polymerizable liquid crystal compound (RM), typically 3-10%. Due to the higher polymer content, the resulting polymer network is denser. The display mode is transparent when the polymer refractive index matches the liquid crystal; when an electric field is applied, the liquid crystal molecules are randomly arranged, and the refractive indices of the polymer and liquid crystal mismatch, creating a hazy, opaque state. PNLC displays do not require a polarizer, making them distinctly different from VA displays.

[0007] VA mode displays have poor vibration resistance. In VA mode LCD displays, liquid crystal molecules are aligned perpendicular to the substrate when no power is applied. This alignment makes the liquid crystal molecules relatively orderly, but its disadvantages are also obvious. Vertically aligned liquid crystal molecules are more sensitive. When subjected to vibration, the vertical alignment of the liquid crystal molecules is easily disrupted, resulting in localized alignment disorder. This can lead to display abnormalities, such as screen flickering, blurring, and color distortion on instrument panels and other screens. Specifically, the vertical anchoring of VA mode liquid crystal molecules relies on vertical PI (pixel-in-place), and the anchoring force of vertical PI is much weaker than that of horizontal PI. The low anchoring force of VA mode liquid crystals means that in environments with strong vibrations, such as in vehicles, the liquid crystal molecules may temporarily align incorrectly due to external influences, resulting in black spots, flickering, and image retention. Many manufacturers have tried to address this problem by adding vibration-damping foam strips, adding vibration-damping spring mechanisms, or using two sets of driver programs. However, adding vibration-damping mechanisms or equipping two sets of IC driver programs increases the cost of the display. Adding anti-vibration foam strips or external vibration damping devices makes the display thicker and heavier. These solutions only improve the vibration resistance of the liquid crystal display device, but do not fundamentally solve the problem of poor anchoring force of VA mode liquid crystal molecules, which makes it prone to display errors due to external interference.

[0008] VA mode displays experience significant power consumption variations under high temperature and high temperature / high humidity conditions. In current technology, the liquid crystals used in VA mode have polar molecules that easily release free radical ions at high temperatures. Some highly polar liquid crystal molecules may even decompose, releasing even more free radical ions, resulting in a significant increase in power consumption. In high temperature and high humidity environments, in addition to temperature effects, water molecules permeate into the liquid crystal layer, altering the dielectric properties and further increasing power consumption. These drawbacks significantly limit the application of VA mode displays. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a liquid crystal composition and a liquid crystal display device comprising the same. The liquid crystal composition has excellent vibration resistance and small power consumption changes after aging treatment under extreme conditions of high temperature (e.g., 85°C) and high temperature (e.g., 85°C)-high humidity (e.g., 85% humidity). It solves the problems of flickering and black spots that easily occur in VA mode displays after vibration and poor reliability after aging under extreme conditions, and has good application prospects.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] On one hand, the present invention provides a liquid crystal composition comprising at least one or more compounds of formula I and one or more compounds of formula II: I II; in, , , Each represents independently , or ; , Each represents independently or ; and , , , , One or more H atoms in the H atom may be optionally replaced by L1; L1, in each occurrence, may represent -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; Z1 may represent -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -(CH2)m3-, -CR0R00- or a single bond each time it appears, and at least one Z1 does not represent a single bond; R0 and R00 each independently represent H or an alkyl group having 1-12 carbon atoms; Sp1, Sp2, Sp3, and Sp4 each independently represent a single bond, an alkyl chain with 1-5 carbon atoms, or a cyclic alkyl chain with 1-5 carbon atoms. Any one or more unconnected -CH2- atoms can be substituted by -O-, -CO-, -CH2O-, -OCH2-, -COO-, or -OOC- in a form where -O- atoms are not connected to each other. Any one or more H atoms in Sp1, Sp2, Sp3, and Sp4 can be independently substituted by F or Cl. Sp1 and Sp2 are not both single bonds, and at least one H atom in Sp1 and / or Sp2 is substituted by G3. G3 represents a tertiary alcohol structure with 1-7 carbon atoms; P1, P2, P3, and P4 are each represented independently. or , where · represents the connection site; m1 represents 0 or 1, m2 represents 1, 2, 3 or 4, and m3 represents an integer from 1 to 10.

[0012] In another aspect, the present invention provides a liquid crystal display device comprising the liquid crystal composition described above.

[0013] The beneficial effects of this invention are as follows:

[0014] In the liquid crystal composition of the present invention, by adding one or more compounds represented by Formula I and one or more compounds represented by Formula II, a specific polymer network structure can be formed on the surface of the alignment layer PI and inside the liquid crystal molecules after UV polymerization. This specific polymer network structure may enhance the vertical alignment anchoring force of the liquid crystal molecules. When subjected to external vibration, the liquid crystal molecules maintain their alignment direction due to the dual anchoring force of the specific polymer structure and the alignment layer PI, thereby enhancing the vibration resistance of the VA mode liquid crystal display device and effectively solving the problem of flickering and black spots that easily occur after vibration of the liquid crystal display device, exhibiting excellent vibration resistance. Moreover, the polymer network formed by the synergistic effect of the components in the liquid crystal composition of the present invention may also have the effect of anti-oxidation and free radical absorption, thereby stabilizing the liquid crystal state under high temperature or humid heat environments and reducing liquid crystal decomposition; the ability of the polymer network to absorb free radicals released by the liquid crystal due to humid heat or high temperature to a certain extent makes the liquid crystal composition not only provide excellent vibration resistance but also good reliability. When this liquid crystal composition is used in a liquid crystal display device, the resulting liquid crystal display device exhibits minimal change in power consumption current after undergoing high-temperature aging and dual 85 (high temperature 85℃ - high humidity 85%) damp heat aging. The technical solution of this invention has promising application prospects and can be widely used in display devices for automotive, aviation, marine, and industrial control applications. Implementation

[0015] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the invention. [Liquid Crystal Composition]

[0016] According to a specific embodiment of the present invention, a liquid crystal composition is provided, the liquid crystal composition comprising at least one or more compounds represented by Formula I and one or more compounds represented by Formula II: I II; in, , , Each represents independently , or ; , Each represents independently or ; and , , , , One or more H atoms in the H atom may be optionally replaced by L1; L1, in each occurrence, may represent -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; Z1 may represent -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -(CH2)m3-, -CR0R00- or a single bond each time it appears, and at least one Z1 does not represent a single bond; R0 and R00 each independently represent H or an alkyl group having 1-12 carbon atoms; Sp1, Sp2, Sp3, and Sp4 each independently represent a single bond, an alkyl chain with 1-5 carbon atoms, or a cyclic alkyl chain with 1-5 carbon atoms. Any one or more unconnected -CH2- atoms can be substituted by -O-, -CO-, -CH2O-, -OCH2-, -COO-, or -OOC- in a form where -O- atoms are not connected to each other. Any one or more H atoms in Sp1, Sp2, Sp3, and Sp4 can be independently substituted by F or Cl. Sp1 and Sp2 are not both single bonds, and at least one H atom in Sp1 and / or Sp2 is substituted by G3. G3 represents a tertiary alcohol structure with 1-7 carbon atoms, preferably... , or More preferably ; P1, P2, P3, and P4 are each represented independently. or , where · represents the connection site; m1 represents 0 or 1, m2 represents 1, 2, 3 or 4, and m3 represents an integer from 1 to 10.

[0017] In this embodiment, the compounds and intermediates of Formula I and its sub-formulas can be prepared in a manner similar to those known to those of ordinary skill in the art to which this invention pertains and described in standard works of organic chemistry (e.g., in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Thieme-Verlag, Stuttgart).

[0018] For example, acrylates or methacrylates can be prepared by esterification of the corresponding alcohol with an acid derivative such as (meth)acrylic acid chloride or (meth)acrylic anhydride in the presence of an alkali such as pyridine or triethylamine and 4-(N,N-dimethylamino)pyridine (DMAP). Alternatively, the ester can be prepared by esterification of an alcohol with (meth)acrylic acid in the presence of a dehydrating agent, for example, according to Steglich with dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC), or N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and DMAP.

[0019] In some examples, the compound represented by Formula I is selected from the group consisting of compounds represented by Formulas I-1 to I-7: I-1 I-2 I-3 I-4 I-5 I-6 I-7; Where a represents 0, 1, or 2. express , , , , , or ; L1, in each occurrence, may represent -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; Sp1 and Sp2 each independently represent a single bond, an alkyl chain with 1-5 carbon atoms, or a cyclic alkyl chain with 1-5 carbon atoms, wherein any one or more unconnected -CH2- atoms can be replaced by -O-, -CO-, -CH2O-, -OCH2-, -COO-, or -OOC- in a form where -O- atoms are not connected to each other, and Sp1 and Sp2 are not both single bonds, and at least one H atom in Sp1 and / or Sp2 is replaced by G3; G3 represents a tertiary alcohol structure with 1-7 carbon atoms, preferably... , or More preferably , where · represents the connection site; P1 and P2 are represented independently. or , where · represents the connection site.

[0020] In some preferred embodiments, the compound represented by Formula I is selected from the group consisting of compounds represented by Formulas I-1-1 to I-7-1: I-1-1、 I-1-2、 I-1-3、 I-1-4、 I-1-5、 I-1-6、 I-1-7、 I-1-8、 I-1-9、 I-1-10、 I-1-11、 I-1-12、 I-1-13、 I-2-1、 I-2-2、 I-2-3、 I-3-1、 I-3-2、 I-3-3、 I-3-4、 I-3-5、 I-3-6、 I-3-7 I-3-8、 I-3-9, I-3-10, I-3-11, I-3-12, I-3-13, I-3-14, I-4-1, I-5-1, I-5-2, I-6-1, I-6-2, I-6-3, I-7-1.

[0021] Among the most selective examples, the formula I-3-1 to I-7-1 compositional set of the formula I-7-1 is the preferred compound. I-3-1, I-3-2, I-3-3, I-3-4, I-3-5, I-3-6, I-3-7, I-3-8, I-3-9, I-3-10, I-3-11, I-3-12, I-3-13, I-3-14, I-4-1, I-5-1, I-5-2, I-6-1, I-6-2, I-6-3, I-7-1.

[0022] In some examples, the mass percentage of the compound represented by Formula I in the liquid crystal composition is 0.01-4%. In some preferred examples, the mass percentage of the compound represented by Formula I in the liquid crystal composition is 0.01-2%, 0.01-1.5%, 0.04-1%, 0.04-0.5%, or 0.04-0.2%. In some specific examples, the mass percentage of the compound represented by Formula I in the liquid crystal composition includes, but is not limited to, values ​​selected from 0.01%, 0.04%, 0.1%, 0.2%, 0.5%, 1.0%, 1.5%, 2.0%, and specific values ​​between these values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0023] In some examples, the compound represented by Formula II is selected from the group consisting of compounds represented by Formulas II-1 to II-7: II-1 II-2, II-3 II-4 II-5 II-6 II-7; Where a represents 0, 1, or 2. express , , , , , or ; L1, in each occurrence, may represent -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; Sp3 and Sp4 each independently represent a single-bonded, 1-5 carbon chain alkyl or a 1-5 carbon cyclic alkyl, wherein any one or more unconnected -CH2- can be replaced by -O-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- in a form where -O- is not connected to each other; Z1, Z2, Z3, and Z4 each independently represent -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -(CH2)m3-, -CR0R0O-, or a single bond, and in each compound shown in formulas II-1 to II-7, at least one group selected from Z1, Z2, Z3, and Z4 does not represent a single bond; R0 and R00 each independently represent H or an alkyl group having 1-12 carbon atoms; m3 represents an integer from 1 to 10; P3 and P4 are represented independently. or , where · represents the connection site.

[0024] The statement "In each of the compounds shown in Formulas II-1 to II-7, at least one group selected from Z1, Z2, Z3, and Z4 does not represent a single bond" means that, in each of the compounds shown in Formulas II-1 to II-7, if present, at least one of the groups Z1, Z2, Z3, and Z4 does not represent a single bond. For example, it can be seen that in Formulas II-1 to II-3, and Formula II-5, Z1 does not represent a single bond; in Formulas II-4 and II-6, at least one of Z1 and Z2 does not represent a single bond; and in Formula II-7, at least one of Z1, Z2, Z3, and Z4 does not represent a single bond.

[0025] In some preferred examples, the compound represented by Formula II is selected from the group consisting of the following compounds: II-4-1、 II-4-2, II-4-3, II-4-4、 II-5-1, II-5-2, II-5-3, II-5-4, II-6-1、 II-6-2, II-6-3、 II-6-4、 II-6-5、 II-6-6、 II-6-7、 II-6-8、 II-7-1 II-7-2, II-7-3、 II-7-4.

[0026] In some examples, the mass percentage of the compound represented by Formula II in the liquid crystal composition is 0.01-4%. In some preferred examples, the mass percentage of the compound represented by Formula II in the liquid crystal composition is 0.1-2%, more preferably 0.1-1.5%, more preferably 0.5-1%, and more preferably 0.7-1%. In some specific examples, the mass percentage of the compound represented by Formula II in the liquid crystal composition includes, but is not limited to, values ​​selected from 0.1%, 0.2%, 0.5%, 0.8%, 0.9%, 1.0%, 1.5%, 2.0%, and specific values ​​between these values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list all the specific values ​​included in the range.

[0027] The compounds represented by Formula I and Formula II in this invention are polymerizable compounds containing polymerizable groups. (acrylate-based) or (Methacrylate group) can undergo polymerization under appropriate UV light.

[0028] In some examples, the liquid crystal composition further comprises at least one or more compounds of Formula III: III in, R1 and R2 each independently represent an alkyl group having 1-10 carbon atoms or an alkenyl group having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene; Z5 represents -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, or a single bond; n1 and n2 each independently represent 0, 1, or 2; , Each represents independently , , , , , or .

[0029] In some specific examples, the compound represented by Formula III is selected from the group consisting of compounds represented by Formulas III-1 to III-18: III-1 III-2, III-3, III-4 III-5 III-6 III-7 III-8 III-9 III-10 III-11 III-12 III-13 III-14 III-15 III-16 III-17 III-18; in, R1 and R2 each independently represent an alkyl group having 1-10 carbon atoms or an alkenyl group having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene.

[0030] In some examples, the mass percentage of the compound represented by Formula III in the liquid crystal composition is 4-70%. In some preferred examples, the mass percentage of the compound represented by Formula III in the liquid crystal composition is 4-50%. In some specific examples, the mass percentage of the compound represented by Formula III in the liquid crystal composition includes, but is not limited to, values ​​selected from 4-40%, 4-25%, 4-10%, 15-30%, 24-40%, 30-50%, etc., and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0031] In some examples, the liquid crystal composition further comprises at least one or more compounds selected from Formula IV: IV in, express , , , , or ; R3 and R4 each independently represent an alkyl group having 1-10 carbon atoms or an alkenyl group having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- groups can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene. Z6 and Z7 independently represent -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, or single bonds; n3 and n4 each independently represent 0, 1, or 2.

[0032] In some examples, the compound represented by Formula IV is selected from the group consisting of compounds represented by Formulas IV-1 to IV-25: IV-1, IV-2, IV-3, IV-4, IV-5, IV-6 IV-7 IV-8 IV-9 IV-10, IV-11, IV-12, IV-13 IV-14, IV-15, IV-16 IV-17 IV-18 IV-19 IV-20 IV-21, IV-22, IV-23 IV-24, IV-25; R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms or an alkenyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropyl, cyclobutyl or cyclopentyl.

[0033] In some examples, the liquid crystal composition contains 20-90% by mass of the compound represented by Formula IV. In some preferred examples, the liquid crystal composition contains 30-80% by mass of the compound represented by Formula IV. In some specific examples, the liquid crystal composition contains, but is not limited to, a mass percentage of the compound represented by Formula IV selected from 30-70%, 30-60%, 50-80%, 50-75%, 60-70%, 60-80%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0034] In some examples, the liquid crystal composition further comprises at least one or more compounds represented by formula V and / or formula VI: in, , Each represents independently. , , , or ; In this context, R5, R6, R7, and R8 each independently represent an alkyl group having 1-10 carbon atoms or an alkenyl group having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- groups can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene. Z8 and Z9 independently represent -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, or single bonds; n5 represents 1 or 2, and n6 and n7 each independently represent 0, 1 or 2.

[0035] In some examples, the compound represented by formula V is selected from the group consisting of compounds represented by formulas V-1 to V-2: V-1, V-2; in, R5 and R6 each independently represent an alkyl group having 1-10 carbon atoms or an alkenyl group having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene.

[0036] In some examples, the mass percentage of the compound represented by Formula V in the liquid crystal composition is 0-40%. In some preferred examples, the mass percentage of the compound represented by Formula V in the liquid crystal composition is 5-30%. In some specific examples, the mass percentage of the compound represented by Formula V in the liquid crystal composition includes, but is not limited to, values ​​selected from 0-20%, 0, 5-15%, 10-20%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0037] In some examples, the compound represented by formula VI is selected from the group consisting of compounds represented by formulas VI-1 to VI-6: VI-1 VI-2 VI-3 VI-4 VI-5 VI-6; R7 and R8 represent alkyl groups having 1-10 carbon atoms or alkenyl groups having 2-10 carbon atoms, wherein one or more non-adjacent -CH2- groups may be replaced by -O-, cyclopropyl, cyclobutyl or cyclopentyl.

[0038] In some examples, the mass percentage of the compound represented by Formula VI in the liquid crystal composition is 0-20%. In some preferred examples, the mass percentage of the compound represented by Formula VI in the liquid crystal composition is 0-15%. In some specific examples, the mass percentage of the compound represented by Formula VI in the liquid crystal composition includes, but is not limited to, values ​​selected from 0-10%, 0, 1-10%, etc., as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range.

[0039] Various functional dopants may also be added to the liquid crystal composition of the present invention. The dopant content is preferably between 0.005-1 wt%. Examples of such dopants include antioxidants, ultraviolet absorbers, and chiral agents.

[0040] The corresponding antioxidants can be listed with the following structures: , , , , , , ; Where t represents an integer from 1 to 10; The corresponding chiral agents (levorotatory or dextrorotatory) can be listed with the following structures: , , . Liquid crystal display device

[0041] Another specific embodiment of the present invention relates to a liquid crystal display device comprising any of the above-described liquid crystal compositions.

[0042] In some examples, the liquid crystal display device is preferably a passively matrix-addressed or actively matrix-addressed liquid crystal display device.

[0043] Exemplary liquid crystal display devices include, but are not limited to, IPS-TFT, FFS-TFT or VA-TFT liquid crystal display elements or other TFT displays, particularly suitable for VA-TFT mode liquid crystal display devices.

[0044] The technical solution of the present invention will be described below with reference to some specific embodiments:

[0045] In this invention, unless otherwise specified, the preparation methods are all conventional methods, and the raw materials used can be obtained from publicly available commercial sources unless otherwise specified. All percentage contents refer to mass percentage (wt%), and temperatures are in degrees Celsius (°C). The specific meanings of other symbols and testing conditions are as follows: Cp represents the liquid crystal clearing point (°C), measured quantitatively using DSC method; Δn represents optical anisotropy, no is the refractive index of the ordinary ray, and ne is the refractive index of the extraordinary ray. The test conditions are 25±2℃, 589 nm, and the test is conducted using an Abbe refractometer. Δε represents dielectric anisotropy, 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. The test conditions are 25 ± 0.5℃, 20-micron vertical cell, INSTEC:ALCT-IR test. K11 is the developmental elastic constant, K33 is the flexural elastic constant, and the test conditions are: 25℃, INSTEC:ALCT-IR1, 20-micron antiparallel box; γ1 represents rotational viscosity (mPa·s), and the test conditions were 25±0.5℃, 20-micron antiparallel cell, and INSTEC:ALCT-IR1 test. V10 represents the threshold voltage (V), which corresponds to the voltage at which the liquid crystal test cell achieves 10% transmittance. V90 represents the threshold voltage (V), which corresponds to the voltage at which the liquid crystal test cell achieves 90% transmittance.

[0046] Liquid crystal vibration resistance test method: The liquid crystal composition is poured into a VA mode liquid crystal cell and subjected to a UV treatment process, i.e., irradiated for 120s under a 365 nm UV-LED lamp with a light intensity of 30 mw / cm2 to complete the liquid crystal UV process. Then, the liquid crystal cell is assembled through steps such as attaching a polarizer and pressing an FPC (flexible printed circuit board) to finally form a liquid crystal display screen capable of driving the test. After the liquid crystal display screen is powered on and displays information, it is placed on a vibration test surface and vibrated for 3 hours under the experimental conditions of vibration programs of 10 Hz (PSD=10), 10 Hz (PSD=10), 100 Hz (PSD=10), 300 Hz (PSD=0.51), 500 Hz (PSD=5), and 2000 Hz (PSD=5). (Power spectral density (PSD) is an important parameter in vibration testing, describing the energy distribution of random vibration). During vibration, screen flickering or black spots are tested. The number of times screen flickering or black spots occur can be counted manually or by camera software. Based on the final frequency of flickering and black spots, they are divided into the following 5 levels: Level 1: No flickering or black spots appear; Level 2: Flashing and black spots appear 1-2 times; Level 3: Flashing and black spots appear 3-10 times; Level 4: Flashing and black spots appear 11-50 times; Level 5: Flashing and black spots appear more than 50 times.

[0047] Liquid crystal power consumption current performance test method: Liquid crystal power consumption current, or simply liquid crystal power consumption, is tested under the following conditions: 25±2℃, 4V voltage, 64HZ pulse square wave, and a Model 3200 electrical testing machine. The test cell uses a 5-micron VA liquid crystal cell, with a Shenzhen Dalton 4811 PI sensor, and the test area of ​​the liquid crystal in the cell is 1cm². The liquid crystal is injected into the liquid crystal cell via room temperature vacuum crystal filling. UV treatment process: Irradiation for 120s under a 365nm UV-LED lamp with a light intensity of 30mw / cm². The power consumption current of the liquid crystal cell is tested initially, after aging at 85℃ for 1000h, and after aging at 85℃-85%RH for 1000h. The aging experiments are all conducted in the corresponding constant temperature and humidity chambers.

[0048] Specific evaluation criteria for each indicator: In the evaluation of LCD vibration resistance performance, the fewer the occurrences of flicker and black spots, the better; that is, level 1 is better than level 2, level 2 is better than level 3, and so on. When the level is ≤ level 2, the vibration resistance performance is verified to be OK in actual panel testing. Therefore, level 1 and level 2 are considered feasible in this scheme.

[0049] In the evaluation of LCD power consumption current performance, compared with the initial power consumption current, the smaller the change in power consumption after aging treatment at 85℃ for 1000 hours and at 85℃-85% humidity for 1000 hours, the better. A power consumption current change of <15% indicates excellent reliability, a change between 15% and 30% indicates good reliability, a change between 30% and 50% indicates average reliability, and a change greater than 50% indicates poor reliability. When the LCD power consumption current performance is ≤30%, the power consumption current is verified to be OK in actual panel testing. Therefore, a power consumption current performance of ≤30% is considered feasible in this solution.

[0050] The liquid crystal monomer structure in the embodiments of the present invention is represented by codes. The code representation methods for liquid crystal ring structure, end groups, and linking groups are shown in Tables 1 and 2 below.

[0051] Table 1 Code Table for Structure Ring structure Corresponding code C P M G GI U C(+N) Y X DO DS

[0052] Table 2. Correspondence codes between terminal groups and linking groups Terminal groups and linking groups Corresponding code CnH2n+1- n- CnH2n+1O- nO- -OCnH2n+1 -On -CH2O- -O- -F -F -CN -CN -CH=CH- -V- -CH2CH2- -E- -C≡C- -T- -COO- -Z- -CH=CH-CnH2n+1 Vn- Cp- Cpr- Cpr1-

[0053] For example: Its code is CZP-3-CN; Its code is CC-3-V; Its code is CP-3-O2; Its code is CC(+N)-5-3; Its code is MDO-3-5; Its code is CCP-V-1; Its code is CDS-3-5; Its code is CPWP-3-2; Its code is UWPP-2-3 Its code is CYYC-3-4; Its code is PZX-Cp-O5; Its code is COC(+N)-Cpr-3; Its code is GTG-V2-2V.

[0054] The structures of some compounds used in the embodiments and comparative examples of this invention are shown in Table 3 below.

[0055] Table 3. Compound structures used in the examples and comparative examples Structure of compounds coding I-1-1 I-1-8 I-3-2 I-3-6 I-3-8 I-4-1 I-5-2 D-1 D-2 II-4-2 II-5-2 II-6-5

[0056] The present invention will be described below using specific embodiments. [Mother Liquid Crystal(] [SLC] [):]

[0057] The composition of the parent liquid crystal SLC-1 is shown in Table 4 below:

[0058] Table 4 Composition of the parent liquid crystal SLC-1 category Liquid crystal unit code Content (wt%) V CC(+N)-3-5 9 V CC(+N)-5-5 9 IV CCOY-3-O2 11 IV CCZY-5-O2 2 III CCZCC-5-3 3 III CC-3-V 15 VI CZX-4-O4 2 IV COY-3-O2 10 IV COY-3-O1 10 IV CCOY-2-O2 10 IV CCOY-2-O4 6 IV CCOY-3-O4 6 III CCZC-3-3 2 III CCZC-3-5 3 III CCZC-4-3 2

[0059] The composition of the parent liquid crystal SLC-2 is shown in Table 5 below:

[0060] Table 5. Composition of the parent liquid crystal SLC-2 Category LCD unit code Content (wt%) III CC-5-3 7 III CCZPC-3-5 4 III CC-3-V 15 IV CCY-3-O2 6 IV CCY-5-O2 6 III CCZPC-3-3 4 III CCZPC-3-4 4 IV CCY-4-O2 3 IV CCEY-3-O2 2 IV CCY-3-O3 7 IV CPY-2-O2 6 IV CY-3-O4 12 IV PY-3-O2 3 IV CY-5-O4 15 III CCZC-3-3 3 III CCZC-4-5 3

[0061] The composition of the parent liquid crystal SLC-3 is shown in Table 6 below:

[0062] Table 6. Composition of the parent liquid crystal SLC-3 Category LCD unit code Content (wt%) V CC(+N)-3-5 5 V CC(+N)-5-5 9 III CC-3-V 5 IV CZY-3-O2 9 IV CZY-5-O2 6 IV CCZY-3-O2 8 IV CCZY-5-O2 6 IV CCY-3-O2 5 IV CCY-5-O2 5 IV PYY-4-O2 4 IV CCY-2-O2 7 IV CCY-4-O2 3 IV CPY-4-O2 3 IV CCY-5-O3 7 IV CCY-3-O3 3 IV CY-3-O4 7 IV PYP-2-3 1 VI CZX-4-O4 2 VI CZX-3-O4 2 VI CZX-2-O4 3

[0063] The relevant physical parameters of the parent liquid crystals SLC-1, SLC-2, and SLC-3 are shown below:

[0064] Table 7. Relevant physical parameters of the parent liquid crystals SLC-1, SLC-2, and SLC-3 physical parameters SLC-1 SLC-2 SLC-3 Cp (°C) 90 101 107 Δn[589nm, 25℃] 0.071 0.091 0.090 ne[589nm, 25℃] 1.547 1.568 1.571 Δε[1kHz, 25℃] -6.7 -4.3 -9.1 ε┴[1KHz, 25℃] 14.7 8.1 13.7 V10 1.89 2.19 1.69 V90 4.67 2.8 2.9 K11 12.3 18.7 13.1 K33 15.7 19.2 17 γ1 248.9 422.2 381.5 γ1 / K 20.18 22.6 29.12 [ ] [Liquid Crystal Composition:]

[0065] Compounds of Formula I and Formula II were added to different parent liquid crystals to form liquid crystal compositions, the specific formulations of which are shown in Table 8 below. In Table 8, the mass percentages of the compounds of Formula I and Formula II are relative to the parent liquid crystal.

[0066] Table 8. Composition of the liquid crystal compositions in the examples and comparative examples mother liquid crystal Compounds represented by Formula I Compounds represented by Formula II type Content / wt% type Content / wt% Example 1 SLC-1 I-1-1 0.1 II-6-5 0.9 Example 2 SLC-1 I-1-8 0.1 II-6-5 0.9 Example 3 SLC-1 I-3-2 0.1 II-6-5 0.9 Example 4 SLC-1 I-3-6 0.1 II-6-5 0.9 Example 5 SLC-1 I-3-8 0.1 II-6-5 0.9 Example 6 SLC-1 I-4-1 0.1 II-6-5 0.9 Example 7 SLC-1 I-5-2 0.1 II-6-5 0.9 Example 8 SLC-1 I-3-2 0.1 II-4-2 0.9 Example 9 SLC-1 I-3-2 0.1 II-5-2 0.9 Example 10 SLC-1 I-3-2 0.2 II-6-5 0.8 Example 11 SLC-1 I-3-2 0.05 II-6-5 0.95 Example 12 SLC-2 I-3-2 0.2 II-6-5 0.8 Example 13 SLC-3 I-3-2 0.2 II-6-5 0.8 Example 14 SLC-3 I-3-2 3.5 II-6-5 0.8 Example 15 SLC-3 I-3-2 0.2 II-6-5 3.5 Comparative Example 1 SLC-1 - - - - Comparative Example 2 SLC-1 - - II-6-5 1.0 Comparative Example 3 SLC-1 - - II-6-5 0.9 Comparative Example 4 SLC-1 I-3-2 1.0 - - Comparative Example 5 SLC-1 D-1 0.1 II-6-5 0.9 Comparative Example 6 SLC-1 D-2 0.1 II-6-5 0.9

[0067] As shown in Table 8, compounds containing different components as shown in Formula I and Formula II were added to the corresponding parent liquid crystals SLC-1, SLC-2 and SLC-3, respectively, and then injected into liquid crystal cells and completed the corresponding UV process. The relevant performance parameters are shown in Table 9 below.

[0068] Table 9. Performance Evaluation Results of Examples and Comparative Examples Vibration resistance performance (level) Initial power consumption current (μA) Power consumption current (μA) after aging at 85℃ for 1000 hours Power consumption current (μA) after aging at 85℃-85%RH for 1000 hours Trustworthiness assessment Example 1 2 0.49 0.52 0.55 Excellent Example 2 2 0.50 0.53 0.56 Excellent Example 3 1 0.50 0.51 0.52 Excellent Example 4 1 0.50 0.52 0.54 Excellent Example 5 1 0.50 0.51 0.51 Excellent Example 6 1 0.50 0.51 0.53 Excellent Example 7 1 0.49 0.51 0.52 Excellent Example 8 1 0.50 0.52 0.53 Excellent Example 9 1 0.49 0.51 0.53 Excellent Example 10 1 0.49 0.51 0.52 Excellent Example 11 1 0.47 0.49 0.50 Excellent Example 12 1 0.50 0.49 0.54 Excellent Example 13 1 0.49 0.52 0.53 Excellent Example 14 2 0.50 0.59 0.63 good Example 15 2 0.49 0.60 0.63 good Comparative Example 1 5 0.50 0.90 1.09 Difference Comparative Example 2 4 0.50 0.80 0.92 Difference Comparative Example 3 4 0.49 0.80 0.91 Difference Comparative Example 4 4 0.50 0.67 0.72 generally Comparative Example 5 4 0.51 0.70 0.75 generally Comparative Example 6 4 0.50 0.66 0.69 generally

[0069] Compared with the examples, Comparative Examples 1 did not contain the compounds shown in Formula I and Formula II, and its vibration resistance was the worst. It also had the largest power consumption changes after aging at 85°C for 1000 hours and after aging at 85°C and 85% humidity for 1000 hours, and its reliability was rated as poor. Comparative Examples 2 and 3 showed some improvement in vibration resistance, but the level 4 level still did not meet the requirements. Comparative Examples 4, 5, and 6 had vibration resistance of level 4. Their power consumption changes after aging at 85°C for 1000 hours and after aging at 85°C and 85% humidity for 1000 hours were improved, but the range was greater than 30%, and their reliability was rated as average. Their reliability was still not feasible, and their vibration resistance also did not meet the requirements. Examples 1-15, through the synergistic effect of the compounds represented by Formula I and Formula II contained in this invention, enable the liquid crystal composition to exhibit excellent vibration resistance while also showing minimal power consumption changes after aging at 85°C for 1000 hours and at 85°C and 85% humidity for 1000 hours, thus meeting the display's requirements for both vibration resistance and power consumption performance. It is worth noting that while Examples 1 and 2 demonstrated good vibration resistance (level 2), Examples 3 to 13 exhibited even better vibration resistance (level 1). In Examples 14 and 15, due to the excessively high mass percentage of the added Formula I and Formula II compounds, although the vibration resistance and power consumption variation were acceptable, the power consumption variation was worse than in other examples. In terms of microstructure, the compounds represented by Formula I containing tertiary alcohol structures and the compounds represented by Formula II containing spacer groups (not single bonds) can form a specific polymer network with strong anchoring force on liquid crystal molecules after polymerization. During external physical vibrations, the polymer relies on this anchoring force to maintain the vertical alignment of the liquid crystals, giving the display device excellent vibration resistance. Based on this, the polymer generated by the synergistic effect of the compounds shown in Formula I and Formula II may have antioxidant and free radical absorption effects, thereby stabilizing the state of liquid crystal under high temperature or humid heat environment and reducing liquid crystal decomposition; in addition, the polymer network may also absorb free radicals released by liquid crystal molecules due to humid heat or high temperature to a certain extent.

[0070] In summary, the liquid crystal composition provided by this invention has the advantages of excellent vibration resistance and small power consumption change after aging treatment under extreme conditions of high temperature and high humidity (85°C-85%). It solves the problems of flickering and black spots in VA mode displays after vibration and poor reliability after aging under extreme conditions. It has good application prospects and can be widely used in display devices such as automotive, aviation, marine, and industrial control systems.

[0071] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A liquid crystal composition comprising at least one or more compounds of formula I and one or more compounds of formula II: I II; wherein, Each of the following independently represents either -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; and one or more H atoms in each of the following can be optionally substituted by L1; L1, in each occurrence, represents either -F, -Cl, an alkyl group with 1-15 carbon atoms, or an alkoxy group with 1-15 carbon atoms; Z1, in each occurrence, represents either -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -(CH2)m3-, -CR0R00-, or a single bond, and at least one Z1 does not represent a single bond; R0 and R00, in each occurrence, independently represent H or an alkyl group with 1-12 carbon atoms; Sp1, Sp2, Sp3, and Sp4 each independently represent a single bond, a chain alkyl group with 1-5 carbon atoms, or a cyclic alkyl group with 1-5 carbon atoms. Any one or more unconnected -CH2- atoms can be substituted by -O-, -CO-, -CH2O-, -OCH2-, -COO-, or -OOC- in a form where -O- atoms are not connected to each other. Any one or more H atoms in Sp1, Sp2, Sp3, and Sp4 can be independently substituted by F or Cl. Sp1 and Sp2 are not simultaneously single bonds, and at least one H atom in Sp1 and / or Sp2 is substituted by G3. G3 represents a tertiary alcohol structure with 1-7 carbon atoms. P1, P2, P3, and P4 each independently represent or, where • represents a linking site. m1 represents 0 or 1, m2 represents 1, 2, 3, or 4, and m3 represents an integer from 1 to 10.

2. The liquid crystal composition according to claim 1, wherein the compound represented by formula I is selected from the group consisting of compounds represented by formulas I-1 to I-7: I-1, I-2, I-3, I-4, I-5, I-6, I-7; wherein, a represents 0, 1, or 2; represents , , , , , or; Sp1 and Sp2 each independently represent a single bond, a chain alkyl group with 1-5 carbon atoms, or a cyclic alkyl group with 1-5 carbon atoms, wherein any one or more unconnected -CH2- can be replaced by -O-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- in the form of -O- not connected to each other, and Sp1 and Sp2 are not both single bonds, and at least one H atom in Sp1 and / or Sp2 is replaced by G3.

3. The liquid crystal composition according to claim 1 or 2, wherein the compound represented by formula I is selected from the group consisting of compounds represented by formula I-1-1 to formula I-7-1: I-1-1, I-1-2, I-1-3, I-1-4, I-1-5, I-1-6, I-1-7, I-1-8, I-1-9, I-1-10, I-1-11, I-1-12, I-1-13, I-2-1, I-2-2, I-2-3, I-3-1, I-3-2, I-3-3, I-3-4, I-3-5, I-3-6, I-3-7, I-3-8, I-3-9, I-3-10, I-3-11, I-3-12, I-3-13, I-3-14, I-4-1, I-5-1, I-5-2, I-6-1, I-6-2, I-6-3, I-7-1.

4. The liquid crystal composition according to claim 1 or 2, wherein the compound represented by Formula I is selected from the group consisting of compounds represented by Formulas I-3-1 to I-7-1: I-3-1, I-3-2, I-3-3, I-3-4, I-3-5, I-3-6, I-3-7, I-3-8, I-3-9, I-3-10, I-3-11, I-3-12, I-3-13, I-3-14, I-4-1, I-5-1, I-5-2, I-6-1, I-6-2, I-6-3, I-7-1.

5. The liquid crystal composition according to claim 1, wherein the compound represented by formula II is selected from the group consisting of compounds represented by formulas II-1 to II-7: II-1, II-2, II-3, II-4, II-5, II-6, II-7; wherein, a represents 0, 1, or 2; represents , , , , , or; Sp3 and Sp4 each independently represent a single bond, an alkyl chain with 1-5 carbon atoms, or a cyclic alkyl chain with 1-5 carbon atoms, wherein any one or more unconnected -CH2- can be replaced by -O-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- in the form that -O- is not connected to each other; Z1, Z2, Z3, and Z4 each independently represent -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -(CH2)m3-, -CR0R00- or a single bond, and in each compound shown in formulas II-1 to II-7, each has at least one group selected from Z1, Z2, Z3, and Z4 that does not represent a single bond.

6. The liquid crystal composition according to claim 1, wherein the mass percentage of the compound represented by Formula I in the liquid crystal composition is 0.01-4%; and / or the mass percentage of the compound represented by Formula II in the liquid crystal composition is 0.01-4%.

7. The liquid crystal composition according to claim 1, wherein the liquid crystal composition further comprises at least one or more compounds of formula III: III; wherein, R1 and R2 each independently represent an alkyl group with 1-10 carbon atoms or an alkenyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene; Z5 represents -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, or a single bond; n1 and n2 each independently represent 0, 1, or 2; and each independently represent , , , , , or .

8. The liquid crystal composition according to claim 7, wherein the liquid crystal composition further comprises at least one or more compounds selected from formula IV: IV; wherein, R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms or an alkenyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene, or cyclopentylene; Z6 and Z7 each independently represent -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, or a single bond; n3 and n4 each independently represent 0, 1, or 2.

9. The liquid crystal composition according to claim 8, wherein the liquid crystal composition further comprises at least one or more compounds of formula V and / or formula VI: V VI; wherein, Each of the following groups independently represents alkyl, alkenyl, alkyl, alkyl, or alkyl; where R5, R6, R7 and R8 each independently represent alkyl with 1-10 carbon atoms or alkenyl with 2-10 carbon atoms, wherein one or more non-adjacent -CH2- can be replaced by -O-, cyclopropylene, cyclobutylene or cyclopentylene; Z8 and Z9 each independently represent -CH2-CH2-, -O-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C- or a single bond; n5 represents 1 or 2, and n6 and n7 each independently represent 0, 1 or 2.

10. A liquid crystal display device, wherein the liquid crystal display device comprises a liquid crystal composition as described in any one of claims 1-9.

11. The liquid crystal display device according to claim 10, wherein the liquid crystal display device is a passive matrix addressing or active matrix addressing display device.