Liquid crystal composition and liquid crystal display device thereof

Abstract

The present application provides a liquid crystal composition and a liquid crystal display device thereof. The liquid crystal composition of the present application comprises at least one compound of general formula O and at least one compound of general formula N. The liquid crystal composition of the present application has smaller polymer residue, smaller roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability, under the conditions of maintaining proper clearing point, proper optical anisotropy, proper absolute value of dielectric anisotropy, larger K value (K 11 and K 33 ) and smaller rotational viscosity, so that the liquid crystal display device comprising the same has proper threshold voltage, better contrast, better response speed, can effectively improve the problems such as "image sticking", display unevenness, "broken bright spots" and the like existing in the existing PSA type liquid crystal display, and has higher practical application value.

Description

Technical Field

[0001] This invention relates to the field of liquid crystals, and more particularly to liquid crystal compositions and liquid crystal display devices comprising said liquid crystal compositions. Background Technology

[0002] Liquid crystal displays (LCDs) have experienced rapid development due to their small size, light weight, low power consumption, and excellent display quality, especially in portable electronic information products. Based on display mode, LCDs can be classified into PC (phase change), TN (twist nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), FFS (fringe field switching), VA (vertical alignment), and PSA (polymer stable alignment). Based on the driving method of the components, LCD elements can be classified into PM (passive matrix) and AM (active matrix) types. PM is further divided into static and multiplex types. AM is divided into TFT (thin film transistor) and MIM (metal-insulator-metal) types. TFTs include amorphous silicon and polycrystalline silicon. The latter is further divided into high-temperature and low-temperature types based on the manufacturing process.

[0003] Liquid crystal display elements contain a liquid crystal composition with a nematic phase, and this composition possesses suitable properties. By improving the properties of the liquid crystal composition, AM elements with excellent characteristics can be obtained. The relationship between the properties of the liquid crystal composition and the AM element is summarized in Table A below. The properties of the liquid crystal composition are further explained based on commercially available AM ​​elements. The temperature range of the nematic phase is related to the operating temperature range of the element. The viscosity of the liquid crystal composition is related to the response time of the element. For the element to display dynamic images, a short response time is preferred.

[0004] Table A: Characteristics of the liquid crystal composition and characteristics of the AM element

[0005] 1 Nematic phases have a wide temperature range Wide range of temperature applications 2 Low viscosity Short response time 3 Large optical anisotropy High contrast 4 Large absolute value of dielectric anisotropy Low threshold voltage, low power consumption, and high contrast. 5 High resistivity High voltage retention and high contrast 6 Stable to ultraviolet light and heat Long lifespan 7 Large elastic constant High contrast, short response time, and fast response speed

[0006] In the application of liquid crystal display devices, contrast ratio is crucial to visual effects. Generally speaking, the higher the contrast ratio, the clearer and more striking the image, and the more vivid and vibrant the colors; conversely, if the contrast ratio is low, the entire image appears hazy and dull. High contrast ratio greatly improves image clarity, detail, and grayscale performance. High-contrast products have advantages in terms of black-and-white contrast, clarity, and image integrity. Contrast ratio also significantly affects the display effect of dynamic video. Because the transitions between light and dark in dynamic images are relatively rapid, the higher the contrast ratio, the easier it is for the human eye to distinguish these transitions.

[0007] To improve the response speed of liquid crystal display devices, it is necessary to minimize the rotational viscosity of the liquid crystal material. However, low-viscosity liquid crystal materials generally have lower clearing points and optical anisotropy. Therefore, when formulating liquid crystal compositions, other performance requirements must be considered while reducing viscosity.

[0008] PSA-type liquid crystal displays incorporate a small amount (e.g., 0.3 wt%, typically <1 wt%) of one or more polymerizable compounds into the liquid crystal composition. This ensures that, after the liquid crystal composition is filled into the liquid crystal cell, the liquid crystal molecules polymerize in situ (usually by UV photopolymerization) or crosslink in an initially oriented state, with or without a voltage applied between the electrodes, thereby fixing the orientation of the liquid crystal molecules. With the continuous development of PSA-type liquid crystal display elements, they have been applied to various conventional liquid crystal display devices, such as the known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS, and PSA-TN type liquid crystal displays. In PSA-type liquid crystal displays, the liquid crystal composition containing the polymerizable compound is located between two substrates, each equipped with an electrode structure, or the two electrode structures are placed on only one of the substrates, and mutually orthogonal polarizers are attached to the outer sides of the substrates. Furthermore, either or both of the two substrates may contain an alignment film disposed on the substrate or the electrode structure (if present). Like conventional liquid crystal displays, PSA-type liquid crystal displays can operate as active-matrix displays or passive-matrix displays. In the case of an active matrix display, each pixel is addressed by an integrated nonlinear active element (such as a transistor); in the case of a passive matrix display, each pixel is typically addressed according to multiplexing methods known in the art.

[0009] After the liquid crystal composition is filled into the display device, the polymerizable compounds contained in the liquid crystal composition are typically polymerized or crosslinked in situ by UV photopolymerization, which is achieved by exposing the liquid crystal composition to UV radiation (preferably while simultaneously applying a voltage to the electrode structure). As a result of UV exposure, the polymerized or crosslinked polymerizable compounds undergo phase separation from other compounds in the liquid crystal composition and form a polymer layer on the substrate surface, where they cause a pre-tilt angle of the liquid crystal molecules relative to the substrate. For PSA-VA, PSA-OCB, PSA-FFS, and PSA-TN type liquid crystal displays, the polymerization of the polymerizable compounds is preferably carried out under applied voltage; for PSA-IPS displays, applying voltage or not applying voltage is acceptable, but not applying voltage is preferred.

[0010] Typically, in the production process of PSA-type liquid crystal displays, UV photopolymerization is achieved through the following two steps:

[0011] In the first step (hereinafter referred to as the "UV1 step"), the liquid crystal composition is exposed to UV radiation emitted by a radiation source (hereinafter referred to as "UV1 radiation") while a voltage is applied to the electrode structure, thereby generating a pre-tilt angle. Preferred polymerizable compounds should generate a smaller pre-tilt angle within the same time period or the same pre-tilt angle within a shorter UV1 radiation period (i.e., a faster angular velocity) to improve production efficiency, shorten tact time in mass production, and reduce costs. Simultaneously, a faster angular velocity of the polymerizable compound is more conducive to complete polymerization, thereby reducing polymer residue. To increase the angular velocity, a shorter wavelength of UV1 radiation is preferred; while to improve the voltage holding ratio (VHR), a longer wavelength of UV1 radiation is preferred. Therefore, a faster angular velocity and a higher voltage holding ratio are generally difficult to achieve simultaneously.

[0012] In the second step (hereinafter referred to as the "UV2 step"), the liquid crystal composition is exposed to UV radiation (hereinafter referred to as "UV2 radiation") without applying voltage to the electrode structure to ensure that any residual polymerizable compounds that did not polymerize in the UV1 step are completely polymerized. It is desirable that the change in the pre-tilt angle after the UV2 step be as small as possible to reduce the possibility of display unevenness in PSA-type liquid crystal displays due to UV process inhomogeneities (uniformity of external conditions such as light, heat, and stress). Simultaneously, the UV radiation intensity in the UV2 step should be reduced to avoid or minimize negative effects (such as reduced reliability or image stickiness).

[0013] In current PSA-type liquid crystal display (LCD) production, a polyimide (PI) alignment layer is coated onto the glass substrate to achieve vertical alignment of liquid crystal molecules. However, this method has significant drawbacks (such as the cumbersome, complex, and time-consuming PI coating process) and numerous other adverse effects, thus greatly limiting the quality of LCDs. The PI alignment process significantly reduces production efficiency and increases production costs. Furthermore, due to the limited precision control of the PI printing area, deviations in the PI printing area affect the sealant sealing and edge display effect of narrow-bezel products, thus severely limiting the development of current mainstream narrow-bezel products and significantly reducing their yield. Existing technologies primarily replace the use of PI alignment layers by adding self-aligning agents to the liquid crystal composition; however, not all liquid crystal compositions can achieve perfect compatibility with polymerizable compounds and self-aligning agents. For example, if the pretilt angle formation rate is too slow during the UV process, a longer UV time is required to form the desired pretilt angle, reducing production efficiency. If the polymerization rate of polymers and self-aligning agents is too fast during UV polymerization and their diffusion is poor, explosive polymerization can easily occur, resulting in a rough polymer layer and forming bright spots that affect the panel display effect. After the UV1 and UV2 steps, there may be high levels of polymerizable compounds and self-aligning agents remaining, causing problems such as deterioration of panel image sticking (IS). Simultaneously, poor miscibility between the liquid crystal composition and polymerizable compounds and self-aligning agents can lead to the precipitation of polymerizable polymers and self-aligning agents during liquid crystal storage, causing liquid crystal performance failure. Furthermore, the poor rigidity of the polymer network formed after polymerizable compound polymerization can cause changes in the polymer network structure when the PSA-type liquid crystal display element continuously displays the same pattern for a long time, subsequently changing the pretilt angle of the liquid crystal molecules and resulting in display defects. If the liquid crystal contact angle of the self-aligning agent is too high, the liquid crystal will diffuse more slowly in the ODF (One Drop Filling) process, resulting in uneven concentration distribution of the self-aligning agent in the panel. This leads to uneven alignment effect or poor alignment effect in the corner areas of the panel, resulting in display defects.

[0014] Furthermore, with the development of display technology, the liquid crystal display industry has placed more stringent demands on the display quality of LCDs, especially in the TV industry. TV sizes are generally increasing, leading to larger LCD generation lines and significantly increasing the manufacturing complexity of large-size LCD panels. Therefore, ensuring display quality is a pressing issue. In addition to continuously optimizing panel manufacturing processes, the development of liquid crystal materials is another solution, particularly for PSA-type liquid crystal displays, where the selection of liquid crystal compositions used in conjunction with polymerizable compounds has become a research hotspot.

[0015] Therefore, the research focus in this field is on developing self-aligning agents with fast polymerization speed, controllable polymerization process, and good comprehensive performance to meet the needs of PSA-type liquid crystal display elements, and providing display technology that can achieve vertical alignment of liquid crystal molecules without the need for a PI alignment layer. Summary of the Invention

[0016] Purpose of the invention: The purpose of this invention is to provide a solution with a suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, and a large K value (K). 11 and K 33 Liquid crystal compositions with lower rotational viscosity, lower polymer residue, lower roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability.

[0017] Furthermore, an object of the present invention is to provide a liquid crystal display device comprising the above-described liquid crystal composition.

[0018] Technical solution: To achieve the above-mentioned objectives, the present invention provides a liquid crystal composition comprising...

[0019] At least one compound of general formula O

[0020] as well as

[0021] At least one compound of general formula N

[0022]

[0023] in,

[0024] R o2 Indicate -Sp o2 -P o1 -H, straight-chain alkyl groups containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, branched alkyl groups containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them, straight-chain alkyl groups containing 1-12 carbon atoms, One or more non-adjacent -CH2- can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H in a straight-chain alkyl group containing 1-12 carbon atoms can be independently replaced by -F or -C1.

[0025] R N1 and R N2Each of these terms independently represents a straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. One or more non-adjacent -CH2- in a straight-chain alkyl group containing 1-12 carbon atoms or a branched alkyl group containing 3-12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-;

[0026] ring express in One or more -CH2- can be replaced by -O-, and a single bond in one or at most two rings can be replaced by a double bond;

[0027] ring and ring Each represents independently in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein One or more -H can be replaced by -F, -Cl or -CN, and one or more -CH= in a ring can be replaced by -N=;

[0028] L o1 and L o3 Each can be independently represented as -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R) o0 )2、-C(O)R o0 A straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms; a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them, straight-chain alkyl groups containing 1-12 carbon atoms, One or more non-adjacent -CH2- groups can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-, and one or more -H groups in a straight-chain alkyl group containing 1-12 carbon atoms can be independently replaced by -F, wherein R o0It refers to a straight-chain alkyl group containing 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.

[0029] L o2 Indicate -Sp o3 -P o2 or

[0030] L N1 and L N2 Each can independently represent -H, an alkyl group containing 1-3 (e.g., 1, 2, or 3) carbon atoms, or a halogen.

[0031] R o1 and R o3 Each independently represents an anchoring group, and the anchoring group is... in This indicates the connection sites in the bonded structure;

[0032] n o4 Represents 1 or 2, where when n o4 When 2 is represented, -Sp o8 -x o2 They can be the same or different;

[0033] n o5 Represents 0 or 1;

[0034] M S1 express in, Representing M S1 The connection site with -CH2- in the six-membered ring;

[0035] I S1 and J S1 Each can be independently represented as -CH2-, -O-, or -S-;

[0036] N S1 This indicates =O or =S;

[0037] V K1 V K2 and V K3 Each can be represented independently as -CH= or -N=;

[0038] X o1 and X o2 Each can be independently represented as -H, -OH, -SH, -NH2, or -NHR. 11 -N(R) 11)2、-NHC(O)R 11 -OR 11 -C(O)OH, -CHO, a straight-chain halo- or non-halogenated alkyl group containing 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a branched halo- or non-halogenated alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, wherein X o1 and X o2 At least one of them is selected from -OH, -SH, -NH2, -NHR 11 The group consisting of -C(O)OH and -CHO, where R 11 It refers to a straight-chain alkyl group containing 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.

[0039] P o1 P o2 and P o3 Each independently represents a polymerizable group;

[0040] Sp o1 Sp o2 Sp o3 Sp o4 Sp o5 Sp o7 and Sp o8 Each can independently represent a spacer group or a single bond;

[0041] Sp o6 Each represents independently Where ------ indicates that it is related to Sp 07 or Sp o8 Connection sites;

[0042] Z o1 and Z o2 Each of these can be independently represented as -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d-, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each of these terms independently represents a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms, and d represents an integer from 1 to 4.

[0043] Z N1 and Z N2 Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)4-, -CF2O-, or -OCF2-;

[0044] p o1 p o2 p o3 and p o4 Each can be independently represented as 0, 1, or 2, where when p o1 When L represents 2, o1 They can be the same or different, where when p o2 When L represents 2, o2 They can be the same or different; where p o3 When 2 is represented, -Sp os -R o3 They can be the same or different; where p o4 When L represents 2, o3 They can be the same or different;

[0045] n o1 Represents integers from 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9);

[0046] n o2 and n o3 Each can be independently represented as 1, 2, or 3, where when n o2 When representing 2 or 3, They can be the same or different, where when n o3 When representing 2 or 3, They can be the same or different; and

[0047] n N1 n represents 0, 1, 2, or 3. N2 Represents 0 or 1, and 0 ≤ n N1 +nN2 ≤3, when nN1=2 or 3, the ring They can be the same or different, Z N1 They can be the same or different.

[0048] In some embodiments of the present invention, compounds of general formula O are selected from the group consisting of:

[0049]

[0050]

[0051] as well as

[0052] in,

[0053] Z o11 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each of these terms independently represents a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms, and d represents an integer from 1 to 4.

[0054] L o11 and L o31 Each can be independently represented as -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R) o0 )2、-C(O)R o0 A straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms; a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them, straight-chain alkyl groups containing 1-12 carbon atoms, One or more non-adjacent -CH2- groups can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-, and one or more -H groups in a straight-chain alkyl group containing 1-12 carbon atoms can be independently replaced by -F, wherein R o0 It refers to a straight-chain alkyl group containing 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.

[0055] L o21 Indicate -Sp o3 -P o2 or and

[0056] p o11 It represents 0, 1, or 2.

[0057] In some embodiments of the present invention, the compound of general formula O is selected from the group consisting of compounds of general formula O-1, compounds of general formula O-4, compounds of general formula O-6, and compounds of general formula O-10.

[0058] In some embodiments of the present invention, the compounds of general formula O-1 are selected from the group consisting of:

[0059] as well as

[0060] in,

[0061] L o22 L o23 and L o24 Each is represented independently -SP o3 -P o2 or

[0062] L o11 L o12 And L. 13 Each can be independently represented as -F, -Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(O)N(R) o0 )2、-C(O)R o0A straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms; a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them, straight-chain alkyl groups containing 1-12 carbon atoms, One or more non-adjacent -CH2- groups can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-, and one or more -H groups in a straight-chain alkyl group containing 1-12 carbon atoms can be independently replaced by -F, wherein R o0 It refers to a straight-chain alkyl group containing 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12) carbon atoms.

[0063] In some embodiments of the present invention, the compounds of general formula O-4 are selected from the group consisting of the following compounds:

[0064] as well as

[0065] In some embodiments of the present invention, the compounds of general formula O-6 are selected from the group consisting of the following compounds:

[0066] as well as

[0067] In some embodiments of the present invention, the compounds of general formula O-10 are selected from the group consisting of the following compounds:

[0068] as well as

[0069] In some embodiments of the present invention, the compounds of general formula O-1-1 are selected from the group consisting of the following compounds:

[0070] as well as

[0071] In some embodiments of the present invention, the compound of general formula O-4-1 is selected from the group consisting of the following compounds:

[0072] as well as

[0073] In some embodiments of the present invention, the compound of general formula O-4-7 is selected from the group consisting of the following compounds:

[0074] as well as

[0075] In some embodiments of the present invention, the compound of general formula O-6-1 is selected from the group consisting of the following compounds:

[0076] as well as

[0077] In some embodiments of the present invention, the compounds of general formula O-6-7 are selected from the group consisting of the following compounds:

[0078] as well as

[0079] In some embodiments of the present invention, the compound of general formula O-10-1 is selected from the group consisting of the following compounds:

[0080] as well as

[0081] In some embodiments of the present invention, R o2 The following are represented: -H, straight-chain alkyl groups containing 1-12 carbon atoms, straight-chain alkoxy groups containing 1-11 carbon atoms, and alkenyl groups containing 2-12 carbon atoms.

[0082] In some embodiments of the present invention, L o1 and L o3 Each can independently represent -F, -Cl, straight-chain alkyl groups containing 1-12 carbon atoms, straight-chain alkoxy groups containing 1-11 carbon atoms, and straight-chain alkenyl groups containing 2-12 carbon atoms.

[0083] In some embodiments of the present invention, the compound of general formula O is selected from the group consisting of compounds of general formula O-1-1-4, compounds of general formula O-6-1-4, and compounds of general formula O-6-7-4.

[0084] In some embodiments of the present invention, the polymerizable group P o1 P o2 and P o3 Each represents independently Or -SH; preferably, polymerizable groups Po1, P o2 and P o3 Each represents independently Or -SH; more preferably, polymerizable group P o1 P o2 and P o3 Each represents independently

[0085] In some embodiments of the present invention, L o2 Indicates -8p o3 -P o2 ,

[0086] In some embodiments of the present invention, Z o2 Indicates a single key.

[0087] In some embodiments of the present invention, Sp o1 Sp o2 Sp o3 Sp o4 Sp o5 Sp o7 and Sp o8 Each can be independently represented as -(CH2)p1-, -(CH2)p1-O-, -(CH2)p1-O-CO-, -(CH2)p1-CO-O-, -(CH2)p1-O-CO-O-, -CR 0 R 00-(CH2)p1- or a single bond, where p1 represents an integer from 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9), and R 0 and R 00 Each can be independently represented as -H, a straight-chain alkyl group containing 1-10 carbon atoms, a branched alkyl group containing 3-10 carbon atoms, or a cycloalkyl group containing 3-10 carbon atoms.

[0088] In some embodiments of the present invention, Sp o1 Sp o3 Sp o4 and Sp o5 Each can be represented independently as -(CH2)p1- or -(CH2)p1-O-.

[0089] In some embodiments of the present invention, R o1 and R o3 Each group is independently selected from the following groups:

[0090] as well as

[0091] in,

[0092] * indicates a connection site in the bonded structure.

[0093] In some embodiments of the present invention, in order to obtain less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability, R o1 and R o3 Each group is independently selected from the following groups:

[0094] as well as

[0095] In some embodiments of the present invention, Ro1 and R o3 Each is preferably selected independently as follows:

[0096] In some embodiments of the present invention, the content of the general formula O compound is preferably adjusted so that the liquid crystal composition of the present invention has less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability.

[0097] In some embodiments of the present invention, the compound of general formula O accounts for 0.001% to 5% (inclusive of any value or subrange within this range) of the liquid crystal composition, for example, 0.001%, 0.005%, 0.05%, 0.1%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, 1.0%, 2%, 3%, 4%, 5%, or a range between any two of these values; preferably, the compound of general formula O accounts for 0.1% to 2% of the liquid crystal composition by weight.

[0098] In this invention, the self-aligning agent of general formula O, when added to the liquid crystal composition, enables the liquid crystal composition of this invention to align liquid crystal molecules even without the presence of a PI alignment layer, and results in the liquid crystal composition containing it having less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability.

[0099] In some embodiments of the present invention, preferably, R N1 and R N2 Each of these terms independently represents a straight-chain alkyl group containing 1-10 carbon atoms, a branched alkyl group containing 3-10 carbon atoms, a straight-chain alkoxy group containing 1-9 carbon atoms, a branched alkoxy group containing 3-9 carbon atoms, a straight-chain alkenyl group containing 2-10 carbon atoms, or a branched alkenyl group containing 2-10 carbon atoms; more preferably, R N1 and R N2 Each can be independently represented as a straight-chain alkyl group containing 1-8 carbon atoms, a straight-chain alkoxy group containing 1-7 carbon atoms, or a straight-chain alkenyl group containing 2-8 carbon atoms.

[0100] In some embodiments of the present invention, the compounds of general formula N are selected from the group consisting of the following compounds:

[0101] as well as

[0102] in,

[0103] R N11 It refers to a straight-chain alkyl group containing 1-5 (e.g., 2, 3, or 4) carbon atoms. One or more non-adjacent -CH2- groups in a straight-chain alkyl group containing 1-5 carbon atoms may be independently replaced by -O-, -CO-, -CO-O-, or -O-CO-.

[0104] R N12 Represents -H, a straight-chain alkyl group containing 1-5 (e.g., 2, 3, or 4) carbon atoms, One or more non-adjacent -CH2- in a straight-chain alkyl group containing 1-5 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-;

[0105] n N3 It represents 0, 1, 2, or 3;

[0106] L N3 and L N4 Independently representing -H, an alkyl group containing 1-3 (e.g., 1, 2, or 3) carbon atoms, or a halogen; and

[0107] ring express in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein One or more -H can be replaced by -F, -Cl or -CN, and one or more -CH= in a ring can be replaced by -N=.

[0108] In some embodiments of the present invention, in order to obtain suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, suitable K value, suitable rotational viscosity, small polymer residue, small roughness, good low-temperature storage stability, small contact angle, good alignment effect, and good pre-tilt angle stability, the compound of general formula N is selected from the group consisting of compounds of general formula N-3, compounds of general formula N-4, compounds of general formula N-5, compounds of general formula N-6, compounds of general formula N-13, and compounds of general formula N-15.

[0109] In some embodiments of the present invention, the compound of general formula N comprises at least one compound selected from the group consisting of a compound of general formula N-3, a compound of general formula N-5, a compound of general formula N-13, and a compound of general formula N-15, and at least one compound selected from the group consisting of a compound of general formula N-4 and a compound of general formula N-6.

[0110] In some embodiments of the present invention, compounds of general formula N are selected from the group consisting of:

[0111]

[0112]

[0113]

[0114]

[0115] as well as

[0116] In some embodiments of the present invention, in order to obtain suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, suitable K value, suitable rotational viscosity, small polymer residue, small roughness, good low-temperature storage stability, small contact angle, good alignment effect, and good pre-tilt angle stability, the compound of general formula N is selected from the group consisting of compounds of general formula N-3-1, compounds of general formula N-3-2, compounds of general formula N-3-4, compounds of general formula N-3-7, compounds of general formula N-4-1, compounds of general formula N-4-3, compounds of general formula N-5-1, compounds of general formula N-5-3, compounds of general formula N-5-5, compounds of general formula N-5-8, compounds of general formula N-6-8, compounds of general formula N-13-1, and compounds of general formula N-15-4.

[0117] In some embodiments of the present invention, the compound of general formula N comprises at least two compounds selected from the group consisting of compounds of general formula N-5-1, compounds of general formula N-5-3, compounds of general formula N-5-8, and compounds of general formula N-15-4.

[0118] In some embodiments of the present invention, the compound of general formula N comprises at least one compound selected from the group consisting of compounds of general formula N-3-1, general formula N-3-2, general formula N-3-4, general formula N-3-7, general formula N-5-1, general formula N-5-3, general formula N-5-5, general formula N-5-8, general formula N-13-1, and general formula N-15-4, and at least one compound selected from the group consisting of compounds of general formula N-4-1, general formula N-4-3, and general formula N-6-8.

[0119] In some embodiments of the present invention, it is preferred to adjust the content of the compound of general formula N so that the liquid crystal composition of the present invention has less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability while maintaining appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, appropriate K value and appropriate rotational viscosity.

[0120] In some embodiments of the invention, the compound of general formula N accounts for 0.1% to 70% by weight of the liquid crystal composition (inclusive of any value or subrange within this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, or a range between any two of these values.

[0121] In some embodiments of the invention, the compound selected from the group consisting of compounds of general formula N-3-1, general formula N-3-2, general formula N-3-4, general formula N-3-7, general formula N-5-1, general formula N-5-3, general formula N-5-5, general formula N-5-8, general formula N-13-1, and general formula N-15-4 accounts for 30% to 70% by weight of the liquid crystal composition (inclusive of any value or subrange within this range), for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, or a range between any two of these values.

[0122] In some embodiments of the invention, the compound selected from the group consisting of compounds of general formula N-4-1, general formula N-4-3, and general formula N-6-8 accounts for 0.1% to 26% by weight of the liquid crystal composition (inclusive of any value or subrange within this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, or a range between any two of these values.

[0123] In some embodiments of the present invention, the liquid crystal composition comprises at least one compound of general formula M:

[0124]

[0125] in,

[0126] R M1 and R M2 Each of these terms independently represents a straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. One or more of the straight-chain alkyl groups containing 1-12 carbon atoms or the branched alkyl groups containing 3-12 carbon atoms, or two or more non-adjacent -CH2-, can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-.

[0127] ring ring and ring Each represents independently in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds. At most one -H in the halogen can be replaced by a halogen;

[0128] Z M1 and Z M2 Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2-, or -(CH2)4-; and

[0129] n M Represents 0, 1, or 2, where when n M When = 2, ring They can be the same or different, Z M2 They can be the same or different.

[0130] In some embodiments of the present invention, preferably, R M1 and R M2 Each of these terms independently represents a straight-chain alkyl group containing 1-10 carbon atoms, a branched alkyl group containing 3-10 carbon atoms, a straight-chain alkoxy group containing 1-9 carbon atoms, a branched alkoxy group containing 3-9 carbon atoms, a straight-chain alkenyl group containing 2-10 carbon atoms, or a branched alkenyl group containing 4-10 carbon atoms; more preferably, R M1 and R M2 Each can be independently represented as a straight-chain alkyl group containing 1-8 carbon atoms, a straight-chain alkoxy group containing 1-7 carbon atoms, or a straight-chain alkenyl group containing 2-8 carbon atoms.

[0131] In some embodiments of the present invention, R M1 and R M2 Preferably, each represents a straight-chain alkenyl group containing 2-8 carbon atoms independently; R M1 and R M2 Further, each of the linear alkenyl groups containing 2-5 carbon atoms is preferred.

[0132] In some embodiments of the present invention, preferably, R M1 and R M2 One of them is a straight-chain alkenyl group containing 2-5 carbon atoms, while the other is a straight-chain alkyl group containing 1-5 carbon atoms.

[0133] In some embodiments of the present invention, preferably, R M1 and R M2 Each independently represents a straight-chain alkoxy group containing 1-8 carbon atoms; more preferably, R M1 and R M2 Each can be used independently to represent a straight-chain alkoxy group containing 1-5 carbon atoms.

[0134] In some embodiments of the present invention, preferably, R M1 and R M2 One of them is a straight-chain alkoxy group containing 1-5 carbon atoms, and the other is a straight-chain alkyl group containing 1-5 carbon atoms.

[0135] In some embodiments of the present invention, when reliability is a priority, R is preferred. M1 and R M2 All are alkyl groups; when reducing the volatility of the compound is of priority, R is preferred. M1 and R M2 All are alkoxy groups; when viscosity reduction is a priority, R is preferred. M1 and R M2 At least one of them is an alkenyl group.

[0136] In some embodiments of the present invention, the compounds of general formula M are selected from the group consisting of the following compounds:

[0137]

[0138]

[0139] as well as

[0140]

[0141] In some embodiments of the present invention, in order to obtain suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, suitable K value, suitable rotational viscosity, small polymer residue, small roughness, good low-temperature storage stability, small contact angle, good alignment effect, and good pre-tilt angle stability, the compound of general formula M is selected from the group consisting of compounds of general formula M-1, compounds of general formula M-2, compounds of general formula M-4, compounds of general formula M-11, and compounds of general formula M-13.

[0142] In some embodiments of the present invention, the compounds of general formula M-2 are selected from the group consisting of:

[0143]

[0144] In some embodiments of the present invention, the compounds of general formula M-11 are selected from the group consisting of:

[0145]

[0146] In some embodiments of the present invention, the compounds of general formula M-13 are selected from the group consisting of:

[0147]

[0148]

[0149] In some embodiments of the present invention, the compound of general formula M contains at least two R. M2 Compounds of the general formula M-1 representing allyl groups.

[0150] In some embodiments of the present invention, the compound of general formula M comprises at least one compound selected from the group consisting of a compound of general formula M-111, a compound of general formula M-131, a compound of general formula M-123, and a compound of general formula M-139.

[0151] In some embodiments of the present invention, it is preferred to adjust the content of the compound of general formula M so that the liquid crystal composition of the present invention has less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability while maintaining appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, appropriate K value and appropriate rotational viscosity.

[0152] In some embodiments of the invention, the compound of general formula M accounts for 0.1% to 60% by weight of the liquid crystal composition (inclusive of any value or subrange within this range), for example, 0.1%, 1%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, or a range between any two of these values.

[0153] In some embodiments of the present invention, the liquid crystal composition of the present invention comprises at least one polymerizable compound of general formula RM:

[0154]

[0155] in,

[0156] R1 represents -H, halogen, -CN, -Sp2-P2, a straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms, or a branched alkyl group containing 3-12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them are straight-chain alkyl groups containing 1-12 carbon atoms, and branched alkyl groups containing 3-12 carbon atoms. One or more non-adjacent -CH2- can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H can be independently replaced by -F or -C1;

[0157] ring and ring Each represents independently in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein One or more -H atoms may be independently replaced by -F, -Cl, -CN, -Sp3-P3, a halogenated or unhalogenated straight-chain alkyl group containing 1-12 carbon atoms, or a halogenated or unhalogenated straight-chain alkoxy group containing 1-11 carbon atoms. Substitution, and in one or more rings -CH= can be replaced by -N=;

[0158] ring express in One or more -H atoms may be independently replaced by -F, -Cl, -CN, -Sp3-P3, a halogenated or unhalogenated straight-chain alkyl group containing 1-12 carbon atoms, or a halogenated or unhalogenated straight-chain alkoxy group containing 1-11 carbon atoms. Substitution, and in one or more rings -CH= can be replaced by -N=;

[0159] P1, P2, and P3 each independently represent polymerizable groups;

[0160] X0 represents -O-, -S-, or -CO-;

[0161] S p1 Sp2 and Sp3 each independently represent spacer groups or single bonds;

[0162] Z1 and Z2 independently represent -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, and -(CH2). d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each of these terms independently represents a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms, and d represents an integer from 1 to 4; and

[0163] a represents 0, 1, or 2, b represents 0 or 1, where when a represents 2, the ring... They can be the same or different; Z1 can be the same or different.

[0164] In some embodiments of the present invention, the polymerizable compound of general formula RM is selected from the group consisting of the following compounds:

[0165]

[0166]

[0167] as well as

[0168] in,

[0169] X1-X 10 and X 12 Each can independently represent -F, -Cl, -Sp3-P3, or straight-chain alkyl or alkoxy groups containing 1-5 carbon atoms.

[0170] In some embodiments of the present invention, X1-X 10 and X 12 Each can be independently represented as -F, -Cl, -Sp3-P3, -CH3, -OCH3, -C2H5, or -OC2H5.

[0171] In some embodiments of the present invention, Sp1 and Sp2 both represent single bonds.

[0172] In some embodiments of the present invention, in order to obtain less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability, the polymerizable compound of general formula RM is selected from the group consisting of compounds of general formula RM-1, compounds of general formula RM-2, compounds of general formula RM-19, and compounds of general formula RM-20.

[0173] The polymerizable groups involved in this invention are groups suitable for polymerization reactions (e.g., free radical or ionic polymerization, addition polymerization, or condensation polymerization), or groups suitable for addition or condensation on the polymer backbone. For chain polymerization, polymerizable groups containing -CH=CH- or -C≡C- are particularly preferred; for ring-opening polymerization, oxetyl or epoxy groups are particularly preferred, for example.

[0174] In some embodiments of the present invention, polymerizable groups P1, P2, and P3 are each independently represented. Or -SH; preferably, polymerizable groups P1, P2, and P3 are each represented independently. Or -SH; more preferably, the polymerizable groups P1, P2 and P3 are each independently represented.

[0175] In some embodiments of the present invention, the polymerizable compound of general formula RM-1 is selected from the group consisting of the following compounds:

[0176] as well as

[0177] In some embodiments of the present invention, the polymerizable compound of general formula RM-2 is selected from the group consisting of the following compounds:

[0178]

[0179]

[0180] as well as

[0181]

[0182] In some embodiments of the present invention, the polymerizable compound of general formula RM-19 is selected from the group consisting of the following compounds:

[0183]

[0184] as well as

[0185]

[0186] In some embodiments of the present invention, the polymerizable compound of general formula RM-20 is selected from the group consisting of the following compounds:

[0187]

[0188] as well as

[0189] As used herein, the term "spacer group" is known to those skilled in the art and is described in the literature (e.g., Pure Appl. Chem. 2001, 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368). As used herein, the term "spacer group" refers to a flexible group that connects a mesocrystalline group and a polymerizable group in a polymerizable compound. A typical spacer group is, for example, -(CH2). p1 -, -(CH2CH2O)q1-CH2CH2-, -(CH2CH2S)q1-CH2CH2-, -(CH2CH2NH)q1-CH2CH2-, -CR 0 R 00 -(CH2) p1 -or-(SiR) 0 R00 -O)p1-, where p1 represents an integer from 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9), q1 represents an integer from 1 to 3 (e.g., 1, 2, or 3), and R 0 and R 00 Each can independently represent -H, a straight-chain alkyl group containing 1-10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms, a branched alkyl group containing 3-10 (e.g., 3, 4, 5, 6, 7, 8, or 9) carbon atoms, or a cycloalkyl group containing 3-10 (e.g., 4, 5, 6, 7, 8, or 9) carbon atoms. Particularly preferred spacer groups are -(CH2)p1-, -(CH2)p1-O-, -O-(CH2)p1-, -(CH2)p1-O-CO-, -O-CO-(CH2)p1-, -(CH2)p1-CO-O-, -CO-O-(CH2)p1-, -(CH2)p1-O-CO-O-, -O-CO-O-(CH2)p1-, or -CR. 0 R 00 -(CH2) p1 -

[0190] In some embodiments of the present invention, the content of the compound of general formula RM is preferably adjusted so that the liquid crystal composition of the present invention has less polymer residue, less roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability.

[0191] In some embodiments of the invention, the polymerizable compound of general formula RM accounts for 0.001%-5% (inclusive of any value or subrange within this range) of the weight percentage of the liquid crystal composition, for example, 0.001%, 0.002%, 0.004%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%. 0.2%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.3%, 0.32%, 0.33%, 0.34%, 0.35%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.6%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a range between any two of these values.

[0192] As used in this article, -CO- and -C(O)- both represent carbonyl groups.

[0193] As used herein, the term "containing 1-r carbon atoms" (where r is an integer greater than 1) can mean containing any integer between 1 and r (inclusive), such as containing 2 carbon atoms, (r-1) carbon atoms, or r carbon atoms. For example, "containing 1-12 carbon atoms" can mean containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

[0194] As used herein, the term "integer between y1 and y2" can be any integer within that range (including the endpoints y1 and y2). For example, "integer between 0 and 12" can be, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0195] In some embodiments of the present invention, the liquid crystal composition further comprises at least one additive.

[0196] In addition to the compounds mentioned above, the liquid crystal compositions of the present invention may also contain conventional nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, dopants, antioxidants, ultraviolet absorbers, infrared absorbers, polymerizable monomers, or light stabilizers.

[0197] The following shows possible dopants that are preferably added to the liquid crystal composition according to the invention:

[0198]

[0199]

[0200] as well as

[0201]

[0202] In some embodiments of the present invention, the dopant accounts for 0%-5% of the weight percentage of the liquid crystal composition; preferably, the dopant accounts for 0.01%-1% of the weight percentage of the liquid crystal composition.

[0203] Furthermore, the antioxidants, light stabilizers, ultraviolet absorbers, and other additives used in the liquid crystal composition of the present invention are preferably the following substances:

[0204]

[0205]

[0206]

[0207]

[0208] Where n represents a positive integer from 1 to 12.

[0209] Preferably, the antioxidant is selected from the compounds listed below:

[0210]

[0211] In some embodiments of the present invention, the additive accounts for 0%-5% of the total weight percentage of the liquid crystal composition; preferably, the additive accounts for 0.01%-1% of the total weight percentage of the liquid crystal composition.

[0212] Even in the absence of a polymerization initiator, the liquid crystal composition containing the polymerizable compound of the present invention can undergo polymerization; however, a polymerization initiator may also be included to promote polymerization. Examples of polymerization initiators include benzoin ethers, benzophenones, acetophenones, benzoin ketals, and phosphine oxides.

[0213] In another aspect, the present invention also provides a liquid crystal display device comprising the above-described liquid crystal composition.

[0214] In some embodiments of the present invention, the above-described liquid crystal composition is particularly suitable for PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN type liquid crystal display devices.

[0215] Beneficial effects: Compared with the prior art, the liquid crystal composition of the present invention maintains appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a larger K value (K0). 11 and K 33 With a lower polymer residue, lower roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability, it exhibits the following characteristics: (i) lower polymer residue, lower roughness, better low-temperature storage stability, smaller contact angle, better alignment effect, and better pre-tilt angle stability. Detailed Implementation

[0216] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0217] Unless otherwise specified, all proportions in this invention are weight ratios, and all temperatures are in degrees Celsius.

[0218] For ease of explanation, the group structures of each compound in the following embodiments are represented by the codes listed in Table 1:

[0219] Table 1. Group structure codes of compounds

[0220]

[0221] Take the following compound with the following structural formula as an example:

[0222]

[0223] If the structure is represented by the codes listed in Table 1, it can be expressed as: nCCPF, where n in the code represents the number of C atoms in the left-end alkyl group. For example, if n is "3", it means that the alkyl group is -C3H7. In the code, C represents 1,4-cyclohexylene, P represents 1,4-phenyleneene, and F represents fluorine substituent.

[0224] The abbreviated codes for the test items in the following examples are as follows:

[0225] Cp (Clearing point, nematic-isotropic phase transition temperature, °C)

[0226] Δn Optical anisotropy (589nm, 20℃)

[0227] Δε dielectric anisotropy (1 kHz, 20 °C)

[0228] K 11 Elastic constant of the stretching curve (20℃)

[0229] K 33 Bending elastic constant (20℃)

[0230] γ1 Rotational viscosity (mPa·s, 20℃)

[0231] t -10℃ Low-temperature storage time (days, -10℃)

[0232] Ra surface roughness (nm)

[0233] PTA pre-tilt angle (°, 20℃)

[0234] Stability of ΔPTA pretilt angle (change in pretilt angle, °, after a fixed voltage application time)

[0235] in,

[0236] Cp: ​​Obtained by testing with a melting point apparatus.

[0237] Δn: Measured using an Abbe refractometer under a sodium lamp (589nm) light source at 20℃.

[0238] Δa: Δε=ε1-ε ⊥ Where ε1 is the dielectric constant parallel to the molecular axis, ε ⊥ The dielectric constant is perpendicular to the molecular axis; test conditions: 20℃, 1KHz, VA type test box with a thickness of 6μm.

[0239] γ1: Measured using the LCM-2 type liquid crystal property evaluation system; test conditions: 20℃, 160-260V, test cell thickness 20μm.

[0240] K 11 and K 33 The CV curve of the liquid crystal was obtained by testing and calculating using an LCR meter and a VA test cell; test conditions: cell thickness 6μm, V = 0.1~20V, 20℃.

[0241] t -10℃ The time when crystal precipitation is observed is recorded when a nematic liquid crystal medium is placed in a glass bottle and stored at -20°C. 7DNG indicates that crystal precipitation was observed after 7 days of storage at -10°C, and 10D OK indicates that it remains normal after 10 days of storage at -10°C.

[0242] Contact angle: 5 μL of liquid crystal containing polymerizable compound and self-aligning agent was dropped onto a 2 cm * 3 cm ITO glass substrate and allowed to stand for 5 min. The contact angle between the liquid crystal and the substrate was measured using an SL200KS contact angle meter, and the unit was °.

[0243] Alignment effect: Liquid crystal containing self-aligning agent and polymerizable compound was poured into a test cell with ITO on both sides (no PI layer, cell thickness 3.2um). The test cell filled with liquid crystal was placed in a 120℃ oven and heated for 1 hour. The test cell was then cooled to room temperature and placed in a fixture with upper and lower polarizers attached (the transmission axes of the upper and lower polarizers are 90° orthogonal). The alignment effect of the liquid crystal was observed on a white backlight. If it was completely black, the alignment effect was good. If there was light leakage in the corner area around the test cell, the alignment effect was average. If there was light leakage in the middle area of ​​the test cell, the alignment effect was poor.

[0244] Ra: After polymerizing a liquid crystal composition containing a polymerizable compound under UV light, the liquid crystal molecules are washed away, and then the surface roughness of the polymer layer after polymerization is tested using an atomic force microscope (AFM).

[0245] ΔPTA: After the test box used for the pre-tilt angle PTA test is formed into a pre-tilt angle of 88±0.2° through UV1 and UV2 steps, a 60 Hz SW wave, a 20 V AC voltage, and a 2 V DC voltage are applied to the test box. Under a 40°C environment with backlighting, the pre-tilt angle of the test box is tested after a fixed time period, and ΔPTA is measured. (165h) =PTA (初始) -PTA (165h) ΔPTA (165h) The smaller the value, the better the stability of the pre-tilt angle.

[0246] Residue concentration: After 90 min of UV2 irradiation, the liquid crystal eluted from the liquid crystal test box was detected by high performance liquid chromatography (HPLC). The concentration of polymerizable compounds and self-aligning agents in the liquid crystal was called the residue concentration, and the unit was ppm.

[0247] All components used in the following examples can be synthesized using known methods or obtained commercially. These synthesis techniques are conventional, and the resulting liquid crystal compounds have been tested and found to meet electronic compound standards.

[0248] Liquid crystal compositions were prepared according to the proportions specified in the following examples. The liquid crystal compositions were prepared using conventional methods in the art, such as mixing in proportions by heating, ultrasound, or suspension.

[0249] The structures of the polymerizable compounds used in the following embodiments are shown in Table 2 below.

[0250] Table 2 shows the polymerizable compounds used in the examples.

[0251]

[0252] The structures of the self-aligning agents used in the following embodiments are shown in Table 3 below.

[0253] Table 3 shows the self-aligning agents used in the examples.

[0254]

[0255]

[0256] Host-1, Host-2, Host-3, Host-4, Host-5 and Host-6 were formulated according to the compounds listed in Table 4 and their weight percentages, and were filled between the two substrates of the liquid crystal display for performance testing.

[0257] Table 4. Formulation and performance parameter test results of the main liquid crystal composition.

[0258]

[0259]

[0260] Comparative Examples 1-4 and Examples 1-8

[0261] The liquid crystal compositions of Comparative Examples 1-4 and Examples 1-8 were prepared according to the weight proportions of each component described in Table 5. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layer and passivation layer) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 1-4 and Examples 1-8 are shown in Table 6 below.

[0262] Comparative Examples 5-8 and Examples 9-16

[0263] The liquid crystal compositions of Comparative Examples 5-8 and Examples 9-16 were prepared according to the weight proportions of each component described in Table 7. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layers and passivation layers) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 5-8 and Examples 9-16 are shown in Table 8 below.

[0264] Comparative Examples 9-12 and Examples 17-24

[0265] The liquid crystal compositions of Comparative Examples 9-12 and Examples 17-24 were prepared according to the weight proportions of each component described in Table 9. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layers and passivation layers) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 9-12 and Examples 17-24 are shown in Table 10 below.

[0266] Comparative Examples 13-16 and Examples 25-32

[0267] The liquid crystal compositions of Comparative Examples 13-16 and Examples 25-32 were prepared according to the weight proportions of each component described in Table 11. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layers and passivation layers) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 13-16 and Examples 25-32 are shown in Table 12 below.

[0268] Comparative Examples 17-20 and Examples 33-40

[0269] The liquid crystal compositions of Comparative Examples 17-20 and Examples 33-40 were prepared according to the weight proportions of each component described in Table 13. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layers and passivation layers) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 17-20 and Examples 33-40 are shown in Table 14 below.

[0270] Comparative Examples 21-24 and Examples 41-48

[0271] The liquid crystal compositions of Comparative Examples 21-24 and Examples 41-48 were prepared according to the weight proportions of each component described in Table 15. The resulting liquid crystal compositions were filled into "unaligned" test cells (cell thickness d of 3.5 μm, with ITO coating on both sides (structured ITO in the case of multi-domain switching), without alignment layer and passivation layer) for performance testing. The relevant performance test results of the liquid crystal compositions of Comparative Examples 21-24 and Examples 41-48 are shown in Table 16 below.

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278] As can be seen from the comparison of Examples 1-8 and Comparative Examples 1-4, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With lower polymer residue (95-123 vs 148-160) and lower rotational viscosity, it exhibits lower roughness (11-11.7 vs 13.5-13.9), better low-temperature storage stability (10D OK vs 6D NG), smaller contact angle (15.7-16.8 vs 22.1-22.4), better alignment effect, and better pre-tilt angle stability (0.21-0.24 vs 0.32-0.34).

[0279] As can be seen from the comparison of Examples 9-16 and Comparative Examples 5-8, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With lower polymer residue (90-118 vs 139-159) and lower rotational viscosity, it exhibits lower roughness (10.5-11.2 vs 13.4-13.8), better low-temperature storage stability (10D OK vs 5-6D NG), smaller contact angle (15.5-16.6 vs 21.9-22.2), better alignment effect, and better pre-tilt angle stability (0.23-0.26 vs 0.34-0.36).

[0280] As can be seen from the comparison of Examples 17-24 and Comparative Examples 9-12, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a lower rotational viscosity, it exhibits lower polymer residue (81-106 vs 129-139), lower roughness (10-10.9 vs 13-13.2), better low-temperature storage stability (10D OK vs 6-7DNG), smaller contact angle (15.2-15.9 vs 21.2-21.5), better alignment effect, and better pre-tilt angle stability (0.22-0.24 vs 0.34-0.36).

[0281] As can be seen from the comparison of Examples 25-32 and Comparative Examples 13-16, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With lower polymer residue (79-103 vs 126-138) and lower rotational viscosity, it exhibits lower roughness (9.9-10.8 vs 13-13.3), better low-temperature storage stability (10D OK vs 6-7DNG), smaller contact angle (15.3-15.8 vs 21.2-21.4), better alignment effect, and better pre-tilt angle stability (0.21-0.25 vs 0.34-0.35).

[0282] As can be seen from the comparison between Examples 33-40 and Comparative Examples 17-20, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With lower polymer residue (61-83 vs 109-119) and lower rotational viscosity, it exhibits lower roughness (11-11.9 vs 14-14.2), better low-temperature storage stability (10D OK vs 6-7D NG), smaller contact angle (16.2-16.9 vs 22.2-22.5), better alignment effect, and better pre-tilt angle stability (0.23-0.27 vs 0.34-0.37).

[0283] As can be seen from the comparison of Examples 41-48 and Comparative Examples 21-24, by optimizing the self-aligning agent structure, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With lower polymer residue (76-93 vs 119-129) and lower rotational viscosity, it exhibits lower roughness (9-9.9 vs 12-12.2), better low-temperature storage stability (10D OK vs 6-7D NG), smaller contact angle (14-14.9 vs 20.7-20.9), better alignment effect, and better pre-tilt angle stability (0.19-0.23 vs 0.3-0.32).

[0284] In summary, the liquid crystal composition of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a low viscosity and low rotational viscosity, it exhibits low polymer residue, low roughness, good low-temperature storage stability, low contact angle, good alignment effect, and good pre-tilt angle stability. This results in liquid crystal display devices containing it having appropriate threshold voltage, good contrast, and good response speed. It can effectively improve problems such as "image stickiness," uneven display, and "bright spots" existing in existing PSA-type liquid crystal displays, and has high practical application value.

[0285] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A liquid crystal composition, characterized in that, Include At least one compound of general formula O, said compound of general formula O being selected from the group consisting of: At least one compound of general formula N in, R o2 Indicate -Sp o2 -P o1 A straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms, wherein one or more non-adjacent -CH2- groups in the straight-chain alkyl group containing 1-12 carbon atoms may be independently replaced by -O-. R N1 and R N2 Each can be independently represented as a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms. , or One or more non-adjacent -CH2- of a straight-chain alkyl group containing 1-12 carbon atoms or a branched alkyl group containing 3-12 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-. ring and ring Each represents independently or ,in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein One or more -H can be replaced by -F, -Cl or -CN, and one or more -CH= in a ring can be replaced by -N=; L o1 and L o3 Each can independently represent -F, -Cl, a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms; L o2 express or ; L N1 and L N2 Each can independently represent -H, an alkyl group containing 1-3 carbon atoms, or a halogen; R o1 and R o3 Each represents independently , , , , ,or ,in This indicates the connection sites in the bonded structure; P o1 P o2 and P o3 Each represents independently or ; Sp o1 Sp o2 Sp o3 Sp o4 and Sp o5 Each can be represented independently as -(CH2) p1 -or-(CH2) p1 -O-, where p1 represents an integer from 1 to 10; Z o1 and Z o2 Each represents a single key independently; Z N1 and Z N2 Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)4-, -CF2O-, or -OCF2-; p o1 Represents 0, p o2 p represents 1 or 2. o3 and p o4 Each can be independently represented as 0, 1, or 2, where when p o2 When L represents 2, o2 They can be the same or different; where p o3 When 2 is represented, They can be the same or different; where p o4 When L represents 2, o3 They can be the same or different; n o1 Represents integers from 1 to 10; n N1 n represents 0, 1, 2, or 3. N2 Represents 0 or 1, and 0 ≤ n N1 +n N2 ≤3, when n N1 When =2 or 3, the ring They can be the same or different, Z N1 They can be the same or different; Z o11 Indicates a single key; L o11 and L o31 Each can independently represent -F, -Cl, a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms; L o21 express or ;and p o11 It represents 0.

2. The liquid crystal composition according to claim 1, characterized in that, The compounds of general formula O-1 are selected from the group consisting of the following compounds: The compounds of general formula O-4 are selected from the group consisting of the following compounds: The compounds of general formula O-6 are selected from the group consisting of the following compounds: The compounds of general formula O-10 are selected from the group consisting of the following compounds: in, L o22 L o23 and L o24 Each represents independently or .

3. The liquid crystal composition according to claim 1, characterized in that, The compounds of general formula N are selected from the group consisting of the following compounds: in, R N11 Indicates a straight-chain alkyl group containing 1-5 carbon atoms. , or One or more non-adjacent -CH2- in a straight-chain alkyl group containing 1-5 carbon atoms may be independently replaced by -O-, -CO-, -CO-O- or -O-CO-; R N12 It represents -H, straight-chain alkyl groups containing 1-5 carbon atoms, , or One or more non-adjacent -CH2- in a straight-chain alkyl group containing 1-5 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-; n N3 It represents 0, 1, 2, or 3; L N3 and L N4 Independently representing -H, alkyl groups containing 1-3 carbon atoms, or halogens; and ring express or ,in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein One or more -H can be replaced by -F, -Cl or -CN, and one or more -CH= in a ring can be replaced by -N=.

4. The liquid crystal composition according to claim 3, characterized in that, The compounds of general formula N are selected from the group consisting of the following compounds: N-24-2。 5. The liquid crystal composition according to claim 1, characterized in that, The liquid crystal composition comprises at least one compound of general formula M: in, R M1 and R M2 Each can be independently represented as a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms. , or One or more of the straight-chain alkyl groups containing 1-12 carbon atoms or the branched alkyl groups containing 3-12 carbon atoms, or two or more of the -CH2- groups, can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-. ring ,ring and ring Each represents independently or ,in One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds. At most one -H in the halogen can be replaced by a halogen; Z M1 and Z M2 Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2-, or -(CH2)4-; and n M Represents 0, 1, or 2, where when n M When =2, the ring They can be the same or different, Z M2 They can be the same or different.

6. The liquid crystal composition according to claim 5, characterized in that, The compounds of general formula M are selected from the group consisting of the following compounds: M-29。 7. The liquid crystal composition according to claim 5, characterized in that, The liquid crystal composition comprises at least one polymerizable compound of general formula RM: in, R1 represents -H, halogen, -CN, -Sp2-P2, straight-chain alkyl with 1-12 carbon atoms, or branched alkyl with 3-12 carbon atoms. , or Among them, straight-chain alkyl groups containing 1-12 carbon atoms, branched alkyl groups containing 3-12 carbon atoms, , or One or more non-adjacent -CH2- can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H can be independently replaced by -F or -Cl; ring and ring Each represents independently , or ,in and One or more -CH2- bonds can be replaced by -O- bonds, and single bonds in one or at most two rings can be replaced by double bonds, wherein and One or more -H atoms may be independently replaced by -F, -Cl, -CN, -Sp3-P3, a halogenated or unhalogenated straight-chain alkyl group containing 1-12 carbon atoms, or a halogenated or unhalogenated straight-chain alkoxy group containing 1-11 carbon atoms. , or Replacement, and in one or more rings -CH= can be replaced by -N=; ring express or ,in or One or more -H atoms may be independently replaced by -F, -Cl, -CN, -Sp3-P3, a halogenated or unhalogenated straight-chain alkyl group containing 1-12 carbon atoms, or a halogenated or unhalogenated straight-chain alkoxy group containing 1-11 carbon atoms. , or Replacement, and in one or more rings -CH= can be replaced by -N=; P1, P2, and P3 each independently represent polymerizable groups; X0 represents -O-, -S-, or -CO-; Sp1, Sp2, and Sp3 each independently represent a spacer group or a single bond; Z1 and Z2 independently represent -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, and -(CH2). d -, -CF2CH2-, -CH2CF2-, -(CF2) d -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2CH2-CO-O-, -O-CO-CH2CH2-, -CHR 1 -、-CR 1 R 2 - or a single bond, where R 1 and R 2 Each of these terms independently represents a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms, and d represents an integer from 1 to 4; and a represents 0, 1, or 2, b represents 0 or 1, where when a represents 2, the ring... They can be the same or different; Z1 can be the same or different.

8. The liquid crystal composition according to claim 7, characterized in that, The polymerizable compounds of the general formula RM are selected from the group consisting of the following compounds: in, X1-X 10 and X 12 Each can independently represent -F, -Cl, -Sp3-P3, or straight-chain alkyl or alkoxy groups containing 1-5 carbon atoms. , or .

9. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1-8.

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