A self-alignment agent and liquid crystal composition thereof

Abstract

The present application provides a self-alignment agent and a liquid crystal composition thereof. The liquid crystal composition comprising the self-alignment agent of the general formula O of the present application has a smaller contact angle (15.8-17), better low-temperature storage stability (10D OK), and better alignment effect under the condition of maintaining a proper clearing point, proper optical anisotropy, proper absolute value of dielectric anisotropy, larger K value (K 11 and K 33 ) and smaller rotational viscosity.

Description

Technical Field

[0001] This invention relates to the field of liquid crystals, and more specifically to a self-aligning agent and a liquid crystal composition thereof, and a liquid crystal display device comprising the liquid crystal composition. 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 nematic liquid crystal composition with suitable properties. By improving the properties of the liquid crystal composition, AM elements with good properties 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 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 shorter response time is preferred.

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

[0005] serial number Characteristics of liquid crystal compositions Characteristics of AM components 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, generally, low-viscosity liquid crystal materials 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 the polymer and self-aligning agent 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 a high concentration 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 the polymerizable compounds and self-aligning agents can lead to the precipitation of these compounds during liquid crystal storage, causing liquid crystal performance failure. Furthermore, the poor rigidity of the polymer network formed after the polymerization of polymerizable compounds 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 altering 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] Objective of the Invention: The objective of this invention is to provide a self-aligning agent of general formula O, which, when applied to a liquid crystal composition, enables the liquid crystal composition containing it to maintain appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a small contact angle (15.5-18.7°) and a small rotational viscosity, it exhibits good low-temperature storage stability (10D OK) and good alignment effect.

[0017] Another object of the present invention is to provide a liquid crystal composition comprising the above-mentioned self-aligning agent.

[0018] Furthermore, an object of the present invention is to provide a liquid crystal display device comprising the above-described liquid crystal composition.

[0019] Technical solution: To achieve the above-mentioned objectives, this invention provides a self-aligning agent of general formula O.

[0020]

[0021] 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 -Cl;

[0022] 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;

[0023] L o1 and Lo3 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.

[0024] L o2 Indicate -Sp o3 -P o2 or

[0025] 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;

[0026] 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;

[0027] n o5 Represents 0 or 1;

[0028] M S1 express in, Representing M S1 The connection site with -CH2- in the six-membered ring;

[0029] I S1 and JS1 Each can be independently represented as -CH2-, -O-, or -S-;

[0030] N S1 This indicates =O or =S;

[0031] V K1 V K2 and V K3 Each can be represented independently as -CH= or -N=;

[0032] 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.

[0033] P o1 P o2 and P o3 Each independently represents a polymerizable group;

[0034] 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;

[0035] Sp o6 express Where -- indicates that it is related to Sp o7 or Sp o8 Connection sites;

[0036] 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.

[0037] 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 o5 -R o3 They can be the same or different; where p o4 When L represents 2, o3 They can be the same or different;

[0038] n o1 Represents integers from 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9); and

[0039] 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.

[0040] In this invention, through numerous experiments, it was discovered that when the left-side end group of the self-aligning agent is a compound of the general formula O of this application, it contains... When the terminal group is alkyl or alkoxy, it is used as a self-aligning agent in liquid crystal compositions, resulting in smaller contact angles, better low-temperature storage stability, and better alignment effects compared to self-aligning agents with alkyl or alkoxy terminal groups.

[0041] In some embodiments of the present invention, the self-aligning agent of general formula O is selected from the group consisting of the following compounds:

[0042]

[0043]

[0044]

[0045] as well as

[0046]

[0047] in,

[0048] 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.

[0049] 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 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 This 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; and

[0050] L o21 Indicate -Sp o3 -P o2 or and

[0051] p o11 It represents 0, 1, or 2.

[0052] In some embodiments of the present invention, the self-aligning agent of general formula O-1 is selected from the group consisting of the following compounds:

[0053]

[0054] in,

[0055] L o22 L o23 and L o24 Each is represented independently -Sp o3 -P o2 or

[0056] L o11 L o12 and L o13 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.

[0057] In some embodiments of the present invention, the self-aligning agent of general formula O-4 is selected from the group consisting of the following compounds:

[0058]

[0059]

[0060] In some embodiments of the present invention, the self-aligning agent of general formula O-6 is selected from the group consisting of the following compounds:

[0061]

[0062]

[0063] In some embodiments of the present invention, the self-aligning agent of general formula O-10 is selected from the group consisting of the following compounds: as well as

[0064] In some embodiments of the present invention, the self-aligning agent of general formula O-1-1 is selected from the group consisting of the following compounds: as well as

[0065] In some embodiments of the present invention, the self-aligning agent of general formula O-4-1 is selected from the group consisting of the following compounds: as well as

[0066] In some embodiments of the present invention, the self-aligning agent of general formula O-4-7 is selected from the group consisting of the following compounds: as well as

[0067] In some embodiments of the present invention, the self-aligning agent of general formula O-6-1 is selected from the group consisting of the following compounds:

[0068] as well as

[0069] In some embodiments of the present invention, the self-aligning agent of general formula O-6-7 is selected from the group consisting of the following compounds:

[0070] as well as

[0071] In some embodiments of the present invention, the self-aligning agent of general formula O-10-1 is selected from the group consisting of the following compounds:

[0072]

[0073] as well as

[0074]

[0075] 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.

[0076] 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.

[0077]

[0078] In some embodiments of the present invention, the polymerizable group P o1 P o2 and P o3 Each represents independently

[0079] Or -SH; preferably, polymerizable group P o1 Po2 and P o3 Each represents independently Or -SH; more preferably, polymerizable group P o1 P o2 and P o3 Each represents independently

[0080] In some embodiments of the present invention, L o2 express

[0081] In some embodiments of the present invention, Z o2 Indicates a single key.

[0082] 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 represented independently 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 key, 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.

[0083] 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-.

[0084] In some embodiments of the present invention, R o1 and R o3 Each group is independently selected from the following groups:

[0085]

[0086]

[0087] as well as

[0088]

[0089] in,

[0090] * indicates a connection site in the bonded structure.

[0091] In some embodiments of the present invention, in order to obtain a suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, a large K value, a small rotational viscosity, a small contact angle, good low-temperature storage stability, and good alignment effect, R o1 and R o3 Each group is independently selected from the following groups:

[0092]

[0093] as well as In some embodiments of the present invention, R o1 and R o3 Each is preferably selected independently as follows:

[0094] In some embodiments of the present invention, the compounds of general formula O-1-1-4 are selected from the group consisting of:

[0095]

[0096] as well as

[0097]

[0098] In some embodiments of the present invention, the compounds of general formula O-4-1-4 are selected from the group consisting of:

[0099]

[0100]

[0101] In some embodiments of the present invention, the compounds of general formula O-4-7-4 are selected from the group consisting of:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] In some embodiments of the present invention, the compounds of general formula O-6-1-4 are selected from the group consisting of:

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] In some embodiments of the present invention, the compounds of general formula O-6-7-4 are selected from the group consisting of:

[0116]

[0117]

[0118] Another aspect of the present invention provides a liquid crystal composition comprising a self-aligning agent of general formula O.

[0119] In some embodiments of the present invention, it is preferable to adjust the content of the compound of general formula O so that the liquid crystal composition of the present invention has a smaller contact angle, better low-temperature storage stability and better alignment effect.

[0120] 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.

[0121] 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 a smaller contact angle, better alignment effect, and better low-temperature storage performance.

[0122] In some embodiments of the present invention, the liquid crystal composition comprises at least one compound of general formula M:

[0123]

[0124] in,

[0125] 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-.

[0126] 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;

[0127] Z M1 and Z M2Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -C≡C-, -CH=CH-, -CH2CH2-, or -(CH2)4-; and

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] In some embodiments of the present invention, the compounds of general formula M are selected from the group consisting of the following compounds:

[0136]

[0137]

[0138] as well as

[0139]

[0140] In some embodiments of the present invention, in order to obtain a suitable cleaning point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, and a large K value (K 11 and K 33 The compounds of general formula M are selected from the group consisting of compounds of general formula M-1, general formula M-4, general formula M-11 and general formula M-13, which have lower rotational viscosity, smaller contact angle, better low-temperature storage stability and better alignment effect.

[0141] In some embodiments of the present invention, the compounds of general formula M-11 are selected from the group consisting of the following compounds:

[0142]

[0143] In some embodiments of the present invention, the compounds of general formula M-13 are selected from the group consisting of the following compounds:

[0144]

[0145] In some embodiments of the present invention, the content of the compound of general formula M must be appropriately adjusted according to the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, drip marks, burn-in, and dielectric anisotropy.

[0146] In some embodiments of the present invention, it is preferable to adjust the content of the compound of general formula M so that the liquid crystal composition of the present invention has a small contact angle, good low-temperature storage stability and good alignment effect while maintaining an appropriate clearing point, appropriate optical anisotropy, a large absolute value of dielectric anisotropy, a large K value and appropriate rotational viscosity.

[0147] In some embodiments of the invention, the compound of general formula M 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.

[0148] In some embodiments of the present invention, the liquid crystal composition further comprises at least one compound of general formula N:

[0149]

[0150] in,

[0151] R N1 and R N2 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 of the -CH2- groups, can be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-.

[0152] 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 -CH= in one or more rings can be replaced by -N=;

[0153] Z N1 and Z N2Each can independently represent a single bond, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)4-, -CF2O-, or -OCF2-;

[0154] L N1 and L N2 Each independently represents -H, a halogen, or an alkyl group containing 1-3 (e.g., 1, 2, or 3) carbon atoms; and

[0155] 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.

[0156] In some embodiments of the present invention, L N1 and L N2 Both represent -H.

[0157] In some embodiments of the present invention, the compounds of general formula N are selected from the group consisting of the following compounds:

[0158]

[0159]

[0160]

[0161] 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 3-10 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.

[0162] In some embodiments of the present invention, in order to achieve a suitable cleaning point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, and a large K value (K 11 and K 33The compounds of general formula N are selected from the group consisting of compounds of general formula N-2, general formula N-3, general formula N-7, general formula N-9, general formula N-12, general formula N-15, general formula N-16, general formula N-19, and general formula N-21, which have lower rotational viscosity, smaller contact angle, better low-temperature storage stability, and better alignment effect.

[0163] In some embodiments of the present invention, it is preferable to adjust the content of compounds of general formula N so that the liquid crystal composition of the present invention has a small contact angle, good low-temperature storage stability and good alignment effect while maintaining an appropriate clearing point, appropriate optical anisotropy, a large absolute value of dielectric anisotropy, a large K value and appropriate rotational viscosity.

[0164] 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.

[0165] In some embodiments of the present invention, the liquid crystal composition of the present invention comprises at least one compound of general formula B:

[0166]

[0167] in,

[0168] R B1 and R B2 Each of the following independently represents a halogen: a halogenated or unhalogenated straight-chain alkyl group containing 1-12 (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms; or a halogenated or unhalogenated branched alkyl group containing 3-12 (e.g., 4, 5, 6, 7, 8, 9, 10, or 11) carbon atoms. Among them are halogenated or non-halogenated straight-chain alkyl groups containing 1-12 carbon atoms, and halogenated or non-halogenated branched alkyl groups containing 3-12 carbon atoms. One or more non-adjacent -CH2- can be independently replaced by -CH=CH-, -CH=CF-, -C≡C-, -O-, -CO-, -CO-O-, or -O-CO-;

[0169] 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 independently replaced by -CN, -F or -Cl, and -CH= in one or more rings can be replaced by -N=;

[0170] X B Indicates -O-, -S-, or -CO-;

[0171] L B1 and L B2 Each can be independently represented as -H, -F, -Cl, -CF3, or -OCF3;

[0172] Z B1 and Z B2 Each can be independently represented as -CO-O-, -O-CO-, -OCH2-, -CH=CH-, -C≡C-, -CH2CH2-, -CF2CF2-, -(CH2)n B3 -、-(CH2)n B3 O-、-(CH2)n B3 S-, -CF2O-, or -OCF2-, where n B3 Represents integers from 0 to 5 (e.g., 1, 2, 3, or 4); and

[0173] n B1 and n B2 Each can be independently represented as 0, 1, or 2, where when n B1 When 2 is represented, the ring They can be the same or different, where when n B2 When 2 is represented, the ring They can be the same or different.

[0174] In some embodiments of the present invention, the compounds of general formula B are selected from the group consisting of the following compounds:

[0175] as well as

[0176]

[0177] Among them, R B1 'Indicates a straight-chain alkyl or alkoxy group containing 1-8 carbon atoms, or a straight-chain alkenyl or alkenyloxy group containing 2-8 carbon atoms; and

[0178] X B1 It represents -O- or -CH2-.

[0179] In some embodiments of the present invention, the compound of general formula B-1 is selected from the group consisting of the following compounds:

[0180] as well as

[0181]

[0182] Among them, R B2 ' indicates a straight-chain alkyl group containing 1-5 carbon atoms; n B4 Represents an integer from 1 to 5 (e.g., 1, 2, 3, or 4); n B5 Represents an integer from 0 to 5 (e.g., 1, 2, 3, or 4).

[0183] In some embodiments of the present invention, it is preferable to adjust the content of the compound of general formula B such that the liquid crystal composition containing it has a suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 It has lower rotational viscosity, smaller contact angle, better low-temperature storage stability, and better alignment effect.

[0184] In some embodiments of the invention, the compound of general formula B accounts for 0.1% to 30% 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%, or a range between any two of these values.

[0185] 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:

[0186]

[0187] in,

[0188] 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 -Cl;

[0189] 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. Replacement, and in one or more rings -CH= can be replaced by -N=;

[0190] 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. Replacement, and in one or more rings -CH= can be replaced by -N=;

[0191] P1, P2, and P3 each independently represent polymerizable groups;

[0192] X0 represents -O-, -S-, or -CO-;

[0193] Sp1, Sp2, and Sp3 each independently represent a spacer group or a single bond;

[0194] 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

[0195] 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.

[0196] In some embodiments of the present invention, the polymerizable compound of general formula RM is selected from the group consisting of the following compounds:

[0197]

[0198]

[0199]

[0200] as well as

[0201]

[0202] in,

[0203] 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.

[0204] In some embodiments of the present invention, X1-X 10 and X 12 Each can be independently represented as -F, -Cl, -Sp3-P3, -CH3, or -OCH3.

[0205] In some embodiments of the present invention, Sp1 and Sp2 both represent single bonds.

[0206] In some embodiments of the present invention, in order to obtain a suitable clearing point, suitable optical anisotropy, suitable absolute value of dielectric anisotropy, a large K value, a small rotational viscosity, a small contact angle, good low-temperature storage stability, and good alignment effect, 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, and compounds of general formula RM-20.

[0207] 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.

[0208] In some embodiments of the present invention, polymerizable groups P1, P2, and P3 are each independently represented.

[0209] 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.

[0210] 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: as well as

[0211]

[0212] 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:

[0213]

[0214] as well as

[0215]

[0216] In some embodiments of the present invention, the polymerizable compound of general formula RM-19 is selected from compounds consisting of the following... as well as

[0217]

[0218] 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:

[0219]

[0220] as well as

[0221]

[0222] 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 R 00 -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 of these 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., 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. A particularly preferred spacer group is -(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 0R 00 -(CH2) p1 -

[0223] In some embodiments of the present invention, it is preferable to adjust the content of the polymerizable compound of general formula RM so that the liquid crystal composition containing it has a smaller contact angle, better low-temperature storage stability and better alignment effect.

[0224] 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.

[0225] As used in this article, -CO- and -C(O)- both represent carbonyl groups.

[0226] 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.

[0227] 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.

[0228] In some embodiments of the present invention, the liquid crystal composition of the present invention further comprises at least one compound selected from the group consisting of compounds of general formula A-1 and compounds of general formula A-2:

[0229]

[0230] in,

[0231] R A1 and RA2 Each of these terms independently represents 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. 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 in a straight-chain alkyl group containing 1-12 carbon atoms or a branched alkyl group containing 3-12 carbon atoms can be independently replaced by -F or -Cl;

[0232] ring 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, wherein One or more -H can be replaced by -F, -Cl or -CN, and -CH= in one or more rings can be replaced by -N=;

[0233] Z A11 It represents a single bond, -CH2CH2-, -CF2CF2-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CH2O-, or -OCH2-;

[0234] Z A21 and Z A22 Each can independently represent a single bond, -CH2CH2-, -CF2CF2-, -CO-O-, -O-CO-, -O-CO-O-, -CH=CH-, -CF=CF-, -CH2O-, or -OCH2-;

[0235] L A11 L A12 L A13 L A21 and L A22 Each can independently represent -H, halogen, or alkyl group containing 1-3 carbon atoms;

[0236] X A1 and X A2Each can independently represent a halogen, a haloalkyl or haloalkoxy group containing 1-5 carbon atoms, or a haloalkenyl or haloalkenoxy group containing 2-5 carbon atoms.

[0237] n A11 Represents 0, 1, 2, or 3, where when n A11 When = 2 or 3, the ring They can be the same or different, Z A11 They can be the same or different;

[0238] n A12 Represents 1 or 2, where when n A12 When = 2, ring They can be the same or different; and

[0239] n A2 Represents 0, 1, 2, or 3, where when n A2 When = 2 or 3, the ring They can be the same or different, Z A21 They can be the same or different.

[0240] In some embodiments of the invention, the compound selected from the group consisting of compounds of general formula A-1 and compounds of general formula A-2 accounts for 0.1% to 60% (inclusive of any value within this range) of the weight percentage of the liquid crystal composition, 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.

[0241] In some embodiments of the present invention, the compounds of general formula A-1 are selected from the group consisting of the following compounds:

[0242]

[0243]

[0244] as well as

[0245]

[0246] in,

[0247] R A1 Indicates a straight-chain alkyl group containing 1-8 carbon atoms. One or more non-adjacent -CH2- groups of straight-chain alkyl groups containing 1-8 carbon atoms may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H groups present in these groups may be independently replaced by -F or -Cl.

[0248] R v and R w Each can be represented independently as -CH2- or -O-;

[0249] L A11 L A12 L A11 '、L A12 '、L A14 L A15 L A16 L A17 and L A18 Each can be represented independently as -H or -F;

[0250] L A13 and L A13 Each can be represented independently as -H or -CH3;

[0251] X A1 It indicates -F, -CF3, or -OCF3; and

[0252] v and w each represent 0 or 1 independently.

[0253] In some embodiments of the invention, the compound of general formula A-1 accounts for 0.1% to 50% 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%, or a range between any two of these values.

[0254] In some embodiments of the present invention, the compounds of general formula A-2 are selected from the group consisting of the following compounds:

[0255]

[0256]

[0257] as well as

[0258]

[0259] in,

[0260] R A2 It indicates a straight-chain alkyl group containing 1-8 carbon atoms, wherein one or more non-adjacent -CH2- groups may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -CO-O- or -O-CO-, and one or more -H groups present in these groups may be independently replaced by -F or -Cl;

[0261] L A21 L A22 L A23 L A24 and L A25 Each can be represented independently as -H or -F; and

[0262] X A2 It represents -F, -CF3, -OCF3, or -CH2CH2CH=CF2.

[0263] In some embodiments of the invention, the compound of general formula A-2 accounts for 0.1% to 50% (inclusive of any value within this range) of the weight percentage of the liquid crystal composition, 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%, or a range between any two of these values.

[0264] In some embodiments of the present invention, the liquid crystal composition further comprises at least one additive.

[0265] 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.

[0266] The following shows possible dopants that are preferably added to the liquid crystal composition according to the invention:

[0267]

[0268] as well as

[0269]

[0270] 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.

[0271] 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:

[0272]

[0273]

[0274]

[0275]

[0276] Where n represents a positive integer from 1 to 12.

[0277] Preferably, the antioxidant is selected from the compounds listed below:

[0278]

[0279] 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.

[0280] 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.

[0281] In another aspect, the present invention also provides a liquid crystal display device comprising the above-described liquid crystal composition.

[0282] 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.

[0283] Beneficial effects: Compared with the prior art, liquid crystal compositions containing the self-aligning agent of the general formula O of the present invention maintain appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a larger K value (K 11 and K 33 With a small contact angle (15.5-18.7), good low-temperature storage stability (10DOK), and good alignment effect, it exhibits the following properties: ) and low rotational viscosity. Detailed Implementation

[0284] 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.

[0285] Unless otherwise specified, all proportions in this invention are weight ratios, and all temperatures are in degrees Celsius.

[0286] For ease of explanation, the group structures of each compound in the following embodiments are represented by the codes listed in Table 1:

[0287] Table 1. Group structure codes of compounds

[0288]

[0289]

[0290] Take the following compound with the following structural formula as an example:

[0291]

[0292] If the structural formula is represented by the codes listed in Table 1, it can be expressed as: nCCGF, where n in the code represents the number of C atoms in the alkyl group at the left end. For example, if n is "3", it means that the alkyl group is -C3H7. In the code, C represents 1,4-cyclohexylene, G represents 2-fluoro-1,4-phenyleneene, and F represents fluorine substituent.

[0293] The abbreviated codes for the test items in the following examples are as follows:

[0294] Cp (Clearing point, nematic-isotropic phase transition temperature, °C)

[0295] Δn Optical anisotropy (589nm, 20℃)

[0296] Δε dielectric anisotropy (1 kHz, 20 °C)

[0297] K 11 Elastic constant of the stretching curve (20℃)

[0298] K 33 Bending elastic constant (20℃)

[0299] γ1 Rotational viscosity (mPa·s, 20℃)

[0300] Storage time at -20℃ (days)

[0301] in,

[0302] Cp: ​​Obtained by testing with a melting point apparatus.

[0303] Δn: Measured using an Abbe refractometer under a sodium lamp (589nm) light source at 20℃.

[0304] Δε: Δε=ε ‖ -ε ⊥ , where ε ‖ ε is the dielectric constant parallel to the molecular axis. ⊥ The dielectric constant is perpendicular to the molecular axis; test conditions: 20℃, 1KHz, VA type test box with a thickness of 6μm.

[0305] γ1: Measured using the LCM-2 type liquid crystal property evaluation system; test conditions: 20℃, 160-260V, test cell thickness 20μm.

[0306] 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℃.

[0307] t -20℃ 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. 7D NG indicates that crystal precipitation was observed after 7 days of storage at -20°C, and 10D OK indicates that no crystal precipitation was observed after 10 days of storage at -20°C.

[0308] 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, left to stand for 5 min, and the contact angle between the liquid crystal and the substrate was measured using an SL200KS contact angle meter.

[0309] 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.

[0310] The compounds of the self-aligning agent of general formula O of this invention can be prepared by conventional organic synthesis methods, wherein the methods for introducing target terminal groups, ring structures and linking groups into the starting materials are described in the following literature: Organic Synthesis (John Wiley & Sons Inc.), Organic Reactions (John Wiley & Sons Inc.), and Comprehensive Organic Synthesis (Pergamon Press).

[0311] The synthesis method of the linking group in the compound of the self-aligning agent of general formula O can be referred to the following procedure, wherein MSG 1 or MSG 2 It is a monovalent organic group having at least one ring, and the multiple MSGs used in the following process 1 (or MSG) 2 They can be the same or different.

[0312] (1) Synthesis of single bonds

[0313]

[0314] The single-bonded compound IA is prepared by reacting arylboronic acid 1 with compound 2 synthesized by a known method in an aqueous sodium carbonate solution in the presence of a catalyst (such as tetrakis(triphenylphosphine)palladium (Pd(PPh3)4)). Alternatively, compound IA can be prepared by reacting compound 3 synthesized by a known method with n-butyllithium (n-BuLi), then with zinc chloride, and finally with compound 2 in the presence of a catalyst (such as dichlorobis(triphenylphosphine)palladium (PdCl2(PPh3)2)).

[0315] (2) Synthesis of -CO-O- and -O-CO-

[0316]

[0317] Compound 3 is reacted with n-butyllithium, followed by reaction with carbon dioxide, to obtain carboxylic acid 4. Compound 4 is then dehydrated with compound 5, synthesized by a known method, in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP) to synthesize compound IB having the -CO-O- group. Compounds having the -O-CO- group can also be synthesized by this method.

[0318] (3) Synthesis of -CF2O- and -OCF2-

[0319]

[0320] Referring to M. Kuroboshi et al., Chemical Letters, 1992, 827, compound 6 was obtained by treating compound IB with a sulfiding agent (such as Lawson's reagent), and then compound IC with -CF2O- was synthesized by fluorinating compound 6 with hydrogen fluoride-pyridine (HF-Py) and N-bromosuccinimide (NBS).

[0321] (4) Synthesis of -CH=CH-

[0322]

[0323] Compound 3 is reacted with n-butyllithium, followed by reaction with formamide (such as N,N-dimethylformamide (DMF)) to obtain compound 7. Potassium tert-butoxide (t-BuOK) is then reacted with a phosphorus endonium generated from the reaction of phosphonium salt 8 synthesized by a known method, and compound 7 to obtain compound ID. Due to the reaction conditions, the above method yields the cis isomer. It should be understood that the cis isomer can be converted to the trans isomer using known methods as needed.

[0324] (5) Synthesis of -CH2CH2-

[0325]

[0326] Compound IE can be prepared by hydrogenating compound ID using a catalyst such as palladium on carbon (Pd / C).

[0327] (6) Synthesis of -CH2O- or -OCH2-

[0328]

[0329] Compound 7 is reduced using sodium borohydride (NaBH4) to obtain compound 9. Compound 9 is then halogenated with hydrobromic acid to obtain compound 10, or the hydroxyl group of compound 9 is protected with p-toluenesulfonic acid (TsOH) to obtain compound 11. Compound 10 or 11 is then reacted with compound 5 in the presence of potassium carbonate to obtain compound IF. Compounds with the -OCH2- group can also be synthesized using these methods.

[0330] (7) Synthesis of -CH=CF2

[0331]

[0332] Compound IG was prepared by removing hydrofluoric acid from the terminal chain of compound 11 using a tetrahydrofuran solution of lithium diisopropylamino (LDA).

[0333] Regarding the cyclic structures of 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, and 2,3,5,6-tetrafluoro-1,4-phenylene, starting materials are commercially available or their synthetic methods are well known in the art.

[0334] Synthesis and Preparation Example 1

[0335] The preparation method of compound O-6-1-4-1 is as follows:

[0336]

[0337] Step 1. Synthesis of compounds of formula 1-c

[0338]

[0339] In a reaction flask, 47.1 g of compound 1-a ([4-(4-methoxybutoxy)phenyl]boronic acid), 58.2 g of compound 1-b (4-(4-bromo-2-ethylphenyl)phenol), and 33.2 g of potassium carbonate were dissolved in toluene. Under nitrogen protection, 1 g of Pd(dppf)₂C was added. l2 The mixture was heated to reflux under nitrogen protection for 4 hours, and the starting material disappeared upon TLC. Extraction with toluene, followed by chromatography and solvent drying. Recrystallization was performed three times with a mixed solvent of 800 mL toluene and ethanol (toluene to ethanol volume ratio 3:1) to give 59.5 g of a white solid of compound 1-c (4-{2-ethyl-4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol), with a yield of 74%.

[0340] Step 2. Synthesis of compounds of formula 1-d

[0341]

[0342] 59.5 g of the compound of formula 1-c and 3.0 g of diisopropylamine were added to a reaction flask and dissolved completely in tetrahydrofuran. Under nitrogen atmosphere and controlled temperature of 0 to -5 °C, 49.2 g of N-bromosuccinimide (NBS) was added in portions. The mixture was allowed to heat naturally for 6 h. The reaction solution was then neutralized to neutral by adding 0.5 L of sodium sulfite aqueous solution. The mixture was separated into liquid and liquid phases. The aqueous phase was extracted twice with 300 mL of dichloromethane. The organic phases were combined and washed twice with 0.5 L of water. The mixture was dried and passed through a 30 g silica gel column. The solution was eluted with 500 mL of dichloromethane and recrystallized from 150 mL of a mixed solvent of n-heptane and ethanol (n-heptane to ethanol volume ratio of 5:1) to give 73.2 g of a yellow viscous oily compound of formula 1-d (2,6-dibromo-4-{2-ethyl-4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol), with a yield of 87%.

[0343] Step 3. Synthesis of compounds of formula 1-e

[0344]

[0345] Under nitrogen protection, 73.2 g of compound of formula 1-d and 47.8 g of 4-[(tert-butyldimethyl)oxy]-3-[(tert-butyldimethyl)oxy]methyl]butane-1-ol were added to a reaction flask and dissolved thoroughly in diethyl azodicarbonate (DEAD). Under nitrogen atmosphere, 0.3 g of triphenylphosphine was added, and the reaction was carried out at room temperature for 2 h. After purification, the mixture was eluted with 2 L of n-heptane and recrystallized from 500 mL of a mixed solvent of toluene and n-heptane (toluene to n-heptane volume ratio 1:3) to give 115.1 g of a white solid compound of formula 1-e (6-[2-(2,6-dibromo-4-{2-ethyl-4-[4-(4-methoxybutoxy)phenyl]phenyl}phenoxy)ethyl]-2,2,3,3,9,9,10,10-octamethyl-4,8-dioxa-3,9-disiloxane), yield 97%.

[0346] Step 4. Synthesis of compounds of formula 1-f

[0347]

[0348] Under nitrogen protection, 13.8 g of the (3-hydroxypropyl)boronic acid compound, 115.1 g of the compound of formula 1-e, and 34.6 g of anhydrous potassium carbonate were added to a reaction flask and dissolved thoroughly with N,N-dimethylformamide. Under nitrogen protection, 0.3 g of tetrakis(triphenylphosphine)palladium was added, and the reaction was carried out at 70 °C for 3 h. After purification, the mixture was eluted with 500 mL of n-hexane and recrystallized from 100 mL of ethanol to give 86.4 g of a white solid compound of formula 1-f (3-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butoxy}-5-{2-ethyl-4-[4-(4-methoxybutoxy)phenyl]phenyl}-3-(3-hydroxypropyl)phenyl)prop-1-ol), in 79% yield.

[0349] Step 5. Synthesis of compounds of formula 1-g

[0350]

[0351] In a reaction flask, 35 g of dicyclohexylcarbodiimide (DCC) was completely dissolved in 100 mL of dichloromethane and set aside. At room temperature, 86.4 g of the compound of formula 1-f and 9.1 g of 2-methylprop-2-enoic acid were added to the reaction flask and completely dissolved in dichloromethane. While stirring, 1.5 g of 4-dimethylaminopyridine (DMAP) was added. Under a nitrogen atmosphere and with the temperature controlled at 0–10 °C, 100 mL of the dichloromethane solution of dicyclohexylcarbodiimide prepared above was added dropwise to the reaction system, and the reaction was allowed to proceed overnight. Purification was performed, followed by elution with 1 L of n-hexane and recrystallization from 150 mL of acetonitrile to give 94.0 g of a white solid of formula 1-g (3-(2-{4-[(tert-butyldimethylsilyl)oxy]-3-{[(tert-butyldimethylsilyl)oxy]methyl}butoxy}-5-{2-ethyl-4-[4-(4-methoxybutoxy)phenyl]phenyl}-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl)2-methylprop-2-enoic acid propyl ester, in 93% yield.

[0352] Step 6. Synthesis of compounds of formula O-6-1-4-1

[0353]

[0354] Under nitrogen protection, 94.0 g of compound of formula 1-g and 7.3 g of ammonium carbonate were added to a reaction flask and dissolved completely in 0.5 L of a mixed solvent consisting of acetic acid, deionized water, and tetrahydrofuran (volume ratio of acetic acid, deionized water, and tetrahydrofuran 10:5:2). The reaction was carried out at 70–80 °C for 2 h. Extraction was performed with 0.5 L of toluene. After purification, elution with 2 L of n-hexane, and recrystallization with 0.2 L of ethanol, 62.9 g of a white solid compound of formula O-6-1-4-1 (propyl 3-(5-{2-ethyl-4-[4-(5-methoxypentyl)phenyl]phenyl}-2-[4-hydroxy-3-(hydroxymethyl)butoxy]-3-{3-[(2-methylprop-2-enoyl)oxy]propyl}phenyl)2-methylprop-2-enoate, yield: 85.7%.

[0355] The compound of formula O-6-1-4-1 has an m / z (mass-to-charge ratio) of 730.1 (M+) and elemental analysis: C, 72.3; H, 8.00; O, 19.70.

[0356] H-NMR (300MHz, CDCl3): 0.85-2.15 (m, 20H), 2.25-3.05 (m, 6H), 3.30 (s, 3H), 3.35-3.73(m, 8H), 3.95-4.78(m, 8H), 6.25-6.89(m, 4H), 6.96-7.95(m, 9H).

[0357] By adjusting the starting materials of Formula 1-a and Formula 1-b and using the same synthesis method as in Synthesis Preparation Example 1, the compounds shown in the table below can be synthesized accordingly.

[0358]

[0359]

[0360]

[0361]

[0362] Synthesis and Preparation Example 2

[0363] The preparation method of compound O-6-7-4-5 is as follows:

[0364]

[0365] Step 1. Synthesis of the compound of formula 2-b

[0366]

[0367] 30.0 g of compound 2-a, 20.3 g of o-methoxy-p-bromophenol, and 25.4 g of anhydrous sodium carbonate were dissolved in toluene in a reaction flask. Under nitrogen atmosphere, 0.1 g of Pd-132 was added, and the reaction was carried out for 4 h. The solution was adjusted to acidity with 1 M dilute hydrochloric acid, and the mixture was separated. The organic phase was washed with water, and the solvent was evaporated under reduced pressure. The solution was dissolved in 500 mL of toluene and passed through a silica gel column. Recrystallization was performed using 100 mL of a mixed solvent of petroleum ether and toluene (volume ratio of petroleum ether to toluene was 4:1) to obtain 34.1 g of white crystals of compound 2-b (2-methoxy-4-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol), with a yield of 90%.

[0368] Step 2. Synthesis of compounds of formula 2-c

[0369]

[0370] 34.1 g of compound 2-b was added to a reaction flask and dissolved completely in carbon tetrachloride. Under nitrogen atmosphere, 0.2 g of Fe powder was added, and 16 g of liquid bromine was added dropwise over 1 hour. After 30 minutes, the bromine color was washed away with sodium bisulfite solution, the organic phase was washed with water, the solvent was evaporated under reduced pressure, and the product was recrystallized with 50 mL of a mixed solvent of petroleum ether and ethanol (volume ratio of petroleum ether to ethanol is 5:2) to give 33.8 g of compound 2-c (2-bromo-6-methoxy-4-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol), with a yield of 82%.

[0371] Step 3. Synthesis of compounds of formula 2-d

[0372]

[0373] 33.8 g of compound 2-c and 10.6 g of sodium carbonate were dissolved in tetrahydrofuran in a reaction flask. Under nitrogen atmosphere, 15.3 g of 4-bromobutanol was added dropwise, and the reaction was carried out at 80 °C for 6 h. The solution was poured into 500 mL of water, extracted with 300 mL of toluene, and the solvent was evaporated under reduced pressure. The solution was recrystallized with 50 mL of a mixed solvent of petroleum ether and ethanol (volume ratio of petroleum ether to ethanol is 3:1) to give 33.9 g of compound 2-d (4-(2-bromo-6-methoxy-4-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenoxy)but-1-ol), yield 86%.

[0374] Step 4. Synthesis of compounds of formula 2-e

[0375]

[0376] In a reaction flask, 20.3 g of 2-bromo-2-methoxyphenol and 13.8 g of sodium carbonate were dissolved in tetrahydrofuran. Under nitrogen atmosphere and controlled temperature of 80 °C, 20.7 g of 2-bromopropanol was added, and the reaction was allowed to proceed for 6 h. The mixture was extracted with 300 mL of toluene, washed with water, and recrystallized from 300 mL of petroleum ether to give 19.8 g of compound of formula 2-e (3-(5-bromo-2-methoxyphenoxy)prop-1-ol), in 76% yield.

[0377] Step 5. Synthesis of compounds of formula 2-f

[0378]

[0379] In a reaction flask, 19.8 g of the compound of formula 2-e, 25.3 g of diboronate, and 8.2 g of anhydrous sodium carbonate were added and dissolved thoroughly in toluene. Under nitrogen atmosphere, 0.4 g of tetrakis(triphenylphosphine)palladium was added, and the mixture was refluxed for 4 h. The mixture was washed with water, distilled under reduced pressure, and recrystallized from 100 mL of ethanol to give 19.5 g of the compound of formula 2-f (3-[2-methoxy-5-(tetramethyl-1,3,2-dioxoboronyl-2-yl)phenoxy]prop-1-ol) in pale yellow crystals, yield 83%.

[0380] Step 6. Synthesis of the compound of formula 2-g

[0381] In a reaction flask, 19.5 g of compound 2-f, 33.9 g of compound 2-d, and 10.6 g of anhydrous sodium carbonate were dissolved in toluene. Under nitrogen atmosphere, 0.5 g of tetrakis(triphenylphosphine)palladium was added, and the mixture was refluxed for 4 h. The mixture was washed with water, distilled under reduced pressure, and recrystallized from 600 mL of a mixed solvent of toluene and ethanol (toluene to ethanol volume ratio 2:1) to give 30.6 g of white crystals of compound 2-g (4-{2-[3-(3-hydroxypropoxy)-4-methoxyphenyl]-6-methoxy-4-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenoxy}but-1-ol), yield 75%.

[0382] Step 7. Synthesis of the compound of formula 2-h

[0383]

[0384] 30.6 g of compound of formula 2-h was added to a reaction flask and dissolved completely in dichloromethane. 35.8 g of boron tribromide was added dropwise at -30°C, and the reaction was carried out for 3 h under controlled temperature. The mixture was washed with water, the organic phase was separated, and recrystallized from 500 mL of a mixed solvent of petroleum ether and ethanol (volume ratio of petroleum ether to ethanol 5:1) to give 22.9 g of compound of formula 2-h (3-[4-hydroxy-3-(3-hydroxypropoxy)phenyl]-2-(4-hydroxybutoxy)-5-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol) as a white solid, with a yield of 81%.

[0385] Step 8. Synthesis of compounds of formula 2-i

[0386]

[0387] 22.9 g of the compound of formula 2-h and 2.8 g of imidazole were dissolved in tetrahydrofuran in a reaction flask. The mixture was cooled to 0 °C under nitrogen protection, and 5.9 g of tert-butyldimethylchlorosilane was added over 40 min. The reaction was maintained at 0 °C for 1.5 h. The reaction was quenched with 500 mL of ammonium chloride solution, extracted with 200 mL of methyl tert-butyl ether, and the organic phase was separated. The organic phase was washed with water until neutral, dried, and rotary evaporated. Recrystallization with 40 mL of a mixed solvent of toluene and ethanol (toluene to ethanol volume ratio 1:4) yielded 19.9 g of the compound of formula 2-i as a white solid (2-{4-[(tert-butyldimethylsilyl)oxy]butoxy}-3-(3-{3-[(tert-butyldimethylsilyl)oxy]propoxy}-4-hydroxyphenyl)-5-{4-[4-(4-methoxybutoxy)phenyl]phenyl}phenol), yield 63%.

[0388] Step 9. Synthesis of compounds of formula 2-j

[0389]

[0390] 19.9 g of compound of formula 2-i and 7.1 g of triethylamine were added to a reaction flask and dissolved completely in dichloromethane. 10 g of methacryloyl chloride was added at room temperature, and the reaction was allowed to proceed for 5 h. 200 mL of water was added, the organic phase was separated, washed with water until neutral, dried, and rotary evaporated. Recrystallization was performed using 30 mL of a mixed solvent of toluene and ethanol (toluene to ethanol volume ratio 1:4) to give 15.5 g of compound of formula 2-j (4-(2-{4-[(tert-butyldimethylsilyl)oxy]butoxy}-5-{4-[4-(4-methoxybutoxy)phenyl]phenyl}-3-[(2-methylprop-2-enoyl)oxy]phenyl)-2-{3-[(tert-butyldimethylsilyl)oxy]propoxy}phenyl-2-methylprop-2-enoate) as a white solid, yield 69%.

[0391] Step 10. Synthesis of compounds of formula O-6-7-4-5

[0392]

[0393] In a reaction flask, 15.5 g of the compound of formula 2-j was completely dissolved in tetrahydrofuran, cooled to 0°C, and 9.5 mL of 2M dilute hydrochloric acid was slowly added dropwise. The reaction was allowed to proceed for 3 h. 200 mL of saturated sodium bicarbonate aqueous solution was added at 0°C, and the mixture was extracted with 100 mL of methyl tert-butyl ether. The organic phase was separated, washed with water until neutral, dried, and rotary evaporated. Recrystallization was performed using 20 mL of a mixed solvent of petroleum ether and ethanol (volume ratio of petroleum ether to ethanol 3:1) to give 8.1 g of the compound of formula O-6-7-4-5 (4-[2-(4-hydroxybutoxy)-5-{4-[4-(4-methoxybutoxy)phenyl]phenyl}-3-[(2-methylprop-2-enoyl)oxy]phenyl]-2-(3-hydroxypropoxy)phenyl 2-methylprop-2-enoate), a white solid, in 70% yield.

[0394] The compound of formula O-6-7-4-5 has an m / z of 730.1 (M+) and elemental analysis: C, 70.66; H, 7.45; O, 21.89.

[0395] H-NMR (300MHz, CDCl3): 0.85-2.15 (m, 14H), 3.30 (s, 3H), 3.35-3.73 (m, 8H), 3.95-4.78 (m, 6H), 6.25-6.89 (m, 4H), 6.96-7.95 (m, 13H).

[0396] By adjusting the raw materials of Formula 2-a and using the same synthesis method as in Synthesis Preparation Example 2, the compounds shown in the table below can be synthesized accordingly.

[0397]

[0398]

[0399] 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.

[0400] Liquid crystal compositions were prepared according to the proportions of the liquid crystal compositions specified in the following examples. The liquid crystal compositions were prepared according to conventional methods in the art, such as mixing in proportion by heating, ultrasound, suspension, etc.

[0401] The structures of the polymerizable compounds used in the following embodiments are shown in Table 2 below.

[0402] Table 2 shows the polymerizable compounds used in the examples.

[0403]

[0404]

[0405] The structures of the self-aligning agents used in the following embodiments are shown in Table 3 below.

[0406] Table 3 shows the self-aligning agents used in the examples.

[0407]

[0408]

[0409] Host-1, Host-2, Host-3, Host-4 and Host-5 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.

[0410] Table 4. Formulation and performance parameter test results of the main liquid crystal composition.

[0411]

[0412]

[0413] Comparative Examples 1-4 and Examples 1-3

[0414] 0.3 parts by weight of polymerizable compound RM-1-1 and 0.7 parts by weight of D-1, D-2, D-3, and D-4 were added to 100 parts by weight of host liquid crystal composition Host-1 to prepare liquid crystal compositions of Comparative Examples 1-4, respectively. Similarly, 0.3 parts by weight of polymerizable compound RM-1-1 and 0.7 parts by weight of AD-1, AD-2, and AD-3 were added to 100 parts by weight of host liquid crystal composition Host-1 to prepare liquid crystal compositions of Examples 1-3, respectively. The physical properties of the resulting liquid crystal compositions showed almost no change relative to their respective host liquid crystal compositions. The resulting liquid crystal compositions were filled into “unaligned” test cells (cell thickness d was 3.5 μm, with ITO coatings 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 1-4 and Examples 1-3 are shown in Table 5 below.

[0415] Table 5. Performance test results of the liquid crystal compositions of Comparative Examples 1-4 and Examples 1-3

[0416] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Contact angle (°) 23.4 22.8 21.8 21.5 17.5 16.4 16.7 <![CDATA[t -20℃ ]]> 7D NG 7D NG 8D NG 6D NG 10D OK 10D OK 10D OK Orientation effect Poor Poor Poor Poor good good good

[0417] The comparison between Example 1 and Comparative Examples 1-2, the comparison between Example 2 and Comparative Example 3, and the comparison between Example 3 and Comparative Example 4 show that the liquid crystal composition containing the self-aligning agent of the general formula O of the present invention maintains appropriate clearing points, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a smaller contact angle (16.4-17.5 vs 21.5-23.4) and lower rotational viscosity, it exhibits better low-temperature storage stability (10D OK vs 7D-8DNG) and better alignment effect.

[0418] Comparative Examples 5-8 and Examples 4-6

[0419] 0.3 parts by weight of polymerizable compound RM-2-1 and 0.9 parts by weight of D-1, D-2, D-3, and D-4 were added to 100 parts by weight of the host liquid crystal composition Host-2 to prepare liquid crystal compositions of Comparative Examples 5-8, respectively. Similarly, 0.3 parts by weight of polymerizable compound RM-2-1 and 0.9 parts by weight of AD-1, AD-2, and AD-3 were added to 100 parts by weight of the host liquid crystal composition Host-2 to prepare liquid crystal compositions of Examples 4-6, respectively. The physical properties of the resulting liquid crystal compositions showed almost no change relative to their respective host liquid crystal compositions. The resulting liquid crystal compositions were filled into “unaligned” test cells (cell thickness d was 3.5 μm, with ITO coatings 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 4-6 are shown in Table 6 below.

[0420] Table 6 shows the performance test results of the liquid crystal compositions of Comparative Examples 5-8 and Examples 4-6.

[0421] Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Example 4 Example 5 Example 6 Contact angle (°) 24.8 24.5 23.4 23.1 18.7 17.9 17.2 <![CDATA[t -20℃ ]]> 6D NG 6D NG 6D NG 5D NG 10D OK 10D OK 10D OK Orientation effect Poor Poor Poor Poor good good good

[0422] The comparisons between Example 4 and Comparative Examples 5-6, Example 5 and Comparative Example 7, and Example 6 and Comparative Example 8 demonstrate that liquid crystal compositions containing a self-aligning agent of the general formula O of this invention maintain appropriate clearing points, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a smaller contact angle (17.2-18.7 vs 23.1-24.8) and lower rotational viscosity, it exhibits better low-temperature storage stability (10D OK vs 5D-6DNG) and better alignment effect.

[0423] Comparative Examples 9-12 and Examples 7-9

[0424] 0.3 parts by weight of polymerizable compound RM-1-1 and 1 part by weight of D-1, D-2, D-3, and D-4 were added to 100 parts by weight of host liquid crystal composition Host-3 to prepare liquid crystal compositions for Comparative Examples 9-12, respectively. Similarly, 0.3 parts by weight of polymerizable compound RM-1-1 and 1 part by weight of AD-1, AD-2, and AD-3 were added to 100 parts by weight of host liquid crystal composition Host-3 to prepare liquid crystal compositions for Examples 7-9, respectively. The physical properties of each liquid crystal composition showed almost no change relative to its respective host liquid crystal composition. The resulting liquid crystal compositions were filled into “unaligned” test cells (cell thickness d was 3.5 μm, with ITO coatings 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 7-9 are shown in Table 7 below.

[0425] Table 7 shows the performance test results of the liquid crystal compositions of Comparative Examples 9-12 and Examples 7-9.

[0426] Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Example 7 Example 8 Example 9 Contact angle (°) 21.5 21.3 21 21.2 16.2 15.7 15.5 <![CDATA[t -20℃ ]]> 8D NG 8D NG 8D NG 7D NG 10D OK 10D OK 10D OK Orientation effect Poor Poor Poor Poor good good good

[0427] The comparison between Example 7 and Comparative Examples 9-10, the comparison between Example 8 and Comparative Example 11, and the comparison between Example 9 and Comparative Example 12 show that the liquid crystal composition containing the self-aligning agent of the general formula O of the present invention maintains appropriate clearing points, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K0). 11 and K 33 With a smaller contact angle (15.5-16.2 vs 21-21.5) and lower rotational viscosity, it exhibits better low-temperature storage stability (10D OK vs 7D-8D NG) and better alignment effect.

[0428] Examples 10-14

[0429] The liquid crystal compositions of Examples 10-14 were prepared according to the weight proportions of each component described in Table 8. 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 Examples 10-14 are shown in Table 9 below.

[0430] Table 8 Performance test results of the liquid crystal compositions in Examples 10-14

[0431]

[0432]

[0433] Table 9 Performance test results of the liquid crystal compositions in Examples 10-14

[0434] Example 10 Example 11 Example 12 Example 13 Example 14 Contact angle (°) 16.8 17 16.4 16.5 15.8 <![CDATA[t -20℃ ]]> 10D OK 10D OK 10D OK 10D OK 15D OK Orientation effect good good good good good

[0435] As can be seen from the performance parameters of Examples 10-14, the liquid crystal composition containing the self-aligning agent of the general formula O of the present invention maintains an appropriate clearing point, appropriate optical anisotropy, appropriate absolute value of dielectric anisotropy, and a large K value (K 11 and K 33 With a small contact angle (15.8-17°C), good low-temperature storage stability (10 DOK), and good alignment effect, it exhibits the following properties: ) and low rotational viscosity.

[0436] 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 small contact angle (15.5-18.7°) and a small rotational viscosity, it exhibits good low-temperature storage stability (10D OK) and good alignment effect.

[0437] 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 self-aligning agent of general formula O, characterized in that, The self-aligning agent of general formula O is selected from the group consisting of the following compounds: O-1； O-2； O-4； O-6； O-10； O-15； O-16； O-17; and O-20； 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 of the straight-chain alkyl group containing 1-12 carbon atoms may be independently replaced by -O-. L o1 L o3 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 o2 and L o21 Each represents independently or ; 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 -、-(CH2) p1 -O- or single key, where p1 represents an integer from 1 to 10; Z o1 Z o11 and Z o2 Each can be represented independently as -(CH2) d - or a single key, where d represents an integer from 1 to 4; 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 Same or different, where when p o2 When L represents 2, o2 Same or different; where p o3 When 2 is represented, Same or different; where p o4 When L represents 2, o3 Same or different; and n o1 Represents integers from 1 to 10.

2. The self-aligning agent according to claim 1, characterized in that, The self-aligning agent of general formula O-1 is selected from the group consisting of the following compounds: O-1-1； O-1-2； O-1-3； O-1-4； O-1-5； as well as O-1-6； The self-aligning agent of general formula O-4 is selected from the group consisting of the following compounds: O-4-1； O-4-2； O-4-3； O-4-4； O-4-5； O-4-6； O-4-7； O-4-8； O-4-9； O-4-10； O-4-11; and O-4-12， The self-aligning agent of general formula O-6 is selected from the group consisting of the following compounds: O-6-1； O-6-2； O-6-3； O-6-4； O-6-5； O-6-6； O-6-7； O-6-8； O-6-9； O-6-10； O-6-11; and O-6-12， The self-aligning agent of general formula O-10 is selected from the group consisting of the following compounds: O-10-1； O-10-2； O-10-3； O-10-4； O-10-5； as well as O-10-6， in, L o22 L o23 and L o24 Each represents independently or ; L o11 L o12 and L o13 Each can be independently represented as -F, -Cl, a straight-chain alkyl group containing 1-12 carbon atoms, or a branched alkyl group containing 3-12 carbon atoms.

3. A liquid crystal composition comprising a self-aligning agent of general formula O as described in claim 1.

4. The liquid crystal composition according to claim 3, characterized in that, The liquid crystal composition comprises at least one compound of general formula M: 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 Same or different, Z M2 Same or different.

5. The liquid crystal composition according to claim 4, characterized in that, The compounds of general formula M are selected from the group consisting of the following compounds: M-1； M-2； M-3； M-4； M-5； M-6； M-7； M-8； M-9； M-10； M-11； M-12； M-13； M-14； M-15； M-16； M-17； M-18； M-19； M-20； M-21； M-22； M-23； M-24； M-25； M-26； M-27； M-28; and M-29。 6. The liquid crystal composition according to claim 3, characterized in that, The liquid crystal composition further comprises at least one compound of the general formula N: N， in, 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=; 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-; L N1 and L N2 Each can independently represent -H, halogen, or alkyl group containing 1-3 carbon atoms; and 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 Same or different, Z N1 Same or different.

7. The liquid crystal composition according to claim 6, characterized in that, The compounds of general formula N are selected from the group consisting of the following compounds: N-1； N-2； N-3； N-4； N-5； N-6； N-7； N-8； N-9； N-10； N-11； N-12； N-13； N-14； N-15； N-16； N-17； N-18； N-19； N-20； N-21； N-22； N-23； N-24； N-25； N-26； N-27； N-28； N-29； N-30； N-31； N-32； N-33； N-34; and N-35。 8. The liquid crystal composition according to claim 3, characterized in that, The liquid crystal composition comprises at least one polymerizable compound of general formula RM: 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. a represents 0, 1, or 2, b represents 0 or 1, where when a represents 2, the ring... Same or different, Z1 is the same or different.

9. The liquid crystal composition according to claim 8, characterized in that, The polymerizable compounds of the general formula RM are selected from the group consisting of the following compounds: RM-1; RM-2; RM-3; RM-4; RM-5; RM-6; RM-7; RM-8; RM-9; RM-10; RM-11; RM-12; RM-13; RM-14; RM-15; RM-16; RM-17; RM-18; RM-19; RM-20; RM-21; RM-22; RM-23; RM-24; RM-25; RM-26; RM-27; RM-28; RM-29; RM-30; RM-31; RM-32; RM-33; RM-34; RM-35; and RM-36, 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 .

10. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 3-9.

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