A compound, a liquid crystal composition comprising the compound, a liquid crystal display element, and a liquid crystal display.
Patent Information
- Authority / Receiving Office
- TW · TW
- Patent Type
- Applications
- Current Assignee / Owner
- SHIJIAZHUANG CHENGZHI YONGHUA DISPLAY MATERIALS CO LTD
- Filing Date
- 2025-03-05
- Publication Date
- 2026-08-01
Smart Images
Figure TWG2TA001070027_001 
Figure TWG2TA001070027_002
Abstract
Description
Technical Field
[0001] This invention relates to the field of liquid crystal additives. More specifically, it relates to a compound, a liquid crystal composition comprising the compound, a liquid crystal display element, and a liquid crystal display. Prior Technology
[0002] Since the first mass production of a color TFT-LCD in 1988, after 37 years of development, TFT-LCD has become the dominant technology in the display field. However, with the continuous emergence of new technologies and the enrichment of application scenarios, increasingly higher requirements are being placed on TFT-LCD panels and the materials used in them. LCD technology, with its stable performance and high reliability, plays a vital role in many fields. First, in the consumer electronics sector, LCD displays dominate due to their thinness, power saving, and high efficiency, and are widely used in televisions, mobile phones, tablets, and other devices. Second, in the industrial sector, industrial LCD screens, with their robust durability and adaptability to various complex environments, have become the ideal choice for many industrial applications. They typically use robust metal casings, have excellent waterproof and dustproof performance, and can withstand a wide temperature range, maintaining stable operation even in extreme environments. Furthermore, the high brightness, high contrast, low power consumption, and high stability of LCD displays make them the preferred product in outdoor advertising billboards, vehicle displays, industrial control and monitoring, and other fields. In the automotive display sector, LCD displays are widely used in in-vehicle information systems and dashboards due to their ability to operate stably under various weather and lighting conditions. With technological advancements, LCD displays are continuously expanding into new application areas, such as flexible LCDs and transparent LCDs, indicating potential future applications in wearable devices, smart curtains, and other emerging scenarios. In general, the stability and reliability of LCD displays are key factors for their widespread adoption across various fields.
[0003] With technological advancements and increasing user demands, automotive and consumer electronics panels face ever-higher requirements for high temperature and humidity resistance. Automotive displays need to operate normally under extreme temperature conditions, such as continuous operation for over 300 hours in environments ranging from -40°C to 105°C. This is because cars may travel in different seasons and at different latitudes, and automotive displays must adapt to these changes to ensure stable operation under extreme conditions, whether exposed to high temperatures or low temperatures. Similarly, in the consumer electronics field, especially for outdoor products such as smartphones and tablets, excellent high temperature and humidity resistance is required to cope with varying outdoor climate conditions. These requirements have driven continuous advancements in LCD technology regarding high temperature and humidity resistance to ensure stable and reliable display performance in various harsh environments.
[0004] Therefore, panel manufacturers must ensure that automotive and mobile phone / tablet displays meet the requirements for long-term 85°C / 85% aging tests during the design and manufacturing process to guarantee stable performance and reliability even in harsh environments with high temperature and humidity. The 85°C / 85% aging test simulates the long-term operation of a product under extreme conditions. This test is crucial for evaluating performance changes under these conditions, such as photoelectric performance parameters, material mechanical properties, and yellowing index. This test is particularly important for automotive displays, as they need to maintain stable display performance throughout the vehicle's entire lifespan—at least 5 to 10 years. Similarly, consumer electronics such as mobile phones and tablets also need to pass the 85°C / 85% aging test to ensure reliable operation under various environmental conditions. These test results are crucial for assessing the long-term reliability and durability of products and serve as important references for product design and material selection.
[0005] While existing hindered amine light stabilizers (HALS) can improve the resistance to photoaging of liquid crystal materials to some extent, their application in high temperature and high humidity environments does face some challenges.
[0006] For example, EP2993216 A1 discloses a stable compound of the following formula for use in dielectric positive liquid crystal compositions.
[0007] For example, CN105339464B proposes a nematic liquid crystal composition with negative dielectric anisotropy containing a small amount of a compound of the following formula as a stabilizer:
[0008] The aforementioned compositions containing stabilizers have been practically used in liquid crystal displays (LCDs). Compared to liquid crystals without stabilizers, they improve the stability of liquid crystal materials under UV and long-term backlight irradiation conditions, thus improving the image retention effect of the display to some extent. However, the chemical stability of this type of structure, especially its chemical stability under high temperature and humidity conditions, is insufficient. This causes such light stabilizers to easily undergo hydrolysis under high temperature and humidity conditions, resulting in the formation of speckled spots on the material surface.
[0009] For example, CN112236499 A1 proposes a liquid crystal medium having a nematic phase and negative dielectric anisotropy, comprising the following compound as a stabilizer.
[0010] However, although the above-mentioned liquid crystal composition uses ethers as linking groups to improve the problem of esters being prone to hydrolysis to some extent, its multifunctional molecular structure greatly reduces its solubility in the liquid crystal medium. At the same time, the multiple ether linking groups also increase the risk of hydrolysis. Therefore, although it is an improvement over ester linking group stabilizers, there is still a risk of bright spots.
[0011] For example, DE 10 2016 009485.0 recommends compounds with ether linkages as stabilizers for liquid crystal compositions, as follows.
[0012] The above-mentioned liquid crystal composition reduces the number of functional groups and the number of ether linkage sites, thus reducing the risk of hydrolysis under high temperature and high humidity conditions. However, due to the limitations of its functional group structure and number, this type of stabilizer has a weak ability to improve the stability of liquid crystal materials under UV and long-term backlight irradiation conditions, and cannot effectively improve the image retention level of liquid crystal materials under harsh aging conditions. Therefore, there are no examples of mass production and use in actual products.
[0013] Therefore, as the requirements for image retention and reliability of displays under high temperature and humidity conditions continue to increase, it is still very necessary to improve the performance of liquid crystals, that is, to develop liquid crystals with excellent high temperature and humidity stability to avoid the risk that liquid crystal displays cannot display normally under high temperature and humidity conditions. Summary of the Invention
[0014] In view of the above problems, the present invention aims to provide a compound, a liquid crystal composition comprising the compound, a liquid crystal display element, and a liquid crystal display. The liquid crystal composition comprising the compound exhibits improved stability against ultraviolet light and thermal stress, particularly reliable stability under high temperature and high humidity conditions, while also ensuring normal operation at low temperatures down to -40°C. The liquid crystal display element and liquid crystal display comprising the liquid crystal composition also possess the aforementioned properties.
[0015] To achieve the above objectives, the present invention adopts the following technical solution:
[0016] On one hand, the present invention provides a compound selected from compounds represented by Formula I. I in, , Each represents independently , ,and , Any hydrogen atom may be substituted by a halogen, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, an alkenyl group having 2-5 carbon atoms, or an alkenyloxy group having 2-5 carbon atoms; c and d each independently represent 1 or 2, and c + d represents 3; Z1 and Z2 represent straight-chain or branched alkyl groups with 1-15 carbon atoms, wherein at least one -CH2- is substituted with -O-; Z represents a single bond, a straight-chain or branched alkyl group with 1-15 carbon atoms, wherein one or more non-adjacent -CH2- are replaced by -O-.
[0017] In another aspect, the present invention provides a liquid crystal composition comprising one or more compounds of Formula I as described in the first aspect above, and one or more compounds selected from Formula II and / or Formula III. II III in, R1 and R2 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups can be substituted with cyclopropylene, cyclobutylene, or cyclopentylene. Z11 indicates a single bond, -CH2O-, or -CH2-CH2-; X1 represents a halogen, a haloalkyl group having 1-3 carbon atoms, or a haloalkoxy group having 1-3 carbon atoms; X2 represents an alkyl group with 1-15 carbon atoms, an alkoxy group with 1-15 carbon atoms, or a haloalkoxy group with 1-15 carbon atoms; X3 represents H or -CH3; m represents 0, 1, or 2; n represents 0 or 1; q represents 1 or 2; , , , Each represents independently , , , , or When m or q represents 2, , Each occurrence can be either the same or different independently.
[0018] In another aspect, the present invention provides a liquid crystal display element comprising the liquid crystal composition described in the second aspect above, wherein the liquid crystal display element is an active matrix display element or a passive matrix display element.
[0019] In another aspect, the present invention provides a liquid crystal display comprising the liquid crystal composition described in the second aspect above, wherein the liquid crystal display is an active matrix display or a passive matrix display.
[0020] In another aspect, the present invention provides a light stabilizer comprising a compound represented by Formula I as described in the first aspect above.
[0021] The beneficial effects of this invention are as follows: The compound represented by Formula I provided in this invention has a bicyclic structure with trifunctional groups linked by ether bonds. Compared to HALS molecules with two or four NH functional groups, the compound represented by Formula I, with three NH functional groups containing ether bonds, is a highly asymmetric molecule, making it easier to reduce molecular packing density and thus easier to combine with the PI surface. This specific structure leads to a specific ordered arrangement of the compound represented by Formula I in the liquid crystal. This ordered arrangement between molecules makes it difficult for hydrogen bonds to form between the NH functional groups and oxygen elements, resulting in better dispersibility of the compound represented by Formula I in the liquid crystal material. At the same time, the formation of the ordered structure fixes the position and orientation of the molecules to a certain extent and develops in the direction of minimizing overall energy, making it easier to form a stable structure. Liquid crystal compositions containing compounds represented by Formula I in this invention exhibit higher stability against ultraviolet light and thermal stress, and in particular, strong tolerance to high temperature and high humidity conditions (85°C / 85% RH). This ensures that they do not suffer from bright spot problems caused by monomer hydrolysis after extreme conditions (high temperature, low temperature, high temperature and low temperature cycle, high temperature and high humidity), reducing the risk of image retention and other problems in the final display. This can provide liquid crystal display devices of higher quality, especially suitable for automotive, mobile phone and tablet applications. Simple Explanation of the Diagram
[0022] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
[0023] Figure 1 shows the MS mass spectrum of the compound represented by formula I-1-1. Implementation
[0024] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.
[0025] According to one specific embodiment of the present invention, a compound is provided, said compound being selected from compounds represented by Formula I. I in, , Each represents independently , ,and , Any hydrogen atom may be substituted by a halogen, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, an alkenyl group having 2-5 carbon atoms, or an alkenyloxy group having 2-5 carbon atoms; c and d each independently represent 1 or 2, and c + d represents 3; Z1 and Z2 represent straight-chain or branched alkyl groups with 1-15 carbon atoms, wherein at least one -CH2- is substituted with -O-; Z represents a single bond, a straight-chain or branched alkyl group with 1-15 carbon atoms, wherein one or more non-adjacent -CH2- are replaced by -O-. In some examples, Z1 and Z2 represent straight-chain or branched alkyl groups with 2-15 or 3-15 carbon atoms.
[0026] In some examples, in Z1 and Z2, at least two -CH2- are replaced by -O-, for example, -CH2- at both ends of the molecular chain segment are replaced by -O-.
[0027] In some examples, the compound represented by Formula I is selected from the group consisting of compounds represented by Formulas I-1 to I-10 below. I-1 I-2 I-3 I-4 I-5 I-6 I-7 I-8 I-9 I-10 in, , Any hydrogen atom may be substituted by a halogen, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, an alkenyl group having 2-5 carbon atoms, or an alkenyloxy group having 2-5 carbon atoms; Z3, Z4, and Z6 each independently represent a straight-chain or branched alkyl group having 1-15 carbon atoms, wherein at least one -CH2- is substituted with -O-; Z5 represents a single-bonded, straight-chain or branched alkyl group with 1-15 carbon atoms, wherein one or more non-adjacent -CH2- are replaced by -O-. In some examples, Z3, Z4, and Z6 each independently represent straight-chain or branched alkyl groups with 2-15 or 3-15 carbon atoms.
[0028] In some examples, in Z3, Z4, and Z6, at least two -CH2- are replaced by -O-, for example, -CH2- at both ends of the molecular chain segment are replaced by -O-.
[0029] In some preferred embodiments, the compound represented by Formula I contains at least one compound selected from Formula I-1, Formula I-2, Formula I-8 or Formula I-9.
[0030] In some more preferred examples, the compound represented by Formula I comprises at least one compound selected from Formula I-1.
[0031] Furthermore, the compounds represented by formulas I-1 to I-10 are selected from the group consisting of compounds represented by formulas I-1-1 to I-10-1. I-1-1 I-1-2 I-1-3 I-1-4 I-1-5 I-1-6 I-1-7 I-1-8 I-1-13 I-1-14 I-1-15 I-2-1 I-3-1 I-4-1 I-5-1 I-6-1 I-7-1 I-8-1 I-9-1 I-10-1.
[0032] In some more specific preferred examples, the compound represented by Formula I is selected from the compounds represented by Formula I-1-1, Formula I-1-2, and Formula I-1-12, and more preferably the compound represented by Formula I-1-1.
[0033] According to another specific embodiment of the present invention, a liquid crystal composition is provided, the liquid crystal composition comprising one or more compounds represented by Formula I, and one or more compounds selected from Formula II and / or Formula III. II III in, R1 and R2 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups can be substituted with cyclopropylene, cyclobutylene, or cyclopentylene. Z11 indicates a single bond, -CH2O-, or -CH2-CH2-; X1 represents a halogen, a haloalkyl group having 1-3 carbon atoms, or a haloalkoxy group having 1-3 carbon atoms; X2 represents an alkyl group with 1-15 carbon atoms, an alkoxy group with 1-15 carbon atoms, or a haloalkoxy group with 1-15 carbon atoms; X3 represents H or -CH3; m represents 0, 1, or 2; n represents 0 or 1; q represents 1 or 2; , , , Each represents independently , , , , or ; When m or q represents 2 , Each occurrence can be either the same or different independently.
[0034] In some examples, the liquid crystal composition contains, by weight percentage, 0.001 wt% to 1 wt% of the compound represented by Formula I. In some specific examples, the liquid crystal composition contains, by weight percentage, the compound represented by Formula I, including but not limited to 0.004 wt% to 0.1 wt%, 0.004 wt% to 0.05 wt%, 0.004 wt% to 0.01 wt%, 0.009 wt% to 0.05 wt%, etc.
[0035] In some examples, the compound represented by Formula II is selected from the group consisting of compounds represented by Formulas II-1 to II-6 below. II-1 II-2 II-3 II-4 II-5 II-6 in, R1 represents an alkyl group with 1-15 carbon atoms, an alkoxy group with 1-15 carbon atoms, or an alkenyl group with 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups may be substituted with cyclopropylene, cyclobutylene, or cyclopentylene. X1 represents a halogen, a haloalkyl group having 1-3 carbon atoms, or a haloalkoxy group having 1-3 carbon atoms; X3 represents H or -CH3.
[0036] In some examples, the liquid crystal composition contains, by weight percentage, 4 wt%-20 wt% of the compound represented by Formula II. In some specific examples, the liquid crystal composition contains, by weight percentage, the compound represented by Formula II, including but not limited to 4 wt%-16 wt%, 4 wt%-15 wt%, 4 wt%-14 wt%, 13 wt%-16 wt%, 13 wt%-15 wt%, etc.
[0037] In some examples, the compound represented by Formula III is selected from the group consisting of compounds represented by Formulas III-1 to III-10. III-1 III-2 III-3 III-4 III-5 III-6 III-7 III-8 III-9 III-10 in, R2 represents an alkyl group with 1-15 carbon atoms, an alkoxy group with 1-15 carbon atoms, or an alkenyl group with 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups may be substituted with cyclopropylene, cyclobutylene, or cyclopentylene. X2 represents an alkyl group with 1-15 carbon atoms, an alkoxy group with 1-15 carbon atoms, or a haloalkoxy group with 1-15 carbon atoms.
[0038] In some examples, the liquid crystal composition comprises, by weight percentage, 4.5 wt%-80 wt% of the compound represented by Formula III. In some specific examples, the liquid crystal composition comprises, by weight percentage, the compound represented by Formula III, including but not limited to 4.5 wt%-76 wt%, 5 wt%-76 wt%, 5 wt%-66 wt%, 10 wt%-60 wt%, 30 wt%-76 wt%, etc.
[0039] Furthermore, the liquid crystal composition comprises one or more compounds represented by Formula IV. IV in, R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms; 'a' represents 1, 2, or 3; , Each represents independently , , or ; When 'a' represents 2 or 3, Each occurrence can be the same or different.
[0040] In some examples, the compound represented by formula IV is selected from the group consisting of compounds represented by formulas IV-1 to IV-9 below. IV-1 IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 IV-8 IV-9 in, R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms.
[0041] In some preferred embodiments, the compound represented by Formula IV is selected from the group consisting of compounds represented by Formulas IV-1-1 and IV-1-2. IV-1-1 IV-1-2. Furthermore, the compound represented by Formula IV is selected from the group consisting of compounds represented by Formula IV-2 below. IV-2 in, R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms.
[0042] In some examples, the liquid crystal composition comprises, by weight percentage, 20 wt%-91 wt% of the compound represented by Formula IV. In some specific examples, the liquid crystal composition comprises, by weight percentage, the compound represented by Formula IV, including but not limited to 20 wt%-85 wt%, 20 wt%-80 wt%, 30 wt%-80 wt%, 40 wt%-80 wt%, 45 wt%-71 wt%, 45 wt%-50 wt%, 50 wt%-85 wt%, 50 wt%-71 wt%, 70 wt%-85 wt%, etc.
[0043] Furthermore, the liquid crystal composition comprises one or more compounds represented by formula V. V in, R5 and R6 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups can be substituted with cyclopropylene, cyclobutylene, or cyclopentylene. X4 represents -S-, -O-, -CH2-S-, or -CH2-O-.
[0044] In some examples, the compound represented by formula V is selected from the group consisting of compounds represented by formulas V-1 to V-4. V-1 V-2 V-3 V-4 in, R5 and R6 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups may be substituted with cyclopropyl, cyclobutyl, or cyclopentylene.
[0045] In some preferred examples, the compound represented by formula V comprises at least one compound represented by formula V-2.
[0046] In some examples, the liquid crystal composition contains, by weight percentage, 4 wt%-15 wt% of the compound represented by Formula V. In some specific examples, the liquid crystal composition contains, by weight percentage, the compound represented by Formula V, including but not limited to 4 wt%-10 wt%, 4 wt%-8 wt%, 4 wt%-5 wt%, etc.
[0047] In some examples, the liquid crystal composition comprises one or more compounds of formula VI. VI in, R7 represents an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms; X5 indicates a halogen, a haloalkyl group with 1-3 carbon atoms, or a haloalkoxy group with 1-3 carbon atoms; b represents 1, 2, or 3; , Each represents independently , , , , or When b represents 2 or 3, Each occurrence can be the same or different.
[0048] In some examples, the compound represented by formula VI is selected from the group consisting of compounds represented by formulas VI-1 to VI-19 below. VI-1 VI-2 VI-3 VI-4 VI-5 VI-6 VI-7 VI-8 VI-9 VI-10 VI-11 VI-12 VI-13 VI-14 VI-15 VI-16 VI-17 VI-18 VI-19 in, R7 represents an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms; X5 represents halogen, haloalkyl with 1-3 carbon atoms, or haloalkoxy with 1-3 carbon atoms.
[0049] In some examples, the liquid crystal composition contains, by weight percentage, 5 wt%-60 wt% of the compound represented by Formula VI. In some specific examples, the liquid crystal composition contains, by weight percentage, the compound represented by Formula VI, including but not limited to 5 wt%-40 wt%, 6 wt%-7 wt%, 30 wt%-60 wt%, 30 wt%-40 wt%, 35 wt%-37 wt%, etc.
[0050] In some examples, the liquid crystal composition further comprises one or more compounds represented by formula VII. VII in, R8 represents an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms. One or more hydrogen atoms in R8 may be replaced by F atoms.
[0051] In some specific examples, the compound represented by formula VII is selected from the group consisting of compounds represented by formulas VII-1 to VII-6 below. VII-1 VII-2 VII-3 VII-4 VII-5 VII-6.
[0052] In the liquid crystal composition provided in this embodiment, other commonly used additives in liquid crystal compositions may also be added as needed.
[0053] According to another specific embodiment of the present invention, a liquid crystal display element is provided, the liquid crystal display element comprising the liquid crystal composition described in the second aspect above, the liquid crystal display element being an active matrix display element or a passive matrix display element.
[0054] In some examples, the liquid crystal display element is preferably an active matrix addressing liquid crystal display element.
[0055] Exemplary active matrix display elements include, but are not limited to, TN-TFT, IPS-TFT, FFS-TFT, or VA-TFT liquid crystal display elements, with FFS-TFT mode liquid crystal display elements being particularly suitable for automotive and mobile phone applications.
[0056] According to another specific embodiment of the present invention, a liquid crystal display is provided, the liquid crystal display comprising the liquid crystal composition described above, the liquid crystal display being an active matrix display or a passive matrix display.
[0057] In some examples, the liquid crystal display is preferably an active matrix addressing liquid crystal display.
[0058] Exemplary active matrix displays include, but are not limited to, TN-TFT, IPS-TFT, FFS-TFT, or VA-TFT liquid crystal displays or other TFT displays, particularly FFS-TFT mode liquid crystal displays for automotive and mobile phone applications. [Example]
[0059] The technical solution of the present invention will be described below with reference to some specific embodiments.
[0060] In this invention, the preparation methods are all conventional unless otherwise specified, and the raw materials used can be obtained from publicly available commercial sources unless otherwise specified. The reaction process is generally monitored by TLC. The post-reaction treatment generally includes water washing, extraction, drying after combining organic phases, solvent removal under reduced pressure, recrystallization, and column chromatography. Those skilled in the art can implement this invention according to the following description.
[0061] All percentages in this instruction manual refer to mass percentages, and temperatures are in degrees Celsius (°C). The specific meanings of other symbols and test conditions are as follows: Cp represents the liquid crystal clearing point (°C), measured quantitatively using DSC method; Δn represents optical anisotropy, Δn = ne - no, where no is the refractive index of the ordinary ray and ne is the refractive index of the extraordinary ray. The test conditions are 25±2℃, 589 nm, and the test is conducted using an Abbe refractometer. Δε represents dielectric anisotropy, Δε = ε∥ - ε⊥, where ε∥ is the dielectric constant parallel to the molecular axis and ε⊥ is the dielectric constant perpendicular to the molecular axis. The test conditions are 25 ± 0.5℃, 20-micron vertical cell, and INSTEC:ALCT-IR1 test. γ1 represents rotational viscosity (mPa·s), and the test conditions were 25±0.5℃, 20-micron vertical box, and INSTEC:ALCT-IR1 test. K11 is the developmental elastic constant, K33 is the flexural elastic constant, and the test conditions are: 25℃, INSTEC:ALCT-IR1, 20-micron vertical box; Low-temperature observation conditions: Pour the liquid crystal into the test box, seal it and place it in a -40℃ low-temperature glove box. Observe whether crystal precipitation occurs in the liquid crystal after 1000 hours.
[0062] The preparation method of the liquid crystal composition is as follows: weigh each liquid crystal monomer according to a certain ratio and put it into a stainless steel beaker. Place the stainless steel beaker containing each liquid crystal monomer on a magnetic stirrer and heat it to melt. After most of the liquid crystal monomer in the stainless steel beaker has melted, add a magnetic rotor to the stainless steel beaker and stir the mixture evenly. After cooling to room temperature, the liquid crystal composition is obtained.
[0063] The method for preparing the liquid crystal display device in the embodiments of the present invention is as follows: The liquid crystal composition is poured into a test box, sealed with frame adhesive, and then the following tests are performed: High-Temperature Image Retention: The test panel was set at 60℃ with a 20,000 nit backlight. After displaying a specified fixed pattern within the display area for 24 hours, the retention level of the inherent pattern was evaluated using a neutral density (ND) filter (a neutral density filter is a light-blocking film that can block image retention; the more severe the image retention, the lower the ND value required to make it invisible). The evaluation was graded from A to E, with a higher ND% value indicating better image retention performance. Grade A, invisible, ND value 10~9; Grade B, slight, ND value 8~7; Grade C, Medium, ND value 6~5; Category D, Severe, ND value 4-3; Grade E, cannot be tested, ND value <3.
[0064] High temperature and humidity tolerance test conditions: The test panel is placed in a high temperature and humidity environment test chamber at 85℃ / 85% RH, and a specific image is displayed in a loop within the display area for 1000 hours. The panel is then removed and the severity of the broken bright spots is determined by human visual observation, and is divided into five levels as follows: A to E. The number of abnormal bright spots in the unit display area of the panel is observed and recorded under a microscope. The fewer the number, the better the high temperature and humidity tolerance. Grade A, invisible, number of abnormal bright spots in the display area <10; Grade B, minor, indicating 10 to <100 abnormal bright spots in the displayed area; Grade C, Medium, Number of abnormal bright spots in the display area: 100~<200; Grade D, severe, indicating 200-500 abnormal bright spots in the displayed area; Grade E, cannot be tested, number of abnormal bright spots in the displayed area > 500.
[0065] The liquid crystal monomer structure in the embodiments of the present invention is represented by code. The code representation methods of liquid crystal ring structure, end group and linking group are shown in Table 1 and Table 2 below.
[0066] Table 1. Corresponding codes for ring structures Ring structure Corresponding code C L P A D G Gi U Y Sb Sc Sa
[0067] Table 2. Correspondence codes between terminal groups and linking groups Terminal groups and linking groups Corresponding code CnH2n+1- n- CnH2n+1O- nO- -CH2O- -O- -OCF3 -OCF3 -F -F -CH2CH2- -E- -CH=CH- -V- -C≡C- -T- -CF2O- -Q- -COO- -Z- -CH=CH-CnH2n+1 -Vn Cp- CpO- Cpr- Cpr1-
[0068] For example: Its code is COY-3-O2; Its code is PP-5-3; Its code is CY-3-O2; Its code is CC-Cp-V1; Its code is PGP-Cpr1-2. [Compound Examples]
[0069] The liquid crystal compound with the structural formula shown in Formula I in this invention can be synthesized via the following synthetic route:
[0070] Compounds and intermediates of Formula I and its sub-formulas can be prepared similarly from commercially available starting materials or by methods known to those skilled in the art. Intermediate 3-[(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)oxy]prop-1-ol (compound A) can be prepared by the synthetic method disclosed in Merck's 2018 authorized patent CN108373441A.
[0071] The present invention will be described below using specific embodiments. [Synthesis example] [1] [Liquid Crystal Compounds] [I-1-1] [Preparation]
[0072] The preparation route is as follows:
[0073] Specific preparation procedure:
[0074] Intermediate 2:
[0075] 0.09 mol of compound 1, 0.097 mol of 4-methoxyphenylboronic acid, 0.3 L of toluene and 0.1 L of water were added to a three-necked flask, along with 0.1 mol of potassium carbonate and 0.1 mmol of Pd-132. The mixture was refluxed under a nitrogen atmosphere for 1 h. The mixture was separated, and the organic phase was subjected to column chromatography, drying, and rotary evaporation to obtain 22 g of yellow intermediate 2, with a yield of 98%.
[0076] Intermediate 3:
[0077] 0.09 mol of compound 2 and 0.2 L of dichloromethane were added to a three-necked flask. Boron tribromide was added dropwise under a nitrogen atmosphere at -20 °C. After the addition was complete, the mixture was reacted at room temperature for 2 h. The mixture was then poured into 0.5 L of ice water and stirred. The mixture was filtered to obtain 10 g of pale yellow solid intermediate 3, with a yield of 55%.
[0078] Intermediate 4:
[0079] 0.01 mol intermediate 3, 0.04 mol alcohol compound A, and 0.04 mol triphenylphosphine were added to a three-necked flask. DIAD was added dropwise under a nitrogen atmosphere at 0°C. After the addition was complete, the reaction was allowed to proceed at room temperature for 12 h. After concentrating the reaction solution, 0.5 L of petroleum ether was added and the mixture was stirred. After filtering off the solid triphenylphosphine, the mother liquor was concentrated to obtain 10 g of pale yellow viscous liquid intermediate 4, with a yield of 94%.
[0080] Product I-1-1:
[0081] 0.01 mol of intermediate 4, 1 g of palladium and 0.2 L of ethyl acetate were added to a three-necked flask and reacted at room temperature for 12 h. The palladium on carbon was removed by filtration, and the mother liquor was rotary evaporated to obtain a yellow oil. The oil was purified by column chromatography with an EA:TEA ratio of 20:1 to obtain 5 g of colorless viscous liquid product I-1-1, with a yield of 67%.
[0082] The MS mass spectrum of the compound represented by Formula I-1-1 is shown in Figure 1.
[0083] Using a similar method, compounds with the following structural formulas were synthesized: I-1-2 I-1-3 I-1-4 I-1-5 I-1-6 I-1-7 I-1-8 I-2-1 I-7-1 I-8-1 I-9-1 I-10-1. [Synthesis example] [2] [Liquid Crystal Compounds] [I-1-9] [Preparation:]
[0084] The preparation route is as follows:
[0085] Intermediate 6:
[0086] 0.1 mol of 3,5-dimethoxyphenylpropionic acid, 0.2 L of dichloromethane and two drops of DMF were added to a three-necked flask. 0.11 mol of dichlorosulfite was added dropwise under a nitrogen atmosphere at 0 °C. The mixture was refluxed for 1 h. The reaction solution was concentrated to obtain 23 g of colorless liquid intermediate 6, with a yield of 98%.
[0087] Intermediate 7:
[0088] 0.09 mol of methoxybenzene, 0.1 mol of anhydrous aluminum trichloride, and 0.15 L of dichloromethane were added to a three-necked flask. A dichloromethane solution of 0.1 mol of compound 6 was added dropwise at 0℃, and the reaction was allowed to proceed for 1 h at room temperature. The reaction mixture was then quenched with 0.2 L of water, separated, and extracted with 0.1 L × 3 dichloromethane. The organic phase was washed with water, dried, and rotary evaporated to obtain 23 g of a yellow oily compound 7, with a yield of 85%.
[0089] Intermediate 8:
[0090] 0.07 mol of compound 7, 0.15 mol of triethylsilane, and 0.15 L of dichloromethane were added to a three-necked flask. The 0.15 mol of triethylsilane was added dropwise at 0℃, and the reaction was carried out at room temperature for 12 h. The reaction was quenched with 0.2 L of water, separated, and extracted with 0.1 L × 3 dichloromethane. The organic phase was washed with water, dried, and rotary evaporated to obtain 12 g of yellow oily compound 8, with a yield of 60%.
[0091] Intermediate 9:
[0092] 0.04 mol of compound 8 and 0.1 L of dichloromethane were added to a three-necked flask. 0.05 mol of boron tribromide was added dropwise at -20 °C, and the reaction was carried out at room temperature for 2 h. The reaction was quenched with 0.2 L of water, separated, and extracted with 0.1 L × 3 dichloromethane. The organic phase was washed with water, dried, and rotary evaporated to obtain 8 g of yellow solid compound 9, with a yield of 78.4%.
[0093] Intermediate 10:
[0094] 0.03 mol of intermediate 9, 0.1 mol of alcohol compound A, and 0.1 mol of triphenylphosphine were added to a three-necked flask. 0.1 mol of DIAD was added dropwise under a nitrogen atmosphere at 0°C. After the addition was complete, the reaction was allowed to proceed at room temperature for 12 h. After concentrating the reaction solution, 0.5 L of petroleum ether was added and the mixture was stirred. After filtering off the solid triphenylphosphine, the mother liquor was concentrated to obtain 18 g of pale yellow viscous liquid intermediate 10, with a yield of 44%.
[0095] Product I-1-9:
[0096] 0.016 mol of intermediate 10, 5 g of palladium and 0.5 L of ethyl acetate were added to a three-necked flask and reacted at room temperature for 12 h. The palladium on carbon was removed by filtration, and the mother liquor was rotary evaporated to obtain a yellow oil. The oil was purified by column chromatography with an EA:TEA ratio of 20:1 to obtain 8.4 g of colorless viscous liquid product I-1-9, with a yield of 62.5%.
[0097] Using a similar method, the following were synthesized: I-1-10 I-1-11 I-1-12.
[0098] Comparative additives: D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D11 D12 D13 D14 D15 D16 D17 D18 D19. [Composition Examples:] [Composition] [1]
[0099] The formulation and some properties of composition 1 are shown in Table 3 below.
[0100] Table 3 Composition 1 category Liquid crystal unit code Content (wt%) IV CC-3-V 40 IV CC-3-V1 10 II PGUQU-3-F 5 II PGUQU-4-F 5 II APUQU-3-F 3 II DGUQU-3-F 3 IV CCP-V-1 10 IV CCP-V2-1 9 IV CPPC-3-3 5 IV PGP-2-2V 10 Cp:100℃ Δn [589nm, 25℃]: 0.110 Δε [1kHz, 25℃]: 4.5 -40℃, 1000 hours: No crystals precipitated. [Composition] [2]
[0101] The formulation and some properties of composition 2 are shown in Table 4 below.
[0102] Table 4 Composition 2 category Liquid crystal unit code Content (wt%) IV CC-3-V 40 IV CC-3-V1 10 II CPUQU-3-F 5 II CDUQU-4-F 7 II APUQU-3-F 2 II DGUQU-3-F 2 IV CCP-V-1 10 IV CCP-V2-1 10 IV CPPC-3-3 4 IV CLP-V-1 10 Cp: 105℃ Δn [589nm, 25℃]: 0.090 Δε [1kHz, 25℃]: 3.9 40℃, 1000 hours: No crystals precipitated. [Composition] [3]
[0103] The formulation and some properties of composition 3 are shown in Table 5 below.
[0104] Table 5 Composition 3 category Liquid crystal unit code Content (wt%) IV CC-3-V 33 IV CC-3-V1 10 II PGUQU-3-F 6 II CPUQU-3-F 5 II APUQU-3-F 5 CCVC-3-V 6 IV CCP-V-1 10 IV CCP-V2-1 10 IV CPPC-3-3 5 IV CLP-V-1 10 Cp: 120℃ Δn [589nm, 25℃]: 0.110 Δε [1kHz, 25℃]: 4.0 40℃, 1000 hours: No crystals precipitated. [Composition] [4]
[0105] The formulation and some properties of composition 4 are shown in Table 6 below.
[0106] Table 6 Composition 4 Category LCD unit code Content (wt%) IV CC-3-V 35 IV CC-3-V1 3 IV PP-1-2V1 2 III CCY-3-O2 10 III CLY-3-O2 10 III CPY-3-O2 10 III CY-3-O2 5 III PY-3-O2 10 III PPY-3-O2 2 III CCOY-3-O2 3 V Sa-5O-O2 5 V Sc-CpO-O4 5 Cp: 80℃ Δn [589nm, 25℃]: 0.110 Δε [1kHz, 25℃]: -4.2 -40℃, 1000 hours: No crystals precipitated. [Composition] [5]
[0107] The formulation and some properties of composition 5 are shown in Table 7 below.
[0108] Table 7 Composition 5 Category LCD unit code Content (wt%) IV CC-3-V 38 IV CC-3-V1 7 IV CCP-V-1 10 IV CLP-3-1 9 IV CPPC-3-3 5 IV PGP-2-2V 2 III CLY-3-O2 8 V Sc-2O-O4 5 II DGUQU-3-F 3 II APUQU-3-F 3 II PGUQU-3-F 5 II PGUQU-4-F 5 Cp: 105℃ Δn [589nm, 25℃]: 0.110 Δε [1kHz, 25℃]: 3.7 ε⊥ [1KHz, 25℃]: 4.0 40℃, 1000 hours: No crystals precipitated. [Composition] [6]
[0109] The formulation and some properties of composition 6 are shown in Table 8 below.
[0110] Table 8 Composition 6 Category LCD unit code Content (wt%) IV CC-3-V 27 IV CC-3-V1 5 IV CCP-V-1 10 IV CCP-V2-1 10 IV CLP-3-1 10 IV CPP-3-1 5 IV CPPC-3-3 4 III CLY-V-O2 8 V Sa-3O-O2 5 II DGUQU-3-F 3 II APUQU-3-F 3 II PGUQU-3-F 5 II PGUQU-4-F 5 Cp: 120℃ Δn [589nm, 25℃]: 0.120 Δε [1kHz, 25℃]: 3.0 ε⊥ [1KHz, 25℃]: 5.2 40℃, 1000 hours: No crystals precipitated. [Composition] [7]
[0111] The formulation and some properties of composition 7 are shown in Table 9 below.
[0112] Table 9 Composition 7 Category LCD unit code Content (wt%) IV CC-3-4 5 IV CC-3-5 5 IV CCP-3-1 6 IV CPP-3-1 8.5 III CY-3-O4 10 III CY-3-O2 12.5 III CCY-2-O2 6 III CCY-3-O2 8 III CCY-4-O2 7 III CCY-5-O2 4 III CCY-3-O1 6 III CPY-2-O2 7 III CPY-3-O2 7 III CPY-3-O4 5 III PYP-3-2 3 Cp: 110℃ Δn [589nm, 25℃]: 0.117 Δε [1kHz, 25℃]: -4.6 -40℃, 1000 hours: No crystals precipitated. [Composition] [8]
[0113] The formulation and some properties of composition 8 are shown in Table 10 below.
[0114] Table 10 Composition 8 category Liquid crystal unit code Content (wt%) IV CC-3-2 12 IV CC-3-4 9 IV CC-3-5 8 IV CP-3-O2 5 III CY-3-O2 5 III CCOY-2-O2 12 III CCOY-3-O2 13 III CCY-2-O2 10 III CCY-3-O1 8 III CCY-3-O2 10 III CCEY-3-O2 8 Cp: 110℃ Δn [589nm, 25℃]: 0.0823 Δε [1kHz, 25℃]: -4.7 -40℃, 1000 hours: No crystals precipitated. [Composition] [9]
[0115] The formulation and some properties of composition 9 are shown in Table 11 below.
[0116] Table 11 Composition 9 category Liquid crystal unit code Content (wt%) IV CC-3-V 8 IV CC-3-V1 10 IV CC-3-2V1 9 IV CC-5-V1 9 IV CCP-3-1 6 III CCOY-3-O2 11 III CCY-3-O2 7 III CCY-5-O2 7 III CCY-1V-O2 5 III CLY-1V-O2 7.5 III CCEY-3-O2 15 CCZPC-3-3 5.5 Cp: 145℃ Δn [589nm, 25℃]: 0.095 Δε [1kHz, 25℃]: -3.3 -40℃, 1000 hours: Crystal precipitation -20℃, 1000 hours: No crystals precipitated. [Composition]
[10]
[0117] The formulation and some properties of composition 10 are shown in Table 12 below.
[0118] Table 12 Composition 10 Category Liquid crystal unit code Content (wt%) IV CC-3-V 28.5 III CY-3-O2 14.5 III COY-3-O2 10 III PPY-3-O2 1 III PPY-5-O2 2 III CCY-V-O2 7 III CCY-3-O2 1 III CPY-2-O2 10 III CPY-3-O2 9 III CLY-V-O2 6 V Sc-4O-O2 6 V Sa-5O-O2 5 Cp: 75℃ Δn [589nm, 25℃]: 0.110 Δε [1kHz, 25℃]: -6.0 -40℃, 1000 hours: No crystals precipitated. [Composition]
[11]
[0119] The formulation and some properties of composition 11 are shown in Table 13 below.
[0120] Table 13 Composition 11 category Liquid crystal unit code Content (wt%) IV CC-3-V 48 IV PP-1-2V1 2.5 IV CPP-3-2 5 III CLY-3-O2 4.5 III PY-1-O2 6 III PY-2-O2 5 III PGiY-2-O4 3.5 III PPY-3-O2 1.5 III CPY-3-O2 9 III CPY-1V-O2 8 V Sc-4O-O2 5 V Sa-5O-O2 2 Cp: 75℃ Δn [589nm, 25℃]: 0.118 Δε [1kHz, 25℃]: -2.5 γ1 [1kHz, 25℃]:50 -40℃, 1000 hours: No crystals precipitated. [Composition]
[12]
[0121] The formulation and some properties of composition 12 are shown in Table 14 below.
[0122] Table 14 Composition 12 category Liquid crystal unit code Content (wt%) IV CC-3-O1 3 IV PP-1-2V1 7.5 IV PGP-1-2V 11 IV PGP-3-2V 11 IV PGP-2-2V 10 III PY-1-O2 5 III PY-3-O2 8.5 III PGiY-2-O4 5 III CPY-2-O2 4 III CPY-3-O2 10 III CPY-1V-O2 7 III PPY-3-O2 1.5 III PYP-2-3 5 V Sc-4O-O2 7 V Sc-5O-O2 4.5 Cp: 102℃ Δn [589nm, 25℃]: 0.212 Δε [1kHz, 25℃]: -3.9 -40℃, 1000 hours: No crystals precipitated. [Composition]
[13]
[0123] The formulation and some properties of composition 13 are shown in Table 15 below.
[0124] Table 15 Composition 13 category Liquid crystal unit code Content (wt%) IV CP-3-O2 10 IV PGP-2-2 5 IV CGPC-5-3 3 IV PGP-3-3 5 IV PGP-1-2V 5 IV PGP-3-2V 8 IV PGP-2-2V 10 IV PGPC-2-5 3 VI PGP-3-F 7 II PGUQU-5-F 5 II PUQU-3-F 5 II PGUQU-3-F 4 III PYP-3-2 5 PTP-3-O2 5 CPTP-3-2 5 CPTP-3-O2 5 PTP-3-1 5 CPTP-5-2 5 Cp: 115℃ Δn [589nm, 25℃]: 0.250 Δε [1kHz, 25℃]: 5.7 -40℃, 1000 hours: No crystals precipitated. [Composition]
[14]
[0125] The formulation and some properties of composition 14 are shown in Table 16 below.
[0126] Table 16 Composition 14 category Liquid crystal unit code Content (wt%) IV CC-5-3 3.5 IV CC-3-2 7 IV CC-3-V 4 CCVC-3-V 5 IV CC-3-2V1 3 IV CC-3-4 3.5 III CY-3-O2 3 CCQU-3-F 15 VI CP-5-F 6 VI CCU-3-F 6 VI CCU-4-F 6 VI CDU-2-F 7 VI CDU-3-F 6 VI CDU-5-F 6 CCZU-5-F 3 CCZU-3-F 7 CCZPC-3-3 1 CCZCC-5-3 4 CCZC-3-3 2 CCZC-3-5 2 Cp: 92℃ Δn [589nm, 25℃]: 0.653 Δε [1kHz, 25℃]: 7.6 -40℃, 1000 hours: No crystals precipitated. [Composition]
[15]
[0127] The formulation and some properties of composition 15 are shown in Table 17 below.
[0128] Table 17 Composition 15 Category LCD unit code Content (wt%) IV CC-3-V 45 IV PP-1-2V1 6 IV CC-3-V1 8 IV CC-3-2V1 6 IV PGP-2-2V 8 IV CCP-V-1 1 IV CPP-1V-2 6.5 IV PGP-1-2V 5 IV PGP-3-2V 5.5 II CDUQU-2-F 2 II PGUQU-3-F 3 PGU-3-OCF3 4 Cp: 75℃ Δn [589nm, 25℃]: 0.123 Δε [1kHz, 25℃]: 3.1 -40℃, 1000 hours: Crystal precipitation -20℃, 1000 hours: No crystals precipitated. [Composition]
[16]
[0129] The formulation and some properties of composition 16 are shown in Table 18 below.
[0130] Table 18 Composition 16 Category LCD unit code Content (wt%) III CPY-3-O2 6 IV CP-3-O2 5 IV CC-2-3 10 IV CC-4-3 12 IV CCP-3-1 5 IV CCP-3-O1 3 VI CCP-3-F 4 VI CCU-2-F 5 VI CCU-3-F 8 VI CPU-3-F 32 VI CPU-5-F 10 Cp: 82℃ Δn [589nm, 25℃]: 0.101 Δε [1kHz, 25℃]: 7.5 -40℃, 1000 hours: No crystals precipitated. [Example of a liquid crystal assembly:] [Implementation Example] [1-1~] [Implementation Example] [1-13] [And comparative examples] [1-1~] [Comparative Example] [1-19] [:]
[0131] The above-mentioned compositions (composition 1, composition 2, or composition 3) are mixed with the compound shown in Formula I or the comparative additive, and the mixing ratios are shown in Table 19 below to obtain the liquid crystal composition. In Table 19, the additive content refers to the percentage by mass of the additive relative to the composition (composition 1, composition 2, or composition 3).
[0132] The experimental data on the low-temperature storage performance, image retention performance, and high temperature and humidity resistance of the obtained liquid crystal composition are shown in Table 19 below.
[0133] Table 19 Comparative data on low-temperature storage performance, image retention performance, and high-temperature and high-humidity tolerance of Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-19 Group Composition Additive types Additive content (wt%) Low temperature performance Afterimage performance High temperature and high humidity tolerance -40℃ for 1000 hours Crystallization Severity ND(%) Severity Number of bright spots (pieces) Example 1-1 1 I-1-1 0.005 Not crystallized A 9 A 1 Examples 1-2 1 I-1-1 0.010 Not crystallized A 10 A 1 Examples 1-3 1 I-1-1 0.050 Not crystallized A 10 A 6 Examples 1-4 1 I-1-2 0.010 Not crystallized A 10 A 5 Examples 1-5 1 I-1-3 0.010 Not crystallized A 10 A 1 Examples 1-6 1 I-1-9 0.010 Not crystallized A 10 A 1 Examples 1-7 1 I-1-12 0.050 Not crystallized A 9 A 5 Examples 1-8 1 I-1-12 0.010 Not crystallized A 10 A 7 Examples 1-9 1 I-2-1 0.010 Not crystallized A 9 A 8 Examples 1-10 1 1-8-1 0.010 Not crystallized A 9 A 9 Examples 1-11 1 1-9-1 0.010 Not crystallized A 9 A 7 Examples 1-12 2 I-1-1 0.010 Not crystallized A 10 A 3 Examples 1-13 3 I-1-1 0.010 Not crystallized A 10 A 2 Comparative Example 1-1 1 D1 0.010 Not crystallized B 8 C 144 Comparative Examples 1-2 1 D2 0.010 Not crystallized B 8 C 151 Comparative Examples 1-3 1 D3 0.010 Not crystallized C 6 D 237 Comparative Examples 1-4 1 D4 0.010 Not crystallized D 4 D 241 Comparative Examples 1-5 1 D5 0.010 Not crystallized D 4 D 252 Comparative Examples 1-6 1 D6 0.010 Not crystallized D 4 D 263 Comparative Examples 1-7 1 D7 0.010 Not crystallized B 7 D 339 Comparative Examples 1-8 1 D8 0.010 Not crystallized A 10 E >500 Comparative Examples 1-9 1 D9 0.010 Not crystallized B 8 D 357 Comparative Examples 1-10 1 D10 0.010 Not crystallized B 8 D 321 Comparative Examples 1-11 1 D11 0.010 Crystallization B 8 E >500 Comparative Examples 1-12 1 D12 0.010 Not crystallized A 9 E 497 Comparative Examples 1-13 1 D13 0.010 Crystallization C 5 D 391 Comparative Examples 1-14 1 D14 0.010 Not crystallized A 10 B 67 Comparative Examples 1-15 1 D15 0.010 Crystallization A 9 B 83 Comparative Examples 1-16 1 D16 0.010 Not crystallized A 9 D 221 Comparative Examples 1-17 1 D17 0.010 Not crystallized B 8 A 2 Comparative Examples 1-18 1 D18 0.010 Not crystallized C 5 A 2 Comparative Examples 1-19 1 D19 0.010 Not crystallized B 7 A 5
[0134] By comparing the high temperature and humidity tolerance of Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-16, it can be seen that the severity of high temperature and humidity bright spots in the embodiments of this invention is significantly improved compared with the comparative examples using the prior art. Furthermore, comparing the image retention performance of Examples 1-2 and Comparative Examples 1-17 to 1-19, it can be seen that the image retention performance of the embodiments of this invention is significantly improved compared with the comparative examples using the prior art. Comparing Examples 1-2, 1-12, and 1-13, it can be seen that additive I-1-1 exhibits excellent low-temperature performance, image retention performance, and high temperature and humidity resistance in different positive dielectric anisotropic substrates, making it adaptable to different substrates. [Example] [2-1~] [Example] [2-8] [And comparative examples] [2-1~] [Comparative Example] [2-33] [:]
[0135] The above composition 4 was mixed with the compound shown in Formula I or the comparative additive, and the mixing ratio is shown in Table 20 below to obtain the liquid crystal composition. In Table 20, the additive content refers to the mass percentage of the additive relative to composition 4.
[0136] The experimental data on the low-temperature storage performance, image retention performance, and high temperature and humidity resistance of the obtained liquid crystal composition are shown in Table 20 below.
[0137] Table 20 Comparative data on low-temperature storage performance, image retention performance, and high temperature and humidity tolerance of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-33 Group Composition Additive types Additive content (wt%) Low temperature performance Afterimage performance High temperature and high humidity tolerance -40℃ for 1000 hours Crystallization Severity ND(%) Severity Number of bright spots (pieces) Example 2-1 4 I-1-1 0.005 Not crystallized A 9 A 2 Example 2-2 4 I-1-1 0.010 Not crystallized A 10 A 1 Example 2-3 4 I-1-1 0.050 Not crystallized A 10 A 8 Examples 2-4 4 I-1-2 0.010 Not crystallized A 10 A 2 Examples 2-5 4 I-1-12 0.010 Not crystallized A 10 A 2 Examples 2-6 4 I-2-1 0.010 Not crystallized A 9 A 6 Examples 2-7 4 I-8-1 0.010 Not crystallized A 9 A 3 Examples 2-8 4 I-9-1 0.010 Not crystallized A 9 A 8 Comparative Example 2-1 4 D1 0.005 Not crystallized B 8 B 75 Comparative Example 2-2 4 D1 0.010 Not crystallized B 8 C 173 Comparative Examples 2-3 4 D1 0.050 Not crystallized A 10 E >500 Comparative Examples 2-4 4 D2 0.010 Not crystallized B 8 C 191 Comparative Examples 2-5 4 D3 0.010 Not crystallized B 8 D 231 Comparative Examples 2-6 4 D4 0.010 Not crystallized C 6 C 185 Comparative Examples 2-7 4 D5 0.005 Not crystallized C 5 B 55 Comparative Examples 2-8 4 D5 0.010 Not crystallized B 7 C 154 Comparative Examples 2-9 4 D5 0.050 Not crystallized B 8 E >500 Comparative Examples 2-10 4 D6 0.010 Not crystallized B 7 C 154 Comparative Example 2-11 4 D7 0.010 Not crystallized B 8 D 279 Comparative Example 2-12 4 D8 0.005 Not crystallized B 8 D 234 Comparative Example 2-13 4 D8 0.010 Not crystallized A 10 E >500 Comparative Example 2-14 4 D8 0.050 Crystallization A 10 E >500 Comparative Example 2-15 4 D9 0.010 Not crystallized B 8 E >500 Comparative Example 2-16 4 D10 0.005 Not crystallized B 8 C 155 Comparative Example 2-17 4 D10 0.010 Not crystallized B 8 D 274 Comparative Example 2-18 4 D10 0.050 Not crystallized A 10 E >500 Comparative Example 2-19 4 D11 0.010 Crystallization A 9 E >500 Comparative Example 2-20 4 D12 0.010 Crystallization A 10 E >500 Comparative Example 2-21 4 D13 0.010 Crystallization A 10 E >500 Comparative Example 2-22 4 D14 0.010 Crystallization A 9 B 37 Comparative Example 2-23 4 D15 0.005 Not crystallized B 8 A 9 Comparative Example 2-24 4 D15 0.010 Not crystallized A 10 B 53 Comparative Example 2-25 4 D15 0.050 Crystallization A 10 C 121 Comparative Example 2-26 4 D16 0.005 Not crystallized B 7 B 47 Comparative Example 2-27 4 D16 0.010 Not crystallized B 8 C 131 Comparative Example 2-28 4 D16 0.050 Not crystallized A 10 E >500 Comparative Example 2-29 4 D17 0.005 Not crystallized B 7 A 7 Comparative Examples 2-30 4 D17 0.010 Not crystallized B 8 A 9 Comparative Example 2-31 4 D17 0.050 Not crystallized B 8 B 11 Comparative Example 2-32 4 D18 0.010 Not crystallized C 6 A 6 Comparative Example 2-33 4 D19 0.010 Not crystallized B 7 A 6
[0138] Comparing the storage results of Examples 2-1 to 2-3 and Comparative Examples 2-12 to 2-14 and Comparative Examples 2-19 to 2-22 at -40°C for 1000 hours, it can be seen that the low-temperature miscibility of each example is better, and they can withstand low-temperature storage for a longer period of time compared with the comparative examples using the prior art. Further comparing the high-temperature and high-humidity tolerance of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3, Comparative Examples 2-16 to 2-18, and Comparative Examples 2-23 to 2-28, it can be seen that the high-temperature and high-humidity resistance of the examples in this case is significantly improved compared with the comparative examples using the prior art at different concentrations. Further comparing Examples 2-1 and 2-3 with Comparative Examples 2-29 to 2-31, it can be seen that the residual performance of additive I-1-1 at different concentrations in the negative dielectric anisotropic matrix is better than that of the comparative examples. [Example] [3-1~] [Example] [3-12] [And comparative examples] [3-1~] [Comparative Example] [3-19] [:]
[0139] The above composition 5 or composition 6 is mixed with the compound shown in Formula I or the comparative additive, and the mixing ratio is shown in Table 21 below to obtain the liquid crystal composition. In Table 21, the additive content refers to the percentage content of the additive relative to the mass of composition 5 or composition 6.
[0140] The experimental data on the low-temperature storage performance, image retention performance, and high temperature and humidity resistance of the obtained liquid crystal composition are shown in Table 21 below.
[0141] Table 21 Comparative data on low-temperature storage performance, image retention performance, and high-temperature and high-humidity tolerance of Examples 3-1 to 3-12 and Comparative Examples 3-1 to 3-19 Group Composition Additive types Additive content (wt%) Low temperature performance Afterimage performance High temperature and high humidity tolerance -40℃ for 1000 hours Crystallization Severity ND(%) Severity Number of bright spots (pieces) Example 3-1 5 I-1-1 0.005 Not crystallized A 9 A 3 Example 3-2 5 I-1-1 0.010 Not crystallized A 10 A 1 Example 3-3 5 I-1-1 0.050 Not crystallized A 10 A 9 Examples 3-4 5 I-1-2 0.010 Not crystallized A 10 A 8 Examples 3-5 5 I-1-3 0.010 Not crystallized A 9 A 5 Examples 3-6 5 I-1-9 0.010 Not crystallized A 10 A 3 Examples 3-7 5 I-1-12 0.050 Not crystallized A 9 A 5 Examples 3-8 5 I-1-12 0.010 Not crystallized A 10 A 4 Examples 3-9 5 I-2-1 0.010 Not crystallized A 9 A 9 Examples 3-10 5 1-8-1 0.010 Not crystallized A 9 A 7 Example 3-11 5 1-9-1 0.010 Not crystallized A 9 A 7 Example 3-12 6 I-1-1 0.010 Not crystallized A 10 A 1 Comparative Example 3-1 5 D1 0.010 Not crystallized A 9 D 264 Comparative Example 3-2 5 D2 0.010 Not crystallized A 9 D 287 Comparative Example 3-3 5 D3 0.010 Not crystallized A 9 D 239 Comparative Examples 3-4 5 D4 0.010 Not crystallized B 7 C 177 Comparative Examples 3-5 5 D5 0.010 Not crystallized B 8 C 182 Comparative Examples 3-6 5 D6 0.010 Not crystallized B 8 D 204 Comparative Examples 3-7 5 D7 0.010 Not crystallized A 9 D 263 Comparative Examples 3-8 5 D8 0.010 Not crystallized A 10 E >500 Comparative Examples 3-9 5 D9 0.010 Not crystallized B 8 D 277 Comparative Examples 3-10 5 D10 0.010 Not crystallized A 9 D 395 Comparative Example 3-11 5 D11 0.010 Not crystallized A 9 E >500 Comparative Example 3-12 5 D12 0.010 Not crystallized A 10 E >500 Comparative Example 3-13 5 D13 0.010 Not crystallized A 10 E >500 Comparative Example 3-14 5 D14 0.010 Not crystallized A 9 B 37 Comparative Example 3-15 5 D15 0.010 Not crystallized A 9 C 106 Comparative Example 3-16 5 D16 0.010 Not crystallized B 8 C 193 Comparative Example 3-17 5 D17 0.010 Not crystallized B 7 A 8 Comparative Example 3-18 5 D18 0.010 Not crystallized C 6 A 5 Comparative Example 3-19 5 D19 0.010 Not crystallized B 7 A 8
[0142] Comparing the high temperature and high humidity resistance of Examples 3-2, 3-12 and Comparative Examples 3-1 to 3-16 above, it can be seen that the high temperature and high humidity resistance of the additive I-1-1 in this case is significantly improved compared with the comparative examples using the prior art solution in different positive and negative mixed parent liquid crystals. [Example] [4-1~] [Example] [4-10] [And comparative examples] [4-1~] [Comparative Example] [4-10] [:]
[0143] Compositions 7-16 were mixed with the compound shown in Formula I or the comparative additive, and the mixing ratios are shown in Table 22 below to obtain the liquid crystal composition. In Table 22, the additive content refers to the percentage content of the additive relative to the mass of compositions 7-16.
[0144] The experimental data on the low-temperature storage performance, image retention performance, and high temperature and humidity resistance of the obtained liquid crystal composition are shown in Table 22 below.
[0145] Table 22 Comparative data on low-temperature storage performance, image retention performance, and high-temperature and high-humidity tolerance of Examples 4-1 to 4-10 and Comparative Examples 4-1 to 4-10 Group Composition Additive types Additive content (wt%) Low temperature performance Afterimage performance High temperature and high humidity tolerance -40℃ for 1000 hours Crystallization Severity ND(%) Severity Number of bright spots (pieces) Example 4-1 7 I-1-1 0.010 Not crystallized A 10 A 6 Example 4-2 8 I-1-1 0.010 Not crystallized A 10 A 7 Example 4-3 9 I-1-1 0.010 Crystallization A 9 A 8 Example 4-4 10 I-1-1 0.010 Not crystallized A 9 A 3 Examples 4-5 11 I-1-1 0.010 Not crystallized A 9 A 5 Examples 4-6 12 I-1-1 0.010 Not crystallized B 8 A 6 Examples 4-7 13 I-1-1 0.010 Not crystallized B 8 A 4 Examples 4-8 14 I-1-1 0.010 Not crystallized A 10 A 2 Examples 4-9 15 I-1-1 0.010 Crystallization A 10 A 9 Examples 4-10 16 1-1-1 0.010 Not crystallized A 10 A 2 Comparative Example 4-1 7 D14 0.010 Not crystallized A 10 B 73 Comparative Example 4-2 8 D14 0.010 Crystallization A 10 B 84 Comparative Example 4-3 9 D14 0.010 Crystallization B 7 B 81 Comparative Example 4-4 10 D14 0.010 Not crystallized B 7 B 59 Comparative Example 4-5 11 D14 0.010 Not crystallized A 9 B 61 Comparative Examples 4-6 12 D14 0.010 Not crystallized C 6 B 74 Comparative Examples 4-7 13 D14 0.010 Crystallization C 5 B 96 Comparative Examples 4-8 14 D14 0.010 Crystallization A 9 B 93 Comparative Examples 4-9 15 D14 0.010 Crystallization A 9 B 89 Comparative Examples 4-10 16 D14 0.010 Not crystallized A 9 B 71
[0146] Comparing the high temperature and humidity resistance of Examples 4-1 to 4-10 and Comparative Examples 4-1 to 4-10, it can be seen that the high temperature and humidity resistance of additive I-1-1 in the embodiments of the present invention is significantly improved compared with the comparative examples using the prior art solution in various types of parent liquid crystals. Further comparing the image retention performance of Examples 4-3 to 4-10 and Comparative Examples 4-3 to 4-10, it can be seen that the image retention performance is significantly improved compared with the comparative examples using the prior art solution in various types of parent liquid crystals. Further comparing the storage results of Examples 4-2, 4-7, 4-8 and Comparative Examples 4-2, 4-7, 4-8 at -40℃ for 1000 hours, it can be seen that the low temperature miscibility of the embodiments of the present invention is better, and it can withstand low temperature storage for a longer period of time compared with the comparative examples using the prior art solution.
[0147] In summary, this invention proposes a compound of Formula I and a liquid crystal composition containing such a compound. Compared to HALS molecules with two or four NH functional groups, the compound of Formula I, with three NH functional groups containing ether bonds, is a highly asymmetric molecule, making it easier to reduce molecular packing density and thus easier to bind to the PI surface. This specific structure leads to a specific ordered arrangement of the compound of Formula I in the liquid crystal. This ordered arrangement between molecules makes it difficult for hydrogen bonds to form between the NH functional groups and oxygen elements, resulting in better dispersibility of the compound of Formula I in the liquid crystal material. At the same time, the formation of the ordered structure fixes the position and orientation of the molecules to a certain extent and develops in the direction of minimizing overall energy, making it easier to form a stable structure. Liquid crystal compositions containing compounds represented by Formula I in this invention exhibit higher stability against ultraviolet light and thermal stress, and in particular, strong tolerance to high temperature and high humidity conditions (85°C / 85% RH). This ensures that they do not suffer from bright spot problems caused by monomer hydrolysis after extreme conditions (high temperature, low temperature, high temperature and low temperature cycle, high temperature and high humidity), reducing the risk of image retention and other problems in the final display. This can provide liquid crystal display devices of higher quality, especially suitable for automotive, mobile phone and tablet applications.
[0148] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.
[0149] none
Claims
1. A compound selected from the compounds shown in Formula I, wherein, Each of the following independently represents , and any hydrogen atom in can be substituted by a halogen, an alkyl group having 1-5 carbon atoms, an alkoxy group having 1-5 carbon atoms, an alkenyl group having 2-5 carbon atoms, or an alkenyloxy group having 2-5 carbon atoms; c and d each independently represent 1 or 2, and c+d represents 3; Z1 and Z2 represent straight-chain or branched alkyl groups having 1-15 carbon atoms, wherein at least one -CH2- is substituted by -O-; Z represents a single bond, a straight-chain or branched alkyl group having 1-15 carbon atoms, wherein one or more non-adjacent -CH2- are substituted by -O-.
2. The compound according to claim 1, wherein the compound represented by formula I is selected from the group consisting of compounds represented by formulas I-1 to I-10 below, where, Any hydrogen atom in Z1, Z2, Z3, Z4, and Z6 can be substituted by halogen, alkyl group with 1-5 carbon atoms, alkoxy group with 1-5 carbon atoms, alkenyl group with 2-5 carbon atoms, or alkenoxy group with 2-5 carbon atoms; Z3, Z4, and Z6 each independently represent straight-chain or branched alkyl group with 1-15 carbon atoms, wherein at least one -CH2- is substituted by -O-; Z5 represents a single bond, straight-chain or branched alkyl group with 1-15 carbon atoms, wherein one or more non-adjacent -CH2- are substituted by -O-.
3. The compound according to claim 2, wherein the compound represented by formulas I-1 to I-10 is selected from the group consisting of the compounds represented by formulas I-1-1 to I-10-1 below, I-1-1 I-1-2 I-1-3 I-1-4 I-1-5 I-1-6 I-1-7 I-1-8 I-1-13 I-1-14 I-1-15 I-2-1 I-3-1 I-4-1 I-5-1 I-6-1 I-7-1 I-8-1 I-9-1 I-10-1.
4. A liquid crystal composition comprising one or more compounds of Formula I as described in any one of claims 1-3, and one or more compounds selected from Formula II and / or Formula III, wherein R1 and R2 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups may be substituted with cyclopropylene, cyclobutylene, or cyclopentylene; Z11 represents a single bond, -CH2O-, or -CH2-CH2-; X1 represents a halogen, a haloalkyl group having 1-3 carbon atoms, or a haloalkoxy group having 1-3 carbon atoms; X2 represents an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or a haloalkoxy group having 1-15 carbon atoms; X3 represents H or -CH3; m represents 0, 1, or 2; n represents 0 or 1; q represents 1 or 2; Each of the following characters can independently represent , , , or; when m or q represents 2, each of the characters can be the same or different each time they appear.
5. The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises one or more compounds represented by formula IV, wherein R3 and R4 each independently represent an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, or an alkenyl group having 2-10 carbon atoms; a represents 1, 2, or 3; and each independently represents , , or; when a represents 2 or 3, the occurrences may be the same or different each time.
6. The liquid crystal composition according to claim 5, wherein the compound represented by formula IV is selected from the group consisting of compounds represented by formulas IV-1-1 and IV-1-2 below, IV-1-1 and IV-1-2.
7. The liquid crystal composition according to claim 5, wherein the compound represented by formula IV is selected from the group consisting of compounds represented by formula IV-2 below; wherein, R3 and R4 each independently represent an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms.
8. The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises one or more compounds of formula V, wherein R5 and R6 each independently represent an alkyl group having 1-15 carbon atoms, an alkoxy group having 1-15 carbon atoms, or an alkenyl group having 2-15 carbon atoms, wherein one or more non-adjacent -CH2- groups may be substituted with cyclopropylene, cyclobutylene, or cyclopentylene; X4 represents -S-, -O-, -CH2-S-, or -CH2-O-.
9. The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises one or more compounds of formula VI, wherein, R7 represents an alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, or an alkenyl group with 2-10 carbon atoms; X5 represents a halogen, a haloalkyl group with 1-3 carbon atoms, or a haloalkoxy group with 1-3 carbon atoms; b represents 1, 2, or 3; 、 each independently represents 、、、、、 or; when b represents 2 or 3, each occurrence can be the same or different.
10. A liquid crystal display element or liquid crystal display comprising a liquid crystal composition as described in any one of claims 4-9, wherein the liquid crystal display element is an active matrix display element or a passive matrix display element; or the liquid crystal display is an active matrix display or a passive matrix display.