Polymerizable compound, liquid crystal composition containing the same, and liquid crystal display device

Abstract

The present invention discloses a polymerizable compound, a liquid crystal composition containing the same, and a liquid crystal display device. The polymerizable compound is a compound represented by the following formula I, wherein Sp represents a single bond, a straight-chain, branched-chain or cyclic alkyl group having 1 to 5 carbon atoms, and Sp is not simultaneously a single bond, and any one or more non-adjacent -CH2- may be replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- or an acrylate group, and O- or S- replaces each other in a non-adjacent form, and one or more H atoms may be independently replaced by F, Cl or G3, and at least one H atom is replaced by G3; G3 represents a tertiary alcohol structure having 1 to 7 carbon atoms; X represents -CH2-, -O- or -S-. The polymerizable compound has good diffusibility, high stability of the formed polymer, and low residue after UV process, and can ensure excellent IS performance of the display under extreme conditions. #imgabs0# I.

Description

Technical Field

[0001] The present invention relates to the field of liquid crystal display, and more specifically, to a polymerizable compound, a liquid crystal composition containing the same, and a liquid crystal display device. Background Art

[0002] In recent years, with the continuous progress and development of science and technology, liquid crystal display technology (Liquid Crystal Display, LCD) has attracted great attention. Compared with traditional display technology, TFT-LCD liquid crystal display not only has many advantages such as small size, light weight, low power consumption, easy to drive, but also can effectively make up for the shortcomings of traditional display technology. It is widely used in various consumer electronic products such as mobile phones, TVs, digital cameras, notebooks, desktop computers, etc.

[0003] Early commercial TFT-LCD products basically adopted the TN display mode, and its biggest problem was the narrow viewing angle. With the increase in product size, especially in the TV field, the IPS display mode and VA display mode with wide viewing angle characteristics were developed and applied one after another. In particular, the improvement based on the VA display mode has achieved breakthrough development in major companies. This is mainly due to the advantages of the VA mode itself, such as wide viewing angle, high contrast and no need for friction alignment. In addition, the contrast of the VA mode display is less dependent on the optical anisotropy of the liquid crystal (△n), the thickness of the liquid crystal box (d) and the wavelength (λ) of the incident light, which will surely make the VA mode a very promising display technology.

[0004] However, the liquid crystal medium used in the display elements of the active matrix addressing mode such as the VA mode is not perfect in itself. For example, the afterimage level is significantly worse than that of the display elements with positive dielectric anisotropy, the response time is relatively slow, and the driving voltage is relatively high. At this time, some new VA display technologies have emerged quietly: such as PSVA (Polymer stabilized vertically aligned) technology, which realizes a wide viewing angle display mode similar to MVA / PVA, simplifies the CF process, thereby reducing the CF cost while increasing the aperture ratio, and can also obtain higher brightness, thereby obtaining higher contrast. In addition, compared with other common liquid crystal modes (such as TN mode and IPS mode), the display device of the PSVA mode also has the advantages of good black state, fast response speed and high transmittance. It has been widely used in many scenarios, but it is still restricted in some fields. For example, in the petroleum, chemical, coal and other industries, the production environment often has problems such as high temperature and high humidity. The current PSVA display screen cannot work stably in these environments. For example, in the field of outdoor display screens, when PSVA display screens are used for commercial advertisements, traffic guides, city signs, sports events and other information displays, they are prone to IS problems (Image Sticking) due to various adverse climatic conditions. As an important component of PSVA, reactive monomers (RM, also known as polymerizable compounds) are the main reason for limiting the above-mentioned use. In these extreme environments, such as high temperature, low temperature, high and low temperature cycles, high temperature and high humidity, the stability of the polymers formed by RM will be problematic, further affecting its display effect.

[0005] The residual RM needs to be further reduced. Another problem in the production of PSVA displays is the presence or removal of residual amounts of unpolymerized RMs, especially after the polymerization step used to create the pretilt angle in the display. For example, such unreacted RMs may adversely affect the properties of the display by, for example, polymerizing in an uncontrolled manner during operation after the display is made, and there is a great need for small residual RM monomers after the UV process.

[0006] The diffusibility of RM needs to be further improved. For RM monomers, due to the requirements of enterprises for cost reduction and efficiency improvement, it is generally expected that its polymerization speed is as fast and controllable as possible, but if its diffusibility is poor, it is easy to cause explosion and form bright spots, which will affect the display effect of the panel. SAVA (Self-Alignment for Vertical Alignment) displays do not have conventional polyimide alignment films by using so-called self-alignment additives for vertical alignment. The liquid crystal medium involved in such displays generally contains a low molecular weight liquid crystal component, a self-alignment agent containing a polar anchoring group, and a polymerizable component (RM). The use of this RM component can stabilize the orientation of the liquid crystal medium and optionally establish the desired "pre-tilt". In order to make the final display panel display excellent, the self-alignment additive and RM need to be quickly and evenly dispersed on the substrate after the ODF (One Drop Filling) process, so as to achieve low concentration differences of monomers in different regions, avoid poor alignment effect or formation of bright spots in the corner area of ​​the panel, and cause poor display. Both modes put forward higher requirements on the diffusibility of RM. Summary of the invention

[0007] Based on this, the object of the present invention is to provide a liquid crystal composition and a liquid crystal display device comprising the liquid crystal composition, so as to at least solve the above technical problems. In the molecular structure of the polymerizable compound provided in the present invention, a ring system is introduced into the structure of a straight-linked biphenyl or terphenyl polymerizable compound containing a tertiary alcohol branch to improve its molecular spatial structure and polymerization properties, and it does not have the above disadvantages (low stability of RM forming polymers in extreme environments; large RM residue; slightly poor RM diffusivity) or the degree of the above disadvantages is reduced. In particular, the polymerizable compound has the advantages of good diffusivity, high stability of forming polymers, and low residue after UV process. At the same time, after the liquid crystal composition formed by the polymerizable compound and the liquid crystal component is used in a liquid crystal display, it can ensure that the display has excellent IS performance after extreme conditions (high temperature, low temperature, high and low temperature cycle, high temperature and high humidity), reducing the risk of problems such as residual images in the final display.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] In one aspect, the present invention provides a polymerizable compound, wherein the polymerizable compound is a compound represented by the following formula I:

[0010] I;

[0011] in,

[0012] L1 and L2 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen, wherein any one or more unconnected -CH2- can be independently replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC-, or -Sp-;

[0013] L3, L4, L5, L6 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen;

[0014] n1 and n2 each independently represent 0, 1, 2, 3 or 4;

[0015] m1 and m2 each independently represent 0 or 1, and m1 and m2 are not 0 at the same time;

[0016] P each occurrence independently represents an acrylate group, a methacrylate group or a fluoroacrylate group;

[0017] Sp represents a single bond, a C1-C5 straight chain, branched or cyclic alkyl group, and Sp is not a single bond at the same time, wherein any one or more unconnected -CH2- can be replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- or acrylate groups with O- or S- in a form that is not connected to each other, one or more H atoms can be independently substituted by F, Cl or G3, and at least one H atom is substituted by G3;

[0018] G3 represents a tertiary alcohol structure of C1-C7;

[0019] X represents -CH2-, -O- or -S-.

[0020] Furthermore, the compound represented by formula I is at least one of the compounds represented by formulas I-1 to I-41:

[0021] I-1, I-2, I-3,

[0022] I-4, I-5, I-6,

[0023] I-7, I-8, I-9,

[0024] I-10、 I-11、 I-12、

[0025] I-13、 I-14、 I-15、

[0026] I-16、 I-17、 I-18、

[0027] I-19、 I-20, I-21、

[0028] I-22、 I-23、 I-24、

[0029] I-25、 I-26、

[0030] I-27、 I-28、

[0031] I-29、 I-30,

[0032] I-31, I-32、

[0033] I-33、 I-34、

[0034] I-35, I-36、

[0035] I-37, I-38、

[0036] I-39, I-40,

[0037] I-41;

[0038] Among them,

[0039] L3, L4, L5, L6 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, halogen;

[0040] P each occurrence independently represents an acrylate group, a methacrylate group or a fluoroacrylate group;

[0041] Sp represents a single bond, a C1-C5 straight chain, branched or cyclic alkyl group, and Sp is not a single bond at the same time, wherein any one or more unconnected -CH2- can be replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- or acrylate groups with O- or S- in a form that is not connected to each other, one or more H atoms can be independently substituted by F, Cl or G3, and at least one H atom is substituted by G3;

[0042] G3 represents a tertiary alcohol structure of C1-C7;

[0043] X represents -CH2-, -O-, or -S-.

[0044] Furthermore, the compound represented by formula I is at least one of the compounds represented by formulas I-1-1 to I-41-5:

[0045] I-1-1, I-1-2,

[0046] I-1-3, I-1-4,

[0047] I-1-5, I-1-6,

[0048] I-1-7, I-1-8,

[0049] I-1-9, I-2-1,

[0050] I-2-2, I-2-3,

[0051] I-2-4, I-2-5,

[0052] I-2-6, I-2-7,

[0053] I-2-8、 I-3-1、

[0054] I-3-2、 I-3-3、

[0055] I-3-4、 I-3-5、

[0056] I-3-6、 I-3-7、

[0057] I-3-8、 I-4-1、

[0058] I-4-2、 I-4-3、

[0059] I-4-4、 I-4-5、

[0060] I-4-6、 I-5-1、

[0061] I-5-2、 I-5-3、

[0062] I-5-4、 I-5-5、

[0063] I-5-6、 I-6-1、

[0064] I-6-2、 I-7-1、

[0065] I-7-2、 I-8-1、

[0066] I-8-2、 I-9-1、

[0067] I-9-2、 I-10-1、

[0068] I-10-2、 I-10-3、

[0069] I-10-4、 I-10-5、

[0070] I-10-6、 I-11-1、

[0071] I-11-2、 I-11-3、

[0072] I-11-4、 I-11-5、

[0073] I-11-6、 I-12-1、

[0074] I-12-2、 I-13-1、

[0075] I-13-2、 I-14-1、

[0076] I-14-2、 I-15-1、

[0077] I-15-2、 I-16-1、

[0078] I-16-2、 I-17-1、

[0079] I-17-2、 I-18-1、

[0080] I-18-2、 I-19-1、

[0081] I-19-2、 I-20-1、

[0082] I-20-2、 I-21-1、

[0083] I-21-2、 I-22-1、

[0084] I-22-2、 I-23-1、

[0085] I-23-2、 I-24-1、

[0086] I-25-1、 I-26-1、

[0087] I-26-2、 I-27-1、

[0088] I-28-1、 I-29-1、

[0089] I-30-1、 I-31-1、

[0090] I-32-1、 I-33-1、

[0091] I-34-1、 I-35-1、

[0092] I-36-1、 I-37-1、

[0093] I-38-1、 I-38-2、

[0094] I-38-3、 I-38-4、

[0095] I-38-5、 I-39-1、

[0096] I-39-2、 I-39-3、

[0097] I-39-4、 I-39-5、

[0098] I-40-1、 I-40-2、

[0099] I-40-3, I-40-4,

[0100] I-40-5, I-41-1,

[0101] I-41-2, I-41-3,

[0102] I-41-4 I-41-5.

[0103] In another aspect, the present invention provides a liquid crystal composition, which comprises one or more polymerizable compounds as described in the first aspect as a first component, one or more compounds represented by formula II as a second component, and one or more compounds represented by formula III as a third component:

[0104] II;

[0105] III;

[0106] in,

[0107] R1, R2, R3, and R4 each independently represent a C1-C10 alkyl group, a C1-C10 alkoxy group, or a C2-C10 alkenyl group, wherein one or more non-adjacent -CH2- groups may be replaced by a cyclopropyl group, a cyclopentyl group, or a cyclobutyl group;

[0108] Z1 and Z2 each independently represent -CH2-CH2-, -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond;

[0109] , each independently represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene;

[0110] , Each independently represents 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene, wherein one or two -CH2- may be replaced by -O-;

[0111] m3 means 1 or 2;

[0112] n3 represents 0, 1 or 2.

[0113] Furthermore, the one or more compounds represented by formula II are one or more compounds of formula II-1 to II-15:

[0114] II-1, II-2, II-3,

[0115] II-4, II-5, II-6,

[0116] II-7, II-8, II-9,

[0117] II-10, II-11, II-12,

[0118] II-13, II-14, II-15.

[0119] Furthermore, the one or more compounds represented by formula III are one or more compounds represented by formula III-1 to III-12:

[0120] III-1, III-2,

[0121] III-3, III-4,

[0122] III-5, III-6,

[0123] III-7, III-8,

[0124] III-9, III-10,

[0125] III-11, III-12;

[0126] in,

[0127] R3 and R4 each independently represent a C1-C10 alkyl group, a C1-C10 alkoxy group or a C2-C10 alkenyl group, wherein one or more non-adjacent -CH2- groups may be replaced by a cyclopropyl group, a cyclopentyl group or a cyclobutyl group.

[0128] Furthermore, the liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by formula IV:

[0129] IV;

[0130] in,

[0131] R5 and R6 each independently represent a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group;

[0132] , Each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a 1,4-cyclohexenylene group.

[0133] Furthermore, the liquid crystal composition further comprises one or more compounds represented by formula V:

[0134] V;

[0135] in,

[0136] R7 and R8 each independently represent an H atom, a halogen, a C1-C10 alkyl group, a C1-C10 fluoroalkyl group, a C1-C10 alkoxy group or a C1-C10 fluoroalkoxy group, and any one or more CH2 groups represented by R7 and R8 may be replaced by a cyclopentyl group, a cyclobutyl group or a cyclopropyl group;

[0137] X1 represents -O-, -S-, -CO- or -CH2O-;

[0138] Z3 and Z4 each independently represent -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond;

[0139] , each independently represents cyclopropyl, cyclobutyl, cyclopentyl, 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene;

[0140] m4 means 0, 1 or 2;

[0141] n4 represents 0, 1 or 2.

[0142] Furthermore, the liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by formula VI:

[0143] VI;

[0144] in,

[0145] R9, R 10 each independently represents a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group;

[0146] represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene;

[0147] Each occurrence of (F) independently represents H or F.

[0148] Furthermore, in the liquid crystal composition, the total mass percentage of the compound represented by formula I is 0.01-1%, the total mass percentage of the compound represented by formula II is 15-60%, and the total mass percentage of the compound represented by formula III is 20-80%.

[0149] In still another aspect, the present invention provides a liquid crystal display device comprising the liquid crystal composition as described above.

[0150] Furthermore, the liquid crystal display device is a PSVA or SAVA display.

[0151] The beneficial effects of the present invention are as follows:

[0152] The main ring of the polymerizable compound in the present invention contains a benzene ring condensation system and must contain a tertiary alcohol side chain structure. The polymerizable compound has the advantages of good diffusivity and low residue after UV process. At the same time, when the liquid crystal composition containing the polymerizable compound is used in a liquid crystal display device, for the display, it can ensure that they have excellent IS performance after extreme conditions (high temperature, low temperature, high and low temperature cycle, high temperature and high humidity), reduce the risk of problems such as afterimages in the final display, and can provide a liquid crystal display device with better quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0153] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0154] Figure 1 The mass spectrum of the compound represented by formula I-1-1 is shown.

[0155] Figure 2 The mass spectrum of the compound represented by formula I-38-2 is shown. DETAILED DESCRIPTION

[0156] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0157] According to a specific embodiment of the present invention, a polymerizable compound is provided, wherein the polymerizable compound is a compound represented by the following formula I:

[0158] I;

[0159] in,

[0160] L1 and L2 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen, wherein any one or more unconnected -CH2- can be independently replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC-, or -Sp-;

[0161] L3, L4, L5, L6 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen;

[0162] n1 and n2 each independently represent 0, 1, 2, 3 or 4;

[0163] m1 and m2 each independently represent 0 or 1, and m1 and m2 are not 0 at the same time;

[0164] P, at each occurrence, independently represents an acrylate group, a methacrylate group or a fluoroacrylate group;

[0165] Sp represents a single bond, a C1-C5 straight chain, branched or cyclic alkyl group, and Sp is not a single bond at the same time, wherein any one or more unconnected -CH2- can be replaced by -O-, -S-, -CO-, -CH2O-, -OCH2-, -COO-, -OOC- or acrylate groups with O- or S- in a form that is not connected to each other, one or more H atoms can be independently substituted by F, Cl or G3, and at least one H atom is substituted by G3;

[0166] G3 represents a tertiary alcohol structure of C1-C7;

[0167] X represents -CH2-, -O- or -S-.

[0168] In this embodiment, the acrylate group , methacrylate group , fluoroacrylate group , where · represents the connection site.

[0169] In this embodiment, exemplary halogens include, but are not limited to, selected from F, Cl, Br, and the like.

[0170] In some preferred examples, the compound represented by Formula I is a compound represented by Formula I-1, Formula I-10 or Formula I-38. Under this condition, the polymerizable compound has better diffusivity and lower residue after UV process. At the same time, when the liquid crystal composition containing the polymerizable compound is used in a liquid crystal display device, it can ensure that the display has better IS performance after extreme conditions (high temperature, low temperature, high and low temperature cycle, high temperature and high humidity).

[0171] According to another specific embodiment of the present invention, a liquid crystal composition is provided, wherein the liquid crystal composition comprises one or more polymerizable compounds as described above as a first component, one or more compounds represented by formula II as a second component, and one or more compounds represented by formula III as a third component:

[0172] II;

[0173] III;

[0174] in,

[0175] R1, R2, R3, and R4 each independently represent a C1-C10 alkyl group, a C1-C10 alkoxy group, or a C2-C10 alkenyl group, wherein one or more non-adjacent -CH2- groups may be replaced by a cyclopropyl group, a cyclopentyl group, or a cyclobutyl group;

[0176] Z1 and Z2 each independently represent -CH2-CH2-, -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond;

[0177] , each independently represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene;

[0178] , Each independently represents 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene, wherein one or two -CH2- may be replaced by -O-;

[0179] m3 means 1 or 2;

[0180] n3 represents 0, 1 or 2.

[0181] The liquid crystal composition is also a polymerizable liquid crystal composition. In a display using the liquid crystal composition, the compound shown in Formula I is added to a liquid crystal medium, and after being introduced into a liquid crystal box, a pre-tilt of the liquid crystal molecules can be formed by UV photopolymerization or cross-linking under voltage applied between electrodes. This is beneficial for simplifying the LCD production process, improving the response speed, and reducing the threshold voltage.

[0182] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula I is 0.01-1%, preferably 0.03-0.5%, and more preferably 0.1-0.5%, 0.2-0.4%.

[0183] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula II is 15-60%, preferably 20-40%, and more preferably 25-35%.

[0184] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula III is 20-80%, preferably 30-70%, and more preferably 45-65%.

[0185] In some examples, the liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by Formula IV:

[0186] IV;

[0187] in,

[0188] R5 and R6 each independently represent a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group;

[0189] , Each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a 1,4-cyclohexenylene group.

[0190] In some preferred examples, the compound represented by formula IV is selected from the compounds represented by the following formulas IV-1 to IV-4:

[0191] IV-1; IV-2;

[0192] IV-3; IV-4;

[0193] Wherein, R51 and R61 each independently represent a C2-C6 alkyl group or a C2-C6 alkenyl group; and R62 represents a C1-C5 alkoxy group.

[0194] In some preferred examples, R 51 , R 61 It is vinyl, 2-propenyl or 3-pentenyl.

[0195] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula IV is 2-15%, preferably 4-15%.

[0196] In some examples, the liquid crystal composition further comprises one or more compounds represented by Formula V:

[0197] V;

[0198] in,

[0199] R7 and R8 each independently represent an H atom, a halogen, a C1-C10 alkyl group, a C1-C10 fluoroalkyl group, a C1-C10 alkoxy group or a C1-C10 fluoroalkoxy group, and any one or more CH2 groups represented by R7 and R8 may be replaced by a cyclopentyl group, a cyclobutyl group or a cyclopropyl group;

[0200] X1 represents -O-, -S-, -CO- or -CH2O-;

[0201] Z3 and Z4 each independently represent -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond;

[0202] , each independently represents cyclopropyl, cyclobutyl, cyclopentyl, 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene;

[0203] m4 means 0, 1 or 2;

[0204] n4 represents 0, 1 or 2.

[0205] In some preferred examples, the compound represented by formula V is selected from the compounds represented by the following formulas V-1 to V-6:

[0206] V-1; V-2;

[0207] V-3; V-4;

[0208] V-5; V-6;

[0209] Among them, R 81 Each independently represents a C2-C6 alkyl group.

[0210] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula V is 2-5%.

[0211] In some examples, the liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by Formula VI:

[0212] VI;

[0213] in,

[0214] R9, R 10 each independently represents a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group;

[0215] represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene;

[0216] (F) each independently represents H or F.

[0217] In some examples, the compound represented by Formula VI is selected from the compounds represented by the following Formulas VI-1 to VI-3:

[0218] VI-1, VI-2,

[0219] VI-3;

[0220] Among them, R9 and R10 each independently preferably represent a C2-C6 alkyl group or a C2-C6 alkenyl group.

[0221] In some examples, in the liquid crystal composition, the total mass percentage of the compound represented by Formula VI is 1-3%.

[0222] Various functional dopants may be added to the liquid crystal compound provided in this embodiment, and the mass percentage of the exemplary dopants is preferably between 0.01-1%. These dopants are mainly antioxidants, ultraviolet absorbers, and chiral agents.

[0223] Exemplary antioxidants, UV absorbers are preferably selected from:

[0224] , ,

[0225] , ,

[0226] , ,

[0227] , ;

[0228] S represents an integer of 1-10.

[0229] According to another specific embodiment of the present invention, a liquid crystal display device is provided. The liquid crystal display device includes the liquid crystal composition as described above.

[0230] In some examples, the liquid crystal display device is a PSVA or SAVA display.

[0231] The technical solution of the present invention is described below in conjunction with some specific embodiments:

[0232] In this manual, unless otherwise specified, percentages refer to mass percentages, temperatures are in degrees Celsius (℃), and the specific meanings of other symbols and test conditions are as follows:

[0233] Cp represents the clearing point of liquid crystal (℃), measured by DSC quantitative method;

[0234] Δn represents optical anisotropy, no is the refractive index of ordinary light, ne is the refractive index of extraordinary light, the test conditions are 25±2℃, 589nm, and Abbe refractometer test;

[0235] Δε represents dielectric anisotropy, Δε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥ is the dielectric constant perpendicular to the molecular axis, the test conditions are 25±0.5℃, 20 micron vertical box, INSTEC:ALCT-IR1 test;

[0236] K 11 is the splay elastic constant, K 33 is the bending elastic constant, the test conditions are: 25°C, INSTEC:ALCT-IR1, 20 μm vertical box;

[0237] γ1 represents rotational viscosity (mPa·s), the test conditions are 25±0.5℃, 20 μm vertical box, INSTEC: ALCT-IR1 test;

[0238] UV2 time indicates the time of UV irradiation in PSVA process (min);

[0239] RM residual indicates the residual content (ppm). Under the same temperature and wavelength, the gradient method is used to detect the RM content. Instrument: Agilent1200;

[0240] The IS grade indicates the level of afterimage. After the PSVA test box with a thickness of 3.5 um is irradiated with UV1 and UV2 to form a pre-tilt angle of 88.5±0.2°, a short wave of 60Hz, an AC voltage of 19V and a DC voltage of 2V are applied to the test box, and the box is placed in different extreme conditions with backlight. After being treated for 500 hours respectively and released for 1 hour, the box is directly observed or observed with an ND filter at medium and low grayscales. Direct observation is best without IS. When observed with an ND filter, the larger the ND value, the better the IS grade. For example, ND10 is better than ND9. This solution considers that ND10 and no IS are both feasible.

[0241] Measurement of RM diffusivity (distribution behavior of additives): Fill the test box (8cm×4cm) with the test mixture. After the mixture is filled, slice the lower part of the test box (close to the filling opening, 4cm×4cm) and the upper part of the test box (opposite to the filling opening, 4cm×4cm). Under the same temperature and wavelength, the gradient method is used to detect the RM content in the lower and upper parts respectively. Instrument: Agilent1200. The quality of diffusivity is determined by the concentration difference. The concentration difference between the lower and upper parts Δ=lower RM content-upper RM content. The smaller Δ, the better its diffusivity. There are two types of diffusion test boxes. One is a test box with no PI on the upper and lower substrates (SAVA mode), and the other is a test box with NISSAN PI on the upper and lower substrates (PSVA mode).

[0242] The preparation method of the liquid crystal composition is as follows: each liquid crystal monomer is weighed according to a certain ratio and put into a stainless steel beaker, and the stainless steel beaker containing each liquid crystal monomer is placed on a magnetic stirring instrument to heat and melt. After most of the liquid crystal monomers in the stainless steel beaker are melted, a magnetic rotor is added to the stainless steel beaker, and the mixture is stirred evenly. After cooling to room temperature, the liquid crystal composition is obtained.

[0243] The liquid crystal monomer structure of the embodiment of the present invention is represented by a code, and the code representation method of the liquid crystal ring structure, end group, and connecting group is shown in Table 1 and Table 2 below.

[0244] Table 1 Corresponding codes of ring structures

[0245]

[0246] Table 2 Corresponding codes of terminal groups and linking groups

[0247]

[0248] Example:

[0249] , whose code is PPY-3-O2;

[0250] , whose code is CPY-2-O2;

[0251] , whose code is CCY-3-O2;

[0252] , whose code is COY-3-O2;

[0253] , whose code is CCOY-3-O2;

[0254] , whose code is CLY-3-O2;

[0255] , its code is Sb-CpO-O4;

[0256] , its code is Sc-CpO-O4.

[0257] Example 1

[0258] The structural formula of the polymerizable compound is shown in the following formula I-1-1:

[0259] I-1-1.

[0260] The preparation route is as follows:

[0261]

[0262]

[0263]

[0264]

[0265] Intermediate 1: In a 1L three-necked flask, add 21.3g (0.1mol) of 7-bromo-2,3-hydrogen-1H-indene-4-ol, 16.6g (0.12mol) of anhydrous potassium carbonate, 15.2g (0.12mol) of benzyl chloride, and 0.5L of N,N-dimethylformamide, and react at 120°C for 4 hours; cool to 40°C, pour into 2L of ice water, stir vigorously, and a brown solid precipitates. Filter by suction, and recrystallize the filter cake with 100ml of ethanol to obtain a white solid intermediate 1, 27.8g, purity: 98.8%, yield: 92%;

[0266] Intermediate 2: Add 27.8g (0.092mol) of intermediate 1 and 100mL of tetrahydrofuran to a 1L three-necked flask, protect with nitrogen, and cool down; T=-80℃, drop 40ml (0.1mol) of n-butyl lithium, drip for 30min, and keep warm for 1h; T=-80℃, drop 10.4g (0.1mol) of trimethyl borate in THF solution, drip for 20min, and keep warm for 1h; naturally heat up, add 200ml of water to quench, separate the phases, extract the aqueous phase with 2x200mL of ethyl acetate, combine the organic phases, dry and concentrate, and obtain white solid intermediate 2, 18g, purity: 92.8%, yield: 73.2%;

[0267] Intermediate 3: Add 259.2 g (0.6 mol) of isopropyltriphenylphosphine iodide and 1000 mL of tetrahydrofuran to a 3L three-necked flask, protect with nitrogen, and cool down; T = 0°C, add 67.2 g (0.6 mol) of potassium tert-butoxide, stir for 30 min, add dropwise 92.5 g (0.5 mol) of THF solution of p-bromobenzaldehyde, keep warm and react for 2 h; add 500 ml of water to quench the reaction, separate the phases, extract the aqueous phase with 2x300 mL of ethyl acetate, combine the organic phases, dry and concentrate, and obtain a white solid. Recrystallize twice with 2 times (mass ratio) of anhydrous ethanol to obtain a white solid intermediate 3, 89.8 g, purity: 93.7%, yield: 85.1%;

[0268] Intermediate 4: Add 21.1g (0.1mol) of intermediate 3, 18.8g (0.14mol) of 4-methylmorpholine-4-oxide, 500ml of acetone and 50ml of distilled water into a 1L three-necked flask, stir to make it dispersed evenly, add 4% by mass fraction of osmium tetroxide aqueous solution (13ml, 0.002mol); stir at room temperature for 48h, add 200ml of water, control the temperature at 0℃, slowly drop 2M HCl until weakly acidic, solid precipitates, the solid is recrystallized with 1 times toluene and 2 times petroleum ether (weight ratio) to obtain white solid intermediate 4, 16.8g, purity: 82.9%, yield: 68.8%;

[0269] Intermediate 5: 18.2 g (0.068 mol) of intermediate 2, 16.8 g (0.068 mol) of intermediate 4, 11.3 g (0.082 mol) of anhydrous potassium carbonate, 0.3 L of toluene, and 0.1 L of water were added to a 1 L three-necked flask, and palladium catalyst was added under nitrogen protection, and the reaction was heated under reflux for 6 hours; the liquid was separated, the organic phase was washed with 0.2 L of water, the organic phase was passed through a 50 g silica gel column, the column was flushed with 150 g of toluene, the organic phase was spin-dried, and slurried with 2 times petroleum ether (weight ratio) to obtain a white solid intermediate 5, 22.1 g, purity: 97.7%, yield: 83.9%;

[0270] Intermediate 6: In a 1L three-necked flask, add intermediate 5 from the previous step, 0.3L toluene, 0.1L anhydrous ethanol, and 0.2g palladium carbon (5%). Evacuate with nitrogen 5 times and hydrogen 3 times. Stir and hydrogenate at room temperature for 4h. Filter to remove palladium carbon. After concentration, add 1x toluene and 2x petroleum ether (weight ratio) for recrystallization to obtain white solid intermediate 6, 13.1g, purity: 98.9%, yield: 95%;

[0271] Product I-1-1: 13.1g (0.054mol) of intermediate 6, 11.6g (0.135mol) of methacrylic acid, and 0.5L of dichloromethane were added to a 1L three-necked flask, and the temperature was cooled to 0°C under nitrogen protection, and the temperature was controlled at 0-5°C. 27.8g (0.135mol) of DCC was added. After the addition, the temperature was naturally raised to room temperature, and the reaction was carried out at room temperature for 8 hours; Filter, remove insoluble matter, concentrate the filtrate, recrystallize twice with 2 times ethanol, and recrystallize once with 1 times toluene and 2 times ethanol to obtain product I-1-1, a white solid, 12.5g, purity: 99.61%, yield: 53.2%, mp: 81.5°C. The mass spectrum results of product I-1-1 are as follows Figure 1 shown.

[0272] Example 2

[0273] The structural formula of the polymerizable compound is shown in the following formula I-1-7:

[0274] I-1-7.

[0275] The preparation route is as follows:

[0276]

[0277]

[0278]

[0279] Intermediate 7: Add 137g (0.5mol) 1,7-dibromo-dihydro-indene and 500mL tetrahydrofuran to a 2L three-necked flask, protect with nitrogen, and cool down; T=-80℃, drop 220ml (0.55mol) n-butyl lithium, drip for 30min, and keep warm for 1h; T=-80℃, drop 43.8g (0.6mol) DMF in THF, drip for 30min, and keep warm for 1h; naturally heat up, add 500ml water to quench, separate the phases, extract the aqueous phase with 2x200mL ethyl acetate, combine the organic phases, dry and concentrate, and obtain light brown viscous liquid intermediate 7, 66g, purity: 91.3%, yield: 58.7%;

[0280] Intermediate 8: Add 150.3 g (0.35 mol) of isopropyltriphenylphosphine iodide and 500 mL of tetrahydrofuran to a 2L three-necked flask, protect with nitrogen, and cool down; T = 0°C, add 39.2 g (0.35 mol) of potassium tert-butoxide, stir for 30 min, dropwise add 66 g (0.29 mol) of THF solution of intermediate 7, keep warm and react for 2 h; add 500 ml of water to quench the reaction, separate the phases, extract the aqueous phase with 2x300 mL of ethyl acetate, combine the organic phases, dry and concentrate, and obtain a white solid, which is recrystallized twice with 200 g of anhydrous ethanol to obtain a white solid intermediate 8, 65.3 g, purity: 81.1%, yield: 91.2%;

[0281] Intermediate 9: Add 65.3g (0.26mol) of intermediate 8, 48.8g (0.36mol) of 4-methylmorpholine-4-oxide, 1000ml of acetone and 100ml of distilled water into a 2L three-necked flask, stir to make it evenly dispersed, add 4% by mass fraction of osmium tetroxide aqueous solution (33.8ml, 0.005mol); stir at room temperature for 48h, add 500ml of water, control the temperature at 0℃, slowly add 2MHCl dropwise until weakly acidic, solid precipitates, the solid is recrystallized with 1 times toluene and 2 times petroleum ether (weight ratio) to obtain white solid intermediate 9, 45.7g, purity: 88.3%, yield: 61.7%;

[0282] Intermediate 10: 45.7 g (0.16 mol) of intermediate 9, 36.5 g (0.16 mol) of 4-benzyloxyphenylboronic acid, 26.5 g (0.19 mol) of anhydrous potassium carbonate, 0.6 L of toluene, and 0.2 L of water were added to a 2 L three-necked flask, and palladium catalyst was added under nitrogen protection, and the reaction was heated under reflux for 6 hours; the liquid was separated, the organic phase was washed with 0.5 L of water, the organic phase was passed through a 100 g silica gel column, the column was flushed with 400 g of toluene, and the organic phase was spin-dried and slurried with 2 times petroleum ether (weight ratio) to obtain a white solid intermediate 10, 53.1 g, purity: 91.6%, yield: 85.5%;

[0283] Intermediate 11: In a 1L three-necked flask, add intermediate 5 from the previous step, 0.3L toluene, 0.1L anhydrous ethanol, and 0.5g palladium carbon (5%). Evacuate with nitrogen 5 times and hydrogen 3 times. Stir and hydrogenate at room temperature for 4h. Filter to remove palladium carbon. After concentration, add 1x toluene and 2x petroleum ether (weight ratio) for recrystallization to obtain white solid intermediate 11, 36.3g, purity: 90.7%, yield: 87.1%;

[0284] Product I-1-7: In a 2L three-necked flask, 36.3g (0.12mol) of intermediate 11, 25.8g (0.3mol) of methacrylic acid, and 0.8L of dichloromethane were added. The temperature was cooled to 0℃ under nitrogen protection and controlled at 0-5℃. 61.7g (0.3mol) of DCC was added. After the addition, the temperature was naturally raised to room temperature and reacted at room temperature for 8 hours. Filter to remove insoluble matter, concentrate the filtrate, recrystallize twice with 2 times ethanol, and recrystallize once with 1 times toluene and 2 times ethanol to obtain product I-1-7, a white solid, 12.5g, purity: 99.49%, yield: 53.2%, mp: 82.7℃.

[0285] Example 3

[0286] The structural formula of the polymerizable compound is shown in the following formula I-10-1:

[0287] I-10-1.

[0288] The preparation route is as follows:

[0289] First, the common intermediate 12 was synthesized according to the following route:

[0290]

[0291]

[0292] Then compound I-10-1 was synthesized according to the following route:

[0293]

[0294]

[0295] Intermediate 13: Add 15.3 g (0.05 mol) of intermediate 12 and 100 mL of tetrahydrofuran to a 0.5 L three-necked flask, protect with nitrogen, and cool down; T = -80 ° C, add 24 ml (0.06 mol) of n-butyl lithium dropwise, and complete the dropwise addition for 20 min, and keep the temperature for reaction for 1 h; T = -80 ° C, add 6.24 g (0.06 mol) of trimethyl borate in THF solution dropwise, and complete the dropwise addition for 150 min, and keep the temperature for reaction for 1 h; naturally heat up, add 100 ml of water to quench, separate the phases, extract the aqueous phase with 2x100 mL of ethyl acetate, combine the organic phases, dry and concentrate, and slurry with 2 times petroleum ether (mass ratio) to obtain a white solid intermediate 13, 10.8 g, purity: 95.1%, yield: 78.3%;

[0296] Intermediate 14: 10.8 g (0.04 mol) of intermediate 13, 9.8 g (0.04 mol) of intermediate 4, 6.6 g (0.048 mol) of anhydrous potassium carbonate, 210 ml of toluene, and 70 ml of water were added to a 0.51 L three-necked flask, and palladium catalyst was added under nitrogen protection, and the reaction was heated under reflux for 6 hours; the liquid was separated, the organic phase was washed with 100 ml of water, the organic phase was passed through a silica gel column, 80 g of toluene was flushed into the column, the column was spin-dried, and 2 times of petroleum ether was used for slurrying (weight ratio) to obtain a white solid intermediate 14, 12.7 g, purity: 93.6%, yield: 81.6%;

[0297] Intermediate 15: 12.7 g of intermediate 14, 150 ml of toluene, 150 ml of anhydrous ethanol, and 0.25 g of palladium carbon (5%) were added to a 1 L three-necked flask. The flask was evacuated with nitrogen for 5 times and hydrogen for 3 times. The flask was stirred at room temperature for 4 h and hydrogenated. The palladium carbon was removed by filtration. After concentration, the flask was recrystallized with 1x toluene and 2x petroleum ether (weight ratio) to obtain a white solid intermediate 15, 8.9 g, purity: 96.2%, yield: 93.1%;

[0298] Product I-10-1: In a 1L three-necked flask, add 8.9g (0.03mol) of intermediate 15, 6.3g (0.075mol) of methacrylic acid, and 100ml of dichloromethane. Cool down to 0℃ under nitrogen protection, control the temperature at 0-5℃, add 15.4g (0.075mol) of DCC, and after the addition, naturally warm to room temperature. React at room temperature for 8 hours; filter to remove insoluble matter, concentrate the filtrate, recrystallize twice with 2 times ethanol, and recrystallize once with 1 times toluene and 2 times ethanol to obtain product I-10-1, white solid, 8.3g, purity: 99.72%, yield: 63.7%, mp: 91.7℃.

[0299] Example 4

[0300] The structural formula of the polymerizable compound is shown in the following formula I-26-1:

[0301] I-26-1.

[0302] The preparation route is as follows:

[0303]

[0304]

[0305] Intermediate 16: 16.2 g (0.05 mol) of 4-bromo-7-iodo-2,3-dihydro-indene, 11.4 g (0.05 mol) of 4-benzyloxyphenylboronic acid, 8.28 g (0.06 mol) of anhydrous potassium carbonate, 300 ml of toluene, and 100 ml of water were added to a 0.5 L three-necked flask, and a palladium catalyst was added under nitrogen protection, and the mixture was heated under reflux for 6 hours; the mixture was separated, the organic phase was washed with 100 ml of water, the organic phase was passed through a silica gel column, the column was flushed with 100 g of toluene, the mixture was spin-dried, 20 times of petroleum ether was heated to dissolve, passed through a silica gel column, 10 times of hot petroleum ether was flushed into the column, the mixture was concentrated, and the mixture was slurried with 2 times of petroleum ether (by weight ratio) to obtain a white solid intermediate 16, 11.8 g, purity: 95.6%, yield: 62.1%;

[0306] Intermediate 17: Add 11.8g (0.031mol) of intermediate 16 and 200mL of tetrahydrofuran to a 1L three-necked flask, protect with nitrogen, and cool down; T=-80℃, drop 15ml (0.037mol) of n-butyl lithium, add dropwise for 20min, and keep warm for 1h; T=-80℃, dropwise add 3.8g (0.037mol) of trimethyl borate in THF solution, add dropwise for 150min, and keep warm for 1h; naturally heat up, add 100ml of water to quench, separate the phases, extract the aqueous phase with 2x200mL of ethyl acetate, combine the organic phases, dry and concentrate, and slurry with 2 times petroleum ether (mass ratio) to obtain white solid intermediate 17, 7.9g, purity: 90.8%, yield: 73.9%;

[0307] Intermediate 18: 7.9 g (0.023 mol) of intermediate 17, 5.6 g (0.023 mol) of intermediate 4, 3.8 g (0.028 mol) of anhydrous potassium carbonate, 500 ml of toluene, and 170 ml of water were added to a 1L three-necked flask, and palladium catalyst was added under nitrogen protection. The mixture was heated under reflux for 6 hours; the mixture was separated, the organic phase was washed with 100 ml of water, the organic phase was passed through a silica gel column, the column was flushed with 200 g of toluene, the column was spin-dried, and the mixture was slurried with 2 times petroleum ether (weight ratio) to obtain a white solid intermediate 18, 9 g, purity: 87.6%, yield: 84.6%;

[0308] Intermediate 19: 9 g of intermediate 18, 300 ml of toluene, 100 ml of anhydrous ethanol, and 0.2 g of palladium carbon (5%) were added to a 1L three-necked flask. The mixture was evacuated with nitrogen for 5 times and hydrogen for 3 times. The mixture was stirred and hydrogenated at room temperature for 7 h. The mixture was filtered to remove palladium carbon. After concentration, the mixture was recrystallized with 3 times toluene (by weight) to obtain a white solid intermediate 19, 6.8 g, purity: 93.3%, yield: 95.8%;

[0309] Product I-26-1: In a 500ml three-necked flask, add 6.8g (0.018mol) of intermediate 19, 3.8g (0.045mol) of methacrylic acid, and 250ml of dichloromethane. Cool down to 0℃ under nitrogen protection, control the temperature at 0-5℃, add 9.3g (0.045mol) of DCC, and after the addition, naturally warm to room temperature. React at room temperature for 8 hours; filter to remove insoluble matter, concentrate the filtrate, recrystallize twice with 1 times toluene and 2 times ethanol, and crystallize once with 3 times toluene and 1 times petroleum ether to obtain product I-26-1, white solid, 5.1g, purity: 99.07%, yield: 55.5%, mp: 122.5℃.

[0310] Example 5

[0311] The structural formula of the polymerizable compound is shown in Formula I-38-2 below:

[0312] I-38-2.

[0313] The preparation route is as follows:

[0314]

[0315]

[0316] Intermediate 20: Add 22.5g (0.06mol) of bromoethane triphenylphosphine salt to a 0.5L three-necked flask, add 100ml of tetrahydrofuran, control the temperature at -10℃, add 6.7g (0.06mol) of potassium tert-butoxide, and stir for 1h; 16g (0.05mol) of 4-bromo-7-benzyloxy-2,3-dihydro-1-indanone is dissolved in 80g of tetrahydrofuran and slowly added dropwise to the reaction flask. After the dropwise addition, remove the ice bath, heat naturally, and react at room temperature for 2h; add 200ml of water and stir, separate the liquids, extract the aqueous phase with 2x100ml of ethyl acetate, combine the organic phases, wash with 2x100ml of water, dry with 20g of anhydrous sodium sulfate, concentrate in vacuo, and recrystallize 4 times with 2 times ethanol (weight ratio) to obtain a white solid intermediate 20, 8.7g, purity: 99.1%, yield: 54%;

[0317] Intermediate 21: Add 8.7 g (0.026 mol) of intermediate 20 and 100 mL of tetrahydrofuran to a 0.5 L three-necked flask, protect with nitrogen, and cool down; T = -80 ° C, add 14 ml (0.034 mol) of n-butyl lithium dropwise, and complete the dropwise addition for 30 min, and keep the temperature for reaction for 1 h; T = -80 ° C, add 3.6 g (0.035 mol) of trimethyl borate in THF solution dropwise, and complete the dropwise addition for 20 min, and keep the temperature for reaction for 1 h; naturally heat up, add 100 ml of water to quench, separate the phases, extract the aqueous phase with 2x100 mL of ethyl acetate, combine the organic phases, dry and concentrate, and obtain white solid intermediate 21, 5 g, purity: 93.3%, yield: 65%;

[0318] Intermediate 22: 5 g (0.017 mol) of intermediate 21, 4 g (0.016 mol) of intermediate 4, 2.9 g (0.021 mol) of anhydrous potassium carbonate, 0.12 L of toluene, and 0.4 L of water were added to a 0.5 L three-necked flask, and palladium catalyst was added under nitrogen protection, and the reaction was heated under reflux for 6 hours; the liquid was separated, the organic phase was washed with 0.1 L of water, the organic phase was passed through a 20 g silica gel column, the column was flushed with 100 g of toluene, and the organic phase was spin-dried and slurried with 2 times petroleum ether (weight ratio) to obtain a white solid intermediate 22, 5.2 g, purity: 90.4%, yield: 78.8%;

[0319] Intermediate 23: In a 0.5L three-necked flask, add intermediate 22 from the previous step, 0.1L toluene, 0.05L anhydrous ethanol, and 0.1g palladium carbon (5%). Evacuate with nitrogen 5 times and hydrogen 3 times. Stir and hydrogenate at room temperature for 4h. Filter to remove palladium carbon. After concentration, add 1x toluene and 2x petroleum ether (weight ratio) for recrystallization to obtain white solid intermediate 23, 4g, purity: 94.3%, yield: 97%;

[0320] Product I-38-2: 4g (0.0123mol) of intermediate 23, 2.74g (0.032mol) of methacrylic acid, and 0.1L of dichloromethane were added to a 0.5L three-necked flask, cooled to 0°C under nitrogen protection, and the temperature was controlled at 0-5°C. 0.56g (0.0.32mol) of DCC was added. After the addition, the temperature was naturally raised to room temperature. The reaction was carried out at room temperature for 8 hours; filtration was performed to remove insoluble matter, and the filtrate was concentrated. The filtrate was recrystallized twice with 2 times ethanol and once with 1 times toluene and 2 times ethanol to obtain product I-38-2, a white solid, 3g, purity: 99.77%, yield: 53.6%, mp: 83.7°C. The mass spectrum of product I-38-2 is shown as follows: Figure 2 shown.

[0321] Embodiment 6-26:

[0322] Referring to the synthesis method of Examples 1-4, the synthesis of the following examples was completed by simple replacement of raw materials:

[0323] Embodiment 6: I-1-2, Example 7: I-1-3,

[0324] Embodiment 8: I-1-4, Example 9: I-2-1,

[0325] Embodiment 10: I-2-6, Example 11: I-3-1,

[0326] Embodiment 12: I-5-4, Example 13: I-6-1,

[0327] Embodiment 14: I-7-1, Example 15: I-11-1,

[0328] Embodiment 16: I-30-1. Example 17: I-33-1,

[0329] Embodiment 18: I-38-3, Example 19: I-38-5,

[0330] Embodiment 20: I-39-2, Example 21: I-39-3,

[0331] Embodiment 22: I-39-5, Example 23: I-40-2,

[0332] Embodiment 24: I-40-5, Example 25: I-41-2,

[0333] Embodiment 26: I-41-5.

[0334] The following 7 representative monomers were selected from the examples for experiment:

[0335] I-1-1, I-2-1,

[0336] I-10-1, I-25-1,

[0337] I-38-2, I-40-2,

[0338] I-41-2.

[0339] Comparative polymerizable compounds:

[0340] D1. D2,

[0341] D3.

[0342] The compositions and performance parameters of the compositions SLC-1, SLC-2 and SLC-3 are shown in Tables 3 and 4 below, respectively.

[0343] Table 3 Compositions of SLC-1, SLC-2 and SLC-3

[0344]

[0345] Table 4 Performance parameters of SLC-1 to SLC-3 compositions

[0346]

[0347] Examples of polymerizable liquid crystal compositions:

[0348] The corresponding polymerizable liquid crystal compositions were prepared by adding 7 representative monomers of polymerizable compounds I-1-1 to I-41-2 to compositions SLC-1, SLC-2, and SLC-3, respectively, at a weight ratio concentration of 0.3%.

[0349] For comparison purposes, corresponding polymerizable liquid crystal compositions were prepared by adding prior art polymerizable compounds D1, D2 and D3 at a weight ratio concentration of 0.3% to liquid crystal compositions SLC-1, SLC-2 and SLC-3, respectively.

[0350] The structure of the self-aligning agent used in the Examples and Comparative Examples for the Diffusion Test without PI is shown below:

[0351]

[0352] As is known to all, the current SAVA mode display has no conventional polyimide alignment film, and the alignment effect is achieved by using the so-called self-alignment additive for vertical alignment. In order to more realistically simulate the diffusibility of RM in a test box without PI, a SAVA self-alignment agent having the above representative structure is added in both the embodiment and the comparative example, and the content of the self-alignment agent added is 1.0% by weight of the SLC composition.

[0353] Table 5 Diffusion data of the examples and comparative examples in the SLC-1 composition

[0354]

[0355] Table 6 Diffusion data of the examples and comparative examples in SLC-3 composition

[0356]

[0357] It can be seen from Table 5 and Table 6 that in the test boxes with PI and without PI, the diffusibility of the embodiments is better than that of the comparative examples. The diffusibility Δ of the embodiments is less than 30 ppm (with PI and without PI), while the diffusibility Δ of the comparative examples is more than 50 ppm (with PI and without PI), and the diffusibility Δ of D1 is even more than 70 ppm (with PI and without PI). Therefore, the polymerizable compounds involved have the advantage of good diffusibility, which means that the probability of the RM of the embodiments to explode and form broken bright spots in displays of different modes is greatly reduced, which is beneficial to improving the display effect of the display.

[0358] The extreme conditions in this experiment were low temperature treatment of -20℃ for 500h, high temperature treatment of 85℃ for 500h, high and low temperature cycle treatment for 500h (-20℃, 2.5h; 85℃, 2.5h; 100 cycles), and high temperature treatment of 85℃-humidity 85% (high temperature and high humidity) for 500h.

[0359] Table 7 Performance parameters of the SLC-1 composition of the examples and comparative examples

[0360]

[0361] Table 8 Performance parameters of the SLC-2 composition of the embodiments and comparative examples

[0362]

[0363] As can be seen from Tables 7 and 8, under the conditions of the same UV2 time of 90 min and the final pretilt angle of 1.5°, the residual RM of the polymerizable compound in each embodiment is basically below 20 ppm, while the residual of the comparative example is above 40 ppm, and the residual of D3 is even above 100 ppm. The polymerizable compound in each embodiment has a lower polymer residual than the polymerizable compound in the comparative example. The polymerizable compound of the present invention has low residual after the UV process, and having a lower polymer residual has a significant positive effect on improving the display effect of the display. From the IS data after low temperature aging, high temperature and high humidity aging, high temperature aging and high and low temperature cycling for 500h, it can be found that the IS of each RM monomer after high temperature and high humidity aging is the worst. This shows that under this condition, the stability of RM is relatively poor, but under each extreme condition, the IS performance of the liquid crystal composition of each embodiment is better than that of the comparative example, and the residual image level of the liquid crystal composition of each embodiment is above ND10 (ND10 or no IS), which greatly reduces the risk of residual image problems in the final display. From the perspective of chemical structure, when a cyclic group with electron-donating function is introduced into a straight-linked biphenyl polymerizable compound, the electron cloud density of the molecule increases due to the electron-donating effect, and the acrylate contained therein is more likely to undergo polymerization reaction, the polymerization reaction is faster and the residue is lower. Therefore, the polymerizable compound of the present invention can have the characteristics of low residue after UV process and excellent IS performance after extreme conditions on the basis of good diffusivity.

[0364] In summary, the present invention provides a polymerizable compound shown in formula I whose main ring contains a benzene ring condensation system and must contain a tertiary alcohol side chain structure, and a liquid crystal composition formed by combining this polymerizable compound with a specific liquid crystal component. The polymerizable compound has the advantages of good diffusivity and low residue after UV process. At the same time, for displays using it, it is ensured that they still have excellent IS performance after extreme conditions (high temperature, low temperature, high and low temperature cycles, high temperature and high humidity), reducing the risk of problems such as afterimages in the final display, and can provide a liquid crystal display device with better quality.

[0365] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A polymerizable compound, characterized in that The polymerizable compound is a compound shown in the following formula I: I； in, L1 and L2 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen, wherein any one or more unconnected -CH2- can be independently replaced by -O- or -S-; L3, L4, L5, L6 are each independently selected from H, C1-C5 alkyl or alkoxy, C2-C5 alkenyl or alkenyloxy, fluorine-substituted C1-C5 alkyl or alkoxy, fluorine-substituted C2-C5 alkenyl or alkenyloxy, halogen; n1 and n2 each independently represent 0, 1, 2, 3 or 4; m1 and m2 each independently represent 0 or 1, and m1 and m2 are not 0 at the same time; P, at each occurrence, independently represents an acrylate group, a methacrylate group or a fluoroacrylate group; Sp represents a single bond, a C1-C5 straight chain, branched or cyclic alkyl group, and Sp is not a single bond at the same time, wherein any one or more unconnected -CH2- can be replaced by -O- or -S-, one or more H atoms can be independently replaced by F, Cl or G3, and at least one H atom is replaced by G3; G3 represents a tertiary alcohol structure of C1-C7; X represents -CH2-, -O- or -S-.

2. The polymerizable compound according to claim 1, characterized in that The compound represented by formula I is at least one of the compounds represented by formulas I-1 to I-37: I-1、 I-2、 I-3、 I-4、 I-5、 I-6、 I-7、 I-8、 I-9、 I-10、 I-11、 I-12、 I-13、 I-14、 I-15、 I-16、 I-17、 I-18、 I-19、 I-20、 I-21、 I-22、 I-23、 I-24、 I-25、 I-26、 I-27、 I-28、 I-29、 I-30、 I-31、 I-32、 I-33、 I-34、 I-35、 I-36、 I-37。 3. The polymerizable compound according to claim 1, characterized in that The compound represented by formula I is at least one of the compounds represented by formulas I-1-1 to I-41-5: I-1-1、 I-1-2、 I-1-3、 I-1-4、 I-1-5、 I-1-6、 I-1-7、 I-1-8、 I-1-9、 I-2-1、 I-2-2、 I-2-3、 I-2-4、 I-2-5、 I-2-6、 I-2-7、 I-2-8、 I-3-1、 I-3-2、 I-3-3、 I-3-4、 I-3-5、 I-3-6、 I-3-7、 I-3-8、 I-4-1、 I-4-2、 I-4-3、 I-4-4、 I-4-5、 I-4-6、 I-5-1、 I-5-2、 I-5-3、 I-5-4、 I-5-5、 I-5-6、 I-6-1、 I-6-2、 I-7-1、 I-7-2、 I-8-1、 I-8-2、 I-9-1、 I-9-2、 I-10-1、 I-10-2、 I-10-3、 I-10-4、 I-10-5、 I-10-6、 I-11-1、 I-11-2、 I-11-3、 I-11-4、 I-11-5、 I-11-6、 I-12-1、 I-12-2、 I-13-1、 I-13-2、 I-14-1、 I-14-2、 I-15-1、 I-15-2、 I-16-1、 I-16-2、 I-17-1、 I-17-2、 I-18-1、 I-18-2、 I-19-1、 I-19-2、 I-20-1、 I-20-2、 I-21-1、 I-21-2、 I-22-1、 I-22-2、 I-23-1、 I-23-2、 I-24-1、 I-25-1、 I-26-1、 I-26-2、 I-27-1、 I-28-1、 I-29-1、 I-30-1、 I-31-1、 I-32-1、 I-33-1、 I-34-1、 I-35-1、 I-36-1、 I-37-1、 I-38-1、 I-38-2、 I-38-3、 I-38-4、 I-38-5、 I-39-1、 I-39-2、 I-39-3、 I-39-4、 I-39-5、 I-40-1、 I-40-2、 I-40-3、 I-40-4、 I-40-5、 I-41-1、 I-41-2、 I-41-3、 I-41-4、 I-41-5。 4. A liquid crystal composition, characterized in that: The liquid crystal composition comprises one or more polymerizable compounds as described in any one of claims 1 to 3 as a first component, one or more compounds represented by formula II as a second component, and one or more compounds represented by formula III as a third component: II; III; in, R1, R2, R3, and R4 each independently represent a C1-C10 alkyl group, a C1-C10 alkoxy group, or a C2-C10 alkenyl group, wherein one or more non-adjacent -CH2- groups may be replaced by a cyclopropyl group, a cyclopentyl group, or a cyclobutyl group; Z1 and Z2 each independently represent -CH2-CH2-, -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond; , each independently represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene; , Each independently represents 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene, wherein one or two -CH2- may be replaced by -O-; m3 means 1 or 2; n3 represents 0, 1 or 2.

5. The liquid crystal composition according to claim 4, characterized in that: The one or more compounds of formula II are one or more compounds of formula II-1 to II-15: II-1、 II-2、 II-3、 II-4、 II-5、 II-6、 II-7、 II-8、 II-9、 II-10, II-11, II-12, II-13, II-14, II-15; Japanese / or The one or more compounds represented by formula III are one or more compounds represented by formula III-1 to III-12: III-1、 III-2、 III-3、 III-4、 III-5、 III-6、 III-7、 III-8、 III-9、 III-10、 III-11、 III-12; in, R3 and R4 each independently represent a C1-C10 alkyl group, a C1-C10 alkoxy group or a C2-C10 alkenyl group, wherein one or more non-adjacent -CH2- groups may be replaced by a cyclopropyl group, a cyclopentyl group or a cyclobutyl group.

6. The liquid crystal composition according to claim 4, characterized in that: The liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by formula IV: IV; in, R5 and R6 each independently represent a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group; , each independently represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene; and / or The liquid crystal composition further comprises one or more compounds represented by formula V: V； in, R7 and R8 each independently represent an H atom, a halogen, a C1-C10 alkyl group, a C1-C10 fluoroalkyl group, a C1-C10 alkoxy group or a C1-C10 fluoroalkoxy group, and any one or more CH2 groups represented by R7 and R8 may be replaced by a cyclopentyl group, a cyclobutyl group or a cyclopropyl group; X1 represents -O-, -S-, -CO- or -CH2O-; Z3 and Z4 each independently represent -O-, -CO-, -CO-O-, -O-CO-, -CH2O-, -OCH2-, -CH=CH-, -CF2O- or a single bond; , each independently represents cyclopropyl, cyclobutyl, cyclopentyl, 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, trans-1,4-cyclohexylene, or 1,4-cyclohexenylene; m4 means 0, 1 or 2; n4 represents 0, 1 or 2.

7. The liquid crystal composition according to claim 4 or 6, characterized in that: The liquid crystal composition is a negative liquid crystal composition, and the liquid crystal composition further comprises one or more compounds represented by formula VI: WE; in, R9, R 10 each independently represents a C1-C10 alkyl group, a fluorine-substituted C1-C10 alkyl group, a C1-C10 alkoxy group, a fluorine-substituted C1-C10 alkoxy group, a C2-C10 alkenyl group, a fluorine-substituted C2-C10 alkenyl group, a C3-C8 alkenyloxy group or a fluorine-substituted C3-C8 alkenyloxy group; represents 1,4-phenylene, 1,4-cyclohexylene or 1,4-cyclohexenylene; Each occurrence of (F) independently represents H or F.

8. The liquid crystal composition according to claim 4, characterized in that: In the liquid crystal composition, the total mass percentage of the compound represented by formula I is 0.01-1%, the total mass percentage of the compound represented by formula II is 15-60%, and the total mass percentage of the compound represented by formula III is 20-80%.

9. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 4 to 8.

10. The liquid crystal display device according to claim 9, characterized in that: The liquid crystal display device is a PSVA or SAVA display.

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