WO2022213750A1

WO2022213750A1 - Self-aligning polymerizable compound and application thereof

Info

Publication number: WO2022213750A1
Application number: PCT/CN2022/079046
Authority: WO
Inventors: 冯静; 董智超; 程友文; 李程辉; 谢佩; 白爽
Original assignee: 北京八亿时空液晶科技股份有限公司
Priority date: 2021-04-06
Filing date: 2022-03-03
Publication date: 2022-10-13
Also published as: CN113214083B; TW202239948A; CN113214083A

Abstract

The present invention provides a self-aligning polymerizable compound and an application thereof. The self-aligning polymerizable compound has a structure represented by a general formula (I). A cyclic structure is introduced to a terminal group of the compound of the present invention. The rigidity of the molecular terminal group is increased, molecules are not easily deformed, and the elastic constant of a liquid crystal compound is increased. The compound has a certain advantage of angular stability. On the other hand, the molecular terminal group is changed from a linear structure to the cyclic structure. The viscous resistance of the molecules is increased, that is to say the rotational viscosity thereof is increased. In addition, the compound has good solubility, a faster polymerization rate, more complete polymerization, and less residue, so that the alignment effect of the overall structure is better, which greatly improves the problems of poor display, residual images, etc. The present invention can be widely used in the field of liquid crystal display, and has important application values.

Description

A kind of self-aligned polymerizable compound and its application

cross reference

This application claims the priority of Chinese Patent Application No. 202110367648.2, filed on April 6, 2021, entitled "A Self-Aligning Polymerizable Compound and Its Application", the entire disclosure of which is incorporated herein by reference in its entirety.

technical field

The present invention relates to the technical field of liquid crystal materials, in particular to a self-aligned polymerizable compound and its application.

Background technique

In recent years, liquid crystal display devices have been widely used in various electronic devices, such as smartphones, tablet computers, car navigators, televisions, and the like. Representative liquid crystal display modes are twisted nematic (TN) type, super twisted nematic (STN) type, in-plane switching (IPS) type, fringe field switching (FFS) type and vertical alignment (VA) type. Among them, the VA mode has received more and more attention due to its fast fall time, high contrast, wide viewing angle, and high-quality images.

However, the liquid crystal medium used in the display elements of the active matrix addressing mode such as VA mode has its own shortcomings. For example, the level of afterimage 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 low. higher. In order to solve the above problems, some new VA display technologies have appeared, such as MVA technology, PVA technology, PSVA technology. Among them, PSVA technology not only realizes a wide viewing angle display mode similar to MVA/PVA, but also simplifies the CF process. It reduces the cost of CF, improves the aperture ratio, and can obtain higher brightness, thereby obtaining higher contrast. In addition, because the entire surface of the liquid crystal has a pre-tilt angle, there is no domino delay phenomenon, and a faster response time can be obtained while maintaining the same driving voltage, and the afterimage level will not be affected.

The prior art has found that LC mixtures and RMs still have some drawbacks in the application of LC mixtures in PSVA displays. First, not every soluble RM desired so far is suitable for use in PSA displays, at the same time, if it is desired to polymerize by means of UV light without adding a photoinitiator (which may be advantageous for some applications) , the selection becomes smaller; in addition, the "material system" formed by the combination of the LC mixture (hereinafter also referred to as the "LC host mixture") and the selected polymerizable components should have the lowest rotational viscosity and the best optoelectronic properties , used to increase the "Voltage Holding Ratio" (VHR) to achieve the effect. In terms of PSVA, high VHR after irradiation with (UV) light is very important, otherwise it will cause problems such as afterimages in the final display. So far, because the polymerizable unit is too short for UV-sensitive wavelength, or there is no or insufficient tilt angle after irradiation, or the homogeneity of the polymerizable component after irradiation is poor. Not all combinations of LC mixture and polymerizable components are suitable for PSVA displays.

Therefore, the synthesis of polymerizable compounds with novel structures with excellent properties and the study of structure-property relationship have become an important work in the field of liquid crystals.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a self-aligning polymerizable compound. In the polymerizable liquid crystal compound of the present invention, the end group is introduced into a cyclic structure, the rigidity of the molecular end group is increased, the molecule is not easily deformed, the elastic constant of the liquid crystal compound is increased, and has certain advantages in angular stability. On the other hand, the molecular end group changes from a linear structure to a cyclic structure, the viscous resistance of the molecule increases, that is, its rotational viscosity increases, and at the same time, it has good solubility, faster polymerization rate, more complete polymerization, and lower residues. The alignment effect of the overall structure is better, thereby greatly improving the problems of poor display and afterimage, and can be widely used in the field of liquid crystal display, and has important application value.

Specifically, the self-aligned polymerizable compound has a structure as shown in the general formula (I):

Wherein, ring A represents a C ₃ -C ₇ cycloalkyl group or a C ₃ -C ₇ cycloalkenyl group; or, the C ₃ -C ₇ cycloalkyl group or a C ₃ -C ₇ cycloalkenyl group At least one hydrogen atom is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH in the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl ₂ - replaced by -O-, -S- in a way that is not directly connected to each other;

A ₁ , A ₂ , and A ₃ each independently represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, the 1,4-cyclohexylene, At least one hydrogen atom in 1,4-cyclohexenylene or 1,4-phenylene is replaced by L or -ZP; or, at least one ring carbon atom in said 1,4-phenylene is replaced by nitrogen atomic substitution;

L represents H, -F, -Cl, -CN, -NO ₂ , -NCS, optionally substituted silyl, C ₃ -C ₇ cycloalkyl or C ₁ -C ₁₂ linear or branched alkane group, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy; or, the C ₃ -C ₇ cycloalkyl or C ₁ -C ₁₂ straight chain Or at least one hydrogen atom in branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy is substituted by F or Cl;

P represents an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or an epoxy group;

Z, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ each independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O- CO-O-, -CH=N-, -N=CH-, -N=N-, C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl; or, the C ₁ - At least one hydrogen atom in the C ₁₂ alkylene group or the C ₂ -C ₁₂ alkenyl group is substituted with F, Cl, or CN; or, the C ₁ -C ₁₂ alkylene group or C ₂ -C ₁₂ An alkenyl group in which one -CH ₂ - or at least two non-adjacent -CH ₂ - is -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO- , -SCO- or -COS- in a way that is not directly connected to each other;

R ₁ and R ₂ each independently represent H, C ₁ -C ₁₂ alkyl or alkoxy, or C ₂ -C ₁₂ alkylalkenyl or alkoxyalkenyl; or, the C ₁ -C ₁₂ alkyl At least one hydrogen atom in the alkyl or alkoxy, C ₂ -C ₁₂ alkenyl or alkoxy alkenyl is substituted by F; or, the C ₁ -C ₁₂ alkyl or alkoxy, C ₂ One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkylalkenyl or alkoxyalkenyl of -C ₁₂ is substituted by -O- in a manner that is not directly connected to each other;

X represents -OH, -SH, or _-NH2 ;

m and n each independently represent 0, 1, or 2 and are not 0 at the same time.

Further, the general formula (I) is selected from one or more of the following structures:

wherein, A ₁ and A ₂ represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, the 1,4-cyclohexylene, 1,4- At least one hydrogen atom H in cyclohexenylene or 1,4-phenylene is substituted by L or -ZP;

L represents H, -F, -Cl, C ₃ -C ₇ cycloalkyl or C ₁ -C ₆ straight or branched chain alkyl; or, the C ₃ -C ₇ cycloalkyl or C At least one hydrogen atom in the straight-chain or branched alkyl of ₁ - _C6 is replaced by F or Cl;

P represents an acrylate group, a methacrylate group, or a fluoroacrylate group;

Z, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ each independently represent a single bond, -O-, a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenyl group; or, all At least one hydrogen atom in the C ₁ -C ₆ alkylene group or the C ₂ -C ₆ alkenyl group is substituted by F; or, the C ₁ -C ₆ alkylene group or the C ₂ -C ₆ alkylene group One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkenyl group is substituted by -O- in a manner that is not directly connected to each other;

R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkylalkenyl or alkoxyalkenyl; or, the C ₁ -C ₆ alkyl or alkoxy, At least one hydrogen atom in the C ₂ -C ₆ alkylalkenyl or alkoxyalkenyl group is substituted by F; or, the C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkylalkenyl group Or one -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkoxyalkenyl group is substituted by -O- in a manner that is not directly connected to each other;

X represents -OH;

m and n each independently represent 0, 1, or 2 and are not 0 at the same time.

Further, selected from one or more of the following compounds:

The second object of the present invention is to provide a liquid crystal composition comprising the above-mentioned self-alignment polymerizable compound, wherein the mass percentage of the self-alignment polymerizable compound in the liquid crystal composition is 0.01-10%, preferably 0.01-5% %, more preferably 0.1 to 3%.

The third object of the present invention is to provide the above-mentioned self-aligned polymerizable compound and the application of the above-mentioned liquid crystal composition in the field of display. Further, the application in the field of liquid crystal display is an application in a liquid crystal display device. Further, the liquid crystal display device is selected from one of TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays, preferably VA and PSVA liquid crystal displays.

Detailed ways

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. All other equivalent changes or modifications accomplished without departing from the spirit disclosed in the present invention should be included in the scope of the claims.

The liquid crystal compounds used in the following examples can be synthesized by known methods or obtained from open commercial sources unless otherwise specified. These synthetic techniques are conventional, and the obtained liquid crystal compounds are tested to meet the electronic compounds. standard.

According to conventional detection methods in the art, various performance parameters of the liquid crystal compound are obtained by linear fitting, wherein the specific meanings of each performance parameter are as follows:

Δn represents optical anisotropy (25°C); Δε represents dielectric anisotropy (25°C, 1000Hz); γ1 represents rotational viscosity (mPa·s, 25°C); Cp represents clearing point.

Example 1

The structural formula of the liquid crystal compound is:

The synthetic route for the preparation of compound BYLC-01 is shown below:

Specific steps are as follows:

(1) Synthesis of compound BYLC-01-1:

Under nitrogen protection, add 100g of 2-ethyl-4-bromoiodobenzene, 45g of p-hydroxyphenylboronic acid, 86g of sodium carbonate, 0.9L of dioxane, 0.3L of water to the reaction flask, then turn on stirring, add 6.7g of Pd (PPh ₃ ) ₂ Cl ₂ , heated to 85°C and reacted for 10h. After the reaction solution was cooled to room temperature, 0.9L of water was added, extracted once with 0.9L of EA, washed once with 3L of water until neutral, dried with 50g of anhydrous sodium sulfate, passed through a 50g silica gel column, eluted with ethyl acetate, and then mixed with 100g of silica gel After purification by 400g silica gel chromatography, n-heptane/EA=100:1 (v/v), spin-dried through the column to obtain 77.7g of colorless liquid (compound BYLC-01-1), LC: 95.458%, yield : 87.3%.

(2) Synthesis of compound BYLC-01-2:

Under nitrogen protection, add 72g compound BYLC-01-1, 69.3g cyclopentylbiphenylboronic acid, 56g sodium carbonate, 430ml toluene, 145ml ethanol, 145ml water to the reaction flask, turn on stirring, add 0.92g Pd0132, heat to 73 The reaction was carried out at °C for 10 h, followed by conventional post-treatment, and recrystallized from ethanol to obtain 93 g of a white solid (compound BYLC-01-2), LC: 97.4%, yield: 85.6%.

(3) Synthesis of compound BYLC-01-3:

Add 93g compound BYLC-01-2, 6.3g diisopropylamine, 1500ml THF to the reaction flask, turn on stirring, cool down to -5°C, control the temperature to 0～-5°C, add 103.3g NBS in batches, then heat up naturally, react 6h post-treatment, add 1L sodium sulfite aqueous solution to the reaction solution to neutralize to neutrality, separate the liquid, extract the aqueous phase twice with 500ml*2 dichloromethane, combine the organic phases, and wash twice with 1L*2 water, 50g anhydrous sodium sulfate After drying, it was passed through 50 g of silica gel, eluted with dichloromethane, and recrystallized from n-heptane and ethanol to obtain 113 g of a white solid (compound BYLC-01-03), LC: 99.194%, yield: 88.2%.

(4) Synthesis of compound BYLC-01-4:

Under nitrogen protection, add 25.8g of compound BYLC-01-3, 19.3g of Y-1, 14.2g of triphenylphosphine, and 200ml of tetrahydrofuran into the reaction flask, start stirring, and add 13.6g of DIAD dropwise under temperature control at -5℃～5℃ The solution formed with 50ml of tetrahydrofuran was dripped, and the temperature was controlled at -5°C to 5°C for 30 minutes, and the reaction was naturally brought to room temperature for 4 hours. After routine post-processing, column chromatography was performed to purify, n-heptane/ethyl acetate=80:1 ( v/v) to obtain 33.2 g of pale yellow liquid (compound BYLC-01-4), LC: 98.8%, yield: 78%.

(5) Synthesis of compound BYLC-01-5:

Under nitrogen protection, add 28.5g compound BYLC-01-4, 15.8g oxolane, 0.56g RuPhos, 12.8g sodium carbonate, 200ml tetrahydrofuran, 50ml water, 0.1g palladium chloride to the reaction flask, start stirring , heated to 75°C for 12 hours, routine post-treatment, purified by column chromatography, n-heptane/ethyl acetate = 30:1 (v/v) to obtain a colorless viscous liquid (compound BYLC-01-5) 20.3 g, LC: 97.8%, yield: 75%.

(6) Synthesis of compound BYLC-01-6:

Under nitrogen protection, 20g of compound BYLC-01-5, 7.5g of methacrylic acid, 1.2g of DMAP, 150ml of DCM were added to the reaction flask, stirring was started, and 18.1g of DCC and 50ml of DCM were added dropwise under temperature control at -5°C to 5°C. After dripping, the solution was naturally warmed to room temperature for 12 hours, followed by routine post-treatment to obtain 17.8 g of a colorless viscous liquid (compound BYLC-01-6), LC: 97.3%, yield: 78%.

(7) Synthesis of compound BYLC-01:

Under nitrogen protection, add 15.0g of compound BYLC-01-6 and 50ml of THF to the reaction flask, start stirring, and control the temperature to 0℃～5℃ and add dropwise a solution composed of 11.2g of tetrabutylammonium fluoride and 20ml of THF, and the dripping is completed. , Naturally warmed to room temperature (20°C) and reacted for 10 hours, 100ml saturated aqueous sodium bicarbonate solution destroyed hydrolysis, conventional post-processing, column chromatography purification, n-heptane/ethyl acetate=10:1 (v/v), n-heptane/ethyl acetate=10:1 (v/v), normal Recrystallization from heptane gave 7.8 g of a white solid (compound BYLC-01), LC: 99.5%, yield: 66.8%.

The resulting white solid BYLC-01 was analyzed by LC-MS and the product had m/z of 814.1 (M+).

Elemental analysis: C, 78.10; H, 8.16; O, 13.74.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.10 (m, 30H), 2.25-2.85 (m, 7H), 3.13-3.74 (m, 6H), 3.95-4.75 (m, 6H), 6.25-6.87 (m, 4H), 6.92-7.98 (m, 13H).

Example 2

The structural formula of the liquid crystal compound is:

The synthetic route for the preparation of compound BYLC-02 is shown below:

Specific steps are as follows:

(1) Synthesis of compound BYLC-02-1:

Under nitrogen protection, add 69.8g compound BYLC-01-1, 60.0g cyclopropyl biphenylboronic acid, 26.7g sodium carbonate, 500ml toluene, 150ml ethanol, 150ml water to the reaction flask, turn on stirring, add 0.8g Pd0132, heat The reaction was carried out at 73° C. for 10 h, followed by conventional post-treatment, and recrystallized from ethanol to obtain 80.9 g of a white solid (compound BYLC-02-01), LC: 98.2%, yield: 82.4%.

(2) Synthesis of compound BYLC-02-2:

Add 80g compound BYLC-02-1, 4.15g diisopropylamine, 1800ml THF to the reaction flask, turn on stirring, cool down to -5°C, control the temperature to 0～-5°C, add 94.9g NBS in batches, then heat up naturally, react 6h post-treatment, add 1L sodium sulfite aqueous solution to the reaction solution to neutralize to neutrality, separate the liquid, extract the aqueous phase twice with 500ml*2 dichloromethane, combine the organic phases, and wash twice with 1L*2 water, 50g anhydrous sodium sulfate After drying, it was passed through 50 g of silica gel, eluted with dichloromethane, and recrystallized from n-heptane and ethanol to obtain 95.0 g of a white solid (compound BYLC-02-2), LC: 99.3%, yield: 84.5%.

(3) Synthesis of compound BYLC-02-3:

Under nitrogen protection, add 50.0g of compound BYLC-02-2, 37.4g of Y-1, 27.5g of triphenylphosphine, and 500ml of tetrahydrofuran into the reaction flask, start stirring, and add 31.2g of DIAD dropwise under temperature control at -5℃～5℃ The solution formed with 50ml of tetrahydrofuran was dripped, and the temperature was controlled at -5°C to 5°C for 30 minutes, and the reaction was naturally brought to room temperature for 4 hours. After routine post-processing, column chromatography was performed to purify, n-heptane/ethyl acetate=80:1 ( v/v) to obtain a pale yellow liquid (compound BYLC-02-3) 63.2 g, LC: 99.1%, yield: 75.6%.

(4) Synthesis of compound BYLC-02-4:

Under nitrogen protection, 60.0g of compound BYLC-02-3, 34.2g of oxolane, 1.2g of RuPhos, 27.7g of sodium carbonate, 200ml of tetrahydrofuran, 50ml of water, 0.18g of palladium chloride were added to the reaction flask, and stirring was started. , heated to 75°C for 12 hours, conventional post-treatment, purified by column chromatography, n-heptane/ethyl acetate=30:1 (v/v), to obtain a colorless viscous liquid (compound BYLC-02-4) 46.2 g, LC: 98.3%, yield: 81%.

(5) Synthesis of compound BYLC-02-5:

Under nitrogen protection, 45g of compound BYLC-02-4, 17.6g of methacrylic acid, 3.0g of DMAP, 150ml of DCM were added to the reaction flask, stirring was started, and 42.0g of DCC and 50ml of DCM were added dropwise at a temperature of -5°C to 5°C. After dripping, the solution was naturally warmed to room temperature for 12 hours, and after conventional post-treatment, 41.6 g of colorless viscous liquid (compound BYLC-02-5) was obtained, LC: 98%, yield: 80.5%.

(6) Synthesis of compound BYLC-02:

Under nitrogen protection, add 40.0g of compound BYLC-02-5 and 200ml of THF to the reaction flask, start stirring, and control the temperature to 0℃～5℃ and add dropwise a solution composed of 30.5g of tetrabutylammonium fluoride and 50ml of THF, and the dripping is completed. , Naturally returned to room temperature (20°C) and reacted for 10 hours, 200ml of saturated aqueous sodium bicarbonate solution destroyed hydrolysis, conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate=10:1 (v/v), n-heptane/ethyl acetate=10:1 (v/v), Recrystallization from heptane gave 19.1 g of a white solid (compound BYLC-02), LC: 99.7%, yield: 62.4%.

The resulting white solid BYLC-02 was analyzed by LC-MS and the product had m/z 786.1 (M+).

Elemental analysis: C, 77.83; H, 7.94; O, 14.23.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.85-2.15 (m, 27H), 2.25-2.95 (m, 6H), 3.16-3.73 (m, 6H), 3.95-4.78 (m, 6H), 6.25-6.89 (m, 4H), 6.96-7.95 (m, 13H).

Example 3

The structural formula of the liquid crystal compound is:

The raw materials were simply replaced, and the reaction conditions were the same as those in Example 1.

The resulting white solid BYLC-03 was analyzed by LC-MS and the product had m/z of 820.1 (M+).

Elemental analysis: C, 77.52; H, 8.84; O, 13.64.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.90-2.12 (m, 40H), 2.27-2.91 (m, 7H), 3.16-3.75 (m, 6H), 3.95-4.75 (m, 6H), 6.26-6.82 (m, 4H), 6.93-7.98 (m, 9H).

Example 4

The structural formula of the liquid crystal compound is:

The resulting white solid, BYLC-04, was analyzed by LC-MS, and the m/z of the product was 792.1 (M+).

Elemental analysis: C, 77.24; H, 8.64; O, 14.12.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.92-2.15 (m, 36H), 2.28-2.95 (m, 7H), 3.13-3.77 (m, 6H), 3.94-4.78 (m, 6H), 6.25-6.87 (m, 4H), 6.95-7.99 (m, 9H).

Example 5

The structural formula of the liquid crystal compound is:

The resulting white solid BYLC-05 was analyzed by LC-MS and the product had m/z of 738.1 (M+).

Elemental analysis: C, 76.39; H, 8.46; O, 15.16.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.95-2.17 (m, 26H), 2.25-2.94 (m, 7H), 3.15-3.78 (m, 6H), 3.95-4.72 (m, 6H), 6.24-6.89 (m, 4H), 6.97-7.98 (m, 9H).

Example 6

The structural formula of the liquid crystal compound is:

The resulting white solid BYLC-06 was analyzed by LC-MS and the product had m/z of 746.1 (M+).

Elemental analysis: C, 72.36; H, 7.56; O, 14.99, F, 5.09.

¹ H-NMR (300MHz, CDCl ₃ ): 0.95-2.17 (m, 27H), 2.25-2.94 (m, 5H), 3.15-3.78 (m, 6H), 3.95-4.72 (m, 6H), 6.24-6.89 (m, 4H), 6.97-7.98 (m, 9H).

Example 7

The structural formula of the liquid crystal compound is:

The resulting white solid BYLC-07 was analyzed by LC-MS and the product had m/z of 828.1 (M+).

Elemental analysis: C, 78.23; H, 8.27; O, 13.51.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.96-2.13 (m, 31H), 2.28-2.97 (m, 8H), 3.13-3.76 (m, 6H), 3.96-4.78 (m, 6H), 6.25-6.85 (m, 4H), 6.95-7.97 (m, 13H).

Example 8

The structural formula of the liquid crystal compound is:

The resulting white solid, BYLC-08, was analyzed by LC-MS, and the m/z of the product was 800.1 (M+).

Elemental analysis: C, 77.97; H, 8.05; O, 13.98.

¹ H-NMR (300 MHz, CDCl ₃ ): 0.95-2.16 (m, 27H), 2.24-2.95 (m, 8H), 3.14-3.78 (m, 6H), 3.95-4.76 (m, 6H), 6.26-6.88 (m, 4H), 6.98-7.96 (m, 13H).

Comparative Example 1

The structural formula of the liquid crystal compound is:

Comparative Example 2

The structural formula of the liquid crystal compound is:

Experimental example

The properties of the liquid crystal mixture BHR87800 are listed in Table 1:

Table 1 Summary of properties of mixed crystal BHR87800

Among them, the mixture BHR87800 was purchased from Bayi Space-Time Liquid Crystal Technology Co., Ltd.

The structural formula of RM monomer is:

Add 0.3% of the polymerizable compound BYLC-01 provided in Example 1 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-1.

Add 0.28% of the polymerizable compound BYLC-02 provided in Example 2 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-2.

Add 0.33% of the polymerizable compound BYLC-03 provided in Example 3 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-3.

Add 0.35% of the polymerizable compound BYLC-04 provided in Example 4 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-4.

Add 0.3% of the polymerizable compound represented by CP-1 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-5.

Add 0.3% of the polymerizable compound represented by CP-2 and 0.3% of the RM monomer RM-1 to 100% of the liquid crystal mixture BHR87800, and dissolve uniformly to obtain the mixture PM-6.

The physical properties of PM-1, PM-2, PM-3, PM-4, PM-5, and PM-6 are almost the same as those of the above-mentioned mixture BHR87800. PM-1, PM-2, PM-3, PM-4, PM-5, PM-6 were injected into "unaligned" test cells (cell thickness d ~ 3.2 μm, on both sides) using the vacuum infusion method. ITO coating (structured ITO in the case of multi-domain switching), no alignment layer and no passivation layer).

Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter for filtering out ultraviolet rays of 310 nm or less. At this time, the illuminance measured on the condition of the center wavelength of 365 nm was adjusted to be 100 mW/cm ² , and ultraviolet rays with a cumulative light amount of 30 J/cm ² were irradiated (irradiation condition 1). Next, using a fluorescent UV lamp, the illuminance measured under the condition of a center wavelength of 313 nm was adjusted to be 3 mW/cm ² , and irradiated with a cumulative light amount of 10 J/cm ² (ultraviolet irradiation condition 2). UV1 is the ultraviolet irradiation process through irradiation condition 1, and UV2 is the process through irradiation condition 1 and irradiation condition 2. The vertically aligned liquid crystal display element after polymerization was obtained, the pretilt angle was measured using an AXO-Step pretilt angle tester, the test box was then decomposed, and the residual polymerizable compounds in the liquid crystal composition were measured by high performance liquid chromatography (HPLC). The results are summarized in Table 2. middle.

Effect test:

1. Pre-tilt angle change

A mixture prepared from various polymerizable compounds and liquid crystal compounds was injected into the test cell. After the polymer compound was polymerized by irradiation with ultraviolet rays, the pretilt angles of the test cells were measured after the UV1 and UV2 irradiation processes, respectively. It is preferable that the pretilt angle change is small after the UV1 and UV2 processes.

In different temperature ranges, there is no significant difference in pretilt angles in different regions after UV2 process, which can effectively improve the regional mura problem.

2. Conversion rate of polymeric compounds

A polymerizable compound is added to the composition, and the polymerizable compound is consumed by polymerization to form a polymer. The conversion of this reaction is preferably a large conversion.

This is because the residual amount of the polymer compound (the amount of the unreacted polymerizable compound) is preferably small from the viewpoint of afterimage of the image.

3. LCD quality test VHR&ION

VHR is the charge retention rate. The higher the VHR, the longer the power-on retention time of the LCD panel. ION is the ion content in the liquid crystal. The lower the ION, the better the quality of the LCD panel. VHR and ION are the quality parameters of the LCD panel. A lower value is preferred;

Table 2

From the comparative data in Table 2, it can be seen that the polymerizable compounds of the present invention have better alignment effect, faster polymerization rate, more complete polymerization and lower residues than the polymerizable liquid crystal compounds CP-1 and CP-2, so that the The problem of poor display has been greatly improved, and the response time has been improved.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be The technical solutions described in the foregoing embodiments are modified, or some technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Industrial Applicability

The present invention provides a self-aligned polymerizable compound and its application, wherein the self-aligned polymerizable compound has a structure represented by the general formula (I). The end group of the compound of the present invention is introduced into a cyclic structure, the rigidity of the molecular end group is increased, the molecule is not easily deformed, the elastic constant of the liquid crystal compound is increased, and the angular stability has certain advantages. On the other hand, the molecular end group changes from a linear structure to a cyclic structure, the viscous resistance of the molecule increases, that is, its rotational viscosity increases, and at the same time, it has good solubility, faster polymerization rate, more complete polymerization, and lower residues, thus The alignment effect of the overall structure is better, thereby greatly improving the problems of poor display and afterimage, and can be widely used in the field of liquid crystal display, and has good economic value and application prospect.

Claims

A self-aligned polymerizable compound, characterized in that it has a structure as shown in general formula (I):

Wherein, ring A represents a C 3 -C 7 cycloalkyl group or a C 3 -C 7 cycloalkenyl group; or, the C 3 -C 7 cycloalkyl group or a C 3 -C 7 cycloalkenyl group At least one hydrogen atom is substituted by F; or, one -CH 2 - or at least two non-adjacent -CH in the C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkenyl 2 - replaced by -O-, -S- in a way that is not directly connected to each other;

A 1 , A 2 , and A 3 each independently represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, the 1,4-cyclohexylene, At least one hydrogen atom in 1,4-cyclohexenylene or 1,4-phenylene is replaced by L or -ZP; or, at least one ring carbon atom in said 1,4-phenylene is replaced by nitrogen atomic substitution;

L represents H, -F, -Cl, -CN, -NO 2 , -NCS, optionally substituted silyl, C 3 -C 7 cycloalkyl or C 1 -C 12 linear or branched alkane group, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy; or, the C 3 -C 7 cycloalkyl or C 1 -C 12 straight chain Or at least one hydrogen atom in branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy is substituted by F or Cl;

P represents an acrylate group, a methacrylate group, a fluoroacrylate group, a chloroacrylate group, a vinyloxy group, an oxetanyl group or an epoxy group;

Z, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 each independently represent a single bond, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O- CO-O-, -CH=N-, -N=CH-, -N=N-, C 1 -C 12 alkylene or C 2 -C 12 alkenyl; or, the C 1 - At least one hydrogen atom in the C 12 alkylene group or the C 2 -C 12 alkenyl group is substituted with F, Cl, or CN; or, the C 1 -C 12 alkylene group or C 2 -C 12 An alkenyl group in which one -CH 2 - or at least two non-adjacent -CH 2 - is -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO- , -SCO- or -COS- in a way that is not directly connected to each other;

R 1 and R 2 each independently represent H, C 1 -C 12 alkyl or alkoxy, or C 2 -C 12 alkylalkenyl or alkoxyalkenyl; or, the C 1 -C 12 alkyl At least one hydrogen atom in the alkyl or alkoxy, C 2 -C 12 alkenyl or alkoxy alkenyl is substituted by F; or, the C 1 -C 12 alkyl or alkoxy, C 2 One -CH 2 - or at least two non-adjacent -CH 2 - in the alkylalkenyl or alkoxyalkenyl of -C 12 is substituted by -O- in a manner that is not directly connected to each other;

X represents -OH, -SH, or -NH2 ;

m and n each independently represent 0, 1, or 2 and are not 0 at the same time.
The self-aligned polymerizable compound according to claim 1, wherein the general formula (I) is selected from one or more of the following structures:

wherein, A 1 and A 2 represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, the 1,4-cyclohexylene, 1,4- At least one hydrogen atom H in cyclohexenylene or 1,4-phenylene is substituted by L or -ZP;

L represents H, -F, -Cl, C 3 -C 7 cycloalkyl or C 1 -C 6 straight or branched chain alkyl; or, the C 3 -C 7 cycloalkyl or C At least one hydrogen atom in the straight-chain or branched alkyl of 1 - C6 is replaced by F or Cl;

P represents an acrylate group, a methacrylate group, or a fluoroacrylate group;

Z, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 each independently represent a single bond, -O-, a C 1 -C 6 alkylene group or a C 2 -C 6 alkenyl group; or, all At least one hydrogen atom in the C 1 -C 6 alkylene group or the C 2 -C 6 alkenyl group is substituted by F; or, the C 1 -C 6 alkylene group or the C 2 -C 6 alkylene group One -CH 2 - or at least two non-adjacent -CH 2 - in the alkenyl group is substituted by -O- in a manner that is not directly connected to each other;

R 2 represents H, C 1 -C 6 alkyl or alkoxy, C 2 -C 6 alkylalkenyl or alkoxyalkenyl; or, the C 1 -C 6 alkyl or alkoxy, At least one hydrogen atom in the C 2 -C 6 alkylalkenyl or alkoxyalkenyl group is substituted by F; or, the C 1 -C 6 alkyl or alkoxy, C 2 -C 6 alkylalkenyl group Or one -CH 2 - or at least two non-adjacent -CH 2 - in the alkoxyalkenyl group is substituted by -O- in a manner that is not directly connected to each other;

X stands for -OH;

m and n each independently represent 0, 1, or 2 and are not 0 at the same time.
The self-aligned polymerizable compound according to claim 1 or 2, characterized in that, it is selected from one or more of the following compounds:
A liquid crystal composition, characterized in that it comprises the self-aligned polymerizable compound according to any one of claims 1-3, and the mass percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01-10% .
The liquid crystal composition according to claim 4, wherein the mass percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.01-5%.
The liquid crystal composition according to claim 4, wherein the mass percentage of the self-aligned polymerizable compound in the liquid crystal composition is 0.1-3%.
Application of the self-aligned polymerizable compound according to any one of claims 1 to 3 in the field of liquid crystal display.
Application of the liquid crystal composition according to any one of claims 4-6 in the field of liquid crystal display.
The application according to claim 7 or 8, wherein the application in the field of liquid crystal display is an application in a liquid crystal display device.
The application according to claim 9, wherein the liquid crystal display device comprises a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display, preferably a VA, PSVA liquid crystal display.