TW202239948A - Self-aligning polymerizable compound and application thereof - Google Patents

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-alignment polymerizable compound and application thereof

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

In recent years, liquid crystal display devices have been widely used in various electronic devices such as smartphones, tablet computers, car navigation systems, televisions, and the like. Representative liquid crystal display modes include 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 attracted 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 active matrix addressing display elements such as VA mode has its own shortcomings, such as the afterimage level is significantly worse than that of 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 emerged, such as MVA technology, PVA technology, and PSVA technology. Among them, PSVA technology not only realizes the wide viewing angle display mode similar to MVA/PVA, but also simplifies the CF process, realizes the reduction of CF cost, improves the aperture ratio, and can obtain higher brightness, and then obtain higher contrast. In addition, since the entire 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 disadvantages for their application in PSVA displays. First of all not every soluble RM desired so far is suitable for use in PSA displays, at the same time if one wishes to polymerize by means of UV light without adding photoinitiators (this may be advantageous for some applications) , the selection becomes smaller; in addition, the "material system" formed by combining the LC mixture (hereinafter also referred to as "LC host mixture") with the selected polymerizable components should have the lowest rotational viscosity and the best optoelectronic properties , used to increase the "Voltage Holding Rate" (VHR) to achieve the effect. In terms of PSVA, it is very important to use a high VHR after (UV) light irradiation, otherwise it will cause problems such as afterimages in the final display. So far, due to the problem that the UV sensitive wavelength of the polymerizable unit is too short, or there is no or insufficient tilt angle after irradiation, or the uniformity of the polymerizable component is poor after irradiation. Not all combinations of LC mixtures and polymerizable components are suitable for PSVA displays.

Therefore, the synthesis of polymeric compounds with novel structures and the study of their structure-property relationship has become an important task in the field of liquid crystals.

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 ring 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 it has certain advantages in angle stability. On the other hand, the molecular end group changes from a linear structure to a ring structure, and the viscosity resistance of the molecule increases, that is, its rotational viscosity increases. At the same time, it has good solubility, the polymerization rate is faster, the polymerization is more complete, and the residue is lower. The alignment effect of the overall structure is better, thereby greatly improving problems such as poor display and afterimage, and can be widely used in the field of liquid crystal display, and has important application value.

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

(I)

Wherein, Ring A represents C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl; or, the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl At least one hydrogen atom in is replaced 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 manner 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 the 1,4-phenylene is 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 straight or branched chain alkane radical, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy; or, the cycloalkyl of C ₃ -C ₇ or straight chain of C ₁ -C ₁₂ Or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy at least one hydrogen atom is replaced by F or Cl;

P stands for acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxetane or epoxy;

Z, Z ₁ , Z ₂ , Z ₃ , Z ₄ , and 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 or C ₂ -C ₁₂ alkenyl is replaced by F, Cl, or CN; or, the C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkenyl group is replaced by -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -OCOO- , -SCO- or -COS- are replaced in a manner 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 alkenyl or alkoxyalkenyl; or, the C ₁ -C ₁₂ At least one hydrogen atom in the alkyl or alkoxy, C ₂ -C ₁₂ alkenyl or alkoxyalkenyl is replaced by F; or, the C ₁ -C ₁₂ alkyl or alkoxy, C ₂ In -C ₁₂ alkenyl or alkoxyalkenyl, one -CH ₂ - or at least two non-adjacent -CH ₂ - are substituted by -O- in a manner that is not directly connected to each other;

X represents -OH, -SH, or -NH ₂ ;

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

（Ⅱ）

（Ⅲ）

（Ⅳ）

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

(Ⅱ)

(Ⅲ)

(Ⅳ)

(V)

Among them, 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 replaced by L or -ZP;

L represents H, -F, -Cl, C ₃ -C ₇ cycloalkyl or C ₁ -C ₆ linear or branched chain alkyl; or, the C ₃ -C ₇ cycloalkyl or C At least one hydrogen atom in a ₁ -C ₆ linear or branched chain alkyl group 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 , and Z ₅ each independently represent a single bond, -O-, C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl; or, At least one hydrogen atom in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is replaced by F; or, the C ₁ -C ₆ alkylene or C ₂ -C ₆ One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkenyl group is replaced by -O- in a way that is not directly connected to each other;

R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkenyl or alkoxyalkenyl; or, the C ₁ -C ₆ alkyl or alkoxy, At least one hydrogen atom in the C ₂ -C ₆ alkenyl or alkoxyalkenyl is replaced by F; or, the C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkenyl Or one -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkoxyalkenyl group is replaced by -O- in a way 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.

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-2 7

I-28

I-29

I-30

I-31

I-32

I-33

I-34

I-35

I-36

I-37

I-38

I-39

I-40。 Further, one or more selected from the following compounds:

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-2 7

I-28

I-29

I-30

I-31

I-32

I-33

I-34

I-35

I-36

I-37

I-38

I-39

I-40.

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

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

The following examples are used to illustrate the present invention, but not to limit the scope of the present invention. All other equivalent changes or modifications that do not deviate 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, unless otherwise specified, can be synthesized by known methods or obtained from public commercial sources. These synthesis techniques are conventional, and the obtained liquid crystal compounds are tested to be in line with electronic compounds. standard.

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

△n stands for optical anisotropy (25°C); △ε stands for dielectric anisotropy (25°C, 1000Hz); γ1 stands for rotational viscosity (mPa.s, 25°C); Cp stands for clearing point.

Example 1

BYLC-01 The structural formula of the liquid crystal compound is:

BYLC-01

The synthetic route for preparing compound BYLC-01 is as follows:

Specific steps are as follows:

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

Under nitrogen protection, add 100g 2-ethyl-4-bromoiodobenzene, 45g p-hydroxyphenylboronic acid, 86g sodium carbonate, 0.9L dioxane, 0.3L water to the reaction flask, then start stirring, add 6.7g Pd (PPh ₃ ) ₂ Cl ₂ , heated to 85°C for 10h. Add 0.9L water to the reaction solution after cooling down to room temperature, extract once with 0.9L EA, wash once with 3L water until neutral, pass through a 50g silica gel column after drying with 50g anhydrous sodium sulfate, elute with ethyl acetate, then mix with 100g silica gel Afterwards, it was purified by 400g silica gel chromatography, n-heptane/EA=100:1(v/v), and spin-dried 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 of compound BYLC-01-1, 69.3g of cyclopentyl biphenylboronic acid, 56g of sodium carbonate, 430ml of toluene, 145ml of ethanol, 145ml of water into the reaction flask, start stirring, add 0.92g of Pd0132, and heat to 73 The reaction was carried out at ℃ 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 of compound BYLC-01-2, 6.3g of diisopropylamine, 1500ml of THF into the reaction flask, start stirring, cool down to -5°C, control the temperature at 0~-5°C, add 103.3g of NBS in batches, then raise the temperature naturally, and react After 6 hours of post-treatment, add 1L sodium sulfite aqueous solution to the reaction solution to neutralize until neutral, separate the liquids, extract the aqueous phase twice with 500ml*2 dichloromethane, combine the organic phases, wash twice with 1L*2 water, and dry with 50g anhydrous sodium sulfate Finally, pass through 50 g of silica gel, elute with dichloromethane, recrystallize from n-heptane and ethanol to obtain 113 g of white solid (compound BYLC-01-03), LC: 99.194%, yield: 88.2%.

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

Under the protection of nitrogen, add 25.8g of compound BYLC-01-3, 19.3g of Y-1, 14.2g of triphenylphosphine, 200ml of tetrahydrofuran into the reaction flask, start stirring, and add 13.6g of DIAD dropwise at -5°C~5°C Add a solution composed of 50ml tetrahydrofuran, after dripping, react at a temperature of -5°C~5°C for 30 minutes, let it naturally rise to room temperature for 4 hours, perform conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate=80:1 (v/v), 33.2 g of light yellow liquid (compound BYLC-01-4) was obtained, LC: 98.8%, yield: 78%.

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

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

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

Under the protection of nitrogen, add 20g of compound BYLC-01-5, 7.5g of methacrylic acid, 1.2g of DMAP, 150ml of DCM into the reaction flask, start stirring, and add 18.1g of DCC and 50ml of DCM dropwise at a temperature of -5°C~5°C. After dropping the solution, it was naturally warmed to room temperature and reacted for 12 hours. After conventional post-treatment, 17.8 g of a colorless viscous liquid (compound BYLC-01-6) was obtained, LC: 97.3%, yield: 78%.

(7) Synthesis of compound BYLC-01:

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

The obtained white solid BYLC-01 was analyzed by LC-MS, and the m/z of the product was 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

BYLC-02 The structural formula of the liquid crystal compound is:

BYLC-02

The synthetic route for preparing compound BYLC-02 is as follows:

Specific steps are as follows:

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

Under nitrogen protection, add 69.8g compound BYLC-01-1, 60.0g cyclopropylbiphenylboronic acid, 26.7g sodium carbonate, 500ml toluene, 150ml ethanol, 150ml water to the reaction flask, start stirring, add 0.8g Pd0132, heat React at 73°C for 10 h, perform conventional post-treatment, and recrystallize 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 of compound BYLC-02-1, 4.15g of diisopropylamine, and 1800ml of THF into the reaction flask, start stirring, cool down to -5°C, control the temperature at 0~-5°C, add 94.9g of NBS in batches, then raise the temperature naturally, and react After 6 hours of post-treatment, add 1L sodium sulfite aqueous solution to the reaction solution to neutralize until neutral, separate the liquids, extract the aqueous phase twice with 500ml*2 dichloromethane, combine the organic phases, wash twice with 1L*2 water, and dry with 50g anhydrous sodium sulfate Finally, pass through 50 g of silica gel, elute with dichloromethane, recrystallize from n-heptane and ethanol to obtain 95.0 g of white solid (compound BYLC-02-2), LC: 99.3%, yield: 84.5%.

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

Under the protection of nitrogen, add 50.0g compound BYLC-02-2, 37.4g Y-1, 27.5g triphenylphosphine, 500ml tetrahydrofuran into the reaction flask, start stirring, and add 31.2g DIAD dropwise at -5℃~5℃ Add a solution composed of 50ml tetrahydrofuran, after dripping, react at a temperature of -5°C~5°C for 30 minutes, let it naturally rise to room temperature for 4 hours, perform conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate=80:1 (v/v), 63.2 g of light yellow liquid (compound BYLC-02-3) was obtained, LC: 99.1%, yield: 75.6%.

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

Under the protection of nitrogen, add 60.0g compound BYLC-02-3, 34.2g oxaborolane, 1.2g RuPhos, 27.7g sodium carbonate, 200ml tetrahydrofuran, 50ml water, 0.18g palladium chloride into the reaction flask, start stirring , heated to 75°C for 12 hours, conventional post-treatment, column chromatography purification, n-heptane/ethyl acetate=30:1 (v/v), obtained 46.2g of colorless viscous liquid (compound BYLC-02-4) , LC: 98.3%, Yield: 81%.

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

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

(6) Synthesis of compound BYLC-02:

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

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

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

¹ H-NMR(300MHz, 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

BYLC-03 The structural formula of the liquid crystal compound is:

BYLC-03

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

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

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

¹ H-NMR(300MHz, 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

BYLC-04 The structural formula of the liquid crystal compound is:

BYLC-04

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

The obtained 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(300MHz, 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

BYLC-05 The structural formula of the liquid crystal compound is:

BYLC-05

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

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

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

¹ H-NMR(300MHz, 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

BYLC-06 The structural formula of the liquid crystal compound is:

BYLC-06

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

The obtained white solid BYLC-06 was analyzed by LC-MS, and the m/z of the product was 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

BYLC-07 The structural formula of the liquid crystal compound is:

BYLC-07

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

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

¹ H-NMR(300MHz, 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

BYLC-08 The structural formula of the liquid crystal compound is:

BYLC-08

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

The obtained 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(300MHz, 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

CP-1 The structural formula of the liquid crystal compound is:

CP-1

Comparative example 2

CP-2 The structural formula of the liquid crystal compound is:

CP-2

Experimental example

The properties of liquid crystal mixture BHR87800 are listed in Table 1: Table 1 Summary of properties of mixed crystal BHR87800 nature Cp Δn Δε ε‖ K3/K1 value +70°C 0.095 -3.5 3.3 0.97

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

RM-1 The structural formula of RM monomer is:

RM-1

Add 0.3% of the polymerizable compound BYLC-01 provided in Example 1 and 0.3% of RM monomer RM-1 to 100% liquid crystal mixture BHR87800, and dissolve uniformly to obtain a 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 the 100% 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 RM monomer RM-1 to 100% liquid crystal mixture BHR87800, and dissolve uniformly to obtain a mixture PM-3.

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

Add 0.3% of the polymerizable compound represented by CP-1 and 0.3% of RM monomer RM-1 to 100% 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 RM monomer RM-1 to 100% 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 were almost the same as those of the above-mentioned mixture BHR87800. Inject PM-1, PM-2, PM-3, PM-4, PM-5, PM-6 into the "non-aligned" test cell (cell thickness d ~ 3.2 μm, on both sides) using vacuum infusion method ITO coating (structured ITO in 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 that cuts out ultraviolet rays of 310 nm or less. At this time, the illuminance measured at a center wavelength of 365 nm was adjusted to be 100 mW/cm ² , and ultraviolet rays with a cumulative light quantity of 30 J/cm ² were irradiated (irradiation condition 1). Next, using a fluorescent UV lamp, the illuminance measured at a center wavelength of 313 nm was adjusted to 3 mW/cm ² , and the accumulated light amount was 10 J/cm ² (ultraviolet irradiation condition 2). UV1 is the ultraviolet irradiation process of irradiation condition 1, and UV2 is the process of irradiation condition 1 and irradiation condition 2. After the polymerized vertically aligned liquid crystal display element was obtained, the pretilt angle was measured using an AXO-Step pretilt angle tester, and then the test box was disassembled, and the residual polymerizable compound in the liquid crystal composition was measured by high performance liquid chromatography (HPLC). The results are summarized in Table 2 middle.

Effect test:

1. Variation of pretilt angle

A mixture prepared by injecting various polymerizable compounds and liquid crystal compounds was injected into the test cell. After polymerizing the polymeric compound by irradiating ultraviolet rays, the pretilt angles of the test cells after the UV1 and UV2 irradiation processes were respectively measured. Small changes in pretilt angle after UV1 and UV2 processes are preferred.

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

2. The conversion rate of polymeric compounds

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

This is because the remaining amount of the polymer compound (the amount of 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 liquid crystal panel is powered on. 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. The higher the VHR value, the ION Low value is preferred; Table 2 PM-1 PM-2 PM-3 PM-4 PM-5 PM-6 Liquid crystal mixture BHR87800 (parts by mass) 100 100 100 100 100 100 Self-aligning additive categories Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Self-aligning additives (parts by mass) 0.3 0.28 0.33 0.35 0.3 0.3 Residual amount of polymerizable compound [ppm] (irradiation condition 1) 1830 1650 1880 2080 2150 2300 Pretilt angle (irradiation condition 1) 2.1 2.3 2.4 2.5 2.5 2.5 Residual amount of polymerizable compound [ppm] (irradiation condition 1 and irradiation condition 2) less than the detection limit less than the detection limit less than the detection limit less than the detection limit less than the detection limit less than the detection limit Pretilt Angle (Irradiation Condition 1 and Irradiation Condition 2) 2.0 2.2 2.3 2.4 2.2 2.1 Variation of pretilt angle 0.1 0.1 0.1 0.1 0.3 0.4 VHR/% 99.37% 99.46% 99.35% 99.47% 97.23% 97.34% ION 148.6 132.0 165.5 168.3 325.2 318.5

From the comparative data in Table 2, it can be known that the polymeric compound of the present invention has a better alignment effect, faster polymerization rate, more complete polymerization and lower residue than the polymeric liquid crystal compound CP-1 and CP-2, thereby being relatively Greatly improved the problem of poor display and improved response time.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than 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 Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; 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 various embodiments of the present invention.

Claims (10)

A self-aligning polymerizable compound, characterized in that it has the structure shown in general formula (I):

(I) Among them, ring A represents C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl; or, the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ ring At least one hydrogen atom in the alkenyl group is replaced by F; or, one -CH ₂ - or at least two of the C ₃ -C ₇ cycloalkyl or C ₃ -C ₇ cycloalkenyl are not adjacent -CH ₂ -is substituted by -O-, -S- in a way that is not directly connected to each other; A ₁ , A ₂ , A ₃ each independently represent 1,4-cyclohexylene, 1,4-cyclohexylene or 1,4-phenylene; or, at least one hydrogen atom in the 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene is replaced by L or -ZP Substitution; or, at least one ring carbon atom in the 1,4-phenylene group is replaced by a nitrogen atom; L represents H, -F, -Cl, -CN, -NO ₂ , -NCS, optionally substituted silane C ₃ -C ₇ cycloalkyl or C ₁ -C ₁₂ linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyl Oxygen; or, the C ₃ -C ₇ cycloalkyl or C ₁ -C ₁₂ linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy Or at least one hydrogen atom in alkoxycarbonyloxy group is replaced by F or Cl; P represents acrylate group, methacrylate group, fluoroacrylate group, chloroacrylate group, vinyloxy group, oxygen heterocycle Butyl or epoxy; 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, at least one hydrogen atom in the C ₁ -C ₁₂ alkylene or C ₂ -C ₁₂ alkenyl is substituted by F, Cl, or CN; or, the C ₁ -C ₁₂ sub One -CH ₂ - or at least two non-adjacent -CH ₂ - in the alkyl or C ₂ -C ₁₂ alkenyl is replaced by -O-, -S-, -NH-, -CO-, -COO- , -OCO-, -OCOO-, -SCO- or -COS- are substituted in a manner 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 alkenyl or alkoxyalkenyl; or, at least one of the C ₁ -C ₁₂ alkyl or alkoxy, C ₂ -C ₁₂ alkenyl or alkoxyalkenyl The hydrogen atom is replaced by F; or, one -CH ₂ - or at least two of the C ₁ -C ₁₂ alkyl or alkoxy, C ₂ -C ₁₂ alkenyl or alkoxyalkenyl are not adjacent The -CH ₂ - is replaced by -O- in a manner that is not directly connected to each other; X represents -OH, -SH, or -NH ₂ ; m and n each independently represent 0, 1 or 2 and are not 0 at the same time. The self-aligning polymerizable compound as described in Claim 1, wherein the general formula (I) is selected from one or more of the following structures:

(Ⅱ)

(Ⅲ)

(Ⅳ)

(V) Among them, A ₁ and A ₂ represent 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene; or, the 1,4-cyclohexylene, 1 , At least one hydrogen atom H in 4-cyclohexenylene or 1,4-phenylene is replaced by L or -ZP; L represents H, -F, -Cl, C ₃ -C ₇ cycloalkyl or C ₁ -C ₆ linear or branched alkyl; or, at least one hydrogen atom in the C ₃ -C ₇ cycloalkyl or C ₁ -C ₆ linear or branched alkyl is replaced by Substituted 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 , and Z ₅ each independently represent a single bond, -O- , C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl; or, at least one hydrogen atom in the C ₁ -C ₆ alkylene or C ₂ -C ₆ alkenyl is substituted by F; or, one -CH ₂ - or at least two non-adjacent -CH ₂ - in the C ₁ -C ₆ alkylene group or C ₂ -C ₆ alkenyl group are replaced by -O- not directly connected to each other; R ₂ represents H, C ₁ -C ₆ alkyl or alkoxy, C ₂ -C ₆ alkenyl or alkoxyalkenyl; or, the C ₁ -C ₆ At least one hydrogen atom in the alkyl or alkoxy, C ₂ -C ₆ alkenyl or alkoxyalkenyl is replaced by F; or, the C ₁ -C ₆ alkyl or alkoxy, C One -CH ₂ - or at least two non-adjacent -CH ₂ - in ₂ -C ₆ alkenyl or alkoxyalkenyl is replaced by -O- in a way that is not directly connected to each other; X represents -OH; m , n each independently represent 0, 1 or 2 and are not 0 at the same time. The self-aligning polymerizable compound as claimed in claim 1 or 2, characterized in that it is selected from one or more of the following compounds:

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

I-38

I-39

I-40. A liquid crystal composition, characterized in that it comprises the self-alignment polymerizable compound described in any one of claims 1-3, and the mass percentage of the self-alignment 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-alignment 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-alignment polymerizable compound in the liquid crystal composition is 0.1-3%. Application of the self-aligning polymerizable compound described in any one of claims 1-3 in the field of liquid crystal display. Application of the liquid crystal composition described in 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 liquid crystal display field is an application in a liquid crystal display device. The application according to claim 9, wherein the liquid crystal display device includes a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display, preferably a VA or PSVA liquid crystal display.