阅读说明：本技术 一种含有聚合性化合物的液晶组合物及其应用 (Liquid crystal composition containing polymerizable compound and application thereof ) 是由 郭云鹏 陈卯先 李承贺 袁瑾 任婕 刘友然 于 2020-04-01 设计创作，主要内容包括：本发明属于液晶材料技术领域,具体涉及一种含有聚合性化合物的液晶组合物及其应用。所述液晶组合物包括向列相液晶组合物及至少包含一种或多种通式I所代表的聚合性化合物。相较于现有液晶组合物,本发明所述液晶组合物中的可聚合性化合物具有聚合速率更快,预倾角变化量更小,转化率更高,残留更低的优点,较大程度改善了现有PSVA型液晶显示不良的问题,减小预倾角变化量,解决区域Mura问题。(The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition containing a polymerizable compound and application thereof. The liquid crystal composition comprises a nematic liquid crystal composition and at least one or more polymerizable compounds represented by the general formula I. Compared with the existing liquid crystal composition, the polymerizable compound in the liquid crystal composition has the advantages of higher polymerization rate, smaller pretilt angle variation, higher conversion rate and lower residue, greatly improves the problem of poor display of the existing PSVA type liquid crystal, reduces the pretilt angle variation and solves the problem of Mura in the area.)

1. A liquid crystal composition comprising a nematic liquid crystal composition and at least one or more polymerizable compounds represented by the general formula I:

wherein L1, L2, L3, L4, L5 and L6 each independently represents H, -F, -Cl, -CH3, -C2H5, -OCH3, -OC2H5 and-CF₃Or OCF₃And L3 and L4 are not H at the same time, and at least one of L1, L2, L5 and L6 is-CH 3 or-OCH 3;

the P1 and P2 independently of one another represent an acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxetane or epoxy group;

z1, Z2 each independently represent a single bond, -O-, -S-, -CO-O-, -O-CO-O-, -CH-N-, -N-CH-, -N-, C1-C12 alkylene or C2-C12 alkenyl, wherein one or more hydrogen atoms in the C1-C12 alkylene or C2-C12 alkenyl may be independently replaced by F, Cl or CN, and one or more non-adjacent-CH 2-groups may be independently replaced by-O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, or, -SCO-, -COS-or-C ═ C-is replaced in a manner not directly linked to each other.

2. The liquid crystal composition of claim 1, wherein L1, L2, L3, L4, L5 and L6 each independently represent H, -F, -CH3 or-OCH 3, and L3 and L4 are not H at the same time.

3. Liquid crystal composition according to claim 2, characterized in that P1, P2 represent independently of each other a methacrylate, acrylate, fluoroacrylate or chloroacrylate group; preferably, P1, P2 represent independently of each other a methacrylate group or an acrylate group;

and/or, Z1, Z2 independently of one another represent a single bond, -O-, -S-, -CO-O-, -O-CO-, alkylene of C1 to C6 or alkenyl of C2 to C6, wherein one or more hydrogen atoms in the alkylene of C1 to C6 or alkenyl of C2 to C6 may be substituted independently of one another by F, and one or more non-adjacent-CH 2-groups may be replaced independently of one another by-O-in such a way that they are not directly linked to one another; preferably, Z1, Z2 independently of one another represent a single bond, an alkylene or alkoxy radical of-O-, C1-C6.

4. The liquid crystal composition of claim 3, wherein the compound represented by formula I is selected from one or more of I1-I28:

preferably, the compound represented by the general formula I is selected from one or more of I1-I5.

5. The liquid crystal composition according to any one of claims 1 to 4, wherein the mass fraction of the compound represented by the general formula I in the liquid crystal composition is 0.01 to 5%, preferably 0.05 to 1%, more preferably 0.1 to 0.5%, and still more preferably 0.15 to 0.32%.

6. The liquid crystal composition of claim 5, wherein the nematic liquid crystal composition comprises at least one or more compounds represented by the formula II:

wherein R is₁、R₂Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂A linear alkenyl group of (a);

A₁、A₂each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene;

z1 is a single bond, -CH₂CH_2-or-CH₂O-；

a is 0 or 1;

and, the liquid crystal composition comprises at least one compound represented by the general formula III:

wherein R is₃、R₄Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂A linear alkenyl group of (a);

A₃、A₄each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene.

7. The liquid crystal composition of claim 6, wherein the compound represented by formula II is one or more compounds selected from IIA to IIF:

preferably, the compound represented by formula II is selected from one or more of formulae IIA-1 to IIF-16:

further preferably, the compound represented by the general formula II is selected from one or more of the compounds of the formulas IIA-9-IIA-24, IIB-19-IIB-38, IIC-9-IIC-24, IID-9-IID-24, IIE-1-IIE-20 and IIF-1-IIF-16;

most preferably, the compound represented by the general formula II is selected from one or more of the compounds represented by the formulas IIA-13-IIA-24, IIB-23-IIB-38, IIC-13-IIC-24, IID-13-IID-24, IIE-1, IIE-2, IIE-5, IIE-6, IIE-9, IIE-10, IIE-13, IIE-14, IIE-17, IIE-18, IIF-1, IIF-2, IIF-5, IIF-6, IIF-9, IIF-10, IIF-13 and IIF-14;

and/or, the compound represented by the general formula III is selected from one or more of formulas IIIA to IIIC:

preferably, the compound represented by formula III is selected from one or more of formulae IIIA1 to IIIC 24:

further preferably, the compound represented by the general formula III is selected from one or more of the compounds in the formulas IIIA-1 to IIIA-24, IIIB-1 to IIIB-24 and IIIC-1 to IIIC-22;

more preferably, the compound represented by the general formula III is selected from one or more of the compounds in the formulas IIIA-1 to IIIA-12, IIIB-17 to IIIB-24, IIIC-1 to IIIC-4 and IIIC-15 to IIIC-18.

8. The liquid crystal composition according to any one of claims 1 to 7, wherein the nematic liquid crystal composition further comprises one or more compounds represented by the general formula IV:

wherein R is₅、R₆Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂Linear alkenyl of (a), halogen; l7, L8, L9 each independently represent-H, -F, -CH3 or-OCH 3;

preferably, the compound represented by formula IV is selected from one or more of IVA-IVD:

wherein R is₅、R₆Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy, C₂～C₁₂Linear alkenyl or halogen of (a);

further preferably, the compound represented by formula IV is selected from one or more of IVA1 to IVD 24:

more preferably, the compound represented by the general formula IV is selected from one or more of IVA-5, IVA-9, IVA-14, IVA-15, IVB-5 to IVB-8, IVB-6 to IVB-10, IVD-21 to IVD-24;

and/or, the nematic liquid crystal composition further comprises one or more compounds represented by the general formula V:

wherein R is₇、R₈Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂A linear alkenyl group of (a); a. the₅Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene;

preferably, the compound represented by formula V is selected from one or more of VA to VB:

wherein R is₇、R₈Each independently represents C₁～C₇Linear alkyl, linear alkoxy or C₂～C₇A linear alkenyl group of (a);

further preferably, the compound represented by the general formula V is selected from one or more of VA1 to VB 63:

more preferably, the compound represented by the general formula V is selected from one or more of VA-39-VA-44 and VB-39-VB-48;

and/or, the liquid crystal composition further comprises one or more antioxidants represented by formula VI:

wherein R is₉Each independently represents C₁～C₇Linear alkyl, linear alkoxy or C₂～C₇A linear alkenyl group of (a); a. the₆Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene, c is 0 or 1;

preferably, the compound represented by the general formula VI is selected from one or more of VI-1 to VI-2:

9. the liquid crystal composition according to any one of claims 1 to 8, wherein the nematic liquid crystal composition comprises the following components in percentage by mass:

(1) 1-80% of a compound represented by the general formula II;

(2) 1 to 70% of a compound represented by the general formula III;

(3) 0 to 25% of a compound represented by IV;

(4) 0 to 25% of a compound represented by the general formula V;

preferably, the liquid crystal compound comprises the following components in percentage by mass:

(1) 5-70% of a compound represented by the general formula II;

(2) 20-60% of a compound represented by the general formula III;

(3) 0 to 15% of a compound represented by IV;

(4) 0 to 15% of a compound represented by the general formula V;

more preferably, the liquid crystal compound comprises the following components in percentage by mass:

(1) 10-70% of a compound represented by the general formula II;

(2) 25 to 60% of a compound represented by the general formula III;

(3) 0 to 10% of a compound represented by IV;

(4) 0 to 10% of a compound represented by the general formula V;

particularly preferably, the liquid crystal compound comprises the following components in percentage by mass:

(1) 20-70% of a compound represented by the general formula II;

(2) 20-50% of a compound represented by the general formula III;

(3) 0-6% of a compound represented by IV;

(4) 0-9% of a compound represented by the general formula V.

10. Use of a liquid crystal composition according to any of claims 1 to 9 in a VA-mode liquid crystal display device, preferably in a PSVA-mode liquid crystal display device.

Technical Field

The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition containing a polymerizable compound and application thereof.

Background

In recent years, liquid crystal display devices have been widely used in various electronic devices, such as smart phones, tablet computers, car navigators, televisions, and the like. Representative liquid crystal display modes include a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane switching (IPS) mode, a Fringe Field Switching (FFS) mode, and a Vertical Alignment (VA) mode. Among them, the VA mode receives increasing attention because of having a fast fall time, a high contrast ratio, a wide viewing angle, and a high quality image.

However, the liquid crystal medium used for the display element of the active matrix addressing type such as VA mode has its own disadvantages, such as a significantly inferior image sticking level to that of the display element of positive dielectric anisotropy, a relatively slow response time, a relatively high driving voltage, and the like.

A PSVA (polymer stabilized vertically aligned liquid crystal) type liquid crystal display element forms a polymer structure in a liquid crystal cell to control a structure of a pretilt angle of liquid crystal molecules, and is used as a liquid crystal display element due to its high-speed response and high contrast. The PSVA type display element is manufactured by injecting a polymerizable composition containing a liquid crystal compound and a polymerizable compound between substrates, irradiating with ultraviolet light, and polymerizing the polymerizable compound in a state in which liquid crystal molecules are aligned. The polymerizable compound as the main material has important significance, and can effectively improve the response speed, enhance the contrast ratio, solve the problem of display residual image and the like by matching with a proper liquid crystal composition.

The existing PSVA type liquid crystal well solves the problems, but has other problems. The existing PSVA liquid crystal display mode needs to experience two ultraviolet irradiation processes in a box forming process, the first irradiation process is electric irradiation, the main effect is a pretilt angle angulation process, the second ultraviolet irradiation process is an RM monomer which is not completely reacted in a consumption mode, the liquid crystal quality is improved, RM residues are reduced, the pretilt angle can continuously change in the second ultraviolet irradiation process, different liquid crystal screen positions pretilt angles affected by temperature have different degrees of difference, and the problem of region Mura is further caused. The problem of Mura in the area is solved, and the reduction of the variation of the pretilt angle in the two ultraviolet irradiation processes is an important subject of the current PSVA liquid crystal research and development.

Disclosure of Invention

The first object of the present invention is to provide a liquid crystal composition containing a polymerizable compound. Compared with the existing liquid crystal composition, the polymerizable compound in the liquid crystal composition has the advantages of higher polymerization rate, smaller pretilt angle variation, higher conversion rate and lower residue, greatly improves the problem of poor display of the existing PSVA type liquid crystal, reduces the pretilt angle variation and solves the problem of Mura in the area.

Specifically, the liquid crystal composition provided by the invention comprises a nematic liquid crystal composition and at least one or more polymerizable compounds represented by the general formula I:

wherein L1, L2, L3, L4, L5 and L6 respectively and independently represent H, -F, -Cl, -CH3, -C2H5, -OCH3, -OC2H5, -CF3 or OCF3, L3 and L4 are not H at the same time, and at least one of L1, L2, L5 and L6 is-CH 3 or-OCH 3;

the P1 and P2 independently of one another represent an acrylate, methacrylate, fluoroacrylate, chloroacrylate, vinyloxy, oxetane or epoxy group;

z1, Z2 each independently represent a single bond, -O-, -S-, -CO-O-, -O-CO-O-, -CH-N-, -N-CH-, -N-, C1-C12 alkylene or C2-C12 alkenyl, wherein one or more hydrogen atoms in the C1-C12 alkylene or C2-C12 alkenyl may be independently replaced by F, Cl or CN, and one or more non-adjacent-CH 2-groups may be independently replaced by-O-, -S-, -NH-, -CO-, COO-, -OCO-, -OCOO-, or, -SCO-, -COS-or-C ═ C-is replaced in a manner not directly linked to each other.

In the experimental process, technicians find that the liquid crystal is poured into a liquid crystal screen in a vacuum environment, and the initial pretilt angle is formed in the first section of UV1 irradiation process after two sections of ultraviolet light irradiation, the initial pretilt angle is mainly solved in the second section of UV2 irradiation process, but the pretilt angle of the liquid crystal cell can be continuously changed in the UV2 process, and the change of the UV2 can be different at different temperatures.

In the experimental process, it is further found that the pretilt angle of different RM monomer structures can be changed in different degrees after two-stage ultraviolet irradiation, and after the two RM monomer structures are mixed in nematic liquid crystal and poured into a liquid crystal screen, the pretilt angle is obviously changed after the two-stage ultraviolet irradiation. The pretilt angle of RM-1 after UV1 ultraviolet irradiation is 2.5 degrees, the pretilt angle of UV2 ultraviolet irradiation is 2.1 degrees, and the variation of the pretilt angle is 0.4 degree; RM-2 had a pretilt of 2.5 after UV1 UV irradiation, a UV2 UV irradiation pretilt of 2.0, and a pretilt variation of 0.5.

In addition, different temperatures also have different degrees of influence on the change of the pretilt angle in the UV2 process, so in the UV2 ultraviolet irradiation process, because the reason that the LCD screen was made, the region that has temperature inequality appears, causes different regional pretilt angles inequality to appear, and then leads to regional Mura problem. Experiments show that the larger the change degree of the pretilt angle from UV1 to UV2 is, the larger the temperature influence is in the UV2 process; the smaller the change degree of the pretilt angle from UV1 to UV2, the smaller the influence of the temperature during UV 2.

Further research proves that when the substituent of at least one site of L1, L2, L5 and L6 in the terphenyl polymerizable compound is-CH 3 or-OCH 3, the variation of the pretilt angle of the polymerizable compound in the process from UV1 to UV2 can be obviously reduced, and the problem of Mura in the area can be effectively solved. The liquid crystal composition added with the polymerizable compound of the type I can fully obtain a pretilt angle (tilt angle) after being irradiated by ultraviolet light, and the problem of no obvious angle return in different temperature areas in the UV2 process is solved, so that the problem of area Mura caused by uneven area temperature in the UV2 process in the production process of a liquid crystal screen is effectively solved; meanwhile, since the polymerization rate of the type I polymerizable compound is high and the residual amount is small, there is no unreacted polymerizable compound or very little unreacted polymerizable compound in the UV2 process, and therefore, there is no problem such as poor alignment or display or such problem can be sufficiently suppressed.

In formula I, preferably, L1, L2, L3, L4, L5 and L6 independently represent H, -F, -CH3 or-OCH 3, and L3 and L4 are not H at the same time.

In formula I, preferably P1, P2 represent independently of each other a methacrylate, acrylate, fluoroacrylate or chloroacrylate group; more preferably, P1, P2 represent independently of each other a methacrylate group or an acrylate group.

In the general formula I, preferably, Z1, Z2 independently of one another represent a single bond, -O-, -S-, -CO-O-, -O-CO-, alkylene of C1 to C6 or alkenyl of C2 to C6, wherein one or more hydrogen atoms in the alkylene of C1 to C6 or alkenyl of C2 to C6 may be substituted independently of one another by F, and one or more non-adjacent-CH 2-groups may be replaced independently of one another by-O-in such a way that they are not directly linked to one another; more preferably, Z1, Z2 represent independently of each other a single bond, -O-, C1-C6 alkylene or alkoxy.

Specifically, the compound represented by the general formula I provided by the invention is selected from one or more of I1-I28:

more preferably, the compound represented by the general formula I provided by the invention is selected from one or more of I1-I5.

The liquid crystal composition provided by the invention contains 0.01-5% by mass of the polymerizable compound represented by the general formula I, preferably 0.05-1% by mass of the polymerizable compound, more preferably 0.1-0.5% by mass of the polymerizable compound, and even more preferably 0.15-0.32% by mass of the polymerizable compound.

Specifically, the invention provides a liquid crystal composition, wherein the nematic phase liquid crystal composition at least comprises one or more compounds represented by the general formula II:

wherein R is₁、R₂Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂Linear alkenyl of (A)₁、A₂Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene; z1 is a single bond, -CH₂CH_2-or-CH₂O-; a is 0 or 1;

and at least one compound represented by the general formula III:

wherein R is₃、R₄Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂Linear alkenyl of (A)₃、A₄Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene.

Specifically, the compound represented by the general formula II provided by the invention is selected from one or more of IIA-IIF:

preferably, the compounds represented by formula II provided by the present invention are selected from one or more of formulas IIA-1 to IIF-16:

more preferably, the compound represented by the general formula II provided by the invention is selected from one or more of the compounds of the formulas IIA-9-IIA-24, IIB-19-IIB-38, IIC-9-IIC-24, IID-9-IID-24, IIE-1-IIE-20 and IIF-1-IIF-16;

most preferably, the compound represented by the general formula II provided by the invention is selected from one or more of the compounds represented by the formulas IIA-13-IIA-24, IIB-23-IIB-38, IIC-13-IIC-24, IID-13-IID-24, IIE-1, IIE-2, IIE-5, IIE-6, IIE-9, IIE-10, IIE-13, IIE-14, IIE-17, IIE-18, IIF-1, IIF-2, IIF-5, IIF-6, IIF-9, IIF-10, IIF-13 and IIF-14;

specifically, the compound represented by the general formula III provided by the invention is selected from one or more of formulas IIIA-IIIC:

preferably, the compound represented by the general formula III provided by the invention is selected from one or more of the following formulas IIIA 1-IIIC 24:

more preferably, the compound represented by the general formula III provided by the invention is selected from one or more of the formulas IIIA-1 to IIIA-24, IIIB-1 to IIIB-24 and IIIC-1 to IIIC-22;

most preferably, the compound represented by the general formula III provided by the invention is selected from one or more of the compounds in the formulas IIIA-1-IIIA-12, IIIB-17-IIIB-24, IIIC-1-IIIC-4 and IIIC-15-IIIC-18.

The liquid crystal composition provided by the invention can also comprise one or more compounds represented by the general formula IV:

wherein R is₅、R₆Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂Linear alkenyl of (a), halogen. L7, L8, L9 each independently represent-H, -F, -CH3 or-OCH 3.

Specifically, the compounds represented by the general formula IV provided by the invention are selected from one or more of IVA-IVD:

wherein R is₅、R₆Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy, C₂～C₁₂Linear alkenyl or halogen.

Specifically, the compound represented by the general formula IV provided by the invention is selected from one or more of IVA 1-IVD 24:

more preferably, the compound represented by the general formula IV provided by the invention is selected from one or more of IVA-5, IVA-9, IVA-14, IVA-15, IVB-5 to IVB-8, IVB-6 to IVB-10 and IVD-21 to IVD-24.

The liquid crystal composition provided by the invention can also comprise one or more compounds represented by the general formula V:

wherein R is₇、R₈Each independently represents C₁～C₁₂Linear alkyl, linear alkoxy or C₂～C₁₂A linear alkenyl group of (a); a. the₅Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene.

Specifically, the compound represented by the general formula V provided by the invention is selected from one or more of VA-VB:

wherein R is₇、R₈Each independently represents C₁～C₇Linear alkyl, linear alkoxy or C₂～C₇Linear alkenyl groups of (a).

Preferably, the compound represented by the general formula V provided by the invention is selected from one or more of VA 1-VB 63:

more preferably, the compound represented by the general formula V provided by the invention is selected from one or more of VA-39-VA-44 and VB-39-VB-48.

The liquid crystal composition provided by the invention can also comprise one or more antioxidants represented by the general formula VI:

wherein R is₉Each independently represents C₁～C₇The linear alkyl group of,Straight-chain alkoxy or C₂～C₇A linear alkenyl group of (a); a. the₆Each independently represents trans-1, 4-cyclohexyl or 1, 4-phenylene, c is 0 or 1;

preferably, the compound represented by the general formula VI provided by the invention is selected from one or more of VI-1 to VI-2:

the liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a conventional antioxidant, ultraviolet absorber, photostabilizer, infrared absorber, or the like.

In order to enable the liquid crystal composition to meet different requirements, wherein the nematic phase liquid crystal components in the liquid crystal composition are composed according to mass percent, the nematic phase liquid crystal composition provided by the invention comprises the following components in mass percent:

(1) 1-80% of a compound represented by the general formula II;

(2) 1 to 70% of a compound represented by the general formula III;

(3) 0 to 25% of a compound represented by IV;

(4) 0 to 25% of a compound represented by the general formula V.

Preferably, the liquid crystal compound provided by the invention comprises the following components in percentage by mass:

(1) 5-70% of a compound represented by the general formula II;

(2) 20-60% of a compound represented by the general formula III;

(3) 0 to 15% of a compound represented by IV;

(4) 0-15% of a compound represented by the general formula V.

More preferably, the liquid crystal compound provided by the invention comprises the following components in percentage by mass:

(1) 10-70% of a compound represented by the general formula II;

(2) 25 to 60% of a compound represented by the general formula III;

(3) 0 to 10% of a compound represented by IV;

(4) 0 to 10% of a compound represented by the general formula V.

Particularly preferably, the liquid crystal compound provided by the invention comprises the following components in percentage by mass:

(1) 20-70% of a compound represented by the general formula II;

(2) 20-50% of a compound represented by the general formula III;

(3) 0-6% of a compound represented by IV;

(4) 0-9% of a compound represented by the general formula V.

In the liquid crystal composition provided by the invention, the polymerizable compound shown in the general formula I is independently added outside the nematic liquid crystal composition in percentage by mass.

The method for producing the liquid crystal composition of the present invention is not particularly limited, and it can be produced by mixing two or more compounds by a conventional method, such as a method of mixing the different components at a high temperature and dissolving each other, wherein the liquid crystal composition is dissolved and mixed in a solvent for the compounds, and then the solvent is distilled off under reduced pressure; alternatively, the liquid crystal composition of the present invention can be prepared by a conventional method, for example, by dissolving the component having a smaller content in the main component having a larger content at a higher temperature, or by dissolving each of the components in an organic solvent, for example, acetone, chloroform or methanol, and then mixing the solutions to remove the solvent.

The invention also provides application of the liquid crystal composition in a Vertical Alignment (VA) type liquid crystal display device, preferably in a PSVA type liquid crystal display device.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Unless otherwise indicated, percentages in the present invention are weight percentages; the temperature units are centigrade; Δ n represents optical anisotropy (25 ℃); epsilon_∥And ε_⊥Respectively, parallel and perpendicular dielectric constants (25 c,1000 Hz); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp represents the clearing point (. degree. C.) of the liquid crystal composition; k₁₁、K₂₂、K₃₃Respectively representing the splay, twist and bend elastic constants (pN, 25 ℃). ρ represents resistivity (Ω · cm) and the test conditions are 25 ± 2 ℃.

In the following examples, the group structures in the liquid crystal compounds are represented by codes shown in Table 1.

Table 1: radical structure code of liquid crystal compound

Take the following compound structure as an example:

expressed as: 3PWO2

Expressed as: 3CCWO2

In the following examples, the liquid crystal composition was prepared by a thermal dissolution method, comprising the steps of: weighing the liquid crystal compound by a balance according to the weight percentage, wherein the weighing and adding sequence has no specific requirements, generally weighing and mixing the liquid crystal compound in sequence from high melting point to low melting point, heating and stirring at 60-100 ℃ to uniformly melt all the components, filtering, performing rotary evaporation, and finally packaging to obtain the target sample.

The weight percentages of the components of the nematic liquid crystal composition and the performance parameters of the liquid crystal composition are given in the following table.

Nematic liquid crystal composition LC 1:

table 2: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC 2:

table 3: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC3

Table 4: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC4

Table 5: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC5

Table 6: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC6

Table 7: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC7

Table 8: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC8

Table 9: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC10

Table 11: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC11

Table 12: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC12

Table 13: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC13

Table 14: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC14

Table 15: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC15

Table 16: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC16

Table 17: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC17

Table 18: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC 18:

table 19: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC19

Table 20: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC20

Table 21: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC21

Table 22: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC22

Table 23: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC24

Table 25: the weight percentage and performance parameters of each component in the liquid crystal composition

Nematic liquid crystal composition LC25

Table 26: the weight percentage and performance parameters of each component in the liquid crystal composition

A polymerizable compound-containing liquid crystal composition was obtained as example 1 by adding 0.265 parts by mass of the compound represented by formula I-3 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 2 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.017 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 3 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.032 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 4 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 5 by adding 0.250 part by mass of the compound represented by formula I-3 and 0.05 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 6 by adding 0.280 part by mass of the compound represented by formula I-3 and 0.05 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 7 by adding 0.320 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A polymerizable compound-containing liquid crystal composition was obtained as example 8 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 2.

A polymerizable compound-containing liquid crystal composition was obtained as example 9 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 3.

A polymerizable compound-containing liquid crystal composition was obtained as example 10 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 4.

A polymerizable compound-containing liquid crystal composition was obtained as example 11 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 5.

A polymerizable compound-containing liquid crystal composition was obtained as example 12 by adding 0.25 part by mass of the compound represented by formula I-3 and 0.017 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 6.

A polymerizable compound-containing liquid crystal composition was obtained as example 13 by adding 0.25 part by mass of the compound represented by formula I-3 and 0.024 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 7.

A polymerizable compound-containing liquid crystal composition was obtained as example 14 by adding 0.25 part by mass of the compound represented by formula I-3 and 0.026 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 8.

A polymerizable compound-containing liquid crystal composition was obtained as example 15 by adding 0.25 part by mass of the compound represented by formula I-3 and 0.028 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 9.

A polymerizable compound-containing liquid crystal composition was obtained as example 16 by adding 0.25 part by mass of the compound represented by formula I-3 and 0.032 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 10.

A polymerizable compound-containing liquid crystal composition was obtained as example 17 by adding 0.28 part by mass of the compound represented by formula I-1 and 0.017 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 11.

A polymerizable compound-containing liquid crystal composition was obtained as example 18 by adding 0.28 part by mass of the compound represented by formula I-1 and 0.024 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 12.

A polymerizable compound-containing liquid crystal composition was obtained as example 19 by adding 0.28 part by mass of the compound represented by formula I-1 and 0.026 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 13.

A polymerizable compound-containing liquid crystal composition was obtained as example 20 by adding 0.28 part by mass of the compound represented by formula I-1 and 0.028 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 14.

A polymerizable compound-containing liquid crystal composition was obtained as example 21 by adding 0.28 part by mass of the compound represented by formula I-1 and 0.032 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 15.

A polymerizable compound-containing liquid crystal composition was obtained as example 22 by adding 0.32 part by mass of the compound represented by formula I-2 and 0.017 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 16.

A polymerizable compound-containing liquid crystal composition was obtained as example 23 by adding 0.32 part by mass of the compound represented by formula I-2 and 0.024 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 17.

A polymerizable compound-containing liquid crystal composition was obtained as example 24 by adding 0.32 part by mass of the compound represented by formula I-2 and 0.026 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 18.

A polymerizable compound-containing liquid crystal composition was obtained as example 25 by adding 0.32 part by mass of the compound represented by formula I-2 and 0.028 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 19.

A polymerizable compound-containing liquid crystal composition was prepared as example 26 by adding 0.32 part by mass of the compound represented by formula I-2 and 0.032 part by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 20.

A polymerizable compound-containing liquid crystal composition was obtained as example 27 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 21.

A polymerizable compound-containing liquid crystal composition was obtained as example 28 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 22.

A polymerizable compound-containing liquid crystal composition was obtained as example 29 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 23.

A polymerizable compound-containing liquid crystal composition was obtained as example 30 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 24.

A polymerizable compound-containing liquid crystal composition was obtained as example 31 by adding 0.265 parts by mass of the compound represented by formula I-3 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 25.

Comparative example 1:

a liquid crystal composition containing a polymerizable compound was obtained as comparative example 1 by adding 0.265 parts by mass of the compound represented by formula RM-1 and 0.05 parts by mass of the compound represented by formula VI-2 to 100 parts by mass of liquid crystal composition LC 1.

A liquid crystal composition containing a polymerizable compound was injected into a PSVA test cell having a cell gap of 3.2 μm by a vacuum injection method. Then, the liquid crystal cell was irradiated with ultraviolet rays using a fluorescent lamp through a color filter that filters ultraviolet rays of 310nm or less. At this time, the illuminance measured under the condition of the central wavelength of 365nm was adjusted to 100mW/cm2, and ultraviolet rays having a cumulative light quantity of 30J/cm2 were irradiated (irradiation condition 1). Subsequently, a fluorescent UV lamp was used to irradiate a cumulative light quantity of 10J/cm2 at an illuminance of 3mW/cm2 measured under a condition of a center wavelength of 313nm (ultraviolet irradiation condition 2). UV1 is an ultraviolet irradiation process through irradiation condition 1, and UV2 is a process through irradiation condition 1 and irradiation condition 2.

And (3) effect testing:

1. variation of pretilt angle

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

Under different temperature ranges, the pretilt angles of different areas have no great difference after the UV2 process, so that the mura problem of the areas can be effectively improved.

2. Conversion rate of polymerizable Compound

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: from the viewpoint of image retention, the residual amount of the polymer compound (the amount of unreacted polymerizable compound) is preferably small.

Table 24:

table 25:

table 26:

table 27:

table 28:

table 29:

table 30:

table 31:

compared with a comparative example, the liquid crystal composition of the polymerizable compound has the advantages of small pretilt angle variation, less residue and high conversion rate, reduces the pretilt angle return angle problem caused by the UV2 process, and effectively solves the Mura problem in the area.