TW202130789A - Polymerizable compound and application thereof - Google Patents

Abstract

The invention relates to a polymerizable compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The structure of the polymerizable compound is represented by formula I shown in the description, the liquid crystal composition containing the polymerizable compound has a high voltage retention rate and a stable pre-tilt angle, and when the polymerizable compound is applied to the PS (polymer stabilization) or PSA (polymer stabilization alignment) type liquid crystal display device, residual images can be reduced, the contrast ratio can be increased, and therefore the product quality can be improved.

Description

A polymerizable compound and its application

The present invention belongs to the technical field of liquid crystal display, and specifically relates to a polymerizable compound, a liquid crystal composition containing the polymerizable compound, and a liquid crystal display element or a liquid crystal display containing the polymerizable compound or the liquid crystal composition.

With the development of display technology, flat-panel display devices such as liquid crystal display (Liquid Crystal Display, LCD) have been widely used in mobile phones, TVs, etc. due to their advantages of high image quality, power saving, thin body and wide application range. Various consumer electronic products such as personal digital assistants, digital cameras, notebook computers, and desktop computers have become the mainstream of display devices.

Reactive Mesogen (RM) is currently a very popular and important research direction in the liquid crystal display industry. Its possible applications include polymer stable alignment (PSA) liquid crystal displays, polymer stable blue phase (PS-BP) liquid crystal displays And graphical bit phase difference film (Pattern Retarder Film) and so on.

However, there are still some shortcomings in the application of the liquid crystal compound and the RM in the PSA mode display. First of all, not all RMs are suitable for PSA displays so far; at the same time, if ultraviolet light (Ultraviolet light) is used without adding a photoinitiator to polymerize RM, fewer types of RM can be selected; and, often It is difficult to find a more suitable selection criterion than the direct PSA test using pretilt measurement; in addition, the liquid crystal composition formed by the combination of the liquid crystal compound and the selected RM is required to have low rotational viscosity, good mutual solubility, and high voltage retention Rate (VHR) to achieve the desired display effect. In PSA-VA display mode, it is very important that the liquid crystal composition after ultraviolet light irradiation still has a high VHR, otherwise it will cause problems such as afterimages of the display; another problem is the stability of the pretilt angle. The pretilt angle is not kept constant during the manufacturing process, which can have a negative impact on the display performance, for example by increasing the black state transmittance, and thus reducing the contrast.

In order to overcome the problems of poor miscibility of reactive liquid crystal (RM), low voltage retention (VHR) and poor pretilt angle stability, and solve the problems of residual image and low contrast of liquid crystal display elements or liquid crystal displays, the inventors conducted in-depth research It was found that this problem can be solved by including the compound of the present invention in a liquid crystal composition, thereby completing the present invention.

Ⅰ 其中， L₁ 、L₂ 、L₃ 、L₄ 各自獨立地表示F原子、Cl原子、-CN、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，其中一個或多個不相鄰的-CH₂ -基團任選地被-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-取代，和其中一個或多個H原子任選地被鹵素原子取代； r₁ 、r₃ 各自獨立地表示0、1、2、3或4； r₂ 、r₄ 各自獨立地表示0、1、2或3； x₁ 、x₂ 、x₃ 、x₄ 各自獨立地表示0、1或2，且x₁ +x₂ +x₃ +x₄ ≥3； Sp₁ 、Sp₂ 、Sp₃ 、Sp₄ 、Sp₅ 、Z₁ 、Z₂ 各自獨立地表示單鍵、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，且其中一個或多個不相鄰的-CH₂ -基團任選地被-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-取代，其中一個或多個H原子任選被F原子或Cl原子取代； P₁ 、P₂ 、P₃ 、P₄ 各自獨立地表示可聚合基團。Specifically, the present invention includes the following content: The first aspect of the present invention provides a polymerizable compound represented by formula I,

Ⅰ Wherein, L ₁ , L ₂ , L ₃ , and L ₄ each independently represent F atom, Cl atom, -CN, linear alkyl group having 1 to 25 C atoms, branched chain having 3 to 25 C atoms Alkyl, cyclic alkyl having 3 to 25 C atoms, alkenyl having 2 to 25 C atoms, or alkynyl having 2 to 25 C atoms, of which one or more non-adjacent -CH ₂ -Groups are optionally substituted by -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more of them The H atom is optionally substituted by a halogen atom; r ₁ and r _{3 each independently represent 0, 1, 2} , 3 or 4; r 2 and r ₄ each independently represent 0, ₁ , 2 or 3; x 1, x ₂ , x ₃ , x ₄ each independently represent 0, 1 or 2, and x ₁ + x ₂ + x ₃ + x ₄ ≥ 3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , Z ₂ each independently represents a single bond, a straight chain alkyl group having 1 to 25 C atoms, a branched chain alkyl group having 3 to 25 C atoms, a cyclic alkyl group having 3 to 25 C atoms, and 2 An alkenyl group having to 25 C atoms or an alkynyl group having 2 to 25 C atoms, and one or more non-adjacent -CH ₂ -groups are optionally substituted by -O-, -S-, -CO -, -CO-O-, -O-CO-, -O-CO-O- substituted, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms; P ₁ , P ₂ , P ₃ , P ₄ each independently represents a polymerizable group.

In a second aspect of the present invention, there is provided a liquid crystal composition, the liquid crystal composition comprising one or more polymerizable compounds represented by formula I.

In a third aspect of the present invention, there is provided a liquid crystal display element or liquid crystal display, the liquid crystal display element or liquid crystal display comprising one or more polymerizable compounds represented by formula I or containing one or more polymerizable compounds represented by formula I Liquid crystal composition. Invention effect

The present invention provides a new type of polymerizable compound. Compared with the prior art, the polymerizable compound containing the present invention has good mutual solubility with liquid crystal compositions, and the marketed liquid crystal compositions have higher voltage retention (VHR). And the liquid crystal composition containing the polymerizable compound of the present invention has a large and stable pretilt angle when it is made into a display element, and is applied to PS- (polymer stabilized) or PSA- (polymer stabilized alignment) type liquid crystal display elements In the middle, it can reduce the residual image and increase the contrast, thereby improving the product quality.

The present invention discloses a polymerizable compound represented by the above formula I.

、

、

、

、

、

、

、

、

、

、

、

或

，其中，結構式中的點表示各基團與式I所示化合物主體的連接位置。The polymerizable compound represented by formula I disclosed in the present invention, preferably, in the compound represented by formula I: L ₁ , L ₂ , L ₃ , and L ₄ each independently represent an alkyl group having 1 to 5 carbon atoms , Fluorine-substituted alkyl groups with 1-5 carbon atoms, alkenyl groups with 2-5 carbon atoms, alkoxy groups with 1-5 carbon atoms, fluorine-substituted alkyl groups with 1-5 carbon atoms Oxy group, F atom or Cl atom; r ₁ and r ₃ each independently represent 0, 1 or 2; r ₂ and r ₄ each independently represent 0 or 1; x ₁ , x ₂ , x ₃ , and x ₄ are each independently Ground represents 0 or 1, and x ₁ + x ₂ + x ₃ + x ₄ ≥ 3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , Z ₂ each independently represent a single bond, a carbon atom Alkyl groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, or alkynyl groups with 2-10 carbon atoms, in which one or more non-adjacent -CH ₂ -groups are optionally -O-, -CO-, -CO-O-, -O-CO- substituted, one or more H atoms are optionally substituted by F atoms; P ₁ , P ₂ , P ₃ , and P ₄ each independently represents

,

,

,

,

,

,

,

,

,

,

,

or

, Where the dot in the structural formula represents the connection position of each group to the main body of the compound represented by formula I.

I-1-1

I-1-2

I-1-3

I-2-1

I-2-2

I-2-3

I-2-4

I-2-5

I-2-6

I-2-7

 I-2-8

I-2-9

I-2-10

I-2-11

 I-2-12

I-3-1

I-3-2

I-3-3

I-4-1

I-4-2

I-4-3

I-4-4

I-4-5

I-4-6

I-4-7

I-4-8

I-4-9

I-4-10

 I-4-11

I-4-12

I-5-1

I-5-2

I-5-3

I-6-1

I-6-2

I-6-3

I-6-4

I-6-5

I-6-6

I-6-7

I-6-8

I-6-9

I-7-1

I-8-1

I-8-2

I-8-3

I-8-4

I-8-5

I-8-6

I-8-7

I-8-8

I-8-9

I-10-1

I-10-2

I-10-3

I-10-4

 I-10-5

I-10-6

I-10-7

I-10-8

 I-10-9

I-12-1

I-12-2

I-12-3

I-12-4

I-12-5

I-12-6

I-12-7

I-12-8

I-12-9

I-14-1

I-14-2

I-14-3

 I-14-4

I-14-5

I-14-6

I-14-7

I-14-8

I-14-9

I-15-1

I-15-2

I-15-3

I-16-1

I-16-2

I-16-3

I-17-1

I-17-2

I-17-3。 The polymerizable compound represented by formula I disclosed in the present invention is more preferably selected from the group consisting of the following compounds represented by formula I-1-1 to formula I-17-3,

I-1-1

I-1-2

I-1-3

I-2-1

I-2-2

I-2-3

I-2-4

I-2-5

I-2-6

I-2-7

I-2-8

I-2-9

I-2-10

I-2-11

I-2-12

I-3-1

I-3-2

I-3-3

I-4-1

I-4-2

I-4-3

I-4-4

I-4-5

I-4-6

I-4-7

I-4-8

I-4-9

I-4-10

I-4-11

I-4-12

I-5-1

I-5-2

I-5-3

I-6-1

I-6-2

I-6-3

I-6-4

I-6-5

I-6-6

I-6-7

I-6-8

I-6-9

I-7-1

I-8-1

I-8-2

I-8-3

I-8-4

I-8-5

I-8-6

I-8-7

I-8-8

I-8-9

I-10-1

I-10-2

I-10-3

I-10-4

I-10-5

I-10-6

I-10-7

I-10-8

I-10-9

I-12-1

I-12-2

I-12-3

I-12-4

I-12-5

I-12-6

I-12-7

I-12-8

I-12-9

I-14-1

I-14-2

I-14-3

I-14-4

I-14-5

I-14-6

I-14-7

I-14-8

I-14-9

I-15-1

I-15-2

I-15-3

I-16-1

I-16-2

I-16-3

I-17-1

I-17-2

I-17-3.

The present invention also provides a liquid crystal composition comprising one or more of the aforementioned polymerizable compounds of the present invention.

The liquid crystal composition, which is an aspect of the present invention, contains the compound represented by the aforementioned formula I. In addition to the compound represented by formula I, the liquid crystal composition may also contain liquid crystal compounds other than the compound represented by formula I and other additives.

Ⅱ

Ⅲ 式II中，R₁ 、R₂ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

、

各自獨立地表示

或

； 式III中，R₃ 、R₄ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，且R₃ 、R₄ 中任意一個或多個不相鄰的-CH₂ -任選被亞環戊基、亞環丁基或亞環丙基取代； Z₁ 、Z₂ 各自獨立地表示單鍵、-CH₂ CH₂ -、-CH₂ O-或-OCH₂ -；

、

各自獨立地表示

、

、

、

、

、

、

或

; m₁ 表示1或2，當m₁ 表示2時，

相同或不同； n₁ 表示0、1或2，當n₁ 表示2時，

相同或不同。Preferably, the liquid crystal composition of the present invention further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

Ⅱ

Ⅲ In formula II, R ₁ and R ₂ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, and an alkoxy group with 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

,

Expressed independently of each other

or

; In formula III, R ₃ and R ₄ each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, and an alkoxy group having 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy group or fluorine-substituted alkenyloxy group having 3-8 carbon atoms, and any one or more of _{R 3} and R _{4 that are not adjacent -CH 2} -are optionally cyclopentylene, Cyclobutylene or cyclopropylene substitution; Z ₁ and Z ₂ each independently represent a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -;

,

Expressed independently of each other

,

,

,

,

,

,

or

; m ₁ means 1 or 2, when m ₁ means 2,

Same or different; n ₁ represents 0, 1 or 2, when n ₁ represents 2,

Same or different.

By containing the combination of the compound represented by formula II and the compound represented by formula III in the liquid crystal composition of the present invention, the obtained liquid crystal composition has a low rotational viscosity, which is beneficial to increase the reaction speed of the liquid crystal composition, and has a negative medium. The electrical anisotropy can adjust the driving voltage of the composition.

In the present invention, the total mass of other compounds except the compound represented by formula I is recorded as 100%, and the percentage of the ratio between the mass of the compound represented by formula I and the total mass of other compounds is recorded as the formula I in the liquid crystal composition The mass fraction of the compound shown. For example, when the liquid crystal composition contains only the compounds represented by formula I, formula II and formula III, the total content of the compounds represented by formula II and formula III is recorded as 100%, and the added amount of the compound represented by formula I The percentage of the ratio to the total mass of the compound represented by formula II and formula III is recorded as the mass fraction of the compound represented by formula I.

Ⅱ-1

Ⅱ-2

Ⅱ-3

Ⅱ-4

Ⅱ-5

Ⅱ-6

Ⅱ-7

Ⅱ-8

Ⅱ-9

Ⅱ-10

Ⅱ-11

Ⅱ-12

Ⅱ-13

Ⅱ-14

Ⅱ-15

Ⅱ-16

Ⅱ-17。 較佳地，前述式Ⅲ所示化合物選自式Ⅲ-1至式Ⅲ-15所示化合物所組成的群組，

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15 其中，R₃₁ 、R₄₁ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R₃ 、R₄ 所示基團中任意一個或多個不相鄰的-CH₂ -任選被亞環戊基、亞環丁基或亞環丙基取代。本發明公開的液晶組合物中，較佳地，還包含一種或多種式Ⅳ所示的化合物，

Ⅳ 其中，R₅ 、R₆ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R₅ 、R₆ 中任意一個或多個不相鄰的-CH₂ -任選被亞環戊基、亞環丁基或亞環丙基替代；W表示-O-、-S-或-CH₂ O-。In the liquid crystal composition of the present invention, preferably, the compound represented by formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,

Ⅱ-1

Ⅱ-2

Ⅱ-3

Ⅱ-4

Ⅱ-5

Ⅱ-6

Ⅱ-7

Ⅱ-8

Ⅱ-9

Ⅱ-10

Ⅱ-11

Ⅱ-12

Ⅱ-13

Ⅱ-14

Ⅱ-15

Ⅱ-16

Ⅱ-17. Preferably, the compound represented by formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15 Wherein, R ₃₁ and R ₄₁ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, and a fluorine-substituted Alkyloxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, and alkenyl with 3-8 carbon atoms Oxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more non-adjacent groups represented by _{R 3} and R _{4 -CH 2} -are optionally cyclopentylene , Cyclobutylene or cyclopropylidene substitution. The liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula IV,

Ⅳ Wherein, R ₅ and R ₆ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy having 3-8 carbon atoms, and _{any one or more of R 5} and R ₆ that are not adjacent to -CH ₂ -are optionally substituted by cyclopentylene or ring Butyl or cyclopropylene substitution; W represents -O-, -S- or -CH ₂ O-.

By including the aforementioned compound represented by Formula IV in the liquid crystal composition of the present application, the liquid crystal composition can be made to have a large negative dielectric anisotropy, which is beneficial to reduce the driving voltage of the device.

Ⅳ-1

Ⅳ-2；

Ⅳ-3

Ⅳ-4；

Ⅳ-5

Ⅳ-6；

Ⅳ-7

Ⅳ-8；

Ⅳ-9；

Ⅳ-10； 其中，R₅₁ 、R₆₁ 表示碳原子數為1-6的烷基； 本發明公開的液晶組合物中，較佳地，還包含一種或多種式Ⅴ所示的化合物，

Ⅴ 其中，R₇ 、R₈ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

、

各自獨立地表示

、

或

。Further, the aforementioned compound represented by formula IV is selected from the group consisting of compounds represented by formula IV-1 to formula IV-10,

Ⅳ-1

Ⅳ-2;

Ⅳ-3

Ⅳ-4;

Ⅳ-5

Ⅳ-6;

Ⅳ-7

Ⅳ-8;

Ⅳ-9;

IV-10; wherein R ₅₁ and R ₆₁ represent an alkyl group with a carbon number of 1-6; the liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula V,

Ⅴ where R ₇ and R ₈ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

,

Expressed independently of each other

,

or

.

Ⅴ-1；

Ⅴ-2；

Ⅴ-3；

Ⅴ-4； 其中，R₇₁ 、R₈₁ 各自獨立的表示碳原子數為2-6的烷基或碳原子數為2-6的烯基；其中，做為碳原子數為2-6的烯基可以列舉出例如乙烯基、2-丙烯基或者3-戊烯基；R₈₂ 表示碳原子數為1-5的烷氧基； 通過在本發明的液晶組合物中含有式Ⅴ所示的化合物，能夠獲得高的清晰點、高的彈性常數，尤其是展曲彈性常數K₃₃ ，有利於提升液晶組合物的參數性能。Further, the compound represented by formula V is preferably selected from the group consisting of compounds represented by formula V-1 to formula V-4,

Ⅴ-1;

Ⅴ-2;

Ⅴ-3;

Ⅴ-4; wherein R ₇₁ and R ₈₁ each independently represent an alkyl group with 2-6 carbon atoms or an alkenyl group with 2-6 carbon atoms; among them, as an alkene with 2-6 carbon atoms Examples of the group include vinyl, 2-propenyl or 3-pentenyl; R ₈₂ represents an alkoxy group having 1 to 5 carbon atoms; by including the compound represented by formula V in the liquid crystal composition of the present invention , It is possible to obtain high sharpness points and high elastic constants, especially the splay elastic constant K ₃₃ , which is beneficial to improve the parameter performance of the liquid crystal composition.

Ⅵ； 其中，R₉ 、R₁₀ 各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基； F₁ 、F₂ 、F₃ 各自獨立地表示H原子或F原子，且F₂ 、F₃ 不同時為F原子；

表示

、

或

。The liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula VI,

Ⅵ; wherein R ₉ and R ₁₀ each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, Fluorine-substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, and 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms; F ₁ , F ₂ , and F ₃ each independently represent a H atom or a F atom, and F ₂ and F _{3 are} not F atoms at the same time ；

Express

,

or

.

Ⅵ-1；

Ⅵ-2；

Ⅵ-3； 其中，R₉₁ 、R₁₀₁ 各自獨立地較佳表示碳原子數為2-6的烷基或原子數為2-6的烯基。通過在液晶組合物中含有選自式Ⅵ-1至Ⅵ-3所示的化合物，能夠提高液晶組合物的清晰點。Further, the compound represented by formula VI is preferably selected from the group consisting of compounds represented by formula VI-1 to VI-3,

Ⅵ-1;

Ⅵ-2;

VI-3: Among them, R ₉₁ and R ₁₀₁ each independently preferably represent an alkyl group having 2-6 carbon atoms or an alkenyl group having 2-6 atoms. By containing a compound selected from formula VI-1 to VI-3 in the liquid crystal composition, the clear point of the liquid crystal composition can be improved.

Preferably, the liquid crystal composition of the present invention contains 0.01-1% of the compound represented by formula I, 30-60% of the compound represented by formula II, 30-60% of the compound represented by formula III, and 1- 10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 15% of the compound represented by formula IV, 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains in mass percentage: 0.03-0.2% of the compound represented by formula I, 35-45% of the compound represented by formula II, 45-50% of the compound represented by formula III, 2- 10% of the compound represented by formula IV, 2-5% of the compound represented by formula VI.

Preferably, the liquid crystal composition of the present invention contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 30% of the compound represented by formula V, 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains 0.03-0.2% of the compound represented by formula I, 25-40% of the compound represented by formula II, 35-50% of the compound represented by formula III, and 5- 20% of the compound represented by formula V, 2-5% of the compound represented by formula VI.

Preferably, the liquid crystal composition of the present invention contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 15% of the compound represented by formula IV, 1-30% of the compound represented by formula V, and 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains in mass percentage: 0.03-0.2% of the compound represented by formula I, 20-40% of the compound represented by formula II, 30-50% of the compound represented by formula III, 2- 10% of the compound represented by formula IV, 5-20% of the compound represented by formula V, and 2-5% of the compound represented by formula VI.

；

；

；

；

；

； t表示1-10的整數。In the liquid crystal composition disclosed in the present invention, various functional dopants can also be added. In the case of containing dopants, the content of the dopants is preferably 0.01-1% by mass in the liquid crystal composition. Examples of these dopants include antioxidants, ultraviolet absorbers, and chiral agents. Antioxidants and UV absorbers can be listed,

；

；

；

；

；

; T represents an integer of 1-10.

The liquid crystal display element of the present invention includes the aforementioned polymerizable compound of the present invention or the aforementioned liquid crystal composition of the present invention, and the display element is an active matrix display element or a passive matrix display element.

Preferably, the liquid crystal display element of the present invention is preferably an active matrix liquid crystal display element.

Preferably, the active matrix display element of the present invention is a PSVA-TFT or IPS-TFT liquid crystal display element.

For the aforementioned liquid crystal display element of the present invention, as long as the compound represented by formula I of the present invention is contained in the liquid crystal composition used, its structure is not limited in any way. Those with ordinary knowledge in the art can determine the required performance Choose the appropriate structure of the liquid crystal display element.

As an embodiment of the liquid crystal display of the present invention, for example, the following structure: including a first substrate, a second substrate, and a liquid crystal composition disposed between the first substrate and the second substrate, the first substrate It is arranged in parallel with the second substrate. The first substrate and the second substrate are provided with an alignment layer on the side close to the liquid crystal composition, the first substrate is provided with a common electrode, the second substrate is provided with a pixel electrode, the first substrate and the second substrate Spacers are scattered between the substrates.

As the method for preparing the liquid crystal display of the present invention, a person with ordinary knowledge in the field can select an appropriate method for preparation according to common knowledge in the field. As an example of the manufacturing method of the liquid crystal display of the present invention, for example, the manufacturing method includes the following steps: uniformly coating the alignment material on the surface of the first substrate and the second substrate. The alignment material can be selected from polyimide. The coated alignment material is heated and cured at a heating temperature of 210-250 ℃ to form an alignment layer; spacers are spread on the surface of the second substrate, and frame glue is applied along the edge of the first substrate, and cured at 100 ℃-150 ℃ ; The first substrate and the second substrate are arranged oppositely and bonded together to form a structure with an interlayer space; the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and cured, so that the liquid crystal composition is sealed in the first Between the one substrate and the second substrate, power-on and ultraviolet light irradiation are carried out at the same time. Ultraviolet light irradiation is divided into two stages: the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, the wavelength of ultraviolet light is 360 nm-370 nm, and the irradiance of ultraviolet light is 60-72 mw/cm ² . As the ultraviolet light irradiation time, it can be, for example, 50-65 s, preferably 50-60 s. After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is performed. The light used in UV2 can be, for example, ultraviolet light. In the second stage ultraviolet light irradiation (UV2), the ultraviolet light wavelength is, for example, 360 nm-370 nm, and the ultraviolet light irradiance used in the UV2 stage is, for example, 3-8 mw/cm ² . By adopting such an irradiance, the compound represented by formula I that has not undergone polymerization can be slowly and completely polymerized, and the conversion rate of the polymerizable compound is increased, so that there is no residue of the polymerizable compound in the liquid crystal composition. And because the polymerization is slow, the process will not affect the pretilt angle that has been formed. The ultraviolet light irradiation time in the UV2 stage can be, for example, 100-150 min. Example

In order to explain the present invention more clearly, the following further describes the present invention in combination with preferred embodiments and drawings. Similar parts in the drawings are represented by the same drawing marks. Those with ordinary knowledge in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

In the present invention, the preparation methods are conventional methods unless otherwise specified. The raw materials used can be obtained from publicly disclosed commercial channels unless otherwise specified. Liquid crystal monomer, the specific meaning of other symbols and test conditions are as follows: Cp represents the clear point of liquid crystal (℃), measured by DSC quantitative method; Δn represents optical anisotropy, Δn = n _e -n _o , where n _o is ordinary light The refractive index of, n _{e is} the refractive index of extraordinary light, the test condition is 25±2 ℃, 589 nm, tested by Abbe refractometer; Δε represents dielectric anisotropy, Δε = ε∥-ε⊥, where ε ∥ is the dielectric constant parallel to the molecular axis, ε⊥ is the dielectric constant perpendicular to the molecular axis, the test condition is 25±0.5 ℃, 20 micron vertical box, INSTEC: ALCT-IR1 test; VHR represents the voltage retention rate (% ), the test conditions are 20±2 ℃, voltage is ±5V, pulse width is 10 ms, and voltage holding time is 16.7 ms. The test equipment is TOYO Model 6254 liquid crystal performance comprehensive tester; γ ₁ represents rotational viscosity (mPa·s), the test condition is 25±0.5 ℃, 20 micron vertical cell, INSTEC: ALCT-IR1 test.

In the embodiment of the present invention, the equipment and instruments used in the preparation of the liquid crystal composition are: The preparation method of the liquid crystal composition is as follows: each polymerizable compound is weighed according to a certain ratio and then put into a stainless steel beaker, the stainless steel beaker containing each polymerizable compound is placed on a magnetic stirring instrument and heated and melted. After the polymerizable compound is melted, a magnetic rotor is added to the stainless steel beaker, the mixture is stirred uniformly, and the liquid crystal composition is obtained after cooling to room temperature.

The preparation method of the liquid crystal display element in the embodiment of the present invention is as follows: firstly, the alignment material is uniformly coated on the surfaces of the first substrate and the second substrate, and the alignment material can be polyimide, and the uniformly coated alignment material is heated and cured , The heating temperature is 230 ℃ to form an alignment layer; secondly, spacers are spread on the surface of the second substrate, and frame glue is applied along the edge of the first substrate and cured at 120 ℃; then, the first substrate and the second substrate The substrates are arranged oppositely and bonded to form a structure with interlayer space; finally, the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, and sealed and cured, thereby sealing the liquid crystal composition on the first substrate and the second substrate In between, and at the same time power up, ultraviolet light irradiation. Ultraviolet light irradiation is divided into two stages, including the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, light irradiation is performed with an ultraviolet wavelength of 365 nm and an irradiance of 64 mw/cm ^2. After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is performed. In UV2, a wavelength of 365 nm is used. Ultraviolet light, the irradiance is 5 mw/cm ² , and the light irradiation time is 100-150 min.

C

P

L

G

Gi

Y

Sb

Sc 表2 端基與鏈接基團的對應代碼 端基與連結基團 對應代碼 C_n H_2n+1 - n- C_n H_2n+1 O- nO- -CF₃ -T -OCF₃ -OT -CH₂ O- -O- -F -F -CH₂ CH₂ - -E- -CH=CH- -V- -CH=CH-C_n H_2n+1 Vn-

Cp-

Cpr-

Cpr1-

CpO

CprO 舉例：

，其代碼為CC-Cp-V1；

，其代碼為PGP- Cpr1-2；

，其代碼為CPY-2-O2；

，其代碼為CCY-3-O2；

，其代碼為COY-3-O2；

，其代碼為CCOY-3-O2；

，其代碼為Sb-CpO-O4；

，其代碼為Sc-CpO-O4；

，其代碼為COYL-Cprl-O2；

，其代碼為COYL-1-OV1。The structure of the liquid crystal monomer used in the embodiment of the present invention is represented by a code, and the code representation method of the liquid crystal ring structure, terminal group, and connecting group is shown in Table 1 and Table 2 below. Table 1 Corresponding codes of ring structure Ring structure Corresponding code

C

P

L

G

Gi

Y

Sb

Sc Table 2 Corresponding codes of end groups and linking groups End group and linking group Corresponding code C _n H _2n+1- n- C _n H _2n+1 O- nO- -CF ₃ -T -OCF ₃ -OT -CH ₂ O- -O- -F -F -CH ₂ CH _2- -E- -CH=CH- -V- -CH=CH-C _n H _2n+1 Vn-

Cp-

Cpr-

Cpr1-

CpO

CprO For example:

, Its code is CC-Cp-V1;

, Its code is PGP- Cpr1-2;

, Its code is CPY-2-O2;

, Its code is CCY-3-O2;

, Its code is COY-3-O2;

, Its code is CCOY-3-O2;

, Its code is Sb-CpO-O4;

, Its code is Sc-CpO-O4;

, Its code is COYL-Cprl-O2;

, And its code is COYL-1-OV1.

The following specific embodiments are used to illustrate the present invention:

其中，L₁ 、L₂ 、L₃ 、L₄ 、r₁ 、r₃ 、r₂ 、r₄ 、x₁ 、x₂ 、x₃ 、x₄ 、Sp₁ 、Sp₂ 、Sp₃ 、Sp₄ 、Sp₅ 、Z₁ 、Z₂ 、P₁ 、P₂ 、P₃ 、P₄ 各自獨立地與上述式Ⅰ所示的可聚合化合物中的定義相同； S₁ 、S₂ 各自獨立地表示醛基、羥基、羧基； B₁ 、B₂ 、B₃ 、B₄ 各自獨立地表示羥基的保護基。[Liquid crystal compound] The compound represented by formula I of the present invention can be synthesized according to the following scheme:

Among them, L ₁ , L ₂ , L ₃ , L ₄ , r ₁ , r ₃ , r ₂ , r ₄ , x ₁ , x ₂ , x ₃ , x ₄ , Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , Z ₂ , P ₁ , P ₂ , P ₃ , and P ₄ are each independently the same as defined in the polymerizable compound represented by the above formula I; S ₁ and S ₂ each independently represent an aldehyde group, Hydroxyl group, carboxyl group; B ₁ , B ₂ , B ₃ , and B ₄ each independently represent a protective group for a hydroxyl group.

The raw materials and reagents in the general synthetic formula can be purchased through conventional synthesis or commercial channels. The principles of such methods, operating procedures, conventional post-treatments, silica gel column, recrystallization purification and other methods are well-known to those skilled in the art. The synthesis process can be realized and the target product can be obtained.

The reactions in all steps of all the above methods are carried out in a solvent; the solvents are selected from at least tetrahydrofuran, N,N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water A sort of.

I-1-1 其製備路線如下：

製備的具體操作流程：Example 1 The structural formula of the compound is shown in the following formula I-1-1,

The preparation route of I-1-1 is as follows:

The specific operation process of preparation:

Intermediate 1 Under the protection of nitrogen, put 0.3 mol of p-benzyloxyphenylboronic acid, 0.3 mol of 3-benzyloxy-6-bromo-2-fluorophenol, 2.0 L of toluene, 0.7 L of water, and 0.36 mol of carbonic acid into a 5 L three-necked flask. Potassium, 0.3 g of catalyst, heated to reflux for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 1 as a yellow solid. HPLC: 90%, yield Y=75%.

Intermediate 2 Under the protection of nitrogen, put 0.22 mol of 1, 0.1 mol of 1,2-dibromopropane, 0.22 mol of anhydrous potassium carbonate in a 2L three-necked flask, 1.2L DMF, _{under the protection of N 2} and control the temperature at 120 ℃ to react 4 Hour. After the reaction is completed, the temperature is lowered, and the mixture is poured into ice water while stirring, stirred for 30 min, filtered, and beaten with 0.5 L petroleum ether to obtain compound 2, HPLC: 90%, yield Y=70%.

Intermediate 3 Add 0.08 mol of compound 2, 6.6 g of Pd/C, 0.3 L of THF and 0.3 L of EtOH into a 1 L three-necked flask, _{replace with N 2 for} three times, and replace with H _{2 for} three times. Hydrodebenzylation at 40 ℃, reaction 6 hours. After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and the mixture was stirred for 10 min to obtain compound 3. HPLC: 98%, yield Y=75%.

Compound I-1-1 was put into a 500 ml three-necked flask with 0.02 mol of 3, 0.1 mol of triethylamine, 0.2L of DCM, and 0.1 mol of methacrylic acid chloride was added dropwise under the protection of _{N 2 and the temperature was controlled at 0°C.} After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times of toluene and 3 times of ethanol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized three times according to the same method, and dried to obtain a white solid compound I-1-1, HPLC: 99.1%, Yield Y=44%.

I-2-1 其製備路線如下：

製備的具體操作流程：Example 2 The structural formula of the compound is shown in the following formula I-2-1,

I-2-1 The preparation route is as follows:

The specific operation process of preparation:

Intermediate 1 The synthesis of intermediate 1 in the reference compound I-1-1 route

Intermediate 4 The raw material 1,2-dibromopropane was replaced with 1,2-dibromohexane, and the synthesis method was referred to the synthesis of intermediate 2 in Example 1.

Intermediate 5 The synthesis method refers to the synthesis of Intermediate 3 in Example 1.

Compound I-2-1 The synthesis method refers to the synthesis of compound I-1-1 in Example 1. The MS mass spectrum of compound I-2-1 is shown in Figure 1, and the H-NMR nuclear magnetic spectrum is shown in Figure 2.

I-4-1 其製備路線如下：

製備的具體操作流程：Example 3 The structural formula of the compound is shown in the following formula I-4-1,

I-4-1 The preparation route is as follows:

The specific operation process of preparation:

Intermediate 6 Under the protection of nitrogen, put 0.3 mol of p-benzyloxyphenylboronic acid, 0.3 mol of 3-benzyloxy-6-bromo-2-fluorobenzaldehyde, 2.0 L of toluene, 0.7 L of water, 0.36 mol into a 5 L three-necked flask Potassium carbonate, 0.3 g of catalyst, heated to reflux for 3 hours. Standing for liquid separation, column chromatography separation, toluene/ethanol recrystallization, compound 6 was obtained as a pale yellow solid. HPLC: 93%, yield Y=72%.

Intermediate 7 Under the protection of nitrogen, put 0.1 mol of phosphine salt in a 3L three-necked flask, add 1L to cool to 0 to -10 ℃, slowly add 0.2 mol of potassium tert-butoxide in batches, and control the temperature to react between 0 to -10 ℃ For 1h, add dropwise a THF solution of compound 6 (0.2 mol), and naturally warm to room temperature to react for 4 hours. After the reaction is completed, add water solution, extract the aqueous phase with ethyl acetate, combine the organic phases to wash with saturated sodium chloride, dry, spin-dry, and recrystallize from ethanol to obtain compound 7, HPLC: 95%, yield Y=60%.

Intermediate 8 Add 0.06 mol of compound 7, 5.0 g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-necked flask, _{replace with N 2} three times, and replace with H ₂ three times. Hydrodebenzylation at 40°C, reaction 6 Hour. After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and the mixture was stirred for 10 min to obtain compound 8, HPLC: 97%, yield Y=83%.

Compound I-4-1 was put into a 500 ml three-necked flask with 0.02 mol 8, 0.1 mol triethylamine, 0.2L DCM, and 0.1 mol methacrylic acid chloride was added dropwise under the protection of _{N 2 and the temperature was controlled at 0°C.} After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 hours, suction filtered, recrystallized four times according to the same method, and dried to obtain white solid compound I-4-1, HPLC: 99.0%, Yield Y=67%.

Ⅰ-6-1 其製備路線如下：

製備的具體操作流程：Example 4 The structural formula of the compound is shown in the following formula I-6-1,

Ⅰ-6-1 The preparation route is as follows:

The specific operation process of preparation:

Intermediate 9 Under the protection of nitrogen, put 0.2 mol of phosphine salt in a 3L three-necked flask, add 1L to cool down to 0 to -10 ℃, slowly add 0.2 mol of potassium tert-butoxide in batches, and control the temperature to react between 0 to -10 ℃ For 1h, add dropwise a THF solution of compound 6 (0.2 mol), and naturally warm to room temperature to react for 4 hours. After the reaction is complete, add water solution, extract the aqueous phase with ethyl acetate, combine the organic phases and wash with saturated sodium chloride, dry, spin-dry, and separate by column chromatography (petroleum ether, ethyl acetate), spin-dry the solvent to obtain compound 9, HPLC : 95%, yield Y=70%.

Intermediate 10 Under the protection of nitrogen, add 0.14 mol of compound 9 and 0.14 mol of compound 1 into a 2 L three-necked flask, then add 0.15 mol of triphenylphosphine, cool to 0 ℃, add 0.15 mol of DIAD dropwise, and naturally rise to React at room temperature for 3 h. The reaction is complete. Add water and ethyl acetate to separate the liquids, extract the aqueous phase with ethyl acetate, combine the organic phases to dry, spin dry, separate by column chromatography (petroleum ether, ethyl acetate), spin dry the solvent to obtain compound 10, HPLC: 96%, yield Y=68 %.

Intermediate 11 Add 0.06 mol of compound 10, 5.2 g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-necked flask, _{replace with N 2} three times, and replace with H ₂ three times. Hydrodebenzylation at 40°C, reaction 6 Hour. After the reaction is completed, the celite is filtered, the filtrate is concentrated, PE:EA=10:1, and the mixture is stirred for 10 min to obtain compound 8, HPLC: 98%, yield Y=80%.

Intermediate I-6-1 was put into a 500 ml three-necked flask with 0.02 mol of 11, 0.1 mol of triethylamine, 0.2L of DCM, and 0.1 mol of methacrylic acid chloride was added dropwise under the protection of _{N 2 and the temperature was controlled at 0°C.} After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized four times according to the same method, and dried to obtain white solid compound I-6-1, HPLC: 99.2% , Yield Y=41%.

Ⅰ-7-1 其製備路線如下：

製備的具體操作流程：Example 5 The structural formula of the compound is shown in the following formula I-7-1,

Ⅰ-7-1 The preparation route is as follows:

The specific operation process of preparation:

Intermediate 12 Under the protection of nitrogen, put 0.3 mol of p-benzyloxyphenylboronic acid, 0.3 mol of 3-benzyloxy-6-bromo-2-fluorobenzoic acid, 2.0 L of toluene, 0.7 L of water, and 0.6 mol into a 5 L three-necked flask. Potassium carbonate, 0.3 g of catalyst, heated to reflux for 3 hours. Standing for liquid separation, column chromatography for separation, and toluene/ethanol recrystallization to obtain compound 12 as a pale yellow solid. HPLC: 95%, yield Y=82%.

Intermediate 13 In a 3L three-necked flask, 0.2 mol of 12, 0.1 mol of propylene glycol, 0.05 mol of DMAP, 1.0 L of THF, and N ₂ protection were added dropwise to 0.3 mol of DCC in THF solution at 0°C. After dripping, react at room temperature for 6 hours. After the reaction is complete, filter, concentrate the filtrate, and recrystallize with 3 times ethanol to obtain compound 13, GC: 93%, yield Y=75%.

Intermediate 14 Add 0.06 mol of compound 13, 5.2g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-necked flask, _{replace with N 2} three times, replace with H ₂ three times, and hydrogenate debenzy at 40°C, reaction 6. Hour. After the reaction is completed, the celite is filtered, the filtrate is concentrated, PE:EA=10:1, and the mixture is stirred for 10 min to obtain compound 14. HPLC: 97%, yield Y=85%.

Compound I-7-1 was dropped into a 500 ml three-necked flask with 0.02 mol of 14, 0.1 mol of triethylamine, 0.2L of DCM, and 0.1 mol of methacrylic acid chloride was added dropwise under the protection of _{N 2 and the temperature was controlled at 0°C.} After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized four times according to the same method, and dried to obtain white solid compound I-7-1, HPLC: 98.9% , The yield Y=53%.

Ⅰ-7-1 其製備路線如下：

製備的具體操作流程：Example 6 The structural formula of the compound is shown in the following formula I-7-1,

Ⅰ-7-1 The preparation route is as follows:

The specific operation process of preparation:

The synthesis of Intermediate 15 refers to Intermediate 13 in Example 5, and the raw material propylene glycol is replaced with 1,6-hexanediol.

The synthesis of Intermediate 16 refers to Intermediate 14 in Example 5.

For the synthesis of compound I-8-1, refer to compound I-7-1 in Example 5.

Ⅰ-10-1 其製備路線如下：

製備的具體操作流程：Example 7 The structural formula of the compound is shown in the following formula I-10-1,

Ⅰ-10-1 The preparation route is as follows:

The specific operation process of preparation:

Intermediate 17 In a 3L three-necked flask, 0.2 mol of 1, 0.1 mol of adipic acid, 0.05 mol of DMAP, 1.0 L of THF, and N ₂ protection were added dropwise with 0.3 mol of DCC in THF solution at 0°C. After dripping, react at room temperature for 6 hours. After the reaction is completed, filter, concentrate the filtrate, and recrystallize with 3 times ethanol to obtain compound 17, GC: 92%, yield Y=80%.

Intermediate 18 Add 0.06 mol of compound 17, 6.0 g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-necked flask, _{replace with N 2} three times, and replace with H ₂ three times. Hydrodebenzylation at 40°C, reaction 6 Hour. After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and the mixture was stirred for 10 min to obtain compound 18, HPLC: 97%, yield Y=80%.

Compound I-10-1 was put into a 500 ml three-necked flask with 0.02 mol of 18, 0.1 mol of triethylamine, 0.2L of DCM, and 0.1 mol of methacrylic acid chloride was added dropwise under the protection of _{N 2 and the temperature was controlled at 0°C.} After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized four times according to the same method, and dried to obtain white solid compound I-10-1, HPLC: 99.4% , The yield Y=37%.

Preparation of the liquid crystal composition: Matrix liquid crystal composition 1 The formula and corresponding properties of the liquid crystal composition are shown in Table 3 below. Table 3: Formulation and corresponding properties of the matrix liquid crystal composition 1 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.7 Δn[589 nm, 25 ℃]: 0.099 Cp: 81℃ γ ₁ : 95 mPa.s Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ COY-5-O2 10 Ⅳ Sb-CpO-O4 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 5 Ⅴ CCP-3-1 5 Ⅵ CPPC-5-3 5

Matrix Liquid Crystal Composition 2 The formula and corresponding properties of the liquid crystal composition are shown in Table 4 below. Table 4: Formulation and corresponding properties of the matrix liquid crystal composition 2 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -3.4 Δn[589 nm, 25 ℃]: 0.099 Cp: 88 ℃ γ _{1: 95mPa.s} Ⅲ CPY-3-O2 10 Ⅲ PYP-3-O2 7 Ⅲ CCOY-5-O2 10 Ⅲ COY-3-O2 10 Ⅲ CY-3-O2 5 Ⅲ LY-Cp-O2 5 Ⅲ CLY-3-OCPr 3 Ⅱ CC-3-V 20 Ⅴ CCP-V-1 4 Ⅴ CPP-3-2V1 5 Ⅴ CPP-1V-2 5 Ⅵ CGPC-3-3 5

Matrix Liquid Crystal Composition 3 The formula and corresponding properties of the liquid crystal composition are shown in Table 5 below. Table 5: Formulation and corresponding properties of matrix liquid crystal composition 3 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.9 Δn[589 nm, 25 ℃]: 0.101 Cp: 83 ℃ γ ₁ : 106 mPa.s Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ CLY-5-O2 10 Ⅳ Sb-CpO-O4 4 Ⅳ Sb-4O-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 10 Ⅵ CPGiP-5-2 5

Matrix Liquid Crystal Composition 4 The formula and corresponding properties of the liquid crystal composition are shown in Table 6 below. Table 6: Formulation and corresponding properties of matrix liquid crystal composition 4 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CY-Cp-O2 11 Δε[1KHz, 25 ℃]: -3.9 Δn[589nm, 25 ℃]: 0.102 Cp: 85 ℃ γ ₁ : 110 mPa.s Ⅲ PY-3O-O2 10 Ⅲ CCOY-3-O2 12 Ⅲ CCOY-5-O2 13 Ⅳ Sb-CpO-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 20 Ⅱ CC-3-V1 10 Ⅵ CPPC-3-3 5 Ⅵ CPGC-5-3 5

Matrix Liquid Crystal Composition 5 The formula and corresponding properties of the liquid crystal composition are shown in Table 7 below. Table 7: Formulation and corresponding properties of matrix liquid crystal composition 5 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CY-5-O2 11 Δε[1KHz, 25 ℃]: -3.0 Δn[589 nm, 25 ℃]: 0.097 Cp: 70 ℃ γ ₁ : 76 mPa.s Ⅲ PY-3-O2 9 Ⅲ COY-3-O2 16 Ⅳ Sc-CpO-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V1 25 Ⅱ CC-3-2 7 Ⅴ CCP-3-1 12 Ⅴ CPP-3-2 6

Matrix Liquid Crystal Composition 6 The formula and corresponding properties of the liquid crystal composition are shown in Table 8 below. Table 8: Formulation and corresponding properties of matrix liquid crystal composition 6 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CY-3-O2 11 Δε[1KHz, 25 ℃]: -2.9 Δn[589 nm, 25 ℃]: 0.106 Cp: 65 ℃ γ ₁ : 82 mPa.s Ⅲ PY-Cp-O2 9 Ⅲ COY-3-O2 12 Ⅲ CCOY-2-O2 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V1 15 Ⅱ CC-3-2 10 Ⅴ CCP-3-1 10 Ⅴ CCP-3-O1 5 Ⅴ CPP-3-2 10

Matrix Liquid Crystal Composition 7 The formula and corresponding properties of the liquid crystal composition are shown in Table 9 below. Table 9: Formulation and corresponding properties of matrix liquid crystal composition 7 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CY-3-O2 9 Δε[1KHz, 25 ℃]: -4.4 Δn[589 nm, 25 ℃]: 0.101 Cp: 70 ℃ γ ₁ : 91 mPa.s Ⅲ CY-5-O2 7 Ⅲ CCY-3-O2 7 Ⅲ CPY-3-O2 10 Ⅲ COY-3-O2 9 Ⅲ CCOY-3-O2 9 Ⅲ PY-3-O2 2 Ⅱ CC-3-V 15 Ⅱ CC-2-3 7 Ⅱ CP-3-O2 4 Ⅱ CP-5-O2 3 Ⅱ CP-3-O1 1 Ⅱ PP-5-1 3 Ⅴ CPP-3-2 3 Ⅴ CPP-1V-2 2 Ⅴ CPP-3-2V1 5 Ⅳ Sc-Cp1O-O4 2 Ⅳ Sb-Cp1O-O4 2

Matrix Liquid Crystal Composition 8 The formula and corresponding properties of the liquid crystal composition are shown in Table 10 below. Table 10: Formulation and corresponding properties of matrix liquid crystal composition 8 category LCD monomer code content(%) Liquid crystal composition performance Ⅲ CY-3-O2 7 Δε[1KHz, 25 ℃]: -3.5 Δn[589 nm, 25 ℃]: 0.120 Cp: 83 ℃ γ ₁ : 95 mPa.s Ⅲ CLY-3-O2 5 Ⅲ CLY-4-O2 2 Ⅲ PY-2O-O2 3 Ⅲ PY-2O-O4 5 Ⅲ PYP-2-3 5 Ⅲ PYP-Cpr1-2 3 Ⅲ CPY-3-O2 7 Ⅲ CCY-3-O2 3 Ⅲ CCOY-3-O2 2 Ⅲ CCOY-4-O2 3 Ⅱ CC-2-3 15 Ⅱ CC-3-V1 3 Ⅱ CC-1-3 2 Ⅱ CC-3-V 7 Ⅱ PP-5-O2 5 Ⅱ PP-1-2V 3 Ⅴ CCP-V-1 3 Ⅴ CPP-3-2 5 Ⅴ CCP-3-1 2 Ⅴ CCP-3-O1 1 Ⅴ CPP-3-2V1 2 Ⅳ Sc-2O-O4 4 Ⅳ Sb-4O-O4 3

RM-1

RM-2

RM-3Comparative compound:

RM-1

RM-2

RM-3

In order to measure the solubility, the polymerizable compounds I-1-1, I-1-2, I-2-1, I-3-1, I-5-1, I-7-1, I-9-1 , I-16-1 and the monomers RM-1 and RM-2 in the prior art are each dissolved in the matrix liquid crystal composition at different concentrations ranging from 0.1 to 2.0% by weight. The samples were stored at room temperature (RT) for 1000 hours and checked whether they remained a homogeneous solution. Then, the sample was centrifuged and filtered, and the concentration of the remaining monomer in the supernatant was determined. The maximum remaining monomer concentration at RT after 1000 hours: Table 11: Solubility data of Examples and Comparative Examples coding Maximum remaining monomer concentration Ⅰ-1-1 (0.1%) 0.43% Ⅰ-1-2 (0.3%) 0.75% Ⅰ-2-1 (0.6%) 0.64% Ⅰ-3-1 (0.5%) 0.57% Ⅰ-5-1 (0.32%) 0.45% Ⅰ-7-1 (0.25 %) 0.85% Ⅰ-9-1 (0.45%) 0.66% Ⅰ-16-1 (0.2%) 0.71% RM-1 0.21% RM-2 0.16% RM-3 0.17%

It can be seen that the monomers according to the present invention exhibit significantly better solubility than the monomers of the prior art. It can be seen that the monomers of the present invention all show a residual concentration of ≥ 0.40%, which is higher than the 0.3% RM concentration usually used in PSA displays, and meets industrial needs, while the monomers RM-1 and RM-2 It is lower than the usual 0.30% RM concentration.

A certain amount of the polymerizable compound represented by formula I was added to the test matrix liquid crystal composition 1-6; as a comparison, a certain amount of RM-1, RM-2, RM-3 was added to the test matrix 1 as a pair In Example 1, Comparative Example 2, and Comparative Example 3, liquid crystal compositions were prepared by the above-mentioned liquid crystal composition preparation method.

The reliability of the liquid crystal composition is carried out through ultraviolet and high temperature aging tests and VHR tests. The smaller the change in the VHR data of the liquid crystal panel before and after the ultraviolet and high temperature tests, the stronger the UV and high temperature resistance. Therefore, the UV resistance and high temperature resistance ability can be judged by comparing the difference of the VHR data before and after the test of each embodiment and comparative example.

Ultraviolet aging test: place the liquid crystal composition under an ultraviolet lamp with a wavelength of 365 nm to irradiate 5000 mJ of energy.

High temperature aging test: place the liquid crystal composition in an oven at 100°C for one hour.

After the aging test, the smaller the change of the VHR data relative to the initial VHR data, the stronger the ability of the liquid crystal composition to resist ultraviolet and high temperature, and the stronger the ability of the liquid crystal composition to resist external environmental damage during the working process can be judged. Therefore, the reliability of the liquid crystal composition is higher. The VHR data of the liquid crystal composition examples and comparative examples are shown in Table 12. Table 12: VHR data of liquid crystal composition examples and comparative examples sample name Sample composition Initial VHR (%) VHR after high temperature (%) VHR after UV (%) Parent number RM and content Example 8 Matrix liquid crystal composition 1 Ⅰ-1-1 (0.1%) 99.90 98.86 98.83 Example 9 Matrix liquid crystal composition 2 Ⅰ-1-2 (0.3%) 99.89 98.71 98.75 Example 10 Matrix liquid crystal composition 3 Ⅰ-2-1 (0.6%) 99.85 98.73 98.80 Example 11 Matrix liquid crystal composition 4 Ⅰ-3-1 (0.5%) 99.86 98.81 98.75 Example 12 Matrix liquid crystal composition 5 Ⅰ-5-1 (0.32%) 99.85 98.82 98.81 Example 13 Matrix liquid crystal composition 6 Ⅰ-7-1 (0.25 %) 99.87 98.65 98.66 Example 14 Matrix liquid crystal composition 7 Ⅰ-9-1 (0.45%) 99.88 98.83 98.80 Example 15 Matrix liquid crystal composition 8 Ⅰ-16-1 (0.2%) 99.83 98.79 98.76 Comparative example 1 Matrix liquid crystal composition 1 RM-1 (0.1%) 99.65 96.23 96.31 Comparative example 2 Matrix liquid crystal composition 1 RM-2 (0.1%) 99.63 96.42 96.33 Comparative example 3 Matrix liquid crystal composition 1 RM-3 (0.1%) 99.59 96.55 96.48

The liquid crystal composition is filled to prepare a liquid crystal display element, the initial pretilt angle is tested, and then UV light is irradiated in the UV1 process to promote the polymerization of the polymerizable compound. The film formed after polymerization is used to align the liquid crystal. After the UV2 process, the pretilt angle is tested. Carry out aging experiment, test the pretilt angle after 24 h, 48 h and 72 h under the 30 V voltage applied to the backlight. The pretilt angle data of the liquid crystal composition examples and comparative examples are shown in Table 13. Table 13: Pretilt angle data of liquid crystal composition examples and comparative examples sample name initial After UV2 Aging test (24 h) Aging test (48 h) Aging test (72 h) Example 8 89.6 87.2 87.1 87.2 87.1 Example 9 89.6 87.5 87.6 87.5 87.5 Example 10 89.5 87.3 87.1 87.2 87.2 Example 11 89.6 87.2 87.2 87.1 87.3 Example 12 89.5 87.1 87.1 87.2 87.1 Example 13 89.5 87.5 87.3 87.3 87.4 Example 14 89.7 87.4 87.4 87.3 87.4 Example 15 89.7 87.2 87.5 87.5 87.4 Comparative example 1 89.6 88.3 87.4 87.1 86.7 Comparative example 2 89.7 88.5 88.1 87.6 88.3 Comparative example 3 89.6 88.6 88.1 87.8 87.0

From the above VHR data and pretilt angle data, it can be seen that, compared with the comparative example, the liquid crystal composition containing the polymerizable compound of the present invention has a high voltage retention rate (VHR) and contains the polymerizable compound of the present invention or contains the polymerizable compound of the present invention. When the liquid crystal composition of the polymerizable compound is made into a display element, it has a larger (here means the difference between 90 ° and the above-mentioned pretilt angle data, that is, the smaller the above-mentioned pretilt angle data, the larger the actual pretilt angle) and stable The pretilt angle, when used in PS- (polymer stabilized) or PSA- (polymer stabilized alignment) type liquid crystal display elements, can reduce residual image and improve contrast, thereby improving product quality.

Obviously, the above-mentioned embodiments of the present invention are merely examples to clearly illustrate the present invention, and are not intended to limit the implementation of the present invention. For those of ordinary knowledge in the field, the above-mentioned description is also used. Other different forms of changes or changes can be made, and it is not possible to list all the embodiments here. Any obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

without

Figure 1 shows the MS mass spectrum of the polymerizable compound represented by formula I-2-1;

^{Figure 2 shows the 1} H-NMR spectrum of the polymerizable compound represented by formula I-2-1;

Claims (10)

A polymerizable compound represented by formula I,

Ⅰ Wherein, L ₁ , L ₂ , L ₃ , and L ₄ each independently represent F atom, Cl atom, -CN, linear alkyl group having 1 to 25 C atoms, branched chain having 3 to 25 C atoms Alkyl, cyclic alkyl having 3 to 25 C atoms, alkenyl having 2 to 25 C atoms, or alkynyl having 2 to 25 C atoms, of which one or more non-adjacent -CH ₂ -Groups are optionally substituted by -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more of them The H atom is optionally substituted by a halogen atom; r ₁ and r _{3 each independently represent 0, 1, 2} , 3, or 4; r 2 and r ₄ each independently represent 0, ₁ , 2 or 3; x 1, x ₂ , x ₃ , x ₄ each independently represent 0, 1 or 2, and x ₁ + x ₂ + x ₃ + x ₄ ≥ 3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , Z ₂ each independently represents a single bond, a straight chain alkyl group having 1 to 25 C atoms, a branched chain alkyl group having 3 to 25 C atoms, a cyclic alkyl group having 3 to 25 C atoms, and 2 An alkenyl group having to 25 C atoms or an alkynyl group having 2 to 25 C atoms, and one or more non-adjacent -CH ₂ -groups are optionally substituted by -O-, -S-, -CO -, -CO-O-, -O-CO-, -O-CO-O- substitution, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms; P ₁ , P ₂ , P ₃ , P ₄ each independently represents a polymerizable group. According to the polymerizable compound according to claim 1, in the compound represented by formula I: L ₁ , L ₂ , L ₃ , and L ₄ each independently represent an alkyl group having 1 to 5 carbon atoms and a fluorine-substituted carbon Alkyl groups with 1-5 atoms, alkenyl groups with 2-5 carbon atoms, alkoxy groups with 1-5 carbon atoms, fluoro-substituted alkoxy groups with 1-5 carbon atoms, F atoms Or Cl atom; r ₁ , r ₃ each independently represent 0, 1 or 2; r ₂ , r ₄ each independently represent 0 or 1; x ₁ , x ₂ , x ₃ , x ₄ each independently represent 0 or 1 , And x ₁ + x ₂ + x ₃ + x ₄ ≥ 3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , Z ₂ each independently represent a single bond, and the number of carbon atoms is 1-10 The alkyl group, the alkenyl group with 2-10 carbon atoms, or the alkynyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH ₂ -groups are optionally replaced by -O-,- CO-, -CO-O-, -O-CO- substituted, one or more H atoms are optionally substituted by F atoms; P ₁ , P ₂ , P ₃ , P ₄ each independently represents

,

,

,

,

,

,

,

,

,

,

,

or

. The polymerizable compound according to claim 2, characterized in that it is selected from the group consisting of the following compounds represented by formula I-1-1 to formula I-17-3,

I-1-1

I-1-2

I-1-3

I-2-1

I-2-2

I-2-3

I-2-4

I-2-5

I-2-6

I-2-7

I-2-8

I-2-9

I-2-10

I-2-11

I-2-12

I-3-1;

I-3-2

I-3-3

I-4-1

I-4-2

I-4-3

I-4-4

I-4-5

I-4-6

I-4-7

I-4-8

I-4-9

I-4-10

I-4-11

I-4-12

I-5-1

I-5-2

I-5-3

I-6-1

I-6-2

I-6-3

I-6-4

I-6-5

I-6-6

I-6-7

I-6-8

I-6-9

I-7-1

I-8-1

I-8-2

I-8-3

I-8-4

I-8-5

I-8-6

I-8-7

I-8-8

I-8-9

I-10-1

I-10-2

I-10-3

I-10-4

I-10-5

I-10-6

I-10-7

I-10-8

I-10-9

I-12-1

I-12-2

I-12-3

I-12-4

I-12-5

I-12-6

I-12-7

I-12-8

I-12-9

I-14-1

I-14-2

I-14-3

I-14-4

I-14-5

I-14-6

I-14-7

I-14-8

I-14-9

I-15-1

I-15-2

I-15-3

I-16-1

I-16-2

I-16-3

I-17-1

I-17-2

I-17-3. A liquid crystal composition characterized in that it contains one or more of the polymerizable compounds described in any one of claims 1-3. The liquid crystal composition according to claim 4, characterized in that it further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

Ⅱ

Ⅲ In formula II, R ₁ and R ₂ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, and an alkoxy group with 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

,

Expressed independently of each other

or

; In formula III, R ₃ and R ₄ each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, and an alkoxy group having 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and _{any one of R 3} and R ₄ or multiple non-adjacent -CH ₂ -are optionally cyclopentylene, Cyclobutylene or cyclopropylene substitution; Z ₁ and Z ₂ each independently represent a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -;

,

Expressed independently of each other

,

,

,

,

,

,

or

m ₁ means 1 or 2, when m ₁ means 2,

Same or different; n ₁ represents 0, 1 or 2, when n ₁ represents 2,

Same or different. The liquid crystal composition according to claim 5, wherein the compound represented by formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,

Ⅱ-1

Ⅱ-2

Ⅱ-3

Ⅱ-4

Ⅱ-5

Ⅱ-6

Ⅱ-7

Ⅱ-8

Ⅱ-9

Ⅱ-10

Ⅱ-11

Ⅱ-12

Ⅱ-13

Ⅱ-14

Ⅱ-15

Ⅱ-16

Ⅱ-17 The compound represented by formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,

Ⅲ-1

Ⅲ-2

Ⅲ-3

Ⅲ-4

Ⅲ-5

Ⅲ-6

Ⅲ-7

Ⅲ-8

Ⅲ-9

Ⅲ-10

Ⅲ-11

Ⅲ-12

Ⅲ-13

Ⅲ-14

Ⅲ-15 Wherein, R ₃₁ and R ₄₁ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, and a fluorine-substituted Alkyloxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, and alkenyl with 3-8 carbon atoms Oxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more of non-adjacent -CH ₂ -is optionally substituted by cyclopentylene, cyclobutylene or cyclopropylene Substitution. The liquid crystal composition according to any one of claims 4-6, wherein the liquid crystal composition further comprises one or more compounds represented by formula IV,

Ⅳ Wherein, R ₅ and R ₆ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more of the non-adjacent -CH ₂ -is optionally substituted by cyclopentylene, cyclobutylene or cyclylene Propyl substitution; W represents -O-, -S- or -CH ₂ O-. The liquid crystal composition according to claim 7, wherein the liquid crystal composition further comprises one or more compounds represented by formula V,

Ⅴ where R ₇ and R ₈ each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

,

Expressed independently of each other

,

or

. The liquid crystal composition according to claim 8, wherein the liquid crystal composition further comprises one or more compounds represented by formula VI,

Ⅵ; wherein R ₉ and R ₁₀ each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, Fluorine-substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, and 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

Express

,

or

; F ₁ , F ₂ , and F ₃ each independently represent an H atom or an F atom, and F ₂ and F _{3 are} not F atoms at the same time. A liquid crystal display element or liquid crystal display, comprising the compound according to any one of claims 1-3, or the liquid crystal composition according to any one of claims 4-9, the display element or display being an active matrix display Element or display or passive matrix display element or display.

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