阅读说明：本技术 化合物、液晶组合物及液晶显示元器件 (Compound, liquid crystal composition and liquid crystal display device ) 是由 王一平 孙新战 周志华 鲍永锋 邢杰浩 姜军 魏天宇 于 2019-03-29 设计创作，主要内容包括：本发明公开了一种化合物、液晶组合物及液晶显示元器件；所述化合物的结构式如式Ⅰ所示：<Image he="208" wi="700" file="DDA0002011887150000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>所述液晶组合物包含一种或多种如式Ⅰ所示化合物、一种或多种如式Ⅱ所示化合物和一种或多种如式Ⅲ所示化合物：<Image he="95" wi="700" file="DDA0002011887150000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>所述液晶显示元器件包含该液晶组合物。本发明提供的液晶组合物具有高的扩散性,将第一阶段光照射时间由75～100s缩短至50～65s,降低因扩散不均造成的残像,具有的高转化速率,可实现快速响应；本发明提供的液晶显示元器件具有较宽的向列相温度范围、合适的或较高的双折射率各向异性Δn、RM转化率高、残留少的特点,可以有效避免残像问题,并能够缩短制备过程,提高生产效率。(The invention discloses a compound, a liquid crystal composition and a liquid crystal display element; the structural formula of the compound is shown as formula I: the liquid crystal composition comprises one or more compounds shown as a formula I, one or more compounds shown as a formula II and one or more compounds shown as a formula III: the liquid crystal display component comprises the liquid crystal composition. The liquid crystal composition provided by the invention has high diffusivityThe light irradiation time of the first stage is shortened from 75-100 s to 50-65 s, the residual image caused by uneven diffusion is reduced, the conversion rate is high, and quick response can be realized; the liquid crystal display component provided by the invention has the characteristics of wider nematic phase temperature range, proper or higher birefringence anisotropy delta n, high RM conversion rate and less residue, can effectively avoid the image sticking problem, can shorten the preparation process and improve the production efficiency.)

1. A compound having a structural formula according to formula i:

in the formula I, the compound has the following structure,

each independently represents a monocyclic or fused ring structure having 4 to 10 carbon atoms;

L₁、L₂each independently represents H, halogen, alkyl with 1-25 carbon atoms, alkoxy with 1-25 carbon atoms, alkenyl with 2-25 carbon atoms, wherein, one or more non-adjacent-CH₂-may be optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-such that-O-and/or-S-are not directly attached to each other, and one or more H atoms may each be optionally substituted by halogen;

r1, r2 each independently represent 0, 1, 2, 3, 4 or 5;

n represents 0, 1, 2 or 3;

Sp₁、Sp₂、Sp₃each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, or a- (CH)₂)p₁-、-O-(CH₂)p₁-、-O-CO-(CH₂)p₁-or-CO-O- (CH)₂)p₁-，p₁Represents 2, 3, 4, 5 or 6; wherein, the Sp₁、Sp₂、Sp₃In which one or more non-adjacent-CH₂-may optionally be substituted by-O-, -S-, -CO-O-, -O-CO-O-, acrylate groups in such a way that-O-and/or-S-are not directly linked to each other, and one or more H atoms may each optionally be substituted by F or Cl; p represents a polymerizable group.

2. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by the following formulae I-1 to I-13,

wherein the content of the first and second substances,

L₁₁、L₂₂、L₃₃、L₄₄each independently represents H, an alkyl group having 1 to 5 carbon atoms, a fluorine-substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine-substituted alkoxy group having 1 to 5 carbon atoms, or a halogen;

n₁₁、n₃₃、n₄₄each independently represents 0, 1, 2, 3 or 4;

n₂₂represents 0, 1 or 2;

p represents

Sp₁、Sp₂、Sp₃Each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms; wherein, the Sp₁、Sp₂Any one or more non-adjacent-CH in the group₂May optionally be substituted by-O-, -S-, -CO-, -CH₂O-、-OCH₂-, -COO-, -OOC-or acrylate group.

3. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by formula I-1-1 through formula I-1-4,

4. a liquid crystal composition comprising one or more compounds according to any one of claims 1 to 3.

5. The liquid crystal composition of claim 4, further comprising one or more compounds represented by formula II and one or more compounds represented by formula III,

in the formula II, R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently represent

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having a fluorine-substituted alkyl,An alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms; r₃、R₄Any one or more non-adjacent-CH₂-may be optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-or-CH₂O-；

m represents 1 or 2; n represents 0, 1 or 2.

6. The liquid crystal composition according to claim 5, wherein the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II and 20-60% of a compound shown as a formula III; preferably, the liquid crystal composition comprises 0.03-0.2% of the compound shown in the formula I, 20-40% of the compound shown in the formula II and 30-50% of the compound shown in the formula III in percentage by mass.

7. The liquid crystal composition of claim 4, further comprising one or more compounds of formula IV,

wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon atomAlkenyloxy having 3 to 8 carbon atoms or fluorine-substituted alkenyloxy having 3 to 8 carbon atoms in a molecule, W represents-O-, -S-or-CH₂O-; wherein R is₅、R₆Any one or more non-adjacent-CH₂-may optionally be replaced by cyclopentylene, cyclobutyl or cyclopropylene.

8. The liquid crystal composition of claim 4, further comprising one or more compounds of formula V,

wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently representOr

9. The liquid crystal composition of claim 4, further comprising one or more compounds of formula VI

Wherein R is₉、R₁₀Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

to represent

F₁、F₂、F₃Each independently represents H or F, and F₂、F₃Not simultaneously F.

10. A liquid crystal display device, comprising the liquid crystal composition according to any one of claims 4 to 9; preferably, the liquid crystal display element is an active matrix display element or a passive matrix display element.

Technical Field

The invention belongs to the technical field of liquid crystal display, and particularly relates to a compound for a liquid crystal composition, a liquid crystal composition containing the compound, and a liquid crystal display component containing the compound or the liquid crystal composition.

Background

With the development of Display technology, flat panel Display devices such as Liquid Crystal Display (LCD) devices have advantages of high image quality, power saving, thin body, and wide application range, and thus are widely used in various consumer electronics products such as mobile phones, televisions, personal digital assistants, digital cameras, notebook computers, and desktop computers, and are becoming the mainstream of Display devices.

Reactive Mesogen (RM) is currently a very popular and important research direction in the lcd industry, and its possible applications include Polymer Sustained Alignment (PSA) lcd, polymer sustained blue phase (PS-BP) lcd, and patterned retardation Film (Pattern recorder Film).

However, the use of liquid crystal compounds in admixture with RMs in PSA mode displays still has some disadvantages. First, not all RMs are suitable for PSA displays to date; meanwhile, if the RM is polymerized using ultraviolet light (Ultravioletlight) without adding a photoinitiator, it becomes possible to select RM species less; in addition, the liquid crystal compound is required to form a liquid crystal composition having a low rotational viscosity and good photoelectric properties in combination with the selected RM. Generally, a liquid crystal composition composed of a liquid crystal compound and an RM needs to undergo two stages of ultraviolet irradiation processes in the preparation process of a liquid crystal display device, so that the RM is polymerized, and the RM is polymerized and remains in the liquid crystal composition as little as possible. The length of the RM polymerization process directly affects the time required for the fabrication process of the liquid crystal display device.

Therefore, it is desirable to provide a liquid crystal compound, a liquid crystal composition and a liquid crystal display device, which solve at least one of the above problems.

Disclosure of Invention

In order to overcome the problem of long polymerization time of Reactive Mesogen (RM) and obtain a liquid crystal composition with short RM polymerization time, high conversion efficiency and less RM residue, the inventors of the present application conducted intensive studies and found that the problem can be solved by adding the compound provided by the present invention to a liquid crystal composition.

The invention also provides a liquid crystal composition containing the compound provided by the invention, and a liquid crystal display component containing the liquid crystal composition.

The invention aims to provide a compound shown as a formula I, which is used as a Reactive Mesogen (RM) in a liquid crystal composition and has the characteristics of high solubility, good diffusivity and good ultraviolet ray tolerance. In addition, the compound shown in the formula I has high conversion efficiency during polymerization, so that the production efficiency can be effectively improved.

The second object of the present invention is to provide a liquid crystal composition comprising the compound.

The third object of the invention is to provide a liquid crystal display device comprising the liquid crystal composition.

Specifically, the present invention comprises the following:

in a first aspect of the invention, there is provided a compound of formula I,

in the formula I, the compound has the following structure,

each independently represents a monocyclic or fused ring structure having 4 to 10 carbon atoms;

L₁、L₂each independently represents H, halogen, alkyl with 1-25 carbon atoms, alkoxy with 1-25 carbon atoms, alkenyl with 2-25 carbon atoms, wherein, one or more non-adjacent-CH₂-may be optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-such that-O-and/or-S-are not directly attached to each other, and one or more H atoms may each be optionally substituted by halogen.

r1, r2 each independently represent 0, 1, 2, 3, 4 or 5;

n represents 0, 1, 2 or 3;

Sp₁、Sp₂、Sp₃each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, or a- (CH)₂)p₁-、-O-(CH₂)p₁-、 -O-CO-(CH₂)p₁-or-CO-O- (CH)₂)p₁-，p₁Represents 2, 3, 4, 5 or 6; wherein, the Sp₁、Sp₂、Sp₃In which one or more non-adjacent-CH₂-may optionally be substituted by-O-, -S-, -CO-O-, -O-CO-O-, acrylate groups in such a way that-O-and/or-S-are not directly linked to each other, and one or more H atoms may each optionally be substituted by F or Cl; p represents a polymerizable group.

It is to be noted that the alkyl group referred to in the present invention includes an alkanyl group and a cycloalkyl group.

Because the compound shown in the formula I has a polymeric group shown in P, the compound shown in the formula I is polymerized to form a stable pretilt after being irradiated and polymerized by ultraviolet light (UV) under the condition of voltage application, and plays a role in aligning liquid crystal molecules in the liquid crystal composition, so that the liquid crystal molecules have a certain pretilt angle when not being subjected to the action of an electric field. The pre-tilt angle refers to an angle formed by the liquid crystal molecules relative to the substrate plane when the liquid crystal molecules are not subjected to the electric field. The smaller the pretilt angle is, the more advantageous the response speed is, and the pretilt angle is, for example, in the range of 88 ° to 89 ° in order to obtain a suitable response speed. The magnitude of the aforementioned pretilt angle is affected by the magnitude of the applied voltage during polymerization, the irradiation intensity of light irradiation, and the irradiation time of light irradiation.

The compound shown in the formula I provided by the invention is used as a Reactive Mesogen (RM) in a liquid crystal composition, and has the characteristics of high solubility, good diffusivity and good ultraviolet tolerance. In addition, the compound shown in the formula I has the advantages of high conversion speed and high conversion completion rate, so that the production efficiency can be effectively improved.

In general, in order to polymerize a substance contained in the liquid crystal composition as a reactive mesogen, the liquid crystal composition is irradiated with light in 2 stages. As the light irradiation here, for example, ultraviolet light is generally used for irradiation. The light irradiation step is usually performed on a liquid crystal panel in which a liquid crystal composition is poured but other elements such as a backlight are not yet mounted. Regarding the time of the first-stage light irradiation (UV1) in the first stage of irradiation with ultraviolet light, for example, a time of 75 to 100 seconds is generally required for the first-stage light irradiation for a liquid crystal panel using a liquid crystal composition containing a general reactive mesogen, whereas the time of the first-stage light irradiation can be shortened to, for example, a time of 50 to 65 seconds for a liquid crystal panel using a liquid crystal composition using the compound represented by formula I of the present invention as a reactive mesogen. Although the light irradiation time saved by using the liquid crystal composition using the compound represented by formula I of the present invention as the reactive mesogen is only in the range of several tens of seconds for each liquid crystal panel, the time required for the manufacturing process of the liquid crystal display device can be greatly saved and the productivity can be improved in the case of industrial mass production. Further, since the equipment used for the first stage of ultraviolet irradiation is expensive, the time required for the irradiation can be reduced, thereby improving the efficiency of the irradiation equipment, reducing the cost of the equipment to be put into use, and reducing the production cost. The second-stage light irradiation (UV2) is performed after the first-stage light irradiation (UV1) is completed, and examples of light used in UV2 include ultraviolet light. The use of UV light at the UV2 stage, which is less than the UV irradiance at the UV1 stage, enables slow complete polymerization of the unpolymerized liquid crystal compound, thereby further reducing RM residues in the liquid crystal composition. And since the polymerization is slow, the process does not affect the pretilt angle that has been formed.

Preferably, the compound represented by the formula I is selected from the group consisting of the compounds represented by the following formulae I-1 to I-13,

wherein the content of the first and second substances,

L₁₁、L₂₂、L₃₃、L₄₄each independently represents H, an alkyl group having 1 to 5 carbon atoms, a fluorine-substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine-substituted alkoxy group having 1 to 5 carbon atoms, or a halogen;

n₁₁、n₃₃、n₄₄each independently represents 0, 1, 2, 3 or 4;

n₂₂represents 0, 1 or 2;

p represents

Or

Sp₁、Sp₂、Sp₃Each independently represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms; wherein, the Sp₁、Sp₂Any one or more non-adjacent-CH in the group₂May optionally be substituted by-O-, -S-, -CO-, -CH₂O-、-OCH₂-、-COO-、-OOC-or acrylate group substitution.

Preferably, the compound represented by the formula I is selected from the group consisting of the compounds represented by the following formulae I-1-1 to I-1-4,

in a second aspect of the invention, there is provided a liquid crystal composition comprising a compound of the first aspect of the invention as hereinbefore described.

A liquid crystal composition according to one embodiment of the present invention comprises the compound represented by the formula I. The liquid crystal composition may contain a liquid crystal compound other than the compound represented by the formula I and other additive materials in addition to the compound represented by the formula I. The compound of formula I is added to a liquid crystal composition, and after being poured into a display element, liquid crystal molecules can be given a pretilt angle by UV photopolymerization or crosslinking under a voltage applied between electrodes. The liquid crystal composition containing the compound shown in the formula I has the advantages of less RM residue, high conversion efficiency, lower viscosity, capability of realizing quick response, moderate dielectric anisotropy delta, moderate optical anisotropy delta n and high stability to heat and light.

The liquid crystal composition of the present invention preferably further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

in the formula II, R₁、R₂Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, a carbon atomAlkenyloxy with a sub-number of 3-8 or alkenyloxy with a carbon number of 3-8 substituted by fluorine; wherein the number of fluorine substitution is not limited;

each independently represent

In the formula III, R₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkyloxy group or cycloalkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, R₃、R₄Any one or more non-adjacent-CH₂-may be optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;

Z₁、Z₂each independently represents a single bond, -CH₂CH₂-or-CH₂O-；

Each independently representm represents 1 or 2; n represents 0, 1 or 2.

The compound shown in the formula II has the characteristics of low rotational viscosity and good intersolubility with other compounds. The lower rotational viscosity is more favorable for improving the response speed of the liquid crystal composition. The compound shown in the formula III has negative dielectric anisotropy, and the driving voltage of the liquid crystal composition is adjusted by the compound shown in the formula III.

As R in the aforementioned formula III₃、R₄One or more non-adjacent-CH in the alkyl with 1-10 carbon atoms₂-quiltExamples of the group obtained by substituting the cyclopropylene group, the cyclobutylene group or the cyclopentylene group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a methylcyclopropylidene group, an ethylcyclopropylidene group, a propylcyclopropylidene group, an isopropylidene group, a n-butylcyclopropylidene group, an isobutylcyclopropylidene group, a tert-butylcyclopropylidene group, a methylcyclobutylene group, an ethylcyclobutyl group, a propylcyclobutyl group, an isopropylidene group, a n-butylidene group, an isobutylidene group, a tert-butylidene group, a methylcyclopentylene group, an ethylcyclopentylene group, a propylcyclopentylene group, an isopropylidene group, a n-butylcyclopentylene group and an isobutylcyclopentylene group. R₃、R₄Among the groups shown, preferred from the viewpoint of the rotational viscosity, solubility and clearing point of the liquid crystal compound is cyclopropyl, cyclobutyl or cyclopentyl.

The liquid crystal composition of the present invention is preferably a negative dielectric anisotropic liquid crystal composition.

In the liquid crystal composition provided by the invention, the total mass of other compounds except the compound shown in the formula I is recorded as 100%, and the percentage of the ratio of the mass of the compound shown in the formula I to the total mass of other compounds is recorded as the mass fraction of the compound shown in the formula I in the liquid crystal composition. If the liquid crystal composition only contains the compounds shown in the formulas I, II and III, the total content of the compounds shown in the formulas II and III is recorded as 100 percent, and the percentage of the adding amount of the compound shown in the formula I to the total mass of the compounds shown in the formulas II and III is recorded as the mass fraction of the compound shown in the formula I. Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II and 20-60% of a compound shown as a formula III; preferably, the liquid crystal composition comprises, by mass, 0.03-0.2% of a compound represented by formula I, 20-40% of a compound represented by formula II and 30-50% of a compound represented by formula III.

Preferably, the aforementioned one or more compounds of formula II are selected from the group consisting of compounds of formulae II-1 to II-17,

preferably, the one or more compounds of formula III are selected from the group consisting of compounds of formulae III-1 to III-15,

wherein R in the compounds of the formulae III-1 to III-15₃、R₄With R in the compound of the formula III₃、R₄Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms; wherein R is₃、R₄Any one or more non-adjacent-CH in the group₂-may be optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.

In some embodiments, the liquid crystal composition of the present invention may further comprise one or more compounds represented by formula IV,

wherein R is₅、R₆Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms, wherein R is₅、R₆Any one or more non-adjacent-CH₂-may optionally be replaced by cyclopentylene, cyclobutyl or cyclopropylene; w represents O, S or-CH₂O-。

By containing the compound shown in the formula IV in the liquid crystal composition, the liquid crystal composition has larger negative dielectric anisotropy, and is favorable for reducing the driving voltage of a device.

Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III and 1-15% of a compound shown as a formula IV;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound of formula I, 20-40% of a compound of formula II, 30-50% of a compound of formula III, and 2-10% of a compound of formula IV.

Preferably, the aforementioned one or more compounds represented by formula IV are selected from the group consisting of compounds represented by formulas IV-1 to IV-10,

wherein R is₅₁、R₆₁Represents an alkyl group having 1 to 6 carbon atoms;

the liquid crystal composition of the present invention may further comprise one or more compounds represented by formula V,

wherein R is₇、R₈Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

each independently representOr

Preferably, the one or more compounds of formula V are selected from the group consisting of compounds of formula V-1 to formula V-4,

wherein R is₇₁、R₈₁Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a 2-propenyl group, or a 3-pentenyl group; r₈₂Represents an alkoxy group having 1 to 5 carbon atoms;

preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III and 1-30% of a compound shown as a formula V;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III and 5-20% of a compound shown as a formula V.

Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV and 1-30% of a compound shown as a formula V;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV and 5-20% of a compound shown as a formula V.

The compounds of the formula V have high clearing point and elastic constants, in particular the splay elastic constant K₃₃And is beneficial to improving the parameter performance of the liquid crystal composition.

Preferably, the liquid crystal composition of the present invention may further comprise one or more compounds represented by formula VI,

wherein R is₉、R₁₀Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorine-substituted alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a fluorine-substituted alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 3 to 8 carbon atoms or a fluorine-substituted alkenyloxy group having 3 to 8 carbon atoms;

to represent

Or

F₁、F₂、F₃Each independently represents H or F, and F₂、F₃Not simultaneously F.

Preferably, the one or more compounds of formula VI are selected from the group consisting of compounds of formulae VI-1 to VI-3,

wherein R is₉、R₁₀Each independently preferably represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.

The compounds shown in the formulas VI-1 to VI-3 have high clearing points which are generally higher than 200 ℃, and can more remarkably improve the clearing points of the liquid crystal composition.

Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV and 2-5% of a compound shown as a formula VI.

Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.

Preferably, the liquid crystal composition comprises, in mass percent: 0.01-1% of a compound shown as a formula I, 15-60% of a compound shown as a formula II, 20-60% of a compound shown as a formula III, 1-15% of a compound shown as a formula IV, 1-30% of a compound shown as a formula V and 1-10% of a compound shown as a formula VI;

preferably, the liquid crystal composition comprises, in mass percent: 0.03-0.2% of a compound shown as a formula I, 20-40% of a compound shown as a formula II, 30-50% of a compound shown as a formula III, 2-10% of a compound shown as a formula IV, 5-20% of a compound shown as a formula V and 2-5% of a compound shown as a formula VI.

Preferably, a dopant having various functions may be added to the liquid crystal composition of the present invention, and when a dopant is contained, the content of the dopant is preferably 0.01 to 1% by mass in the liquid crystal composition, and examples of the dopant include an antioxidant, an ultraviolet absorber, and a chiral agent.

Examples of the antioxidant and ultraviolet absorber include,

t represents an integer of 1 to 10.

In a third aspect of the present invention, there is provided a liquid crystal display device comprising the above-mentioned compound or the above-mentioned liquid crystal composition, wherein the display device is an active matrix display device or a passive matrix display device.

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

Preferably, the active matrix display component is a PSVA-TFT or IPS-TFT liquid crystal display component.

The liquid crystal display component containing the compound or the liquid crystal composition has the characteristics of wide nematic phase temperature range, proper or higher birefringence anisotropy delta n, less RM residue, high conversion efficiency and high voltage holding ratio, can effectively avoid the image retention problem, can effectively shorten the preparation process and improve the production efficiency.

The liquid crystal display device of the present invention is not limited in its structure as long as the compound represented by formula I of the present invention is contained in the liquid crystal composition used for the liquid crystal display device, and those skilled in the art can select an appropriate structure of the liquid crystal display device according to the desired performance.

As an embodiment of the liquid crystal display device of the present invention, for example, the following structures can be cited: the liquid crystal display panel comprises a first substrate, a second substrate and a liquid crystal composition arranged between the first substrate and the second substrate, wherein the first substrate and the second substrate are arranged in parallel and oppositely, one sides of the first substrate and the second substrate, which are close to the liquid crystal composition, are provided with alignment layers, the first substrate is provided with a common electrode, the second substrate is provided with a pixel electrode, and spacers are scattered between the first substrate and the second substrate.

As the method for manufacturing the liquid crystal display of the present invention, those skilled in the art can select an appropriate method for manufacturing according to common knowledge in the art. As an example of the manufacturing method of the liquid crystal display of the present invention, for example, a manufacturing method including the steps of:

uniformly coating alignment materials, which can be selected from polyimide, on the surfaces of the first substrate and the second substrate, heating and curing the uniformly coated alignment materials at the heating temperature of 210-250 ℃ to form alignment layers;

spreading a spacer on the surface of the second substrate, coating frame glue along the edge of the first substrate, and curing at 100-150 ℃;

arranging the first substrate and the second substrate oppositely, and attaching to form a structure with an interlayer space;

injecting a liquid crystal composition into the interlayer space between the first substrate and the second substrate, sealing and curing to seal the liquid crystal composition between the first substrate and the second substrate, and simultaneously performing electrification and ultraviolet irradiation. The ultraviolet irradiation is divided into two stages of first stage ultraviolet irradiation (UV1) and second stage ultraviolet irradiation (UV 2). At the UV1 stage, the wavelength of ultraviolet light is 360-370 nm, and the illumination of ultraviolet light is 60-72 mw/cm². The time for the ultraviolet irradiation may be, for example, 50 to 65 seconds, preferably 50 to 60 seconds.

After the first-stage light irradiation is completed, the second-stage light irradiation (UV2) is performed, and examples of the light used in UV2 include ultraviolet light. The second stage ultraviolet irradiation (UV2) has an ultraviolet wavelength of 360-370 nm, and the second stage UV2 uses an ultraviolet irradiation of 3-8 mw/cm². By adopting the irradiance, the unpolymerized compound shown in the formula I can be slowly and completely polymerized, the conversion rate of the polymerizable compound is improved, and no polymerizable compound is remained in the liquid crystal composition. And since the polymerization is slow, the process does not affect the pretilt angle that has been formed. The ultraviolet irradiation time in the UV2 stage may be, for example, 100 to 150 min.

The invention has the following beneficial effects:

the liquid crystal composition containing the compound shown in the formula I has the advantages of high conversion rate and high conversion efficiency, so that the liquid crystal composition has less residue in a liquid crystal system and can effectively reduce the deterioration influence of impurities on display. In addition, the liquid crystal composition containing the compound shown in the formula I has high diffusivity, greatly shortens the time in the process, shortens the light irradiation time of the first stage from 75-100 s to 50-65 s, reduces the problem of residual images caused by uneven diffusion, has high conversion rate, can realize quick response, and has moderate dielectric anisotropy delta, moderate optical anisotropy delta n and high stability to heat and light.

The liquid crystal display component containing the compound or the liquid crystal composition has the characteristics of wider nematic phase temperature range, proper or higher birefringence anisotropy delta n, high RM conversion rate and less residue, can effectively avoid the problem of image sticking, can effectively shorten the preparation process, and improves the production efficiency.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 is a NMR spectrum of compound I-1-1 of example 1.

FIG. 2 shows the NMR spectrum of compound I-1-2 in example 2.

FIG. 3 is a NMR chart of compound I-1-3 of example 3.

FIG. 4 is a NMR chart of Compound I-1-4 of example 4.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

In the invention, the preparation method is a conventional method if no special description is provided, the used raw materials can be obtained from a public commercial way if no special description is provided, the percentages refer to mass percentage, the temperature is centigrade (DEG C), the liquid crystal compound also becomes a liquid crystal monomer, and the specific meanings and test conditions of other symbols are as follows:

cp represents a liquid crystal clearing point (DEG C), and is measured by a DSC quantitative method;

Δ n represents optical anisotropy, and Δ n ═ n_e-n_oWherein n is_oRefractive index of ordinary light, n_eThe refractive index of the extraordinary ray is measured under the conditions of 25 +/-2 ℃ and 589nm, and the Abbe refractometer is used for testing;

Δ represents dielectric anisotropy, Δ ═/-, where/is the dielectric constant parallel to the molecular axis,/-is the dielectric constant perpendicular to the molecular axis, the test conditions were 25 ± 0.5 ℃, 20 micron parallel cells, INSTEC: ALCT-IR1 test;

VHR represents the voltage holding ratio (%), and the test conditions are 20 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model6254 liquid crystal performance comprehensive tester;

γ 1 represents rotational viscosity (mPas) and the test conditions are 25. + -. 0.5 ℃ in 20 μm parallel cells, INSTEC: ALCT-IR1 test.

The preparation method of the liquid crystal composition comprises the following steps: weighing each liquid crystal monomer according to a certain proportion, putting the liquid crystal monomers into a stainless steel beaker, putting the stainless steel beaker filled with each liquid crystal monomer on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after most of the liquid crystal monomers in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.

The preparation method of the liquid crystal display device comprises the following steps: firstly, uniformly coating alignment materials, which can be selected from polyimide, on the surfaces of a first substrate and a second substrate, heating and curing the uniformly coated alignment materials at the heating temperature of 230 ℃ to form alignment layers; secondly, spreading spacers on the surface of the second substrate, coating frame glue along the edge of the first substrate, and curing at 120 ℃; then, the first substrate and the second substrate are oppositely arranged and are attached to form a structure with an interlayer space; finally, the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and cured, thereby sealing the liquid crystal composition between the first substrate and the second substrate, and simultaneously performing electrification and ultraviolet irradiation. The ultraviolet irradiation is divided into two stages, including first stage ultraviolet irradiation (UV1) and second stage ultraviolet irradiation (UV 2). In the UV1 stage, the wavelength of ultraviolet light is 365nm, and the irradiance is 64mw/cm²Light irradiation is performed, and the irradiation time of ultraviolet light is controlled so that the liquid crystal molecules form a pretilt angle of about 89 ° (generally, the RM conversion is required to be about 50%). The higher the RM conversion, the shorter the uv exposure time. Performing second stage light irradiation (UV2) after the first stage light irradiation is finished, wherein UV light with the wavelength of 365nm is used in UV2, and the irradiance is 5mw/cm²The light irradiation time is 100-150 min.

The formula for the conversion of RM is:

the liquid crystal monomer structure used in the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following tables 1 and 2.

Table 1: corresponding code of ring structure

Table 2: corresponding codes for end groups and linking groups

Examples are:

the code is CC-Cp-V1;

the code is PGP-Cpr 1-2;

the code is CPY-2-O2;

the code is CCY-3-O2;

the code is COY-3-O2;

the code is CCOY-3-O2;the code is Sb-Cp 1O-O4;

the code is Sc-Cp 1O-O4.

The compounds of formula I can be prepared by the following illustrative synthetic routes

In the formula I, the compound has the following structure,

each independently represents a monocyclic or fused ring structure having 4 to 10 carbon atoms;

L₁、L₂each independently represents H, halogen, alkyl with 1-25 carbon atoms, alkoxy with 1-25 carbon atoms, alkenyl with 2-25 carbon atoms, wherein, one or more non-adjacent-CH₂-may be optionally substituted by-O-, -S-, -CO-O-, -O-CO-O-such that-O-and/or-S-are not directly attached to each other, and one or more H atoms may each be optionally substituted by halogen.

r1, r2 each independently represent 0, 1, 2, 3, 4 or 5;

n represents 0, 1, 2 or 3;

Sp₁、Sp₂、Sp₃each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, or a- (CH)₂)p₁-、-O-(CH₂)p₁-、 -O-CO-(CH₂)p₁-or-CO-O- (CH)₂)p₁-，p₁Represents 2, 3, 4, 5 or 6; wherein, the Sp₁、Sp₂、Sp₃In which one or more non-adjacent-CH₂-may optionally be substituted by-O-, -S-, -CO-O-, -O-CO-O-, acrylate groups in such a way that-O-and/or-S-are not directly linked to each other, and one or more H atoms may each optionally be substituted by F or Cl;

p represents a polymerizable group, P may be

Or