CN111747853A - Compound, liquid crystal composition and liquid crystal display device - Google Patents

Compound, liquid crystal composition and liquid crystal display device Download PDF

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CN111747853A
CN111747853A CN201910255900.3A CN201910255900A CN111747853A CN 111747853 A CN111747853 A CN 111747853A CN 201910255900 A CN201910255900 A CN 201910255900A CN 111747853 A CN111747853 A CN 111747853A
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carbon atoms
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fluorine
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CN111747853B (en
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王一平
孙新战
周志华
鲍永锋
邢杰浩
姜军
魏天宇
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

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Abstract

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:
Figure DDA0002011887150000011
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:
Figure DDA0002011887150000012
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.

Description

Compound, liquid crystal composition and liquid crystal display device
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,
Figure BDA0002011887130000021
in the formula I, the compound has the following structure,
Figure BDA0002011887130000022
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,
Figure BDA0002011887130000031
Figure BDA0002011887130000041
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
Figure BDA0002011887130000042
Figure BDA0002011887130000051
Or
Figure BDA0002011887130000052
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,
Figure BDA0002011887130000053
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,
Figure BDA0002011887130000054
Figure BDA0002011887130000061
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;
Figure BDA0002011887130000062
each independently represent
Figure BDA0002011887130000063
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-；
Figure BDA0002011887130000064
Each independently represent
Figure BDA0002011887130000065
m 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,
Figure BDA0002011887130000071
preferably, the one or more compounds of formula III are selected from the group consisting of compounds of formulae III-1 to III-15,
Figure BDA0002011887130000072
Figure BDA0002011887130000081
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,
Figure BDA0002011887130000082
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,
Figure BDA0002011887130000091
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,
Figure BDA0002011887130000092
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;
Figure BDA0002011887130000093
each independently represent
Figure BDA0002011887130000094
Or
Figure BDA0002011887130000095
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,
Figure BDA0002011887130000096
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,
Figure BDA0002011887130000101
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;
Figure BDA0002011887130000102
to represent
Figure BDA0002011887130000103
Or
Figure BDA0002011887130000104
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,
Figure BDA0002011887130000105
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,
Figure BDA0002011887130000111
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 ═ ne-noWherein n isoRefractive index of ordinary light, neThe 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:
Figure BDA0002011887130000141
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
Figure BDA0002011887130000142
Table 2: corresponding codes for end groups and linking groups
Figure BDA0002011887130000143
Figure BDA0002011887130000151
Examples are:
Figure BDA0002011887130000152
the code is CC-Cp-V1;
Figure BDA0002011887130000153
the code is PGP-Cpr 1-2;
Figure BDA0002011887130000154
the code is CPY-2-O2;
Figure BDA0002011887130000155
the code is CCY-3-O2;
Figure BDA0002011887130000156
the code is COY-3-O2;
Figure BDA0002011887130000157
the code is CCOY-3-O2;
Figure BDA0002011887130000158
the code is Sb-Cp 1O-O4;
Figure BDA0002011887130000159
the code is Sc-Cp 1O-O4.
The compounds of formula I can be prepared by the following illustrative synthetic routes
Figure BDA0002011887130000161
In the formula I, the compound has the following structure,
Figure BDA0002011887130000162
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
Figure BDA0002011887130000163
Figure BDA0002011887130000164
Or
Figure BDA0002011887130000165
Example 1
The structural formula of the compound is shown as the following formula I-1-1:
Figure BDA0002011887130000171
the preparation route is as follows:
Figure BDA0002011887130000172
the specific operation flow of the preparation is as follows:
the first step is as follows: preparation of intermediate 3
0.1mol of Compound 1, 0.1mol of Compound 2, 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") and 0.5L of tetrahydrofuran were put into a 1L three-necked flask, and reacted at room temperature for 2 hours under a nitrogen atmosphere. The solid was filtered off, the organic phase was washed with 0.2L of water, passed through a 50g silica gel column, washed with 0.1L of toluene, and spin-dried to give intermediate 3.
The second step is that: compound I-1
A1L three-necked flask was charged with 0.02mol of the above intermediate 3, 0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC, and reacted at room temperature under nitrogen atmosphere for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of multiplied by 2 ethyl acetate, combining organic phases, washing with 500ml of multiplied by 2 salt water, drying with anhydrous sodium sulfate, evaporating to dryness, passing 30g of silica gel through a column with 3 times of petroleum ether (90-120 ℃), flushing the column with 2 times of petroleum ether (90-120 ℃), evaporating to dryness and recrystallizing with 2 times of ethanol to obtain a compound I-1-1, wherein the nuclear magnetic resonance hydrogen spectrogram of the compound I-1 is shown in figure 1.
Example 2
The structural formula of the compound is shown as the following formula I-1-2:
Figure BDA0002011887130000173
the preparation route is as follows:
Figure BDA0002011887130000181
the specific operation flow of the preparation is as follows:
the first step is as follows: preparation of intermediate 6
0.1mol of Compound 5, 0.1mol of Compound 2, 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") and 0.5L of tetrahydrofuran were put into a 1L three-necked flask, and reacted at room temperature for 2 hours under a nitrogen atmosphere. The solid was filtered off, the organic phase was washed with 0.2L of water, passed through a 50g silica gel column, washed with 0.1L of toluene, and spin-dried to give intermediate 6.
The second step is that: preparation of Compound I-1-2
0.02mol of the intermediate 6, 0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC, and a nitrogen atmosphere were charged into a 1L three-necked flask and reacted at room temperature for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of multiplied by 2 ethyl acetate, combining organic phases, washing with 500ml of multiplied by 2 salt water, drying with anhydrous sodium sulfate, evaporating to dryness, passing 30g of silica gel through a column with 3 times of petroleum ether (90-120 ℃), flushing the column with 2 times of petroleum ether (90-120 ℃), evaporating to dryness and recrystallizing with 2 times of ethanol to obtain a compound I-1-2, wherein the nuclear magnetic resonance hydrogen spectrogram of the compound I-1-2 is shown in figure 2.
Example 3
The structural formula of the compound is shown as the following formula I-1-3:
Figure BDA0002011887130000182
the preparation route is as follows:
Figure BDA0002011887130000183
the specific operation flow of the preparation is as follows:
the first step is as follows: preparation of intermediate 8
0.1mol of Compound 7, 0.1mol of Compound 2, 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") and 0.5L of tetrahydrofuran were put into a 1L three-necked flask, and reacted at room temperature for 2 hours under a nitrogen atmosphere. The solid was filtered off, the organic phase was washed with 0.2L of water, passed through a 50g silica gel column, washed with 0.1L of toluene, and spin-dried to give intermediate 8.
The second step is that: preparation of Compound I-1-3
0.02mol of the intermediate 8, 0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC, and a nitrogen atmosphere were charged into a 1L three-necked flask and reacted at room temperature for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of multiplied by 2 ethyl acetate, combining organic phases, washing with 500ml of multiplied by 2 salt water, drying with anhydrous sodium sulfate, evaporating to dryness, passing 30g of silica gel through a column with 3 times of petroleum ether (90-120 ℃), flushing the column with 2 times of petroleum ether (90-120 ℃), evaporating to dryness and recrystallizing with 2 times of ethanol to obtain a compound I-1-3, wherein the nuclear magnetic resonance hydrogen spectrogram of the compound I-1-3 is shown in figure 3.
Example 4
The structural formula of the compound is shown as the following formula I-1-4:
Figure BDA0002011887130000191
the preparation route is as follows:
Figure BDA0002011887130000192
the specific operation flow of the preparation is as follows:
the first step is as follows: preparation of intermediate 10
Putting into a 1L three-necked bottle; 0.02 mol; the reaction mixture was reacted with 0.02mol of the compound 9 (above), 0.1mol of dicyclohexylcarbodiimide (hereinafter, referred to as "DCC") and 0.5L of tetrahydrofuran under a nitrogen atmosphere at room temperature for 2 hours. The solid was filtered off, the organic phase was washed with 0.2L of water, passed through a 50g silica gel column, washed with 0.1L of toluene, and spin-dried to give intermediate 10.
The second step is that: preparation of Compounds I-1-4
0.02mol of the intermediate 10, 0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC were put into a 1L three-necked flask, and reacted at room temperature under nitrogen atmosphere for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of multiplied by 2 ethyl acetate, combining organic phases, washing with 500ml of multiplied by 2 salt water, drying with anhydrous sodium sulfate, evaporating to dryness, passing 30g of silica gel through a column with 3 times of petroleum ether (90-120 ℃), flushing the column with 2 times of petroleum ether (90-120 ℃), evaporating to dryness and recrystallizing with 2 times of ethanol to obtain a compound I-1-4, wherein the nuclear magnetic resonance hydrogen spectrogram of the compound I-1-4 is shown in figure 4.
[ 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.
Example 5:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 3 below.
Table 3: formulation and corresponding Properties of the liquid Crystal composition of example 5
Figure BDA0002011887130000201
In the liquid crystal composition of example 5, the total mass of the compounds represented by the formulae II and III is 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-1 to the total mass of the compounds represented by the formulae II and III is the mass fraction of the compound represented by the formula I-1-1, i.e., 1%.
Example 6:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 4 below.
Table 4: formulation and corresponding Properties of the liquid Crystal composition of example 6
Figure BDA0002011887130000202
Figure BDA0002011887130000211
In the liquid crystal composition of example 6, the total mass of the compounds represented by the formulae II, III and IV was 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-2 to the total mass of the compounds represented by the formulae II, III and IV was 0.1% based on the mass fraction of the compound represented by the formulae I-1-2.
Example 7:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 5 below.
Table 5: formulation and corresponding Properties of the liquid Crystal composition of example 7
Figure BDA0002011887130000212
In the liquid crystal composition of example 7, the total mass of the compounds represented by the formulae II, III and V was 100%, and the percentage of the ratio of the amount of the compound represented by the formulae I-1 to 3 to the total mass of the compounds represented by the formulae II, III and V was 0.03% based on the mass fraction of the compound represented by the formulae I-1 to 3.
Example 8:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 6 below.
Table 6: formulation and corresponding Properties of the liquid Crystal composition of example 8
Figure BDA0002011887130000221
In the liquid crystal composition of example 8, the total mass of the compounds represented by the formulae II, III, IV and V was 100%, and the percentage of the ratio of the amount of the compound represented by the formulae I-1 to 4 to the total mass of the compounds represented by the formulae II, III, IV and V was 0.2% based on the mass fraction of the compound represented by the formulae I-1 to 4.
Example 9:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 7 below.
Table 7: formulation and corresponding Properties of the liquid Crystal composition of example 9
Figure BDA0002011887130000222
Figure BDA0002011887130000231
In the liquid crystal composition of example 9, the total mass of the compounds represented by the formulae II, III, IV, V and VI is 100%, and the percentage of the ratio of the amount of the compound represented by the formulae I-1 to 4 to the total mass of the compounds represented by the formulae II, III, IV, V and VI is the mass fraction of the compound represented by the formulae I-1 to 4, i.e., 0.15%.
Example 10:
the formulation and corresponding properties of the liquid crystal compositions are shown in Table 8 below.
Table 8: formulation and corresponding Properties of the liquid Crystal composition of example 10
Figure BDA0002011887130000232
Figure BDA0002011887130000241
In the liquid crystal composition of example 10, the total mass of the compounds represented by the formulae II, III, IV and VI is 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-2 to the total mass of the compounds represented by the formulae II, III, IV and VI is the mass fraction of the compound represented by the formulae I-1-4, i.e., 0.5%.
Example 11:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 9 below.
Table 9: formulation and corresponding Properties of the liquid Crystal composition of example 11
Figure BDA0002011887130000242
In the liquid crystal composition of example 11, the total mass of the compounds represented by the formulae II, III, IV and V was 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-2 to the total mass of the compounds represented by the formulae II, III, IV and V was 0.13% based on the mass fraction of the compound represented by the formulae I-1-2.
Example 12:
the formulation and corresponding properties of the liquid crystal composition are shown in table 10 below.
Table 10: formulation and corresponding Properties of the liquid Crystal composition of example 12
Figure BDA0002011887130000243
Figure BDA0002011887130000251
In the liquid crystal composition of example 12, the total mass of the compounds represented by the formulae II, III, IV and V was 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-1 to the total mass of the compounds represented by the formulae II, III, IV and V was 0.6% based on the mass fraction of the compound represented by the formula I-1-1.
Comparative example 1:
i-1-4 in example 8 was replaced by the existing compound of formula RM-1 as Reactive Mesogen (RM),
Figure BDA0002011887130000252
the formulation and corresponding properties of the liquid crystal compositions are shown in Table 11 below.
Table 11: formulation and corresponding Properties of the liquid Crystal composition of comparative example 1
Figure BDA0002011887130000253
Figure BDA0002011887130000261
In the liquid crystal composition in the comparative example 1, the total mass of the compounds shown in the formulas II, III, IV and V is 100%, and the percentage of the ratio of the addition amount of the compound shown in the formula RM-1 to the total mass of the compounds shown in the formulas II, III, IV and V is the mass fraction of the compounds shown in the formulas I-1 to 4, namely 0.2%.
Example 8 and comparative example 1 were poured into the same test cell, and a voltage of 15V was applied to both sides of the test cell while irradiating uv light. The ultraviolet irradiation is divided into two stages, a UV1 stage and a UV2 stage. The UV1 stage adopts a wavelength of 365nm and irradiance of 64mw/cm2Is irradiated with ultraviolet light. To obtain a pretilt angle of around 89 °, RM conversions of around 50% are generally required. By UV1 stage UV irradiation under the same conditions, 47s of irradiation is required for 50% conversion of the compound of formula I-1-4, and 80s of irradiation is required for 50% conversion of the compound of formula RM-1. Therefore, the compound shown in the formula I-1-4 is used as the Reactive Mesogen (RM), so that the preparation process of the liquid crystal display device can be effectively shortened, and the production efficiency is improved.
The formula for the conversion of RM is:
Figure BDA0002011887130000264
after the UV1 stage, performing a UV2 stage, wherein the UV2 stage adopts a wavelength of 365nm and irradiance of 5mw/cm2The irradiation is carried out for 150min to ensure that the RM is completely polymerized as much as possible. After UV2 stage, the compound of formula I-1-4 remained at 50ppm, while the compound of formula RM-1 remained at 85 ppm. The residual quantity of RM is small, and the problem of residual image can be effectively avoided.
Comparative example 2:
i-1-2 in example 10 was replaced with a conventional compound represented by the formula RM-2 as a Reactive Mesogen (RM),
Figure BDA0002011887130000262
the formulation and corresponding properties of the liquid crystal compositions are shown in table 12 below.
Table 12: comparative example 2 liquid crystal composition formulation and corresponding Properties
Figure BDA0002011887130000263
Figure BDA0002011887130000271
In the liquid crystal composition in the comparative example 2, the total mass of the compounds shown in the formulas II, III, IV and VI is 100%, and the percentage of the ratio of the addition amount of the compound shown in the formula RM-2 to the total mass of the compounds shown in the formulas II, III, IV and VI is the mass fraction of the compounds shown in the formulas I-1 to 4, namely 0.5%.
Example 10 and comparative example 2 were poured into the same test cell, and a voltage of 15V was applied to both sides of the test cell while irradiating uv light. The ultraviolet irradiation is divided into two stages, a UV1 stage and a UV2 stage. The UV1 stage adopts a wavelength of 365nm and irradiance of 64mw/cm2Is irradiated with ultraviolet light. To obtain a pretilt angle of around 89 deg., the compound of formula I-1-2 needs to be irradiated for 55s, while the compound of formula RM-2 needs to be irradiated for 83 s. Therefore, the compound shown in the formula I-1-2 is used as the Reactive Mesogen (RM), so that the preparation process of the liquid crystal display device can be effectively shortened, and the production efficiency is improved.
After the UV1 stage, performing a UV2 stage, wherein the UV2 stage adopts a wavelength of 365nm and irradiance of 5mw/cm2Irradiating for 120min by using the ultraviolet light to ensure that the RM is completely polymerized as much as possible. After UV2 stage, the compound of formula I-1-2 remained at 50ppm, while the compound of formula RM-2 remained at 85 ppm. The residual quantity of RM is small, and the problem of residual image can be effectively avoided.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A compound having a structural formula according to formula i:
Figure FDA0002011887120000011
in the formula I, the compound has the following structure,
Figure FDA0002011887120000012
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,
Figure FDA0002011887120000013
Figure FDA0002011887120000021
Figure FDA0002011887120000031
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
Figure FDA0002011887120000032
Figure FDA0002011887120000033
Or
Figure FDA0002011887120000034
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,
Figure FDA0002011887120000035
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,
Figure FDA0002011887120000041
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;
Figure FDA0002011887120000042
each independently represent
Figure FDA0002011887120000043
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-；
Figure FDA0002011887120000044
Each independently represent
Figure FDA0002011887120000045
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,
Figure FDA0002011887120000046
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,
Figure FDA0002011887120000051
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;
Figure FDA0002011887120000052
each independently represent
Figure FDA0002011887120000053
Or
Figure FDA0002011887120000054
9. The liquid crystal composition of claim 4, further comprising one or more compounds of formula VI
Figure FDA0002011887120000055
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;
Figure FDA0002011887120000056
to represent
Figure FDA0002011887120000057
Or
Figure FDA0002011887120000058
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.
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US5641850A (en) * 1994-11-10 1997-06-24 Consortium Fur Electrochemische Industrie Gmbh Process for the preparation of liquid-crystalline polyorganosiloxanes containing (meth)acryloxy groups
CN102314015A (en) * 2010-07-06 2012-01-11 Dic株式会社 Liquid crystal polymer and liquid crystal device
JP2016011346A (en) * 2014-06-27 2016-01-21 Jnc株式会社 Polymerizable compound, polymerizable composition, and liquid crystal display element

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US5641850A (en) * 1994-11-10 1997-06-24 Consortium Fur Electrochemische Industrie Gmbh Process for the preparation of liquid-crystalline polyorganosiloxanes containing (meth)acryloxy groups
CN102314015A (en) * 2010-07-06 2012-01-11 Dic株式会社 Liquid crystal polymer and liquid crystal device
JP2016011346A (en) * 2014-06-27 2016-01-21 Jnc株式会社 Polymerizable compound, polymerizable composition, and liquid crystal display element

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