CN111747853B - Compound, liquid crystal composition and liquid crystal display element - Google Patents

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

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CN111747853B
CN111747853B CN201910255900.3A CN201910255900A CN111747853B CN 111747853 B CN111747853 B CN 111747853B CN 201910255900 A CN201910255900 A CN 201910255900A CN 111747853 B CN111747853 B CN 111747853B
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liquid crystal
formula
crystal composition
compound
carbon atoms
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CN111747853A (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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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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

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: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 diffusivity, shortens the light irradiation time of the first stage from 75-100 s to 50-65 s, reduces residual images caused by uneven diffusion, has high conversion rate, and can realize quick response; 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 problem of afterimage, shortens the preparation process and improves the production efficiency.

Description

Compound, liquid crystal composition and liquid crystal 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 element containing the compound or the liquid crystal composition.
Background
With the development of display technology, flat display devices such as liquid crystal display devices (Liquid Crystal Display, LCD) have been widely used in various consumer electronic products such as mobile phones, televisions, personal digital assistants, digital cameras, notebook computers, and desktop computers, and have become the mainstream of display devices, because of their advantages such as high image quality, power saving, thin body, and wide application range.
Reactive Mesogen (RM) is currently a very popular and important research direction in the liquid crystal display industry, and the possible application fields thereof include Polymer Stabilized Alignment (PSA) liquid crystal display, polymer stabilized blue phase (PS-BP) liquid crystal display, and patterned retardation film (Pattern Retarder Film).
However, the liquid crystal compounds have some drawbacks for application in PSA mode displays after mixing with RM. First, not all RMs have been suitable for PSA displays to date; meanwhile, if the RM is polymerized using ultraviolet light (Ultraviolet light) without adding a photoinitiator, the RM species can be selected to become smaller; in addition, the liquid crystal composition formed by combining the liquid crystal compound with the selected RM is required to have low rotational viscosity and good electro-optical properties. In general, the liquid crystal composition composed of the liquid crystal compound and the RM needs to undergo two-stage ultraviolet irradiation process in the preparation process of the liquid crystal display element, so that the RM is polymerized, and as little residue as possible remains in the liquid crystal composition after the RM is polymerized. The length of the RM polymerization process directly affects the time required for the preparation process of the liquid crystal display device.
Accordingly, there is a need 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
The present inventors have conducted intensive studies in order to overcome the problem of long Reactive Mesogen (RM) polymerization time, obtain a liquid crystal composition having a short RM polymerization time, high conversion efficiency, and less RM residue, and found that the problem can be solved by adding the compound provided by the present application to the liquid crystal composition.
The application also provides a liquid crystal composition containing the compound and a liquid crystal display element containing the liquid crystal composition.
The application aims to provide a compound shown in 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 resistance. In addition, the compound shown in the formula I has high conversion efficiency in polymerization, so that the production efficiency can be effectively improved.
The second object of the present application is to provide a liquid crystal composition comprising the compound.
The third object of the present application is to provide a liquid crystal display element comprising the liquid crystal composition.
Specifically, the present application includes the following:
In a first aspect of the present invention, there is provided a compound of formula I,
in the formula I, the compound of the formula I,
each independently represents a monocyclic or condensed ring structure having 4 to 10 carbon atoms;
L 1 、L 2 each independently represents H, halogen, alkyl having 1 to 25 carbon atoms, alkoxy having 1 to 25 carbon atoms, alkenyl having 2 to 25 carbon atoms, wherein one or more non-adjacent-CH 2 Can optionally be covered with-O-; -S-, -CO-, -CO-O-, -O-CO-O-substitution, such that-O-and/or-S-are not directly connected to each other and one or more H atoms may each be optionally substituted with halogen.
r1, r2 each independently represent 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2 or 3;
Sp 1 、Sp 2 、Sp 3 each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, - (CH) 2 )p 1 -、-O-(CH 2 )p 1 -、-O-CO-(CH 2 )p 1 -or-CO-O- (CH) 2 )p 1 -，p 1 Represents 2, 3, 4, 5 or 6; wherein the Sp is 1 、Sp 2 、Sp 3 One or more non-adjacent-CH(s) 2 -may optionally be substituted with-O-, -S-, -CO-O-, -O-CO-O-, acrylate groups in such a way that-O-and/or-S-are not directly connected to each other, and one or more H atoms may each optionally be substituted with F or Cl; p represents a polymerizable group.
The alkyl group referred to in the present invention includes an alkyl group and a cycloalkyl group.
Because the compound shown in the formula I has the polymeric group shown as P, the compound shown in the formula I is polymerized to form stable pretilt after Ultraviolet (UV) irradiation polymerization under the condition of voltage application, and the compound has the function of aligning liquid crystal molecules in the liquid crystal composition, so that the liquid crystal molecules have a certain pretilt angle when not subjected to the action of an electric field. The pretilt angle refers to an angle formed by the liquid crystal molecules with respect to the substrate plane when the liquid crystal molecules are not subjected to an electric field. The smaller the pretilt angle, the more advantageous the response speed is, and the range of the pretilt angle is, for example, 88 ° to 89 ° in order to obtain an appropriate response speed. The magnitude of the pretilt angle is affected by the magnitude of the applied voltage, the irradiation intensity of the light irradiation, and the irradiation time of the light irradiation in the polymerization process.
The compound shown in the formula I provided by the invention is used as Reactive Mesogen (RM) in a liquid crystal composition, and has the characteristics of high solubility, good diffusivity and good ultraviolet resistance. 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 a liquid crystal composition as a reactive mesogen, the liquid crystal composition is irradiated with light for 2 stages. As the light irradiation here, irradiation with, for example, ultraviolet light is generally used. The light irradiation step is usually performed on a liquid crystal panel filled with a liquid crystal composition, but not yet provided with other elements such as a backlight. In the first stage of irradiation with ultraviolet light, as for the time of first stage light irradiation (UV 1), the time of first stage light irradiation is generally required to be, for example, 75 to 100 seconds for a liquid crystal panel using a liquid crystal composition containing a usual reactive mesogen, whereas the time of first stage light irradiation can be shortened to, for example, 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 employing the compound of formula I of the present invention as a reactive mesogen is only in the range of tens of seconds for each liquid crystal panel, in the case of industrial mass production, the time required for the preparation process of the liquid crystal display device can be greatly saved, and productivity can be improved. In addition, the equipment used for the ultraviolet irradiation in the first stage is expensive, and the time required for the irradiation can be reduced, so that the use efficiency of the irradiation equipment can be improved, the cost of the input equipment can be reduced, and the production cost can be reduced. After the first-stage light irradiation (UV 1) is completed, the second-stage light irradiation (UV 2) is performed, and the light used in UV2 includes, for example, ultraviolet light. The use of ultraviolet light in the UV2 stage, which has a smaller irradiance than the ultraviolet light in the UV1 stage, enables slow complete polymerization of the liquid crystal compound that has not undergone polymerization, thereby further reducing the residual of RM in the liquid crystal composition. And because of the slow polymerization, the process does not have an effect on the pretilt angle that has already been formed.
Preferably, the compound of formula I is selected from the group consisting of compounds of formulas I-1 to I-13 described below,
wherein, the liquid crystal display device comprises a liquid crystal display device,
L 11 、L 22 、L 33 、L 44 each 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, or a fluorine-substituted alkyl groupAlkoxy or halogen with 1-5C atoms;
n 11 、n 33 、n 44 each independently represents 0, 1, 2, 3 or 4;
n 22 represents 0, 1 or 2;
p represents Or->
Sp 1 、Sp 2 、Sp 3 Each 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 Sp is 1 、Sp 2 Any one or more of the non-adjacent-CH groups in the radicals shown 2 Can optionally be substituted by-O-, -S-, -CO-, -CH 2 O-、-OCH 2 -, -COO-, -OOC-or an acrylate group.
Preferably, the compound of formula I is selected from the group consisting of compounds of formulas I-1-1 to I-1-4 described below,
in a second aspect of the present invention, there is provided a liquid crystal composition comprising the compound of the first aspect of the present invention described above.
The liquid crystal composition according to an embodiment of the present invention contains the compound represented by formula I. The liquid crystal composition may contain a liquid crystal compound other than the compound represented by formula I and other additive materials. The compounds of formula I are added to liquid crystal compositions and, after pouring into a display element, the liquid crystal molecules can be brought to a pretilt angle by UV photopolymerization or crosslinking under a voltage applied between the electrodes. The liquid crystal composition containing the compound shown in the formula I has the advantages of less RM residues, high conversion efficiency, low viscosity, quick response, moderate dielectric anisotropy delta epsilon, 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, R 1 、R 2 Each 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, the number base positions of the fluorine substitution are not limited;
each independently represents->
In the formula III, R 3 、R 4 Each independently represents an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 10 carbon atoms, a chain alkoxy group or a cyclic 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, R 3 、R 4 Any one or more non-adjacent-CH(s) 2 Can optionally be cyclopentylene, cyclo-yleneButyl or cyclopropyl ene substitution;
Z 1 、Z 2 each independently represents a single bond, -CH 2 CH 2 -or-CH 2 O-；
Each independently represents->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. Lower rotational viscosity is more advantageous 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 regulated by the compound shown in the formula III.
R as in the aforementioned formula III 3 、R 4 One or more non-adjacent-CH in the alkyl group having 1 to 10 carbon atoms 2 Examples of the group substituted with a cyclopropylene group, a cyclobutylene group or a cyclopentylene group include a cyclopropyl group, a cyclobutylene group, a cyclopentyl group, a methylcyclopropylene group, an ethylcyclopropylene group, a propylcyclopropylene group, an isopropylcyclopropylene group, a n-butylcyclopropylene group, an isobutylcyclopropylene group, a tert-butylcyclopropylene group, a methylcyclobutylene group, an ethylcyclobutylene group, a propylcyclobutylene group, an isopropylcyclobutylene group, a n-butylcyclobutylene group, an isobutylcyclobutylene group, a tert-butylcyclobutylene group, a methylcyclopentylene group, an ethylcyclopentylene group, a propylcyclopentylene group, an isopropylcyclopentylene group, a n-butylcyclopentylene group, an isobutylcyclopentylene group and the like. R is R 3 、R 4 Among the groups shown, cyclopropyl, cyclobutyl or cyclopentyl are preferable from the viewpoints of the rotational viscosity, solubility and clearing point of the liquid crystal compound.
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 100%, and the percentage of the ratio between the mass of the compound shown in the formula I and the total mass of the other compounds is shown as the mass fraction of the compound shown in the formula I in the liquid crystal composition. If the liquid crystal composition only comprises 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%, and the percentage of the ratio between the addition amount of the compound shown in the formula I and 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 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II and 20 to 60 percent of compound shown in 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 according to mass percentage.
Preferably, the one or more compounds of formula II are selected from the group consisting of compounds of formulas II-1 to II-17,
preferably, the one or more compounds of formula III are selected from the group consisting of compounds of formulas III-1 to III-15,
wherein R in the compounds of the formulae III-1 to III-15 3 、R 4 R in the compound represented by the formula III 3 、R 4 Each 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 fluorineSubstituted alkenyloxy having 3 to 8 carbon atoms; wherein R is 3 、R 4 Any one or more of the non-adjacent-CH groups in the radicals shown 2 Optionally substituted with cyclopentylene, cyclobutylene or cyclopropyl ene.
In some embodiments, the liquid crystal composition of the present invention may preferably further comprise one or more compounds of formula IV,
wherein R is 5 、R 6 Each 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 5 、R 6 Any one or more non-adjacent-CH(s) 2 Optionally substituted with cyclopentylene, cyclobutylene or cyclopropyl ene; w represents O, S or-CH 2 O-。
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 beneficial to reducing the driving voltage of a device.
Preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III and 1 to 15 percent of compound shown in 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 one or more compounds of formula IV are selected from the group consisting of compounds of formulas IV-1 to IV-10,
wherein R is 51 、R 61 An alkyl group having 1 to 6 carbon atoms;
in some embodiments, the liquid crystal composition of the present application may further comprise one or more compounds represented by formula V,
wherein R is 7 、R 8 Each 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 represents->Or->
Preferably, the one or more compounds of formula V are selected from the group consisting of compounds of formulas V-1 to V-4,
wherein R is 71 、R 81 Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; wherein the alkenyl group having 2 to 6 carbon atoms includes, for example, vinyl, 2-propenyl, or 3-pentylAlkenyl groups; r is R 82 An alkoxy group having 1 to 5 carbon atoms;
preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III and 1 to 30 percent of compound shown in a formula V;
preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III and 5 to 20 percent of compound shown in a formula V.
Preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III, 1 to 15 percent of compound shown in a formula IV and 1 to 30 percent of compound shown in a formula V;
Preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III, 2 to 10 percent of compound shown in a formula IV and 5 to 20 percent of compound shown in a formula V.
The compounds of formula V have a high clearing point and elastic constant, in particular the splay elastic constant K 33 Is beneficial to improving the parameter performance of the liquid crystal composition.
Preferably, the liquid crystal composition of the present invention may further comprise, in some embodiments, one or more compounds represented by formula VI,
wherein R is 9 、R 10 Each 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 alkenyl groupAn alkenyloxy group having 3 to 8 carbon atoms;
representation->Or->
F 1 、F 2 、F 3 Each independently represents H or F, and F 2 、F 3 And F is not the same time.
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 is 9 、R 10 Each independently preferably represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
The compounds of formulas VI-1 to VI-3 have a high clearing point, typically above 200℃, which can more significantly enhance the clearing point of the liquid crystal composition of the invention.
Preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III and 1 to 10 percent of compound shown in a formula VI;
preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III and 1 to 10 percent of compound shown in a formula VI;
preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III, 1 to 15 percent of compound shown in a formula IV and 1 to 10 percent of compound shown in a formula VI;
preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III, 2 to 10 percent of compound shown in a formula IV and 2 to 5 percent of compound shown in a formula VI.
Preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III, 1 to 30 percent of compound shown in a formula V and 1 to 10 percent of compound shown in a formula VI;
preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III, 5 to 20 percent of compound shown in a formula V and 2 to 5 percent of compound shown in a formula VI.
Preferably, the liquid crystal composition comprises, in mass percent: 0.01 to 1 percent of compound shown in a formula I, 15 to 60 percent of compound shown in a formula II, 20 to 60 percent of compound shown in a formula III, 1 to 15 percent of compound shown in a formula IV, 1 to 30 percent of compound shown in a formula V and 1 to 10 percent of compound shown in a formula VI;
preferably, the liquid crystal composition comprises, in mass percent: 0.03 to 0.2 percent of compound shown in a formula I, 20 to 40 percent of compound shown in a formula II, 30 to 50 percent of compound shown in a formula III, 2 to 10 percent of compound shown in a formula IV, 5 to 20 percent of compound shown in a formula V and 2 to 5 percent of compound shown in a formula VI.
In the liquid crystal composition of the present invention, various functional dopants may be added, and when the dopants are contained, the content of the dopants is preferably 0.01 to 1% by mass based on the liquid crystal composition, and examples of the dopants include antioxidants, ultraviolet absorbers, and chiral agents.
Examples of the antioxidant and the 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 element comprising the compound or the liquid crystal composition, wherein the display element is an active matrix display element or a passive matrix display element.
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 an IPS-TFT liquid crystal display component.
The liquid crystal display element= containing the compound or the liquid crystal composition has the characteristics of wider nematic phase temperature range, proper or higher birefringence anisotropy delta n, less RM residue, high conversion efficiency and high voltage retention rate, can effectively avoid the problem of afterimage, can effectively shorten the preparation process and improve the production efficiency.
The structure of the liquid crystal display device of the present invention is not limited as long as the compound of the present invention represented by the formula I is contained in the liquid crystal composition used in the liquid crystal display device, and a person skilled in the art can select a suitable structure of the liquid crystal display device according to the desired performance.
As an embodiment of the liquid crystal display of the present invention, for example, the following structure is given: the liquid crystal display device 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 opposite to each other, an alignment layer is arranged on one side, close to the liquid crystal composition, of the first substrate and the second substrate, a common electrode is arranged on the first substrate, a pixel electrode is arranged on the second substrate, and spacers are scattered between the first substrate and the second substrate.
As a method for manufacturing the liquid crystal display of the present invention, a person skilled in the art can select an appropriate method to manufacture according to common knowledge in the art. As an example of the method for producing a liquid crystal display of the present invention, for example, a production method comprising the steps of:
uniformly coating alignment materials on the surfaces of the first substrate and the second substrate, wherein polyimide can be selected as the alignment materials, and heating and curing the uniformly coated alignment materials at the heating temperature of 210-250 ℃ to form an alignment layer;
Dispersing spacers on the surface of the second substrate, coating frame glue along the edge of the first substrate, and curing at 100-150 ℃;
the first substrate and the second substrate are oppositely arranged and are bonded to form a structure with an interlayer space;
and injecting the liquid crystal composition into an interlayer space between the first substrate and the second substrate, sealing and curing, so that the liquid crystal composition is sealed between the first substrate and the second substrate, and simultaneously carrying out power-up and ultraviolet irradiation. The ultraviolet light irradiation is divided into two stages of first stage ultraviolet light irradiation (UV 1) and second stage ultraviolet light irradiation (UV 2). In the UV1 stage, the ultraviolet wavelength is 360-370 nm, and the ultraviolet irradiance is 60-72 mw/cm 2 . The time of irradiation with ultraviolet light may be, for example, 50 to 65 seconds, and preferably 50 to 60 seconds.
After the completion of the first-stage light irradiation, the second-stage light irradiation (UV 2) is performed, and the light used for UV2 includes, for example, ultraviolet light. The second stage of ultraviolet irradiation (UV 2) has an ultraviolet wavelength of, for example, 360nm to 370nm, and the ultraviolet irradiance during the UV2 stage is, for example, 3 to 8mw/cm 2 . By using such irradiance, the compound represented by the formula I, which is not polymerized, can be slowly and completely polymerized, and the conversion rate of the polymerizable compound is improved, so that no residue of the polymerizable compound exists in the liquid crystal composition. And because of the slow polymerization, the process does not have an effect on the pretilt angle that has already been formed. The ultraviolet light irradiation time in the UV2 stage may be, for example, 100 to 150 minutes.
The beneficial effects of the utility model are as follows:
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 residue in a liquid crystal system is less, and the deterioration influence of impurities on display can be effectively reduced. 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 in the first stage from 75-100 s to 50-65 s, reduces the afterimage problem caused by uneven diffusion, has high conversion rate, can realize quick response, has moderate dielectric anisotropy delta epsilon and moderate optical anisotropy delta n, and has high stability to heat and light.
The liquid crystal display element 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 afterimage, can effectively shorten the preparation process, and improves the production efficiency.
Drawings
The following describes the embodiments of the present utility model in further detail with reference to the drawings.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the compound I-1-1 in example 1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the compound I-1-2 in example 2.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the compound I-1-3 in example 3.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the compound I-1-4 in example 4.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described 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 that this invention is not limited to the details given herein.
In the invention, the preparation method is a conventional method unless specified otherwise, the raw materials used can be obtained from the disclosed commercial path unless specified otherwise, the percentages refer to mass percentages, the temperature is in degrees centigrade (DEG C), the liquid crystal compound is also a liquid crystal monomer, and the specific meanings and testing conditions of other symbols are as follows:
cp represents a liquid crystal clearing point (DEG C), and is tested by DSC quantification;
Δn represents optical anisotropy, Δn=n e -n o Wherein n is o Refractive index of ordinary ray, n e The refractive index of the extraordinary ray is 25+/-2 ℃ and is measured by an Abbe refractometer at 589 nm;
Delta epsilon represents dielectric anisotropy, delta epsilon=epsilon-epsilon, wherein epsilon is the dielectric constant parallel to the molecular axis, epsilon is the dielectric constant perpendicular to the molecular axis, and the test condition is 25+/-0.5 ℃ and 20-micrometer parallel box, INSTEC is an ALCT-IR1 test;
VHR represents a voltage holding ratio (%), and the test conditions were 20±2 ℃, voltage ±5V, pulse width 10ms, and voltage holding time 16.7ms. The test equipment is a TOYO Model6254 liquid crystal performance comprehensive tester;
gamma 1 represents rotational viscosity (mPas) under the test conditions of 25+ -0.5deg.C, 20 μm parallel box, INSTEC: ALCT-IR1 test.
The preparation method of the liquid crystal composition comprises the following steps: and weighing all the liquid crystal monomers according to a certain proportion, putting the liquid crystal monomers into a stainless steel beaker, putting the stainless steel beaker with all the liquid crystal monomers on a magnetic stirring instrument, 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 on the surfaces of a first substrate and a second substrate, wherein polyimide can be selected as the alignment materials, and heating and curing the uniformly coated alignment materials to a heating temperature of 230 ℃ to form an alignment layer; secondly, dispersing 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 bonded to form a structure with an interlayer space; and finally, injecting the liquid crystal composition into an interlayer space between the first substrate and the second substrate, sealing and curing, so that the liquid crystal composition is sealed between the first substrate and the second substrate, and simultaneously carrying out power-up and ultraviolet irradiation. The ultraviolet irradiation is divided into two stages, including a first stage ultraviolet irradiation (UV 1) and a second stage ultraviolet irradiation (UV 2). In UV1 stage, at ultraviolet wavelength 365nm with irradiance of 64mw/cm 2 The irradiation time of ultraviolet light is controlled so that the liquid crystal molecules form a pretilt angle of about 89 ° (usually, about 50% RM conversion is required). The higher the RM conversion, the shorter the irradiation time of the ultraviolet light. After the completion of the first-stage light irradiation, the second-stage light irradiation (UV 2) was performed, wherein ultraviolet light having a wavelength of 365nm was used for UV2, and irradiance was 5mw/cm 2 The light irradiation time is 100-150min.
The conversion of RM is calculated as:
the structures of the liquid crystal monomers used in the examples of the present invention are represented by codes, and the codes of the liquid crystal ring structures, the terminal groups and the linking groups are represented by the following tables 1 and 2.
Table 1: corresponding code of ring structure
Table 2: corresponding codes of end groups and linking groups
Examples:
the code is CC-Cp-V1; />
The code is PGP-Cpr1-2;
the code is thatCPY-2-O2；
The code is CCY-3-O2;
the code is COY-3-O2;
the code is CCOY-3-O2; />The code is Sb-Cp1O-O4;
the code is Sc-Cp1O-O4.
The compounds of formula I can be prepared by the following illustrative synthetic routes
In the formula I, the compound of the formula I,
each independently represents a monocyclic or condensed ring structure having 4 to 10 carbon atoms;
L 1 、L 2 each independently represents H, halogen, alkyl having 1 to 25 carbon atoms, alkoxy having 1 to 25 carbon atoms, alkenyl having 2 to 25 carbon atoms, wherein one or more non-adjacent-CH 2 Can optionally be covered with-O-; -S-, -CO-, -CO-O-, -O-CO-O-substitution, such that-O-and/or-S-are not directly connected to each other and one or more H atoms may each be optionally substituted with halogen.
r1, r2 each independently represent 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2 or 3;
Sp 1 、Sp 2 、Sp 3 each independently represents a single bond, an alkenyl group having 2 to 25 carbon atoms, - (CH) 2 )p 1 -、-O-(CH 2 )p 1 -、-O-CO-(CH 2 )p 1 -or-CO-O- (CH) 2 )p 1 -，p 1 Represents 2, 3, 4, 5 or 6; wherein the Sp is 1 、Sp 2 、Sp 3 One or more non-adjacent-CH(s) 2 -may optionally be substituted with-O-, -S-, -CO-O-, -O-CO-O-, acrylate groups in such a way that-O-and/or-S-are not directly connected to each other, and one or more H atoms may each optionally be substituted with F or Cl;
p represents a polymerizable group, and P may be Or->
Example 1
The structural formula of the compound is shown as the following formula I-1-1:
the preparation route is as follows:
the specific operation flow of the preparation is as follows:
the first step: preparation of intermediate 3
Into a 1L three-necked flask, 0.1mol of Compound 1, 0.1mol of Compound 2 and 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") were charged, and the mixture was reacted at room temperature under the protection of nitrogen for 2 hours in 0.5L of tetrahydrofuran. The solid was filtered off, the organic phase was washed with 0.2L water, the organic phase was passed through a 50g silica gel column, and 0.1L toluene was washed, and dried to give intermediate 3.
And a second step of: compound I-1
Into a 1L three-necked flask, 0.02mol of the intermediate 3,0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran and 0.02mol of DCC were charged, and the reaction was carried out at room temperature under nitrogen atmosphere for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of ethyl acetate multiplied by 2, mixing the organic phases, washing with 500ml of salt water multiplied by 2, drying with anhydrous sodium sulfate, evaporating to dryness, taking 30g of silica gel, 3 times of petroleum ether (90-120 ℃) to pass through a column, 2 times of petroleum ether (90-120 ℃) to wash the column, evaporating to dryness and 2 times of ethanol to recrystallize to obtain a compound I-1-1, wherein the nuclear magnetic resonance hydrogen spectrum 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:
the preparation route is as follows:
the specific operation flow of the preparation is as follows:
the first step: preparation of intermediate 6
Into a 1L three-necked flask, 0.1mol of Compound 5, 0.1mol of Compound 2 and 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") were charged, and the mixture was reacted at room temperature under the protection of nitrogen for 2 hours in 0.5L of tetrahydrofuran. The solid was filtered off, the organic phase was washed with 0.2L water, the organic phase was passed through a 50g silica gel column, 0.1L toluene column, and dried by spin to give intermediate 6.
And a second step of: preparation of Compound I-1-2
Into a 1L three-necked flask, 0.02mol of the intermediate 6,0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC and nitrogen were charged, and the reaction was carried out at room temperature for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of ethyl acetate multiplied by 2, mixing the organic phases, washing with 500ml of salt water multiplied by 2, drying with anhydrous sodium sulfate, evaporating to dryness, taking 30g of silica gel, 3 times of petroleum ether (90-120 ℃) to pass through a column, 2 times of petroleum ether (90-120 ℃) to wash the column, evaporating to dryness and 2 times of ethanol to recrystallize to obtain a compound I-1-2, wherein a nuclear magnetic resonance hydrogen spectrum 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:
the preparation route is as follows:
the specific operation flow of the preparation is as follows:
the first step: preparation of intermediate 8
Into a 1L three-necked flask, 0.1mol of Compound 7, 0.1mol of Compound 2 and 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC") were charged, and the mixture was reacted at room temperature under the protection of nitrogen for 2 hours in 0.5L of tetrahydrofuran. The solid was filtered off, the organic phase was washed with 0.2L water, the organic phase was passed through a 50g silica gel column, and 0.1L toluene was washed, and dried to give intermediate 8.
And a second step of: preparation of Compound I-1-3
Into a 1L three-necked flask, 0.02mol of the intermediate 8,0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC and nitrogen were charged, and the reaction was carried out at room temperature for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of ethyl acetate multiplied by 2, mixing the organic phases, washing with 500ml of salt water multiplied by 2, drying with anhydrous sodium sulfate, evaporating to dryness, taking 30g of silica gel, 3 times of petroleum ether (90-120 ℃) to pass through a column, 2 times of petroleum ether (90-120 ℃) to wash the column, evaporating to dryness and 2 times of ethanol to recrystallize to obtain a compound I-1-3, wherein a nuclear magnetic resonance hydrogen spectrum 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:
the preparation route is as follows:
The specific operation flow of the preparation is as follows:
the first step: preparation of intermediate 10
Putting into a 1L three-mouth bottle; 0.02mol; 0.02mol of Compound 2, 0.1mol of dicyclohexylcarbodiimide (hereinafter referred to as "DCC"), 0.5L of tetrahydrofuran, and 2 hours at room temperature under nitrogen. The solid was collected, the organic phase was washed with 0.2L of water, the organic phase was passed through a 50g silica gel column, and 0.1L of toluene was washed with water, and dried to give intermediate 10.
And a second step of: preparation of Compounds I-1-4
Into a 1L three-necked flask, 0.02mol of the intermediate 10,0.02mol of cyclopentenecarboxylic acid, 0.5L of tetrahydrofuran, 0.02mol of DCC and nitrogen were placed, and the reaction was carried out at room temperature for 3 hours. Adding 500ml of water, separating, extracting the water phase with 100ml of ethyl acetate multiplied by 2, mixing the organic phases, washing with 500ml of salt water multiplied by 2, drying with anhydrous sodium sulfate, evaporating to dryness, taking 30g of silica gel, 3 times of petroleum ether (90-120 ℃) to pass through a column, 2 times of petroleum ether (90-120 ℃) to wash the column, evaporating to dryness and recrystallizing 2 times of ethanol to obtain a compound I-1-4, wherein a nuclear magnetic resonance hydrogen spectrum 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 100%, and the percentage of the ratio between the mass of the compound shown in the formula I and the total mass of the other compounds is shown 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 composition are shown in Table 3 below.
Table 3: formulation and corresponding Properties of the liquid Crystal composition of example 5
In the liquid crystal composition of example 5, the total mass of the compounds represented by the formula II and the formula III was 100%, and the percentage of the ratio between the amount of the compound represented by the formula I-1-1 to the total mass of the compounds represented by the formula II and the formula III was 1% which is the mass fraction of the compound represented by the formula I-1-1.
Example 6:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 4 below.
Table 4: formulation and corresponding Properties of the liquid Crystal composition of example 6
In the liquid crystal composition of example 6, the total mass of the compounds represented by the formula II, the formula III and the formula IV was 100%, and the percentage of the ratio between the amount of the compound represented by the formula I-1-2 to the total mass of the compounds represented by the formula II, the formula III and the formula IV was 0.1%.
Example 7:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 5 below.
Table 5: formulation and corresponding Properties of the liquid Crystal composition of example 7
In the liquid crystal composition of example 7, the total mass of the compounds represented by the formulas II, III and V was 100%, and the percentage of the ratio between the amount of the compound represented by the formula I-1-3 to the total mass of the compounds represented by the formulas II, III and V was 0.03%.
Example 8:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 6 below.
Table 6: formulation and corresponding Properties of the liquid Crystal composition of example 8
In the liquid crystal composition of example 8, the total mass of the compounds represented by the formulas II, III, IV and V was 100%, and the percentage of the ratio of the amount of the compound represented by the formula I-1-4 to the total mass of the compounds represented by the formulas II, III, IV and V was 0.2%.
Example 9:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 7 below.
Table 7: formulation and corresponding Properties of the liquid Crystal composition of example 9
/>
In the liquid crystal composition of example 9, the total mass of the compounds represented by the formulas II, III, IV, V and VI was 100%, and the percentage of the ratio between the amount of the compound represented by the formula I-1-4 to the total mass of the compounds represented by the formulas II, III, IV, V and VI was 0.15% of the mass fraction of the compound represented by the formula I-1-4.
Example 10:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 8 below.
Table 8: formulation and corresponding Properties of the liquid Crystal composition of example 10
/>
In the liquid crystal composition of example 10, the total mass of the compounds represented by the formulas II, III, IV and VI 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 formulas II, III, IV and VI was 0.5% as the mass fraction of the compound represented by the formula I-1-4.
Example 11:
the formulation and corresponding properties of the liquid crystal composition are shown in Table 9 below.
Table 9: formulation and corresponding Properties of the liquid Crystal composition of example 11
In the liquid crystal composition of example 11, the total mass of the compounds represented by the formulas 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 formulas II, III, IV and V was 0.13%.
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
/>
In the liquid crystal composition of example 12, the total mass of the compounds represented by the formulas 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 formulas II, III, IV and V was 0.6%.
Comparative example 1:
the compound of example 8I-1-4 was replaced with the existing compound of formula RM-1 as Reactive Mesogen (RM),
the formulation and corresponding properties of the liquid crystal composition are shown in Table 11 below.
Table 11: formulation and corresponding Properties of the liquid Crystal composition of comparative example 1
The total mass of the compounds represented by formula II, formula III, formula IV and formula V in the liquid crystal composition of comparative example 1 was 100%, and the percentage of the ratio between the amount of the compound represented by formula RM-1 to the total mass of the compounds represented by formula II, formula III, formula IV and formula V was 0.2% which is the mass fraction of the compound represented by formula I-1-4.
Example 8 was poured into the same test cassette as comparative example 1, and a voltage of 15V was applied to both sides of the test cassette while irradiating ultraviolet light. The ultraviolet irradiation is divided into two stages, UV1 stage and UV2 stage. The UV1 stage adopts the wavelength of 365nm and irradiance of 64mw/cm 2 Is irradiated by ultraviolet light of the above-mentioned formula. To obtain a pretilt angle of around 89 deg., a RM conversion of around 50% is usually required. The UV1 stage ultraviolet irradiation under the same conditions requires 47s for 50% conversion of the compound of formula I-1-4 and 80s for 50% conversion of the compound of formula RM-1. Therefore, the compound shown in the formula I-1-4 is adopted as the Reactive Mesogen (RM) to effectively shorten the preparation process of the liquid crystal display element and improve the production efficiency.
The conversion of RM is calculated as:
After the UV1 stage, a UV2 stage is carried out, wherein the wavelength of the UV2 stage is 365nm, and the irradiance is 5mw/cm 2 Is irradiated for 150min to polymerize RM completely as much as possible. After the UV2 stage, the residual amount of the compound represented by the formula I-1-4 was 50ppm, and the residual amount of the compound represented by the formula RM-1 was 85ppm. The RM residual quantity is small, and the problem of afterimage can be effectively avoided.
Comparative example 2:
the compound of example 10I-1-2 was replaced with the existing compound of formula RM-2 as Reactive Mesogen (RM),
the formulation and corresponding properties of the liquid crystal composition are shown in Table 12 below.
Table 12: formulation and corresponding Properties of comparative example 2 liquid Crystal composition
The total mass of the compounds represented by the formulas II, III, IV and VI in the liquid crystal composition of comparative example 2 was 100%, and the percentage of the ratio between the amount of the compound represented by the formula RM-2 added and the total mass of the compounds represented by the formulas II, III, IV and VI was 0.5% which is the mass fraction of the compound represented by the formulas I-1 to 4.
Example 10 and comparative example 2 were poured into the same test cell, and a 15V voltage was applied to both sides of the test cell while uv light was irradiated. The ultraviolet irradiation is divided into two stages, UV1 stage and UV2 stage. The UV1 stage adopts the wavelength of 365nm and irradiance of 64mw/cm 2 Is irradiated by ultraviolet light of the above-mentioned formula. To obtain a pretilt angle of around 89℃the compound of formula I-1-2 needs to be irradiated for 55s, whereas the compound of formula RM-2 needs to be irradiated for 83s. From this, it can be seen thatThe compound shown in the formula I-1-2 is adopted as the Reactive Mesogen (RM) so as to effectively shorten the preparation process of the liquid crystal display element and improve the production efficiency.
After the UV1 stage, a UV2 stage is carried out, wherein the wavelength of the UV2 stage is 365nm, and the irradiance is 5mw/cm 2 Is irradiated for 120min to polymerize RM completely as much as possible. After the UV2 stage, the residual amount of the compound represented by the formula I-1-2 was 50ppm, and the residual amount of the compound represented by the formula RM-2 was 85ppm. The RM residual quantity is small, and the problem of afterimage can be effectively avoided.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

1. A compound, which is characterized in that the structural formula of the compound is shown as a formula I-1:
in the formula I-1, L 11 、L 22 Each independently represents H, halogen or an alkoxy group having 1 to 5 carbon atoms;
n 11 represents 0 or 1;
n 22 represents 0;
p represents
Sp 1 、Sp 2 、Sp 3 Each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms; wherein the Sp is 2 Any one or more of the non-adjacent-CH groups in the radicals shown 2 Optionally substituted by-OOC-.
2. A compound according to claim 1, wherein the compound is selected from the group consisting of compounds represented by the following formulas I-1-1 to I-1-3,
3. a liquid crystal composition comprising one or more compounds according to any one of claims 1 to 2.
4. The liquid crystal composition according to claim 3, wherein the liquid crystal composition further comprises one or more compounds represented by the following formulas II-1 to II-17 and one or more compounds represented by the following formulas III-1 to III-15,
wherein R in the compounds of the formulae III-1 to III-15 3 、R 4 Each 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 is 3 、R 4 Any one or more of the non-adjacent-CH groups in the radicals shown 2 Optionally substituted with cyclopentylene, cyclobutylene or cyclopropyl ene.
5. The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises, in mass%, 0.01 to 1% of the compound represented by formula I-1, 15 to 60% of the compound represented by formula II-1 to formula II-17, and 20 to 60% of the compound represented by formula III-1 to formula III-15.
6. The liquid crystal composition according to claim 4, wherein the liquid crystal composition comprises, in mass%, 0.03 to 0.2% of the compound represented by formula I-1, 20 to 40% of the compound represented by formula II-1 to formula II-17, and 30 to 50% of the compound represented by formula III-1 to formula III-15.
7. The liquid crystal composition according to claim 3, wherein the liquid crystal composition further comprises one or more compounds represented by the formulae IV-1 to IV-10,
wherein R is 51 、R 61 Represents an alkyl group having 1 to 6 carbon atoms.
8. The liquid crystal composition according to claim 3, wherein the liquid crystal composition further comprises one or more compounds represented by the formulae V-1 to V-4,
wherein R is 71 、R 81 Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms; r is R 82 An alkoxy group having 1 to 5 carbon atoms.
9. A liquid crystal composition according to claim 3, further comprising one or more compounds of the formulae VI-1 to VI-3,
wherein R is 9 、R 10 Each independently represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
10. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 3 to 9; the liquid crystal display component is an active matrix display component or a passive matrix display component.
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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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