CN111518570A - Liquid crystal composition, liquid crystal display element and liquid crystal display - Google Patents
Liquid crystal composition, liquid crystal display element and liquid crystal display Download PDFInfo
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- CN111518570A CN111518570A CN202010350544.6A CN202010350544A CN111518570A CN 111518570 A CN111518570 A CN 111518570A CN 202010350544 A CN202010350544 A CN 202010350544A CN 111518570 A CN111518570 A CN 111518570A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 197
- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 98
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003342 alkenyl group Chemical group 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 12
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 9
- 125000004979 cyclopentylene group Chemical group 0.000 claims description 9
- 125000004980 cyclopropylene group Chemical group 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 3
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 206010047571 Visual impairment Diseases 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 7
- 230000006750 UV protection Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 45
- 230000000875 corresponding effect Effects 0.000 description 26
- 238000009472 formulation Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 230000032683 aging Effects 0.000 description 20
- -1 methylcyclopropylidene group Chemical group 0.000 description 18
- 230000004044 response Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000006872 improvement Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 1
- 101100263680 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) VHR2 gene Proteins 0.000 description 1
- 101000803389 Viola hederacea Root cyclotide 1 Proteins 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
-
- 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
-
- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
Abstract
The invention relates to a liquid crystal composition, a liquid crystal display element comprising the liquid crystal composition and a liquid crystal display, belonging to the field of liquid crystal display. The liquid crystal composition comprises one or more compounds shown as a formula I and one or more compounds shown as a formula II with the mass ratio of 0.5-20%, can improve the afterimage defect, and has good ultraviolet resistance, high temperature resistance and good low-temperature solubility. In addition, the liquid crystal composition of the present invention has moderate optical anisotropy Δ n, and lower viscosity.
Description
Technical Field
The invention belongs to the technical field of liquid crystal display, and particularly relates to a liquid crystal composition and a liquid crystal display element or a liquid crystal display containing the liquid crystal composition.
Background
With the development of Display technology, flat panel Display devices such as Liquid Crystal Displays (LCDs) 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 become the mainstream of Display devices. The demand for the liquid crystal flat panel display is increasing. Therefore, higher requirements are also placed on the quality characteristics of the liquid crystal materials used in liquid crystal flat panel displays.
In the process of using the liquid crystal display, the liquid crystal composition is constantly influenced by light radiation and heat radiation, and meanwhile, in the process of manufacturing the liquid crystal display or the liquid crystal composition, the liquid crystal composition is inevitably contacted by light and heat, and the light and heat contact, especially the light and high temperature in an ultraviolet band, can cause that liquid crystal molecules are negatively influenced on the aspect of impurities, so that the change of anchoring capability of the liquid crystal molecules is influenced, and further the display effect of the liquid crystal display is influenced.
Therefore, it is a problem to be solved in the art to provide a liquid crystal composition having good uv and high temperature resistance and capable of improving the afterimage defect.
Disclosure of Invention
In order to solve the technical problems in the prior art, the inventors of the present invention have conducted intensive studies and found that the liquid crystal composition of the present invention has a low ratio of rotational viscosity to splay elastic constant, good low temperature solubility, and good uv and high temperature resistance, and can improve the afterimage defect.
The invention also provides a liquid crystal display element or a liquid crystal display containing the liquid crystal composition.
Specifically, the present invention comprises the following:
in a first aspect of the invention, a liquid crystal composition is provided, which comprises one or more compounds shown as formula I, 0.5-20% by mass of one or more compounds shown as formula II,
in the formula I, Z1Represents an alkylene group having 1 to 20 carbon atoms, any of the alkylene groupsMeaning one or more hydrogens are optionally substituted with halogen, any one or more non-adjacent-CH2-optionally substituted by-O-;
in the formula II, R1Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms.
In another aspect of the present invention, there is provided a liquid crystal display element or a liquid crystal display comprising the liquid crystal composition of the present invention, the liquid crystal display element being an active matrix display element or a passive matrix display element, and the liquid crystal display being an active matrix display or a passive matrix display.
The liquid crystal composition has good ultraviolet resistance, high temperature resistance and low-temperature solubility, and can improve the defect of afterimage. In addition, the liquid crystal composition has moderate optical anisotropy delta n and lower ratio of rotational viscosity to splay elastic constant.
The liquid crystal display element and the liquid crystal display have the advantages of no residual image or unobvious residual image, high response speed, high voltage holding ratio, good ultraviolet resistance and high temperature resistance, and low threshold voltage.
Detailed Description
[ liquid Crystal composition ]
The liquid crystal composition of the present invention comprises: comprises one or more compounds shown as a formula I, 0.5-20% of one or more compounds shown as a formula II by mass ratio,
in the formula I, Z1Represents an alkylene group having 1 to 20 carbon atoms, wherein any one or more hydrogen atoms in the alkylene group are optionally substituted by halogen, and any one or more non-adjacent-CH2-optionally substituted by-O-;
in the formula II, R1Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a C1Is an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms.
Z of the foregoing1The alkylene group having 1 to 20 carbon atoms may be a straight chain or a branched chain. In addition, the aforementioned alkylene group optionally has a ring structure.
In the liquid crystal composition, the combination of the compound shown in the formula I and the compound shown in the formula II with the mass ratio of 0.5-20% is used, so that the liquid crystal composition has good low-temperature solubility, a low ratio of rotational viscosity to splay elastic constant, good ultraviolet resistance and high-temperature resistance, and can improve the afterimage defect.
Optionally, the one or more compounds of formula I are selected from the group consisting of compounds of formula I1 to formula I13,
optionally, the one or more compounds represented by the formula II are selected from the group consisting of compounds represented by the formulae II 1 to II 4,
the liquid crystal composition of the present invention is preferably a positive dielectric anisotropic liquid crystal composition.
In the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by formula i added to the liquid crystal composition is not particularly limited, and may be 0.001 to 1%, preferably 0.05 to 0.1%, relative to the total amount of other components of the liquid crystal composition excluding the compound represented by formula i; the amount (mass ratio) of the compound represented by the formula II added to the liquid crystal composition is preferably 3 to 10% based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.
The liquid crystal composition of the invention optionally further comprises one or more compounds shown in the following formula III,
in the formula III, R2、R3Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms;
The compound shown in the formula III has the characteristics of low rotational viscosity and good intersolubility with other compounds. The liquid crystal composition of the present invention containing the compound represented by the formula III is advantageous for further improving the response speed of the liquid crystal composition.
The amount (mass ratio) of the compound represented by the formula III added to the liquid crystal composition is not particularly limited, and may be 10 to 70%, preferably 20 to 60%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.
Optionally, the compound shown in the formula III is selected from the group consisting of compounds shown in formulas III 1 to III 16,
the liquid crystal composition of the present invention optionally further comprises one or more compounds represented by the following formula IV in addition to the aforementioned compound represented by the formula II,
in the formula IV, R4Represents a carbon number of 1 to 10An alkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and R4Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z2Represents a single bond, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
X1、X2each independently represents H or F; x3Represents H, F or methyl;
Y1represents-F, -CF3、-OCF3、-OCF2H or-OCH2F；
m represents 0, 1 or 2, and when m represents 2,
may be the same or different.
The compound shown in the formula IV is a positive dielectric anisotropy compound, and the threshold voltage of the liquid crystal composition can be further adjusted by the compound shown in the formula IV.
The amount (mass ratio) of the compound represented by the formula IV added to the liquid crystal composition is not particularly limited, and may be 1 to 50%, preferably 5 to 30%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.
As R in the aforementioned formula IV4One or more non-adjacent-CH in the alkyl with 1-10 carbon atoms2Examples of the group substituted with a cyclopropylene group, a cyclobutylene group or a cyclopentylene group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a methylcyclopropylidene group, an ethylcyclopropylidene group, a propylcyclopropylidene group, an isopropylcyclopropylidene group, a n-butylcyclopropylidene group, an isobutylcyclopropylidene group, a tert-butylcyclopropylidene group, a methylcyclobutylene group, an ethylcyclobutylidene group, a propylcyclobutylidene group, an isopropylidene group, a n-butylidene group, an isobutylcyclobutylidene group, a tert-butylidene group, a methylcyclopentylene group, an ethylcyclopentylidene group, a propylcyclopentylidene group, an isopropylcyclopentylidene group, a n-butylcyclopentylidene group and an isobutylcyclopentylidene group.
Optionally, the one or more compounds shown as the formula IV are selected from the group consisting of compounds shown as formulas IV 1 to IV 25,
r in the formulae IV 1 to IV 254With R in the compound of the formula IV4Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and R4Any one or more-CH of the groups shown2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; (F) in the formulae IV 1 to IV 6 each independently represents H or F; - (O) CF in the formula IV 73represents-CF3or-OCF3。
The liquid crystal composition of the invention optionally further comprises one or more compounds shown as the following formula V,
in formula V, R5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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;
The compounds of the formula V have high clearing point and elastic constants, in particular the splay elastic constant K11The liquid crystal composition of the invention containing the compound shown in the formula V is beneficial to improving the clearing point and the splay elastic constant K of the liquid crystal composition11。
When the compound represented by the formula v is contained in the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by the formula v added to the liquid crystal composition is not particularly limited, and may be 1 to 30%, preferably 5 to 20%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula i.
Optionally, the compound shown in the formula V is selected from the group consisting of compounds shown in formulas V1 to V4,
wherein R is51、R61Each 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 and a 3-pentenyl group. R62Represents an alkoxy group having 1 to 5 carbon atoms.
The liquid crystal composition of the invention optionally further comprises one or more compounds shown in the formula VI,
in formula VI, R7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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;
F1、F2、F3Each independently represents H or F, and F2、F3Not simultaneously F.
The compounds of formula VI have a high clearing point. The liquid crystal composition contains the compound shown in the formula VI, so that the clearing point of the liquid crystal composition can be remarkably improved.
When the liquid crystal composition of the present invention contains the compound represented by the formula vi, the amount (mass ratio) of the compound represented by the formula vi added to the liquid crystal composition is not particularly limited, and may be 1 to 10%, preferably 2 to 5%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula i.
Optionally, the compound shown in the formula VI is selected from the group consisting of compounds shown in formulas VI 1 to VI 3,
wherein R is71、R81Each independently preferably represents an alkyl group having 2 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
The liquid crystal composition of the present invention optionally further comprises one or more compounds represented by the following formula VII,
in the formula VII, R9、R10Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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, and R9、R10Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z3represents a single bond, -CF2O-、-CH2CH2-or-CH2O-；Z4Represents a single bond, -CH2CH2-or-CH2O-；
q represents 1 or 2, and when q represents 2,
may be the same or different;
n represents 0, 1 or 2, and when n represents 2,
may be the same or different.
The compound shown in the formula VII has a large vertical dielectric constant, the vertical dielectric constant of the liquid crystal composition can be adjusted according to different use conditions, the liquid crystal composition can keep low rotational viscosity, the vertical dielectric constant of the liquid crystal composition is further improved on the premise of slightly sacrificing the response speed, and the transmittance of the liquid crystal composition is improved on the basis of maintaining a certain response speed.
In the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by the formula VII added to the liquid crystal composition is not particularly limited, and may be, for example, 1 to 35%, preferably 5 to 30%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by the formula I.
Optionally, the one or more compounds shown in the formula VII are selected from the group consisting of compounds shown in formulas VII 1 to VII 21,
wherein R is91、R101Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and R91、R101Any one or more of the radicals indicated being unconnected-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene.
The liquid crystal composition of the invention optionally further comprises one or more compounds shown as a formula VIII,
in the formula VIII, R11、R12Each 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, and R11、R12Any one or more non-adjacent-CH2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene; w represents-O-, -S-or-CH2O-。
The compound shown in the formula VIII has a larger vertical dielectric constant compared with the compound shown in the formula VII, and the larger vertical dielectric constant can be obtained by adding a small amount of the compound shown in the formula VIII, so that the transmittance of the liquid crystal composition is further improved.
In the liquid crystal composition of the present invention, the amount (mass ratio) of the compound represented by formula viii added to the liquid crystal composition is not particularly limited, and may be 1 to 15%, preferably 2 to 10%, based on the total amount of other components of the liquid crystal composition excluding the compound represented by formula i.
Alternatively, the compound represented by the formula VIII is selected from the group consisting of compounds represented by the formulae VIII 1 to VIII 8,
wherein R is111、R121Each independently represents an alkyl group having 2 to 6 carbon atoms.
In the liquid crystal composition of the present invention, a dopant having various functions may be optionally added, 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.
The antioxidant may be exemplified by the group consisting of,
wherein t represents an integer of 1 to 10.
[ liquid Crystal display element, liquid Crystal display ]
The present invention also relates to a liquid crystal display element or a liquid crystal display comprising the liquid crystal composition of the present invention, wherein the display element is an active matrix display element or a passive matrix display element, and the display is an active matrix display or a passive matrix display.
Optionally, the liquid crystal display element or the liquid crystal display of the invention includes a first substrate and a second substrate, and the first substrate and the second substrate are arranged in parallel relatively. The first substrate comprises a pixel electrode, a first alignment layer is arranged on the pixel electrode, the second substrate comprises a common electrode, and a second alignment layer is arranged on the common electrode. The liquid crystal composition is poured between the first substrate and the second substrate, and a One Drop Fill (ODF) method may be used.
Optionally, the liquid crystal display element or the liquid crystal display comprises an alignment layer formed by a PI with medium and high resistivity. By medium to high resistivity PI is meant a resistivity higher than 1013PI (polyimide) of Ω · m.
The liquid crystal display element and the liquid crystal display provided by the invention have the advantages that no residual image exists or the residual image is not obvious, in addition, the high voltage holding ratio is realized, the ultraviolet resistance and the high temperature resistance are good, and the quick response speed is realized.
The liquid crystal display element and the liquid crystal display of the present invention are not limited in structure as long as they contain the liquid crystal composition of the present invention, and those skilled in the art can select an appropriate structure of the liquid crystal display element and the liquid crystal display according to the desired performance.
Examples
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. 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 is also called 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 ═∥-⊥Wherein, in the step (A),∥is the dielectric constant parallel to the molecular axis,⊥the dielectric constant is perpendicular to the molecular axis, the test conditions are 25 +/-0.5 ℃, 20-micron antiparallel cells, INSTEC is ALCT-CUST-4C test;
VHR represents the voltage holding ratio (%), and the test conditions are 60 +/-2 ℃, voltage +/-5V, pulse width 10ms and voltage holding time 16.7 ms. The testing equipment is a TOYO Model 6254 liquid crystal performance comprehensive tester;
K11for the splay spring constant, the test conditions were: 25 plus or minus 2 ℃, INSTEC is ALCT-CUST-4C, 20 micron parallel box;
γ1expressed as rotational viscosity (mPas) at 25. + -. 0.5 ℃ in 20 μm antiparallel boxes, INSTEC: ALCT-CUST-4C.
Afterimage: the residual image of the liquid crystal display device was evaluated by visually observing the residual level of the fixed pattern in the case of performing uniform display in the full screen, on a 4-scale basis as follows, after displaying the fixed pattern for 1000 hours in the display region:
very good without residue
O very little residue at an acceptable level
The delta is remained at an unallowable level
X remained quite poor.
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 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 liquid crystal monomer structure used in the embodiment of the invention is represented by codes, and the code representation methods of the liquid crystal ring structure, the end group and the connecting group are shown in the following tables 1 and 2.
Table 1: corresponding code of ring structure
Table 2: corresponding codes for end groups and linking groups
Examples are:
Example 1:
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 1
Example 2:
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 2
Example 3:
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 3
Example 4:
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 4
Example 5:
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 5
Example 6:
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 6
Example 7:
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 7
Example 8:
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 8
Liquid crystal compositions obtained by replacing the compound represented by the formula I7 in example 8 with compounds represented by the formulae I2, I6 and I11 in equal amounts were prepared as examples 9, 10 and 11, respectively.
Comparative example 1:
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
In contrast to example 6, the liquid crystal composition of comparative example 1, which did not contain the compound represented by formula I or formula II, used the compound PGUQU-3-F, PGUQU-4-F in place of the compound DPUQU-3-F, DPUQU-4-F in equal amounts.
Comparative example 2:
the formulation and corresponding properties of the liquid crystal compositions are shown in table 12 below.
Table 12: formulation and corresponding Properties of the liquid Crystal composition of comparative example 2
In contrast to example 6, comparative example 2 does not contain the compound of formula I, and the compound of formula T-1 is used in place of the compound of formula I in equal amounts.
Comparative example 3:
the formulation and corresponding properties of the liquid crystal compositions are shown in Table 13 below.
Table 13: formulation and corresponding Properties of the liquid Crystal composition of comparative example 3
In contrast to example 6, in comparative example 3, which does not contain the compound of formula II, the compound DGUQU-3-F, DGUQU-4-F is used in equal amounts instead of the compound DPUQU-3-F, DPUQU-4-F of formula II. Example 6 provides a liquid crystal composition1/K11Comparative example 3 provides a liquid crystal composition γ of 4.71/K11(5.2) response speed of liquid crystal composition and its gamma1/K11Ratio dependent, γ1/K11The smaller the ratio, the faster the response speed, and thus, the liquid crystal composition provided by example 6 has a faster response speed relative to comparative example 3.
Comparative example 4:
the formulation and corresponding properties of the liquid crystal compositions are shown in Table 14 below.
Table 14: formulation and corresponding Properties of the liquid Crystal composition of comparative example 4
Comparative example 4 the compound of formula ii was used in an amount exceeding 20%.
The reliability of the liquid crystal composition can be evaluated by testing the change of VHR by ultraviolet and high temperature aging tests. The smaller the VHR data change before and after the ultraviolet and high temperature test of the liquid crystal composition, the stronger the ultraviolet and high temperature resistance of the liquid crystal composition. Therefore, the stronger the capability of the liquid crystal composition to resist the damage of the external environment in the working process, the higher the reliability of the liquid crystal composition. Therefore, the ultraviolet and high temperature resistance can be judged by comparing the change of VHR data of the liquid crystal compositions provided by each example and comparative example before and after the aging test.
First, before the ultraviolet and high-temperature aging test, VHR data of the liquid crystal composition was measured as initial VHR data, and then, the ultraviolet and high-temperature aging test was performed on the liquid crystal composition, and after the test, VHR data of the liquid crystal composition was measured again.
The aging test is divided into two stages,
the first stage aging test conditions are as follows. Ultraviolet aging test: placing the liquid crystal composition at a wavelength of 365nm and an irradiance of 50mw/cm2Under an ultraviolet lamp, irradiating 5000mJ energy; high-temperature aging test: the liquid crystal composition was placed in an oven at 100 ℃ for 1 hour.
The second stage aging test conditions are as follows. Ultraviolet aging test: the liquid crystal composition is placed under 20000nit backlight for 1000 hours; high-temperature aging test: the liquid crystal composition was placed in an oven at 60 ℃ for 120 hours.
The liquid crystal compositions provided in examples and comparative examples were tested for VHR and afterimage after being subjected to the first-stage and second-stage aging tests, respectively.
The VHR test uses the same liquid crystal test cell. The liquid crystal compositions provided in examples and comparative examples were respectively poured into liquid crystal test cells containing two different PI (polyimide) -forming alignment layers, and an afterimage test was performed. Liquid crystal cell a contains an alignment layer formed of a medium to high resistivity PI, e.g., Nissan SE-7492, Nissan SE-6414, and liquid crystal cell B contains an alignment layer formed of a low resistivity PI, e.g., Nissan SE-5414, JSR AL 16301. The test results are shown in tables 15 and 16 below.
In tables 15 and 16, VHR1 is the test data after the first stage aging test, VHR2 is the test data after the second stage aging test, afterimage a is the afterimage test result of the liquid crystal composition in liquid crystal test cell a, and afterimage B is the afterimage test result of the liquid crystal composition in liquid crystal test cell B.
Table 15: data for testing reliability of examples and comparative examples after first stage aging test
As can be seen from Table 15, the liquid crystal compositions provided in the examples of the present invention have very small VHR decrease after UV and high temperature aging test as compared with the comparative examples 1-2. In addition, the improvement on the afterimage defect is very obvious. Compared with the comparative example 3, after the first-stage aging test, although the residual image improvement effect is consistent when the middle-high resistivity PI liquid crystal test box is used, the residual image improvement effect is better when the low resistivity PI liquid crystal test box is used.
Table 16: data for testing reliability of examples and comparative examples after second stage aging test
As can be seen from Table 16, the liquid crystal compositions provided in the examples have less VHR drop after UV and high temperature aging tests and more significant improvement of the afterimage compared with the comparative examples. In particular, the liquid crystal composition of the example using the compound represented by formula I7 can achieve a better afterimage improvement effect in combination with high-resistivity PI.
As can be seen from comparison between example 6 and comparative example 4, although the VHR changes and the image sticking improvement of the liquid crystal compositions provided in example 6 and comparative example 4 are substantially the same after the two-stage aging test, the liquid crystal composition provided in example 6 has better low-temperature solubility and can be adapted to complete the display work in a lower-temperature environment.
In conclusion, the liquid crystal composition provided by the invention can improve the afterimage defect, has the characteristics of good ultraviolet resistance and high temperature resistance, has good low-temperature solubility, and can be suitable for displaying in a low-temperature environment.
Claims (9)
1. A liquid crystal composition is characterized by comprising one or more compounds shown as a formula I and 0.5-20% by mass of one or more compounds shown as a formula II,
in the formula I, Z1Represents an alkylene group having 1 to 20 carbon atoms, wherein any one or more hydrogen atoms in the alkylene group are optionally substituted by halogen, and any one or more non-adjacent-CH2-optionally substituted by-O-;
in the formula II, R1Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms.
2. The liquid crystal composition of claim 1, further comprising one or more compounds of formula III,
in the formula III, R2、R3Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms;
3. The liquid crystal composition according to any one of claims 1 or 2, further comprising one or more compounds represented by the following formula IV in addition to the compound represented by the formula II,
in the formula IV, R4Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 8 carbon atoms, and R4Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z2Represents a single bond, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、
-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
X1、X2each independently represents H or F; x3Represents H, F or methyl;
Y1represents-F, -CF3、-OCF3、-OCF2H or-OCH2F；
m represents 0, 1 or 2, and when m represents 2,
may be the same or different.
4. The liquid crystal composition according to any one of claims 1 to 3, further comprising one or more compounds represented by the following formula V,
in formula V, R5、R6Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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;
5. The liquid crystal composition according to any one of claims 1 to 4, further comprising one or more compounds represented by the following formula VI,
in formula VI, R7、R8Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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;
F1、F2、F3Each independently represents H or F, and F2、F3Not simultaneously F.
6. The liquid crystal composition according to any one of claims 1 to 5, further comprising one or more compounds represented by the following formula VII,
in the formula VII, R9、R10Each independently represents an alkyl group having 1 to 10 carbon atoms, an 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, and R9、R10Any one or more non-adjacent-CH2-optionally substituted with cyclopentylene, cyclobutyl or cyclopropylene;
Z3represents a single bond, -CF2O-、-CH2CH2-or-CH2O-；Z4Represents a single bond, -CH2CH2-or-CH2O-；
q represents 1 or 2, and when q represents 2,
may be the same or different;
n represents 0, 1 or 2, and when n represents 2,
may be the same or different.
7. The liquid crystal composition according to any one of claims 1 to 6, further comprising one or more compounds represented by formula VIII,
in the formula VIII, R11、R12Each 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, and R11、R12Any one or more non-adjacent-CH2-optionally substituted by cyclopentylene, cyclobutyl or cyclopropylene;
w represents-O-, -S-or-CH2O-。
8. A liquid crystal display element or a liquid crystal display, comprising the liquid crystal composition according to any one of claims 1 to 7, wherein the display element is an active matrix display element or a passive matrix display element, and the display is an active matrix display or a passive matrix display.
9. The liquid crystal display element or the liquid crystal display according to claim 8, wherein the liquid crystal display element or the liquid crystal display comprises an alignment layer formed of a PI with a medium-high resistivity.
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