CN114350380A - Negative dielectric anisotropy liquid crystal composition, optical anisotropic medium and liquid crystal display device - Google Patents
Negative dielectric anisotropy liquid crystal composition, optical anisotropic medium and liquid crystal display device Download PDFInfo
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- CN114350380A CN114350380A CN202210034488.4A CN202210034488A CN114350380A CN 114350380 A CN114350380 A CN 114350380A CN 202210034488 A CN202210034488 A CN 202210034488A CN 114350380 A CN114350380 A CN 114350380A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 128
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 230000003287 optical effect Effects 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- -1 fluoro pentyl Chemical group 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004450 alkenylene group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims description 6
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical group CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical group CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- HBOPZSSJYKWZRY-UHFFFAOYSA-N fluoro 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OF HBOPZSSJYKWZRY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005817 fluorobutyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
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- 238000000034 method Methods 0.000 description 5
- 206010047571 Visual impairment Diseases 0.000 description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 description 2
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 2
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- 125000005569 butenylene group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000005922 tert-pentoxy group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- FWYUJGXEYOXHRJ-UHFFFAOYSA-N fluoromethyl prop-2-enoate Chemical compound FCOC(=O)C=C FWYUJGXEYOXHRJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- 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
-
- 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic 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
- C09K19/42—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
-
- 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 negative dielectric anisotropy liquid crystal composition, an optical anisotropy and a liquid crystal display device. The negative dielectric anisotropic liquid crystal composition of the present invention comprises: at least one compound shown as a formula I, at least one compound shown as a formula II and at least one compound shown as a formula III. Compared with the prior art, the liquid crystal composition of the invention has the advantages of good low-temperature storage property and fast polymerization rate on the basis of maintaining proper optical anisotropy value and dielectric anisotropy, further has high reliability and is difficult to generate poor display caused by change of a pretilt angle.
Description
Technical Field
The invention relates to the technical field of liquid crystal materials. And more particularly, to a liquid crystal composition, an optical anisotropic agent, and a liquid crystal display device.
Background
In a liquid crystal display device, pixels are generally made into multi-domains to improve visual characteristics, and therefore protrusions or the like are provided to divide the pixels. However, when the protrusion is provided, there is a difference in pretilt angle between the vicinity of the protrusion and the separated portion, resulting in a decrease in response speed of the separated portion.
Then, a psa (polymer Stabilized alignment) liquid crystal display device and a psva (polymer Stabilized Vertical alignment) liquid crystal display device were developed. In a PSA or PSVA liquid crystal display device, a non-polymerizable liquid crystal composition and a polymerizable compound are disposed between substrates, and a voltage is optionally applied between the substrates to align liquid crystal molecules. In the aligned state, the polymerizable compound is polymerized by irradiation with ultraviolet rays or the like, and the aligned state of the liquid crystal is stored in the cured product.
Such a liquid crystal display device still has problems in terms of reliability such as occurrence of "afterimage" when the same display is continued for a long time, and also problems in terms of storage stability, productivity due to manufacturing processes, and the like.
With respect to reliability, in the case of using a polymerization initiator, the polymerization initiator and its decomposition products are causes of a decrease in voltage holding ratio and image sticking of the liquid crystal display device. It is also known that the occurrence of afterimage is also related to a change in the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. That is, if the polymer which is a cured product of the polymerizable compound is flexible, when the same pattern is continuously displayed for a long time in forming a display device, the polymer structure changes, and as a result, the pretilt angle changes, and the excellent pretilt angle greatly affects the response speed, thereby affecting the reliability of display. Thus, in order to solve the problem of the change in the pretilt angle, it is effective to form a polymerizable compound of a polymer having a rigid structure in which the polymer structure is not changed, but in such a case, there is a problem that the low-temperature storage property of the liquid crystal composition is deteriorated.
Therefore, it is required to develop a polymerizable compound-containing liquid crystal composition which can improve both the low-temperature storage stability and the productivity of the production process. Further, a liquid crystal composition containing a polymerizable compound is desired which solves the problem of reliability such as "sticking" which occurs when the same display is continued for a long time.
Disclosure of Invention
The purpose of the present invention is to provide a liquid crystal composition containing a polymerizable compound, which has an excellent polymerization reaction rate, improves the productivity of the production process, and has low-temperature storage stability.
Further, when the liquid crystal composition of the present invention is used in PSA and PSVA display devices, the VHR value after uv irradiation can be increased, and thus defects of display defects such as "afterimages" of liquid crystal display devices can be reduced or eliminated, and reliability is improved.
The present inventors have conducted intensive studies to solve the above problems and found that the above problems can be solved by using the negative dielectric anisotropic liquid crystal composition of the present application, thereby completing the present invention.
In one aspect, the present invention provides a negative dielectric anisotropic liquid crystal composition comprising:
at least one compound represented by formula I;
at least one compound represented by formula II; and the number of the first and second groups,
at least one compound of formula III;
in the formula I, P1、P2Each independently represents an acrylate group, a methacrylate group, an ethacrylate group, a propyl acrylate group, a butyl acrylate group, a pentyl acrylate group, a fluoro methacrylate group, a fluoro ethacrylate group, a fluoro propyl acrylate group, a fluoro butyl acrylate group or a fluoro pentyl acrylate group;
Z1、Z2each independently represents a single bond, a C1-8 linear alkylene group, a C1-8 linear alkyleneoxy group, a C2-8 linear alkenylene group, or a C2-8 linear alkyleneoxy group, wherein one or two of the groups are non-adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom;
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10each independently represents-H, -F, -CH3、-CH2F、-CHF2、-CF3、-C2H5、-OCH3、-OCH2F、-OCHF2、-OCF3or-OC2H5；
n represents 0, 1 or 2;
in the formula II, R3、R4Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R3、R4Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
ring C, ring D are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl;
p represents 0, 1, 2 or 3;
in the formula III, R5、R6Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R5、R6Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
Z3represents a single bond or-CH2O-；
q and r each independently represent 0, 1 or 2;
ring E, ring F are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl.
In another aspect, the present invention provides an optical anisotropic crystal composed of the polymer of the negative dielectric anisotropic liquid crystal composition described above.
In another aspect, the present invention provides a liquid crystal display device having liquid crystal alignment properties imparted thereto by polymerizing a polymerizable compound in the negative dielectric anisotropic liquid crystal composition using the negative dielectric anisotropic liquid crystal composition.
Effects of the invention
The negative dielectric anisotropy liquid crystal composition has excellent polymerization reaction rate and low-temperature storage stability. Further, when the liquid crystal composition of the present invention is used in a liquid crystal display device of PSA, PSVA, or other modes, an improved VHR value after ultraviolet irradiation can be obtained, and defects of display defects such as "afterimages" of the liquid crystal display device can be reduced or eliminated. The optical anisotropic liquid crystal composition of the present invention, which is composed of the polymer of the negative dielectric anisotropic liquid crystal composition of the present invention, has a small amount of residual polymer, a stable pretilt angle, and good low-temperature storage stability. The liquid crystal display device of the present invention has improved productivity of the manufacturing process and reduced defects of defective display such as "ghost".
Detailed Description
[ liquid Crystal composition ]
The negative dielectric anisotropic liquid crystal composition of the present invention comprises:
at least one compound represented by formula I;
at least one compound represented by formula II; and the number of the first and second groups,
at least one compound shown as a formula III.
In the formula I, P1、P2Each independently represents a polymerizable group as polymerizableExamples of the group include the following groups: acrylate, methacrylate, ethacrylate, propylacrylate, butylacrylate, pentylacrylate, fluoroacrylate, fluoromethylacrylate, fluoroethylacrylate, fluoropropylacrylate, fluorobutylacrylate or fluoropentyl acrylate.
The "fluoro" may be mono-fluoro, poly-fluoro, or perfluoro.
These groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, anionic polymerization, or the like. Particularly in the case of ultraviolet polymerization, P is preferred1、P2Each independently represents an acrylate group or a methacrylate group.
In the formula I, Z1、Z2Each independently represents a single bond, a C1-8 linear alkylene group, a C1-8 linear alkyleneoxy group, a C2-8 linear alkenylene group, or a C2-8 linear alkyleneoxy group, wherein one or two of the groups are non-adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom. Preferably, Z1、Z2Each independently represents a single bond, a C1-5 linear alkylene group, a C1-5 linear alkyleneoxy group, a C2-5 linear alkenylene group, or a C2-5 linear alkyleneoxy group, wherein one or two of the groups are non-adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom. Further preferably, Z1、Z2Each independently represents a single bond, a C1-3 linear alkylene group, a C1-3 linear alkyleneoxy group, a C2-4 linear alkenylene group, or a C2-4 linear alkyleneoxy group, wherein one or two of the groups are non-adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom.
Examples of the "linear alkylene group having 1 to 3 carbon atoms" include a methylene group, an ethylene group and a propylene group. The above-mentioned "number of carbon atoms isExamples of the linear alkyleneoxy group "of 1 to 3 include methyleneoxy group, ethyleneoxy group and propyleneoxy group. Examples of the "linear alkenylene group having 2 to 3 carbon atoms" include vinylene, propenylene and butenylene. Examples of the "linear alkenylene group having 2 to 4 carbon atoms" include a vinylene group, a propenylene group, a butenylene group, and the like. One or two of these radicals not being adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom.
In the compounds of the formula I, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10Each independently represents-H, -F, -CH3、-CH2F、-CHF2、-CF3、-C2H5、-OCH3、-OCH2F、-OCHF2、-OCF3or-OC2H5. Wherein, Y1、Y2Optionally the same or different.
In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, preferably, Y in the compound of formula I1、Y2Each independently represents-H, -F, -CH3、-CF3、-OCH3、-C2H5、-OC2H5or-OCF3. More preferably Y1、Y2Each independently represents-H, -F, -CF3or-OCF3. Further preferably Y1、Y2Each independently is-H, or-F.
In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, preferably, Y in the compound of formula I3、Y4、Y5、Y6、Y7、Y8、Y9、Y10represents-H or-F. More preferably Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10Are all-H.
In some embodiments of the negative dielectric anisotropic liquid crystal composition of the present invention, n is preferably 0 or 1, and more preferably n is 1, from the viewpoint of obtaining a faster polymerization reaction rate.
In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, it is preferred that the compound represented by formula I is selected from the group consisting of compounds represented by formulae I-1 to I-57 shown below, wherein P is1、P2、Z1、Z2The definitions are the same as previously described.
Further, the aforementioned compound represented by formula I is preferably selected from the group consisting of the compounds represented by formulae IA-1 to IA-258 described below.
In the liquid crystal composition of the present invention, the structural formula of the compound represented by the formula II is shown below.
In the formula II, R3、R4Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R3、R4Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
ring C, ring D are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl;
p represents 0, 1, 2 or 3.
As the aforementioned R3、R4The "alkyl group having 1 to 5 carbon atoms" independently represented by each other may be a straight-chain alkyl group or a branched-chain alkyl groupAn alkyl group or a cyclic alkyl group, preferably a straight-chain alkyl group. Examples of such a straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, and a tert-butyl group. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, and methylcyclobutyl.
As the aforementioned R3、R4Examples of the "alkoxy group having 1 to 5 carbon atoms" which are independently represented include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-pentoxy group, and tert-pentoxy group.
As the aforementioned R3、R4Examples of the "alkenyl group having 2 to 5 carbon atoms" which are independently represented include an ethenyl group, a propenyl group, a butenyl group, a 2-methylpropenyl group, a 1-pentenyl group, a 2-methyl-1-butenyl group, a 3-methyl-1-butenyl group, and a 2-methyl-2-butenyl group.
As the aforementioned R3、R4Examples of the "alkenyloxy group having 2 to 5 carbon atoms" which are independently represented include an vinyloxy group, a propenyloxy group, a butenyloxy group, a 2-methylpropenyloxy group, a 1-pentenyloxy group, a 2-methyl-1-butenyloxy group, a 3-methyl-1-butenyloxy group, and a 2-methyl-2-butenyloxy group.
As the compound represented by the above formula II, it is preferable to select from the group consisting of the compounds represented by the following formulae II-1 to II-11. Wherein R is3、R4The definitions of (a) are the same as those described above.
(F) Represents F or H.
In the liquid crystal composition of the present invention, the structural formula of the compound represented by the formula iii is shown below.
In the formula III, R5、R6Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R5、R6Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
Z3represents a single bond or-CH2O-；
q and r each independently represent 0, 1 or 2;
ring E, ring F are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl.
As the aforementioned R5、R6The "alkyl group having 1 to 5 carbon atoms" independently of each other may be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and is preferably a straight-chain alkyl group. Examples of such a straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, and a tert-butyl group. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, and methylcyclobutyl.
As the aforementioned R5、R6Examples of the "alkoxy group having 1 to 5 carbon atoms" which are independently represented include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, n-pentoxy group, and tert-pentoxy group.
As the aforementioned R5、R6Examples of the "alkenyl group having 2 to 5 carbon atoms" independently of each other include an ethenyl group and an propenyl groupButenyl, 2-methylpropenyl, 1-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl and the like.
As the aforementioned R5、R6Examples of the "alkenyloxy group having 2 to 5 carbon atoms" which are independently represented include an vinyloxy group, a propenyloxy group, a butenyloxy group, a 2-methylpropenyloxy group, a 1-pentenyloxy group, a 2-methyl-1-butenyloxy group, a 3-methyl-1-butenyloxy group, and a 2-methyl-2-butenyloxy group.
Preferably, the aforementioned compound represented by the formula III is selected from the group consisting of the compounds represented by the formulae III-1 to III-17 described below. Wherein R is5、R6The definitions of (a) are the same as those described above.
In one embodiment of the negative dielectric anisotropy liquid crystal composition, the compound represented by the formula I, the compound represented by the formula II, and the compound represented by the formula III may be contained, for example, in the following proportions: the amount of the compound represented by the formula I is 0.001-1 part by mass, the amount of the compound represented by the formula II is 10-60 parts by mass, and the amount of the compound represented by the formula III is 10-70 parts by mass, based on 100 parts by mass of the liquid crystal composition.
In some embodiments of the negative dielectric anisotropic liquid crystal composition of the present invention, compounds represented by the following formulae IV-1 to IV-50 may be further contained.
Wherein R is1' represents H or an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and optionally 4 or less of H are substituted by F;
R2' represents H or alkyl having 1 to 8 carbon atoms or alkenyl having 2 to 8 carbon atoms, wherein one or two non-adjacent-CH2-is optionally substituted by-O-, and optionally 4 or fewer H are substituted by F.
In some embodiments of the negative dielectric anisotropic liquid crystal composition of the present invention, the components may be contained in the following mass ratios: the amount of the compound represented by the formula I is 0.001-0.3 part by mass, the amount of the compound represented by the formula II is 20-60 parts by mass, the amount of the compound represented by the formula III is 20-60 parts by mass, and the amount of the compound represented by the formula IV is 1-20 parts by mass, based on 100 parts by mass of the negative dielectric anisotropy liquid crystal composition.
Some embodiments of the negative dielectric anisotropic liquid crystal composition of the present invention optionally further comprise one or more compounds represented by the following formulas V-1 to V-78:
in some embodiments of the negative dielectric anisotropic liquid crystal composition of the present invention, when the compound represented by formula V is contained, the following components may be contained in the following mass ratio: the amount of the compound represented by the formula I is 0.001-0.3 part by mass, the amount of the compound represented by the formula II is 20-60 parts by mass, the amount of the compound represented by the formula III is 20-60 parts by mass, the amount of the compound represented by the formula IV is 1-20 parts by mass, and the amount of the compound represented by the formula V is 1-10 parts by mass, based on 100 parts by mass of the negative dielectric anisotropy liquid crystal composition.
In the negative dielectric anisotropic liquid crystal composition of the present invention, various functional additives may be optionally added, and these additives may be exemplified by, for example, a UV stabilizer, an antioxidant, a chiral dopant, a polymerization initiator, and may contain one or more of them.
[ optical anisotropy ]
The optical anisotropic of the present invention is polymerized by using the negative dielectric anisotropic liquid crystal composition of the present invention. The aforementioned optical anisotropic crystals are produced by polymerizing the polymerizable compound in the negative dielectric anisotropic liquid crystal composition of the present invention in an aligned state. The optical anisotropic agent of the present invention has optical anisotropy. Such an optical anisotropic agent can be produced, for example, as follows: the liquid crystal composition of the present invention is polymerized by sandwiching the liquid crystal composition of the present invention between substrates having an organic thin film formed on the surface thereof and subjected to rubbing treatment with cloth or the like.
In the case of controlling the orientation state by an electric field, a substrate having an electrode layer may be used. In this case, an organic thin film such as a polyimide film is preferably formed on the electrode.
As a method for polymerizing the liquid crystal composition of the present invention, a method of polymerizing by irradiating active energy rays such as ultraviolet rays and electron rays is preferable from the viewpoint of rapid polymerization. When polymerization is carried out in a state where a liquid crystal polymer is sandwiched between 2 substrates, at least the substrate on the irradiation surface side is made transparent to active energy rays. The irradiation intensity and time of the active energy ray may be determined as needed.
The optical anisotropic of the present invention produced by such a method may be used alone after being peeled from the substrate or may be used without being peeled. In addition, it can be used by bonding to another substrate.
[ liquid Crystal display device ]
The liquid crystal display device of the present invention is a liquid crystal display device to which the liquid crystal alignment performance is imparted by polymerizing the polymerizable compound in the negative dielectric anisotropic liquid crystal composition using the negative dielectric anisotropic liquid crystal composition of the present invention.
The liquid crystal display device of the present invention is preferably driven in a PS-VA mode, a PVA mode, or a PS-IPS mode, for example.
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.
The following preparation methods are all conventional methods unless otherwise specified, and the raw materials used are all available from public commercial sources unless otherwise specified, the percentages refer to mass percentages, the temperature is in degrees centigrade (DEG C), and the liquid crystal compound is also a liquid crystal monomer.
In examples and comparative examples, liquid crystal compositions having negative dielectric anisotropy and different compositions were prepared, wherein the monomer structure, the amount (parts by mass) of the specific compound used in each example, and the results of the performance parameter test of the obtained liquid crystal medium are shown in the following tables, respectively.
The temperature units involved in each example are as follows, and the specific meanings and test conditions of other symbols are as follows:
g1(mpa.s) represents the rotational viscosity coefficient of the liquid crystal compound, and the measurement method: the equipment INSTEC comprises ALCT-IR1, a vertical box with the thickness of 18 microns in a test box, the temperature of 25 ℃, and the short term G1;
K11is a torsional elastic constant, K33For the splay spring constant, the test conditions were: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ ε represents dielectric anisotropy, and Δ ε∥-ε⊥Wherein, epsilon∥Is a dielectric constant parallel to the molecular axis,. epsilon⊥For the dielectric constant perpendicular to the molecular axis, test conditions: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ n represents optical anisotropy, and Δ n ═ ne-noWherein n isoRefractive index of ordinary light, neFor the refractive index of extraordinary rays, test conditions: 589nm, 25 + -0.2 deg.C.
Tni: nematic phase-isotropic liquid phase transition temperature (. degree. C.).
Low-temperature storage property: after cooling the example of the liquid crystal composition containing the polymerizable compound at-20 ℃ for 240 hours, the presence or absence of the deposition of the polymerizable compound was observed as an index of low-temperature storage stability. The case where no precipitation was observed and no display defects such as bright spots were observed was marked as good, and the case where precipitation was observed was marked as "X".
Polymerization reaction rate: the main wave band of the ultraviolet wavelength is 365nm, and the illumination value is 2mW/cm2The liquid crystal compositions of comparative example 1 and example were irradiated under fixed irradiation conditions with total irradiation energy of 3J, 6J, and 9J, respectively, and then the concentrations of the polymerizable monomers before and after irradiation were obtained by measuring high performance liquid chromatography, and the ratio (concentration (%) of the polymerizable monomer after irradiation/concentration (%) of the polymerizable monomer before irradiation) was calculated according to the formula: the reaction polymerization conversion rate was calculated as 1- (concentration of polymerizable monomer after irradiation/concentration of polymerizable monomer before irradiation).
VHR test: and testing the voltage retention ratio (%) before and after ultraviolet irradiation under the conditions of 60 +/-2 ℃, voltage +/-5V, pulse width of 1ms and voltage retention time of 16.7 ms. The testing equipment is a VHR-AMP01 liquid crystal VHR tester. VHR exacerbation was performed using UV 365nm wavelength at 2.5Mw/cm intensity2Light irradiation was carried out for 34 minutes.
The preparation method of each negative dielectric anisotropy liquid crystal composition in the examples is as follows: weighing each liquid crystal monomer according to a certain proportion, putting the liquid crystal monomers into a stainless steel beaker, putting the stainless steel beaker filled with each liquid crystal monomer on a magnetic stirring instrument for heating and melting, adding a magnetic rotor into the stainless steel beaker after most of the liquid crystal monomers in the stainless steel beaker are melted, uniformly stirring the mixture, and cooling to room temperature to obtain the liquid crystal composition.
The structures of the liquid crystal monomers used in the examples are represented by the following codes, and the methods for representing the structures of the liquid crystal rings, the terminal groups, and the linking groups are shown in the following tables (one) and (two).
Table (one): corresponding code of ring structure
Table (ii): corresponding codes for end groups and linking groups
Examples are:
liquid crystal compositions of examples 1 to 8 and comparative examples 1 to 2 were prepared in the following formulation ratios shown in tables 1 to 10.
TABLE 1 component proportions of the liquid crystal composition LC-1 of example 1
| The compound of the general formula | Liquid crystal structure | Mass portion of |
| Ⅱ | CC-3-V | 35.0 |
| III | CCY-3-O2 | 10.0 |
| III | CLY-3-O2 | 10.0 |
| III | CPY-3-O2 | 10.0 |
| III | CY-3-O2 | 12.0 |
| I | BH(S)-MAO-OMA | 0.1 |
| Ⅱ | PP-1-2V1 | 5.0 |
| Ⅱ | CLP-3-1 | 10.0 |
| III | PYP-2-3 | 8.0 |
TABLE 2 component proportions of liquid crystal composition LC-2 of example 2
TABLE 3 component proportioning ratio of liquid crystal composition LC-3 of example 3
| The compound of the general formula | Liquid crystal structure | Mass portion of |
| Ⅱ | CC-3-V | 32.0 |
| Ⅲ | CCY-2-O2 | 11.0 |
| Ⅲ | CCOY-3-O2 | 7.0 |
| I | BH(S)-AO-OA | 0.1 |
| Ⅱ | CCP-3-O1 | 6.0 |
| Ⅲ | CPY-3-O2 | 12.0 |
| Ⅲ | CY-3-O2 | 4.0 |
| Ⅲ | PGY-3-O2 | 11.0 |
| Ⅲ | CY-3-O4 | 7.0 |
| Ⅱ | PP-1-2V1 | 10.0 |
TABLE 4 component proportioning ratio of liquid crystal composition LC-4 of example 4
TABLE 5 component proportioning ratio of liquid-crystalline medium LC-5 of example 5
| The compound of the general formula | Liquid crystal junctionStructural formula | Mass portion of |
| Ⅱ | CC-2-3 | 20.0 |
| I | B(S)[F,H]-MAO-OMA | 0.1 |
| Ⅲ | COY-3-O2 | 5.0 |
| Ⅲ | CPY-3-O2 | 10.0 |
| Ⅱ | CC-3-5 | 10.0 |
| Ⅱ | CCP-3-O1 | 10.0 |
| Ⅱ | PP-1-3 | 5.0 |
| IV | CVECCY-V-O2 | 5.0 |
| IV | CVECPY-V-O2 | 12.0 |
| Ⅲ | CY-3-O2 | 13.0 |
| Ⅱ | PP-1-2V1 | 5.0 |
| V | COB(S)OIC-3-3 | 5.0 |
TABLE 6 component proportioning ratio of liquid-crystalline medium LC-6 of example 6
TABLE 7 component proportioning ratio of liquid-crystalline medium LC-7 of example 7
TABLE 8 component proportioning ratio of liquid-crystalline medium LC-8 of example 8
| The compound of the general formula | Liquid crystal structure | Mass portion of |
| Ⅱ | CC-3-V | 32.0 |
| Ⅱ | CC-2-3 | 10.0 |
| Ⅱ | CCP-3-O1 | 5.0 |
| Ⅱ | CPP-3-2V1 | 3.0 |
| Ⅲ | CPY-3-O2 | 11.0 |
| I | PB(S)-MAO-OMA | 0.1 |
| IV | CVCPY-V-O2 | 10.0 |
| IV | CVEPY-1V-O2 | 5.0 |
| Ⅲ | PYP-2-4 | 10.0 |
| Ⅲ | CLY3-O4 | 5.0 |
| V | CVEB(S)-C(3)V-O2 | 9.0 |
Table 9: component ratio of liquid-crystalline Medium C-01 of comparative example 1
Table 10: component ratio of liquid-crystalline Medium C-02 of comparative example 2
| The compound of the general formula | Liquid crystal structure | Mass portion of |
| Ⅱ | CC-3-V | 35.0 |
| III | CCY-3-O2 | 10.0 |
| III | CLY-3-O2 | 10.0 |
| III | CPY-3-O2 | 10.0 |
| III | CY-3-O2 | 12.0 |
| Ⅱ | PP-1-2V1 | 5.0 |
| Ⅱ | CLP-3-1 | 10.0 |
| III | PYP-2-3 | 8.0 |
The liquid crystal composition prepared in the above-mentioned examples and comparative examples was filled between two substrates of a liquid crystal display and subjected to a performance test, and the test results are shown in the following table. It is to be noted that comparative example 2 does not contain a polymerizable monomer, and therefore, no polymerization rate test was conducted.
TABLE 11 results of performance testing of the examples and comparative liquid crystal compositions
As shown in Table 11, the liquid crystal compositions of examples 1 to 8 have a polymerization reaction rate faster than that of comparative example 1 after the compositions of examples 1 to 8 containing polymerizable monomer compounds are irradiated with Ultraviolet (UV) radiation energy of 3J to 9J, compared to the liquid crystal composition of comparative example 1, and thus the conventional stable alignment process time for mass-produced polymers can be shortened.
Further, the amount of the polymerizable compound remaining in the liquid crystal display devices obtained in examples 1 to 8 was confirmed, and as a result, the remaining amount was sufficiently small.
In addition, the liquid crystal compositions of examples 1 to 8 exhibited more excellent low-temperature storage stability than comparative example 1.
From the above, it was confirmed that the liquid crystal composition of the present invention can obtain good low-temperature storage stability and a high polymerization rate when used in a PS-VA liquid crystal display device, a PS-VA display device, or the like.
Further, the VHR after Ultraviolet (UV) irradiation of the compositions of examples 1 to 8 was higher than that of the composition of comparative example 1 containing the polymerizable monomer compound used in the prior art, which also demonstrates that the liquid crystal compositions of examples 1 to 8 had high voltage holding ratio and the like, had high reliability, and were less likely to cause display defects due to a change in pretilt angle.
Although the present invention is not exhaustive of all liquid crystal mixtures claimed, it is anticipated by those skilled in the art that other liquid crystal materials of the same type can be obtained in a similar manner without creative efforts based on the disclosed embodiments, only by combining with their own professional efforts. And are merely representative of embodiments, given the limited space available.
Claims (12)
1. A negative dielectric anisotropy liquid crystal composition, comprising:
at least one compound represented by formula I;
at least one compound represented by formula II; and the number of the first and second groups,
at least one compound of formula III;
in the formula I, P1、P2Each independently represents an acrylate group, a methacrylate group, an ethacrylate group, a propyl acrylate group, a butyl acrylate group, a pentyl acrylate group, a fluoro methacrylate group, a fluoro ethacrylate group, a fluoro propyl acrylate group, a fluoro butyl acrylate group or a fluoro pentyl acrylate group;
Z1、Z2each independently represents a single bond, a C1-8 linear alkylene group, a C1-8 linear alkyleneoxy group, a C2-8 linear alkenylene group, or a C2-8 linear alkyleneoxy group, wherein one or two of the groups are non-adjacent-CH2-optionally substituted by-O-, any H being optionally substituted by a F atom;
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10each independently represents-H, -F, -CH3、-CH2F、-CHF2、-CF3、-C2H5、-OCH3、-OCH2F、-OCHF2、-OCF3or-OC2H5；
n represents 0, 1 or 2;
in the formula II, R3、R4Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R3、R4Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
ring C, ring D are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl;
p represents 0, 1, 2 or 3;
in the formula III, R5、R6Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; and, R5、R6Each independently of the other, H on any carbon atom in (a) is optionally substituted with F;
Z3represents a single bond or-CH2O-；
q and r each independently represent 0, 1 or 2;
ring E, ring F are each independently selected from the group consisting of: 1, 4-cyclohexylene, cyclohexene-1, 4-diyl, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, oxacyclohexane-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1, 4-diyl.
2. The negative dielectric anisotropic liquid crystal composition of claim 1, wherein the compound of formula I is selected from the group consisting of compounds of formulae I-1 to I-57 wherein P is1、P2、Z1、Z2The definitions are the same as in claim 1,
3. the negative dielectric anisotropic liquid crystal composition of claim 1 or 2, wherein the compound represented by formula I is selected from the group consisting of compounds represented by formulae IA-1 to IA-258;
4. the negative dielectric anisotropic liquid crystal composition of any one of claims 1 to 3, wherein the compound represented by formula II is selected from the group consisting of the following compounds represented by formulae II-1 to II-11:
R3、R4each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; r3、R4Each hydrogen on any carbon atom in (a) is independently optionally substituted with fluorine;
(F) represents F or H.
5. The negative dielectric anisotropic composition of any one of claims 1 to 4, wherein the compound represented by formula III is selected from the group consisting of compounds represented by formulae III-1 to III-17 below:
R5、R6each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, and R5、R6Each independently of the other, is optionally substituted with F.
6. The negative dielectric anisotropic liquid crystal composition of any one of claims 1 to 5, wherein the liquid crystal composition further comprises one or more compounds represented by formulae IV-1 to IV-50 below:
wherein R is1' represents H or an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and optionally 4 or less of H are substituted by F;
R2' represents H or alkyl having 1 to 8 carbon atoms or alkenyl having 2 to 8 carbon atoms, wherein one or two non-adjacent-CH2-is optionally substituted by-O-, and optionally 4 or fewer H are substituted by F.
7. The negative dielectric anisotropic liquid crystal composition of any one of claims 1 to 6, wherein the liquid crystal composition further comprises one or more compounds represented by the following formulas V-1 to V-78:
8. the negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 5, wherein the compound represented by formula I is 0.001 to 1 part by mass, the compound represented by formula II is 10 to 60 parts by mass, and the compound represented by formula III is 10 to 70 parts by mass, based on 100 parts by mass of the negative dielectric anisotropic liquid crystal composition.
9. The negative dielectric anisotropic liquid crystal composition of claim 6, wherein the amount of the compound represented by formula I is 0.001 to 0.3 part by mass, the amount of the compound represented by formula II is 20 to 60 parts by mass, the amount of the compound represented by formula III is 20 to 60 parts by mass, and the amount of the compound represented by formula IV is 1 to 20 parts by mass, based on 100 parts by mass of the negative dielectric anisotropic liquid crystal composition.
10. The negative dielectric anisotropic liquid crystal composition of claim 7, wherein the amount of the compound represented by formula I is 0.001 to 0.3 part by mass, the amount of the compound represented by formula II is 20 to 60 parts by mass, the amount of the compound represented by formula III is 20 to 60 parts by mass, the amount of the compound represented by formula IV is 1 to 20 parts by mass, and the amount of the compound represented by formula V is 1 to 10 parts by mass, based on 100 parts by mass of the negative dielectric anisotropic liquid crystal composition.
11. An optical anisotropic product comprising the polymer of the negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 10.
12. A liquid crystal display device to which a liquid crystal alignment property is imparted by polymerizing a polymerizable compound in the negative dielectric anisotropic liquid crystal composition using the negative dielectric anisotropic liquid crystal composition according to any one of claims 1 to 10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115287083A (en) * | 2022-09-01 | 2022-11-04 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN115305096A (en) * | 2022-09-01 | 2022-11-08 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN116083091A (en) * | 2022-12-26 | 2023-05-09 | 北京八亿时空液晶科技股份有限公司 | High-contrast negative liquid crystal composition and application thereof |
| WO2023134596A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropier, and liquid crystal display component |
| WO2023134598A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Polymerisable compound, composition, and liquid crystal display device |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011195795A (en) * | 2010-03-24 | 2011-10-06 | Adeka Corp | Liquid crystal composition containing polymerizable compound and liquid crystal displaying element using the same liquid crystal composition |
| WO2014126129A1 (en) * | 2013-02-15 | 2014-08-21 | Dic株式会社 | Liquid crystal composition and liquid crystal display element using same |
| CN104342167A (en) * | 2013-08-02 | 2015-02-11 | 江苏和成显示科技股份有限公司 | Polymerizable liquid crystal composition and display device |
| JP2015040285A (en) * | 2013-08-23 | 2015-03-02 | Dic株式会社 | Liquid crystal composition and liquid crystal display using the same |
| CN105637065A (en) * | 2013-10-08 | 2016-06-01 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| WO2017082062A1 (en) * | 2015-11-10 | 2017-05-18 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN108084029A (en) * | 2017-12-20 | 2018-05-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
| CN109943346A (en) * | 2019-03-05 | 2019-06-28 | 曹亚宁 | Compound, liquid crystal media, liquid crystal display device and electronic equipment |
| JP2019112607A (en) * | 2017-12-22 | 2019-07-11 | Dic株式会社 | Polymerizable compound and liquid crystal composition containing the same |
| US20190292459A1 (en) * | 2018-03-23 | 2019-09-26 | Shijiazhuang Chengzhi Yonghua Display Material Co. , Ltd. | Liquid crystal composition |
| US20190375986A1 (en) * | 2018-06-11 | 2019-12-12 | Shijiazhuang Chengzhi Yonghua Display Material Co., Ltd. | Negative dielectric anisotropic liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN110922983A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzothiophene polymerizable monomer and application thereof |
| CN112143508A (en) * | 2020-10-09 | 2020-12-29 | 烟台显华化工科技有限公司 | Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device |
| CN112940755A (en) * | 2019-12-30 | 2021-06-11 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN112980464A (en) * | 2019-12-30 | 2021-06-18 | 石家庄诚志永华显示材料有限公司 | Negative liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN113403088A (en) * | 2021-06-17 | 2021-09-17 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN113493693A (en) * | 2020-04-01 | 2021-10-12 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing polymerizable compound and application thereof |
| CN113512430A (en) * | 2021-08-17 | 2021-10-19 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN113736479A (en) * | 2021-07-23 | 2021-12-03 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5257805B1 (en) * | 2011-07-20 | 2013-08-07 | Ｄｉｃ株式会社 | (Meth) acrylate compound, radical polymerizable composition, cured product, and plastic lens |
| JP2021028299A (en) * | 2017-11-30 | 2021-02-25 | Jnc株式会社 | Compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display element |
| CN110343531A (en) * | 2018-04-02 | 2019-10-18 | 北京八亿时空液晶科技股份有限公司 | A kind of dibenzothiophenes class can poly- property compound and its application |
| CN110386917A (en) * | 2018-04-16 | 2019-10-29 | 北京八亿时空液晶科技股份有限公司 | A kind of novel dibenzothiophenes class can poly- property compound and its application |
| CN108865177B (en) * | 2018-08-13 | 2020-06-09 | 石家庄晶奥量新材料有限公司 | Liquid-crystalline medium and use in liquid-crystal displays |
| CN109503534A (en) * | 2018-12-19 | 2019-03-22 | 西安瑞立电子材料有限公司 | Polymerizable compound and liquid crystal media |
| CN111592890B (en) * | 2019-02-20 | 2021-09-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
| CN111592517A (en) * | 2019-02-20 | 2020-08-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing dibenzofuran structure and preparation method and application thereof |
| JP2021051281A (en) * | 2019-09-20 | 2021-04-01 | Jnc株式会社 | Horizontal alignment type liquid crystal display element, liquid crystal composition, display device, and method of manufacturing horizontal alignment type liquid crystal display element |
| CN113512428A (en) * | 2020-04-09 | 2021-10-19 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition with negative dielectric anisotropy and application thereof |
| KR20210125922A (en) * | 2020-04-09 | 2021-10-19 | 메르크 파텐트 게엠베하 | Liquid-crystalline medium |
| JP2022065315A (en) * | 2020-10-15 | 2022-04-27 | Dic株式会社 | Polymerizable compound and liquid crystal composition containing the same |
| CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
| CN114350380A (en) * | 2022-01-13 | 2022-04-15 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition, optical anisotropic medium and liquid crystal display device |
-
2022
- 2022-01-13 CN CN202210034488.4A patent/CN114350380A/en active Pending
- 2022-08-23 TW TW111131710A patent/TWI797047B/en active
-
2023
- 2023-01-08 WO PCT/CN2023/071140 patent/WO2023134596A1/en unknown
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011195795A (en) * | 2010-03-24 | 2011-10-06 | Adeka Corp | Liquid crystal composition containing polymerizable compound and liquid crystal displaying element using the same liquid crystal composition |
| WO2014126129A1 (en) * | 2013-02-15 | 2014-08-21 | Dic株式会社 | Liquid crystal composition and liquid crystal display element using same |
| CN104342167A (en) * | 2013-08-02 | 2015-02-11 | 江苏和成显示科技股份有限公司 | Polymerizable liquid crystal composition and display device |
| JP2015040285A (en) * | 2013-08-23 | 2015-03-02 | Dic株式会社 | Liquid crystal composition and liquid crystal display using the same |
| CN105637065A (en) * | 2013-10-08 | 2016-06-01 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| WO2017082062A1 (en) * | 2015-11-10 | 2017-05-18 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display element using same |
| CN108084029A (en) * | 2017-12-20 | 2018-05-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition and liquid crystal display element |
| JP2019112607A (en) * | 2017-12-22 | 2019-07-11 | Dic株式会社 | Polymerizable compound and liquid crystal composition containing the same |
| US20190292459A1 (en) * | 2018-03-23 | 2019-09-26 | Shijiazhuang Chengzhi Yonghua Display Material Co. , Ltd. | Liquid crystal composition |
| US20190375986A1 (en) * | 2018-06-11 | 2019-12-12 | Shijiazhuang Chengzhi Yonghua Display Material Co., Ltd. | Negative dielectric anisotropic liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN110922983A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzothiophene polymerizable monomer and application thereof |
| CN109943346A (en) * | 2019-03-05 | 2019-06-28 | 曹亚宁 | Compound, liquid crystal media, liquid crystal display device and electronic equipment |
| CN112940755A (en) * | 2019-12-30 | 2021-06-11 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN112980464A (en) * | 2019-12-30 | 2021-06-18 | 石家庄诚志永华显示材料有限公司 | Negative liquid crystal composition, liquid crystal display element and liquid crystal display |
| CN113493693A (en) * | 2020-04-01 | 2021-10-12 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing polymerizable compound and application thereof |
| CN112143508A (en) * | 2020-10-09 | 2020-12-29 | 烟台显华化工科技有限公司 | Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device |
| CN113403088A (en) * | 2021-06-17 | 2021-09-17 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN113736479A (en) * | 2021-07-23 | 2021-12-03 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN113512430A (en) * | 2021-08-17 | 2021-10-19 | 烟台显华化工科技有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023134596A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropier, and liquid crystal display component |
| WO2023134598A1 (en) * | 2022-01-13 | 2023-07-20 | 烟台显华科技集团股份有限公司 | Polymerisable compound, composition, and liquid crystal display device |
| CN115287083A (en) * | 2022-09-01 | 2022-11-04 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN115305096A (en) * | 2022-09-01 | 2022-11-08 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
| CN115287083B (en) * | 2022-09-01 | 2024-03-01 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
| CN115305096B (en) * | 2022-09-01 | 2024-04-26 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
| CN116083091A (en) * | 2022-12-26 | 2023-05-09 | 北京八亿时空液晶科技股份有限公司 | High-contrast negative liquid crystal composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023134596A1 (en) | 2023-07-20 |
| TWI797047B (en) | 2023-03-21 |
| TW202328405A (en) | 2023-07-16 |
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