WO2023134596A1 - 负介电各向异性液晶组合物、光学各向异构体及液晶显示器件 - Google Patents

负介电各向异性液晶组合物、光学各向异构体及液晶显示器件 Download PDF

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WO2023134596A1
WO2023134596A1 PCT/CN2023/071140 CN2023071140W WO2023134596A1 WO 2023134596 A1 WO2023134596 A1 WO 2023134596A1 CN 2023071140 W CN2023071140 W CN 2023071140W WO 2023134596 A1 WO2023134596 A1 WO 2023134596A1
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liquid crystal
group
carbon atoms
formula
crystal composition
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French (fr)
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舒克伦
郝祥云
由翔
赖育宏
尹硕
丰佩川
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烟台显华科技集团股份有限公司
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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

Definitions

  • the invention relates to the technical field of liquid crystal materials. More specifically, it relates to liquid crystal compositions, optical anisotropes, and liquid crystal display devices.
  • pixels are usually made into multiple domains to improve visual characteristics, so protrusions and the like are provided to divide the pixels.
  • protrusions and the like are provided to divide the pixels.
  • the protrusion there is a difference in pretilt angle between the vicinity of the protrusion and the separation part, resulting in a decrease in the response speed of the separation part.
  • PSA Polymer Sustained Alignment
  • PSVA Polymer Stabilized Vertical Alignment
  • a non-polymeric liquid crystal composition and a polymeric compound are disposed between substrates, and a voltage is optionally applied between the substrates to align the liquid crystal molecules.
  • the polymerizable compound is polymerized by irradiation with ultraviolet light or the like, and the aligned state of the liquid crystal is stored in the cured product.
  • Such liquid crystal display devices still have problems in reliability such as "image sticking" when the same display is continued for a long time, storage stability, productivity due to manufacturing process, and the like.
  • the polymerization initiator and its decomposition products cause a reduction in the voltage retention ratio of a liquid crystal display device and image sticking.
  • the occurrence of image sticking is also related to the change in the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. That is, if the polymer that is the cured product of the polymerizable compound is flexible, when the same pattern is continuously displayed for a long time when forming a display device, the polymer structure changes, and as a result, the pretilt angle changes, and an excellent pretilt angle greatly affects the response speed , thereby affecting the reliability of the display.
  • An object of the present invention is to provide a liquid crystal composition containing a polymerizable compound, which has an excellent polymerization reaction rate, thereby improving the productivity of the manufacturing process, and having low-temperature storage stability.
  • PSVA display device when the liquid crystal composition of the present invention is used in PSA, PSVA display device, can obtain the VHR value after the ultraviolet ray irradiation that improves, thereby can reduce/eliminate the defect of poor display such as " afterimage " of liquid crystal display device, reliability improve.
  • the inventors of the present invention conducted intensive studies to solve the above-mentioned problems, found that the above-mentioned problems can be solved by using the negative dielectric anisotropy liquid crystal composition of the present application, and completed the present invention.
  • One aspect of the present invention provides a negative dielectric anisotropy liquid crystal composition, which comprises:
  • At least one compound represented by formula II At least one compound represented by formula II;
  • At least one compound represented by formula III At least one compound represented by formula III;
  • P 1 and P 2 each independently represent an acrylate group, a methacrylate group, an ethacrylate group, a propyl acrylate group, a butyl acrylate group, an amyl acrylate group, a fluoroacrylic acid group ester group, fluoromethacrylate group, fluoroethylacrylate group, fluoropropylacrylate group, fluorobutylacrylate group or fluoropentylacrylate group;
  • Z 1 and Z 2 each independently represent a single bond, a linear alkylene group having 1 to 8 carbon atoms, a linear alkyleneoxy group having 1 to 8 carbon atoms, a straight chain alkylene group having 2 to 8 carbon atoms, Alkenylene, or a straight-chain alkenyleneoxy group with 2 to 8 carbon atoms, in which one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is optionally replaced by an F atom replace;
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each independently represent -H, -F, -CH 3 , -CH 2 F, -CHF 2 , -CF 3 , -C 2 H 5 , -OCH 3 , -OCH 2 F, -OCHF 2 , -OCF 3 or -OC 2 H 5 ;
  • n 0, 1 or 2;
  • R 3 and R 4 each independently represent 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 a carbon atom
  • the number is 2-5 alkenyloxy groups; and, the H on any carbon atom in R 3 and R 4 is independently optionally substituted by F;
  • Ring C and ring D are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5 -diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl;
  • p 0, 1, 2 or 3;
  • R 5 and R 6 each independently represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or a carbon atom Alkenyloxy groups with a number of 2 to 5; and, H on any carbon atom in R 5 and R 6 is independently optionally substituted by F;
  • Z 3 represents a single bond or -CH 2 O-;
  • q and r independently represent 0, 1 or 2;
  • Ring E and ring F are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5 -diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl.
  • the present invention provides an optical anisotropy composed of a polymer of the aforementioned negative dielectric anisotropy liquid crystal composition.
  • the present invention provides a liquid crystal display device, which uses the above-mentioned negative dielectric anisotropy liquid crystal composition, and polymerizes the polymerizable compound in the negative dielectric anisotropy liquid crystal composition to give liquid crystal alignment performance liquid crystal display devices.
  • the negative dielectric anisotropy liquid crystal composition of the present invention has excellent polymerization reaction rate and low-temperature storage stability. Further, when the liquid crystal composition of the present invention is used in liquid crystal display devices of modes such as PSA and PSVA, the VHR value after ultraviolet irradiation can be obtained to be improved, thereby reducing/eliminating the defects of poor display such as "image sticking" of the liquid crystal display device. defect.
  • the optical anisotropy of the present invention composed of the polymer of the negative dielectric anisotropy liquid crystal composition of the present invention has little remaining polymer, has a stable pretilt angle, and has good low-temperature storage stability. In the liquid crystal display device of the present invention, the productivity of the manufacturing process is improved, and defects such as "image sticking" and other display defects are reduced.
  • the negative dielectric anisotropy liquid crystal composition of the present invention comprises:
  • At least one compound represented by formula II At least one compound represented by formula II;
  • At least one compound represented by formula III At least one compound represented by formula III.
  • P 1 and P 2 each independently represent a polymerizable group, as the polymerizable group, the following groups can be listed: acrylate group, methacrylate group, ethacrylate group, propyl group Acrylate, Butylacrylate, Amylacrylate, Fluoroacrylate, Fluoromethacrylate, Fluoroethylacrylate, Fluoropropylacrylate, Fluorobutyl Acrylate or fluoropentyl acrylate.
  • fluoro can be monofluoro, polyfluoro, or perfluoro.
  • P 1 and P 2 are cured by radical polymerization, radical addition polymerization, cationic polymerization, anionic polymerization, and the like.
  • P 1 and P 2 each independently represent an acrylate group or a methacrylate group.
  • Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 8 carbon atoms, a straight-chain alkyleneoxy group with 1 to 8 carbon atoms, and a straight-chain alkyleneoxy group with 2 carbon atoms.
  • Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 5 carbon atoms, a straight-chain alkyleneoxy group with 1 to 5 carbon atoms, and a straight chain alkyleneoxy group with 2 to 5 carbon atoms.
  • Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 3 carbon atoms, a straight-chain alkyleneoxy group with 1 to 3 carbon atoms, and a straight-chain alkyleneoxy group with 2 carbon atoms.
  • Examples of the aforementioned "straight-chain alkylene group having 1 to 3 carbon atoms” include a methylene group, an ethylene group, and a propylene group.
  • Examples of the "straight-chain alkyleneoxy group having 1 to 3 carbon atoms” include methyleneoxy, ethyleneoxy, and propyleneoxy.
  • Examples of the "straight-chain alkenylene group having 2 to 3 carbon atoms” include vinylene, propenylene and butenylene.
  • Examples of the aforementioned “straight-chain alkenyleneoxy group having 2 to 4 carbon atoms” include vinyleneoxy, propenyleneoxy, butenyleneoxy and the like.
  • One or two non-adjacent -CH 2 -s in these groups are optionally substituted by -O-, and any H is optionally substituted by F atoms.
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each independently represent -H, -F, -CH 3. -CH 2 F, -CHF 2 , -CF 3 , -C 2 H 5 , -OCH 3 , -OCH 2 F, -OCHF 2 , -OCF 3 or -OC 2 H 5 .
  • Y 1 and Y 2 are optionally the same or different.
  • Y 1 and Y 2 in the compound represented by formula I each independently represent -H, -F, -CH 3 , -CF 3 , -OCH 3 , -C 2 H 5 , -OC 2 H 5 or -OCF 3 . More preferably, Y 1 and Y 2 each independently represent -H, -F, -CF 3 , or -OCF 3 . More preferably, Y 1 and Y 2 are each independently -H or -F.
  • Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 in the compound represented by formula I Indicates -H or -F. More preferably, Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 are all -H.
  • the compound represented by formula I is selected from the group consisting of compounds represented by the following formulas I-1 to I-57, wherein P 1 , P 2.
  • the definitions of Z 1 and Z 2 are the same as above.
  • the compound represented by the aforementioned formula I is preferably selected from the group consisting of the compounds represented by the following formulas IA-1 to IA-258.
  • R 3 and R 4 each independently represent 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 a carbon atom
  • the number is 2-5 alkenyloxy groups; and, the H on any carbon atom in R 3 and R 4 is independently optionally substituted by F;
  • Ring C and ring D are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5 -diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl;
  • p 0, 1, 2 or 3.
  • alkyl group having 1 to 5 carbon atoms independently represented by R 3 and R 4 described above may be a straight chain alkyl group, branched chain alkyl group or cyclic alkyl group, and is preferably a straight chain alkyl group.
  • straight-chain alkyl groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and n-pentyl groups.
  • a branched alkyl group an isopropyl group, an isobutyl group, a tert-butyl group etc. are mentioned, for example. Cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, methylcyclobutyl etc. are mentioned as a cyclic alkyl group.
  • alkoxy group having 1 to 5 carbon atoms each independently represented by R 3 and R 4 above include methoxy, ethoxy, n-propoxy, isopropoxy, n-propoxy, Butoxy, isobutoxy, n-pentyloxy, tert-amyloxy, etc.
  • alkenyl group having 2 to 5 carbon atoms each independently represented by the aforementioned R 3 and R 4 include vinyl, propenyl, butenyl, 2-methacryl, 1-pentyl Alkenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl and the like.
  • alkenyloxy group having 2 to 5 carbon atoms each independently represented by the aforementioned R 3 and R 4 include ethyleneoxy, propyleneoxy, butenyloxy, 2-methacryloxy, Base, 1-pentenyloxy, 2-pentenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 2-methyl-2-butenyloxy Base etc.
  • the compound represented by the aforementioned formula II is preferably selected from the group consisting of compounds represented by the following formulas II-1 to II-11. Wherein, the definitions of R 3 and R 4 are the same as above.
  • R 5 and R 6 each independently represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or a carbon atom Alkenyloxy groups with a number of 2 to 5; and, H on any carbon atom in R 5 and R 6 is independently optionally substituted by F;
  • Z 3 represents a single bond or -CH 2 O-;
  • q and r independently represent 0, 1 or 2;
  • Ring E and ring F are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5 -diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl.
  • alkyl group having 1 to 5 carbon atoms independently represented by R 5 and R 6 described above may be a straight chain alkyl group, branched chain alkyl group or cyclic alkyl group, and is preferably a straight chain alkyl group.
  • straight-chain alkyl groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and n-pentyl groups.
  • a branched alkyl group an isopropyl group, an isobutyl group, a tert-butyl group etc. are mentioned, for example. Cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, methylcyclobutyl etc. are mentioned as a cyclic alkyl group.
  • alkoxy group having 1 to 5 carbon atoms each independently represented by the aforementioned R 5 and R 6 include methoxy, ethoxy, n-propoxy, isopropoxy, n-propoxy, Butoxy, isobutoxy, n-pentyloxy, tert-amyloxy, etc.
  • alkenyl group having 2 to 5 carbon atoms each independently represented by the aforementioned R 5 and R 6 include vinyl, propenyl, butenyl, 2-methacryl, 1-pentyl Alkenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl and the like.
  • alkenyloxy group having 2 to 5 carbon atoms each independently represented by the aforementioned R 5 and R 6 include ethyleneoxy, propyleneoxy, butenyloxy, 2-methacryloxy, Base, 1-pentenyloxy, 2-pentenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 2-methyl-2-butenyloxy Base etc.
  • the compound represented by the aforementioned formula III is selected from the group consisting of the compounds represented by the following formulas III-1 to III-17.
  • the definitions of R 5 and R 6 are the same as above.
  • the compound represented by formula I, the compound represented by formula II, and the compound represented by formula III can be contained in the following ratio, for example: relative to 100 parts by mass of the liquid crystal composition , the amount of the compound represented by the formula I is 0.001-1 parts 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.
  • compounds represented by the following formulas IV-1 to IV-50 may also be included.
  • R 1 ' represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, and optionally 4 or less Hs are substituted by F;
  • R 2 ' represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, wherein one or two non-adjacent -CH 2 - are optionally substituted by -O-, And optionally 4 or less of H are replaced by F.
  • each component may be contained in the following mass ratio: relative to 100 parts by mass of the negative dielectric anisotropy liquid crystal composition, the aforementioned formula I 0.001-0.3 parts by mass of the compound shown, 20-60 parts by mass of the compound shown by the aforementioned formula II, 20-60 parts by mass of the compound shown by the aforementioned formula III, and 1-20 parts by mass of the compound shown by the aforementioned formula IV.
  • negative dielectric anisotropy liquid crystal composition of the present invention also optionally contain one or more compounds shown in the following formulas V-1 ⁇ V-78:
  • each component when containing the compound represented by the aforementioned formula V, each component can be contained according to the following mass ratio: relative to 100 parts by mass of negative
  • the dielectrically anisotropic liquid crystal composition comprises 0.001-0.3 parts by mass of the compound represented by the aforementioned formula I, 20-60 parts by mass of the compound represented by the aforementioned formula II, 20-60 parts by mass of the compound represented by the aforementioned formula III, and 20-60 parts by mass of the compound represented by the aforementioned formula III.
  • the compound represented by IV is 1 to 20 parts by mass
  • the compound represented by the aforementioned formula V is 1 to 10 parts by mass.
  • additives of various functions can also be added, and these additives can enumerate such as UV stabilizers, antioxidants, chiral dopants, polymerization initiators , may contain one or more of them.
  • the optical anisotropy of the present invention is polymerized by using the negative dielectric anisotropy liquid crystal composition of the present invention.
  • the aforementioned optical anisotropy is produced by polymerizing the polymerizable compound in the negative dielectrically anisotropic liquid crystal composition of the present invention in an aligned state.
  • the optical anisotropy of the present invention has optical anisotropy.
  • Such an optical anisotropy can be produced, for example, by sandwiching the negative dielectric anisotropy liquid crystal composition of the present invention between substrates on which the surface of the substrate on which the organic thin film is formed is rubbed with cloth or the like, and then making the composition
  • the inventive liquid crystal composition is polymerized.
  • a substrate having an electrode layer can be used.
  • an organic thin film such as a polyimide thin film
  • a method of polymerizing by irradiating active energy rays such as ultraviolet rays and electron beams is preferable from the viewpoint of rapid polymerization.
  • active energy rays such as ultraviolet rays and electron beams
  • substrate of an irradiation surface side is made transparent to an active energy ray.
  • the irradiation intensity and time of active energy rays may be appropriately determined as needed.
  • optical anisotropy of the present invention produced by such a method may be used alone after peeling off the substrate, or may be used without peeling off. In addition, it can also be used by bonding it to other substrates.
  • the liquid crystal display device of the present invention is a liquid crystal display device provided with liquid crystal alignment performance by polymerizing a polymerizable compound in the negative dielectric anisotropy liquid crystal composition using the above-mentioned negative dielectric anisotropy liquid crystal composition of the present invention.
  • the driving mode of the liquid crystal display device of the present invention is preferably, for example, PS-VA mode, PVA mode, or, or PS-IPS mode.
  • the following preparation methods are conventional methods unless otherwise specified, and the raw materials used can be obtained from public commercial sources unless otherwise specified, and the percentages refer to mass percentages, the temperature is degrees Celsius (°C), and the liquid crystal compound is also a liquid crystal monomer.
  • Negative dielectric anisotropy liquid crystal compositions of different compositions were prepared in the examples and comparative examples, wherein, the monomer structure, dosage (mass parts) of the specific compounds used in each example, and the performance parameter test of the obtained liquid crystal medium The results are shown in the tables described later.
  • G1 (mPa.s) represents the rotational viscosity coefficient of the liquid crystal compound
  • the test box is 18 microns thick vertical box
  • the temperature is 25 ° C, abbreviated as "G1";
  • K 11 is the torsional elastic constant
  • K 33 is the splay elastic constant
  • the test conditions are: 25°C
  • INSTEC ALCT-IR1, 18 micron vertical box;
  • ⁇ n represents optical anisotropy
  • ⁇ n n e -n o
  • n o is the refractive index of ordinary light
  • ne is the refractive index of extraordinary light. Test conditions: 589nm, 25 ⁇ 0.2°C.
  • Tni nematic phase-isotropic liquid phase transition temperature (° C.).
  • Low-temperature storage stability After cooling the examples of the liquid crystal composition containing the polymerizable compound at -20°C for 240 hours, the presence or absence of precipitation of the polymerizable compound was observed, which was used as an indicator of low-temperature storage stability. The case where there is no precipitation and does not cause display defects such as bright spots is marked as 0, and the case where precipitation is present is marked as x.
  • VHR test test the voltage retention rate (%) before and after ultraviolet light irradiation, the test condition is 60 ⁇ 2°C, the voltage is ⁇ 5V, the pulse width is 1ms, and the voltage retention time is 16.7ms.
  • the test equipment is VHR-AMP01 liquid crystal VHR tester.
  • VHR deterioration use ultraviolet light with a wavelength of 365nm and an irradiation intensity of 2.5Mw/cm 2 for light irradiation, and the irradiation time is 34 minutes.
  • each negative dielectric anisotropic liquid crystal composition in the examples is as follows: each liquid crystal monomer is weighed according to a certain ratio and put into a stainless steel beaker, and the stainless steel beaker containing each liquid crystal monomer is placed in a magnetic stirring Heat and melt on the instrument. After most of the liquid crystal monomers in the stainless steel beaker are melted, add a magnetic rotor to the stainless steel beaker, stir the mixture evenly, and obtain the liquid crystal composition after cooling to room temperature.
  • liquid crystal monomers used in the examples are represented by the following codes, and the code representation methods of liquid crystal ring structures, terminal groups, and linking groups are shown in Table (1) and Table (2) below.
  • the composition containing the polymerizable monomer compound in Examples 1 to 8 was irradiated with ultraviolet rays (UV). After the energy is 3J to 9J, the polymerization reaction rate is faster than that of Comparative Example 1, which can shorten the process time of the existing mass-produced polymer stable alignment.
  • UV ultraviolet rays
  • the liquid crystal composition of Examples 1-8 showed the more excellent low-temperature storage property.
  • liquid crystal composition of the present invention when used in PS-VA liquid crystal display devices, PS-VA display devices, etc., it can obtain good low-temperature storage properties and a relatively fast polymerization rate.
  • the VHR after ultraviolet (UV) irradiation of the compositions of Examples 1 to 8 is higher than that of the composition of Comparative Example 1 containing the polymerizable monomer compound used in the prior art, which also shows that Example 1
  • the liquid crystal composition of ⁇ 8 has properties such as high voltage retention rate, high reliability, and is not prone to display defects caused by changes in pretilt angles.

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Abstract

本发明涉及负介电各向异性液晶组合物、光学各向异构体及液晶显示器件。本发明的负介电各向异性液晶组合物包含：至少一种式（I）所示化合物、至少一种式（Ⅱ）所示化合物以及至少一种式（Ⅲ）所示化合物。与现有技术相比，本发明的液晶组合物获得了在维持合适的光学各向异性值、介电各向异性的基础上获得良好的低温保存性、较快的聚合速率，进一步兼顾较高的可靠性、不容易发生预倾角的变化导致的显示不良。

Description

负介电各向异性液晶组合物、光学各向异构体及液晶显示器件 技术领域
本发明涉及液晶材料技术领域。更具体地，涉及液晶组合物、光学各向异构体及液晶显示器件。
背景技术
液晶显示器件中通常将像素制成多畴以改善视觉特性，因此设置突起等以分割像素。然而，当设置突起时，突起附近和分离部分之间存在预倾角差异，导致分离部分响应速度降低。
之后开发了PSA(Polymer Sustained Alignment)液晶显示装置和PSVA(Polymer Stabilized Vertical Alignment)液晶显示装置。在PSA或PSVA液晶显示装置中，非聚合性液晶组合物和聚合性化合物设置在基板之间，任选地在基板之间施加电压以使液晶分子取向。在取向状态下，通过紫外线等照射使聚合性化合物聚合，并将液晶的取向状态储存在固化产物中。
这种液晶显示器件仍然存在如长时间持续相同显示时出现“残影”等可靠性方面的问题，以及存储稳定性、制造工艺引起的生产率等问题。
关于可靠性，使用聚合引发剂的情况下，聚合引发剂及其分解产物是导致液晶显示器件的电压保持率降低和残影的原因。另外，还已知残影的发生与由含有聚合性化合物的液晶组合物中的液晶分子的预倾角的变化也是相关的。即，如果作为聚合性化合物的固化产物的聚合物是柔性的，当在形成显示器件时长时间连续显示相同图案时，聚合物结构改变，结果，预倾角改变，优异预倾角会极大影响响应速度，从而影响显示的可靠性。由此，为了解决预倾角改变的问题，形成具有其中聚合物结构不改变的刚性结构的聚合物的聚合性化合物是有效的，但是这样的情况下，存在液晶组合物的低温储存性劣化的问题。
因此，需要开发兼顾低温存储稳定性、制造工艺的生产率提高的含有聚合性化合物的液晶组合物。另外，还期望解决了长时间持续相同显示时出现“残影”等可靠性方面的问题的含有聚合性化合物的液晶组合物。
发明内容
本发明的目的是提供一种含有聚合性化合物的液晶组合物，其具有优异的聚合反应速率从而制作工艺的生产率提高、低温存储稳定性。
进一步，本发明的液晶组合物用在PSA、PSVA显示器件中时能够获得提高的紫外线照射后的VHR值，从而能够减小/消除液晶显示装置的“残影”等显示不良的缺陷，可靠性提高。
本发明人等为了解决上述课题而进行了深入研究，发现通过使用本申请的负介电各向异性液晶组合物可以解决上述课题，由此完成了本发明。
本发明一方面提供一种负介电各向异性液晶组合物，其包含：
至少一种式I所示化合物；
至少一种式Ⅱ所示化合物；以及，
至少一种式Ⅲ所示化合物；
Figure PCTCN2023071140-appb-000001
式I中，P 1、P 2各自独立地表示丙烯酸酯基、甲基丙烯酸酯基、乙基丙烯酸酯基、丙基丙烯酸酯基、丁基丙烯酸酯基、戊基丙烯酸酯基、氟代丙烯酸酯基、氟代甲基丙烯酸酯基、氟代乙基丙烯酸酯基、氟代丙基丙烯酸酯基、氟代丁基丙烯酸酯基或氟代戊基丙烯酸酯基；
Z 1、Z 2各自独立地表示单键、碳原子数为1～8的直链亚烷基、碳原子数为1～8的直链亚烷氧基、碳原子数为2～8的直链亚烯基、或者碳原子数为2～8的直链亚烯氧基，其中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选 被F原子取代；
Y 1、Y 2、Y 3、Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10各自独立地表示-H、-F、-CH 3、-CH 2F、-CHF 2、-CF 3、-C 2H 5、-OCH 3、-OCH 2F、-OCHF 2、-OCF 3或者-OC 2H 5；
n表示0、1或2；
式II中，R 3、R 4各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 3、R 4中任意碳原子上的H各自独立地任选被F取代；
环C、环D各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5-二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基；
p表示0、1、2或3；
式Ⅲ中，R 5、R 6各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 5、R 6中任意碳原子上的H各自独立地任选被F取代；
Z 3表示单键或-CH 2O-；
q、r各自独立地表示0、1或2；
环E、环F各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5-二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基。
另一方面，本发明提供光学各向异构体，其由前述的负介电各向异性液晶组合物的聚合物构成。
又一方面，本发明提供液晶显示器件，其为使用前述的的负介电各向异性液晶组合物，使所述负介电各向异性液晶组合物中的聚合性化合物聚合而被赋予液晶取向性能的液晶显示器件。
发明效果
本发明的负介电各向异性液晶组合物具有优异的聚合反应速率、低温存储稳定性。进一步，本发明的液晶组合物用在PSA、PSVA等模式的液晶显示器 件中时能够获得提高的紫外线照射后的VHR值，从而能够减小/消除液晶显示装置的“残影”等显示不良的缺陷。由本发明的负介电各向异性液晶组合物的聚合物构成的本发明的光学各向异构体中残留的聚合物少，具有稳定的预倾角，低温存储稳定性良好。本发明的液晶显示器件，制作工艺的生产率提高，并且“残影”等显示不良的缺陷减少。
具体实施方式
[液晶组合物]
本发明的负介电各向异性液晶组合物，其包含：
至少一种式I所示化合物；
至少一种式Ⅱ所示化合物；以及，
至少一种式Ⅲ所示化合物。
Figure PCTCN2023071140-appb-000002
式I中，P 1、P 2各自独立地表示聚合性基团，作为聚合性基团，可以列举出如下的基团：丙烯酸酯基、甲基丙烯酸酯基、乙基丙烯酸酯基、丙基丙烯酸酯基、丁基丙烯酸酯基、戊基丙烯酸酯基、氟代丙烯酸酯基、氟代甲基丙烯酸酯基、氟代乙基丙烯酸酯基、氟代丙基丙烯酸酯基、氟代丁基丙烯酸酯基或氟代戊基丙烯酸酯基。
前述的“氟代”可以是单氟取代、多氟取代，也可以是全氟取代。
这些基团通过自由基聚合、自由基加成聚合、阳离子聚合、阴离子聚合等而进行固化。尤其在紫外线聚合的情况下，优选P 1、P 2各自独立地表示丙烯酸酯基或者甲基丙烯酸酯基。
式I中，Z 1、Z 2各自独立地表示单键、碳原子数为1～8的直链亚烷基、碳原子数为1～8的直链亚烷氧基、碳原子数为2～8的直链亚烯基、或者碳原子数为2～8的直链亚烯氧基，其中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选被F原子取代。优选地，Z 1、Z 2各自独立地表示单键、碳原子数为1～5的直链亚烷基、碳原子数为1～5的直链亚烷氧基、碳原子数为2～5的直链亚烯基、或者碳原子数为2～5的直链亚烯氧基，其中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选被F原子取代。进一步优选地，Z 1、Z 2各自独立地表示单键、碳原子数为1～3的直链亚烷基、碳原子数为1～3的直链亚烷氧基、碳原子数为2～4的直链亚烯基、或者碳原子数为2～4的直链亚烯氧基，其中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选被F原子取代。
作为前述的“碳原子数为1～3的直链亚烷基”，可以列举出亚甲基、亚乙基、亚丙基。作为前述的“碳原子数为1～3的直链亚烷氧基”，可以列举出例如亚甲基氧基、亚乙基氧基、亚丙基氧基。作为前述的“碳原子数为2～3的直链亚烯基”，有例如亚乙烯基、亚丙烯基、亚丁烯基。作为前述的“碳原子数为2～4的直链亚烯氧基”，可以列举出例如亚乙烯基氧基、亚丙烯基氧基、亚丁烯基氧基等。这些基团中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选被F原子取代。
前述的式I所示化合物中，Y 1、Y 2、Y 3、Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10各自独立地表示-H、-F、-CH 3、-CH 2F、-CHF 2、-CF 3、-C 2H 5、-OCH 3、-OCH 2F、-OCHF 2、-OCF 3或者-OC 2H 5。其中，Y 1、Y 2任选相同或者不同。
本发明的负介电各向异性液晶组合物的一些实施方式中，优选地，式I所示化合物中Y 1、Y 2各自独立地表示-H、-F、-CH 3、-CF 3、-OCH 3、-C 2H 5、-OC 2H 5或者-OCF 3。更优选Y 1、Y 2各自独立地表示-H、-F、-CF 3、或者-OCF 3。进一步优选Y 1、Y 2各自独立地为-H、或者、-F。
本发明的负介电各向异性液晶组合物的一些实施方式中，优选地，式I所示化合物中Y 3、Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10表示-H或者-F。更优选Y 3、 Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10均为-H。
本发明的负介电各向异性液晶组合物的一些实施方式中，从获得更快的聚合反应速率等方面考虑，n优选为0或者1，进一步优选n＝1。
本发明的负介电各向异性液晶组合物的一些实施方式中，优选式I所示化合物为选自下述的式I-1～I-57所示化合物组成的组，其中P 1、P 2、Z 1、Z 2定义与前述相同。
Figure PCTCN2023071140-appb-000003
Figure PCTCN2023071140-appb-000004
Figure PCTCN2023071140-appb-000005
Figure PCTCN2023071140-appb-000006
Figure PCTCN2023071140-appb-000007
Figure PCTCN2023071140-appb-000008
Figure PCTCN2023071140-appb-000009
Figure PCTCN2023071140-appb-000010
进一步地，前述的式I所示化合物优选选自下述的式IA-1～IA-258所示化合物组成的组。
Figure PCTCN2023071140-appb-000011
Figure PCTCN2023071140-appb-000012
Figure PCTCN2023071140-appb-000013
Figure PCTCN2023071140-appb-000014
Figure PCTCN2023071140-appb-000015
Figure PCTCN2023071140-appb-000016
Figure PCTCN2023071140-appb-000017
Figure PCTCN2023071140-appb-000018
Figure PCTCN2023071140-appb-000019
Figure PCTCN2023071140-appb-000020
Figure PCTCN2023071140-appb-000021
Figure PCTCN2023071140-appb-000022
Figure PCTCN2023071140-appb-000023
Figure PCTCN2023071140-appb-000024
Figure PCTCN2023071140-appb-000025
Figure PCTCN2023071140-appb-000026
Figure PCTCN2023071140-appb-000027
Figure PCTCN2023071140-appb-000028
Figure PCTCN2023071140-appb-000029
Figure PCTCN2023071140-appb-000030
Figure PCTCN2023071140-appb-000031
Figure PCTCN2023071140-appb-000032
Figure PCTCN2023071140-appb-000033
Figure PCTCN2023071140-appb-000034
Figure PCTCN2023071140-appb-000035
Figure PCTCN2023071140-appb-000036
Figure PCTCN2023071140-appb-000037
Figure PCTCN2023071140-appb-000038
Figure PCTCN2023071140-appb-000039
Figure PCTCN2023071140-appb-000040
Figure PCTCN2023071140-appb-000041
Figure PCTCN2023071140-appb-000042
Figure PCTCN2023071140-appb-000043
Figure PCTCN2023071140-appb-000044
Figure PCTCN2023071140-appb-000045
Figure PCTCN2023071140-appb-000046
本发明的液晶组合物中，前述的式II所示化合物的结构式如下所示。
Figure PCTCN2023071140-appb-000047
式II中，R 3、R 4各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 3、R 4中任意碳原子上的H各自独立地任选被F取代；
环C、环D各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5-二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基；
p表示0、1、2或者3。
作为前述的R 3、R 4各自独立地表示的“碳原子数为1～5的烷基”，可以为直链烷基、支链烷基或者环状烷基，优选为直链烷基。作为这样的直链烷基，可以列举出例如甲基、乙基、正丙基、正丁基、正戊基。作为支链烷基，可以列 举出例如异丙基、异丁基、叔丁基等。作为环状烷基，可以列举出环丙基、环丁基、环戊基、甲基环丙基、甲基环丁基等。
作为前述的R 3、R 4各自独立地表示的“碳原子数为1～5的烷氧基”，可以列举出例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、正戊氧基、叔戊氧基等。
作为前述的R 3、R 4各自独立地表示的“碳原子数为2～5的烯基”，可以列举出例如乙烯基、丙烯基、丁烯基、2-甲基丙烯基、1-戊烯基、2-戊烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、2-甲基-2-丁烯基等。
作为前述的R 3、R 4各自独立地表示的“碳原子数为2～5的烯氧基”，可以列举出例如乙烯氧基、丙烯氧基、丁烯氧基、2-甲基丙烯氧基、1-戊烯氧基、2-戊烯氧基、2-甲基-1-丁烯氧基、3-甲基-1-丁烯氧基、2-甲基-2-丁烯氧基等。
作为前述的式Ⅱ所示的化合物，优选选自下述的式Ⅱ-1至Ⅱ-11所示化合物组成的组。其中，R 3、R 4的定义与前述相同。
Figure PCTCN2023071140-appb-000048
Figure PCTCN2023071140-appb-000049
(F)表示F或H。RRRA11HCZCZCHH1RBZ2m22Rn112
本发明的液晶组合物中，前述的式Ⅲ所示化合物的结构式如下所示。
Figure PCTCN2023071140-appb-000050
式Ⅲ中，R 5、R 6各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 5、R 6中任意碳原子上的H各自独立地任选被F取代；
Z 3表示单键或-CH 2O-；
q、r各自独立地表示0、1或2；
环E、环F各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5-二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基。
作为前述的R 5、R 6各自独立地表示的“碳原子数为1～5的烷基”，可以为直链烷基、支链烷基或者环状烷基，优选为直链烷基。作为这样的直链烷基，可以列举出例如甲基、乙基、正丙基、正丁基、正戊基。作为支链烷基，可以列举出例如异丙基、异丁基、叔丁基等。作为环状烷基，可以列举出环丙基、环丁基、环戊基、甲基环丙基、甲基环丁基等。
作为前述的R 5、R 6各自独立地表示的“碳原子数为1～5的烷氧基”，可以列举出例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、正戊氧基、叔戊氧基等。
作为前述的R 5、R 6各自独立地表示的“碳原子数为2～5的烯基”，可以列举出例如乙烯基、丙烯基、丁烯基、2-甲基丙烯基、1-戊烯基、2-戊烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、2-甲基-2-丁烯基等。
作为前述的R 5、R 6各自独立地表示的“碳原子数为2～5的烯氧基”，可以列举出例如乙烯氧基、丙烯氧基、丁烯氧基、2-甲基丙烯氧基、1-戊烯氧基、2-戊烯氧基、2-甲基-1-丁烯氧基、3-甲基-1-丁烯氧基、2-甲基-2-丁烯氧基等。
优选地，前述的式Ⅲ所示的化合物选自下述的式Ⅲ-1至Ⅲ-17所示化合物组成的组。其中，R 5、R 6的定义与前述相同。
Figure PCTCN2023071140-appb-000051
Figure PCTCN2023071140-appb-000052
Figure PCTCN2023071140-appb-000053
前述的负介电各向异性液晶组合物的一个实施方式中，式I所示化合物、式II所示化合物、式III所示化合物例如可以以下述的比例含有：相对于100质量份液晶组合物，所述式I所示化合物为0.001～1质量份，所述式Ⅱ所示化合物为10～60质量份，所述式Ⅲ所示化合物为10～70质量份。
本发明的负介电各向异性液晶组合物的一些实施方式中，还可以含有下述的式Ⅳ-1～Ⅳ-50所示的化合物。
Figure PCTCN2023071140-appb-000054
Figure PCTCN2023071140-appb-000055
Figure PCTCN2023071140-appb-000056
Figure PCTCN2023071140-appb-000057
Figure PCTCN2023071140-appb-000058
其中，R 1’表示H或者碳原子数为1～8的烷基或碳原子数为2～8的烯基,并且任选4个以下H被F取代；
R 2’表示H或者碳原子数为1～8的烷基或碳原子数为2～8的烯基，其中一个或两个不相邻的-CH 2-任选被-O-所取代，并且任选4个以下H被F取代。
本发明的负介电各向异性液晶组合物的一些实施方式中，各组分可以以下述的质量配比的方式含有：相对于100质量份负介电各向异性液晶组合物，前述式I所示化合物为0.001～0.3质量份，前述式Ⅱ所示化合物为20～60质量份，前述式Ⅲ所示化合物为20～60质量份，前述式Ⅳ所示的化合物为1～20质量份。
本发明的负介电各向异性液晶组合物的一些实施方式中，还任选含有一种 或多种下述的式Ⅴ-1～Ⅴ-78所示的化合物：
Figure PCTCN2023071140-appb-000059
Figure PCTCN2023071140-appb-000060
Figure PCTCN2023071140-appb-000061
Figure PCTCN2023071140-appb-000062
Figure PCTCN2023071140-appb-000063
Figure PCTCN2023071140-appb-000064
Figure PCTCN2023071140-appb-000065
Figure PCTCN2023071140-appb-000066
本发明的负介电各向异性液晶组合物的一些实施方式中，含有前述的式V所示的化合物的情况下，可以按照下述的质量配比含有各组分：相对于100质量份负介电各向异性液晶组合物，前述式I所示化合物为0.001～0.3质量份，前述式Ⅱ所示化合物为20～60质量份，前述式Ⅲ所示化合物为20～60质量份，前述式Ⅳ所示的化合物为1～20质量份，前述式Ⅴ所示的化合物为1～10质量份。
本发明的负介电各向异性液晶组合物中，可选的，还可以加入各种功能的 添加剂，这些添加剂可以列举出例如UV稳定剂、抗氧化剂、手性掺杂剂、聚合起始剂，可以含有它们中的一种，或者多种。
[光学各向异构体]
本发明的光学各向异构体通过使用本发明的负介电各向异性液晶组合物聚合而成。通过在本发明的负介电各向异性液晶组合物取向的状态下使其中的聚合性化合物聚合而制造得到前述的光学各向异构体。本发明的光学各向异构体具有光学各向异性。这样的光学各向异构体例如可以如下制造：将本发明的负介电各向异性液晶组合物夹于利用布等对形成有有机薄膜的基板表面进行了摩擦处理的基板间，然后使本发明的液晶组合物聚合。
另外，通过电场控制取向状态的情况下，可以使用具有电极层的基板。这种情况下，优选在电极上形成有聚酰亚胺薄膜等有机薄膜。
作为使本发明的液晶组合物聚合的方法，从快速聚合的角度考虑，优选通过照射紫外线、电子射线等活性能量射线进行聚合的方法。在使液晶聚合物夹持于2片基板的状态下进行聚合的情况下，使至少照射面侧的基板对活性能量射线具有透过性。活性能量射线的照射强度及时间等根据需要适宜确定即可。
通过这样的方法制造的本发明的光学各向异构体可以从基板剥离后单独使用，也可以不剥离而使用。另外，也可将其贴合于其他基板进行使用。
[液晶显示器件]
本发明的液晶显示器件为使用前述的本发明的负介电各向异性液晶组合物，使负介电各向异性液晶组合物中的聚合性化合物聚合而被赋予液晶取向性能的液晶显示器件。
本发明的液晶显示器件的驱动方式优选为例如PS-VA模式、PVA模式、或者、或者PS-IPS模式。
实施例
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
下述的制备方法如无特殊说明则均为常规方法，所用的原料如无特别说明均可从公开的商业途径获得，百分比均是指质量百分比，温度为摄氏度(℃)，液晶化合物也为液晶单体。
实施例及对比例中制备了不同组成的负介电各向异性液晶组合物，其中，各例中所使用的具体化合物的单体结构、用量(质量份)、所得的液晶介质的性能参数测试结果分别如后述的表所示。
各实施例中所涉温度单位为℃，其他符号的具体意义及测试条件如下：
G1(mPa.s)表示液晶化合物的旋转粘滞系数，测定方法：仪器设备INSTEC:ALCT-IR1、测试盒盒厚18微米垂直盒、温度25℃，简写为“G1”；
K 11为扭曲弹性常数，K 33为展曲弹性常数，测试条件为：25℃、INSTEC:ALCT-IR1、18微米垂直盒；
Δε表示介电各向异性，Δε＝ε ∥-ε ⊥，其中，ε ∥为平行于分子轴的介电常数，ε ⊥为垂直于分子轴的介电常数，测试条件：25℃、INSTEC:ALCT-IR1、18微米垂直盒；
Δn表示光学各向异性，Δn＝n e-n o，其中，n o为寻常光的折射率，n e为非寻常光的折射率，测试条件：589nm、25±0.2℃。
Tni：向列相-各向同性液体相转变温度(℃)。
低温保存性：将含聚合性化合物的液晶组合物的实施例在-20℃下冷却240小时后，观察有无聚合性化合物的析出，作为低温保存性的指标。将无析出且不会引起亮点等显示不良的情况标记为〇，将存在析出的情况标记为×。
聚合反应速率：在紫外线波长主波段＝365nm、照度值为2mW/cm 2、照射总能量分别为3J、6J、及9J的固定照射条件下，分别照射对比例1以及实施例的液晶组合物，然后通过测量高效液相色谱得到照射前后聚合性单体的浓度，计算比值(照射后聚合性单体的浓度(％)/照射前聚合性单体的浓度(％))，根据公式：反应聚合转化率＝1-(照射后聚合性单体的浓度/照射前聚合性单体的浓度)计算得到聚合反应速率。
VHR测试：测试紫外光照射前后的电压保持率(％)，测试条件为60±2℃、电压为±5V、脉冲宽度为1ms、电压保持时间16.7ms。测试设备为VHR-AMP01 液晶VHR测试仪。VHR恶化使用紫外光365nm波长，照射光强为2.5Mw/cm 2进行光辐照，辐照时间为34分钟。
实施例中各负介电各向异性液晶组合物的制备方法如下：将各液晶单体按照一定配比称量后放入不锈钢烧杯中，将装有各液晶单体的不锈钢烧杯置于磁力搅拌仪器上加热融化，待不锈钢烧杯中的液晶单体大部份融化后，往不锈钢烧杯中加入磁力转子，将混合物搅拌均匀，冷却到室温后即得液晶组合物。
实施例中所使用的液晶单体的结构用下述代码表示，液晶环结构、端基、连接基团的代码表示方法见下表(一)、表(二)。
表(一)：环结构的对应代码
Figure PCTCN2023071140-appb-000067
Figure PCTCN2023071140-appb-000068
Figure PCTCN2023071140-appb-000069
Figure PCTCN2023071140-appb-000070
表(二)：端基与链接基团的对应代码
Figure PCTCN2023071140-appb-000071
举例：
Figure PCTCN2023071140-appb-000072
按照下述的表1～10所示的配比，制备实施例1～8以及对比例1～2的液晶组合物。
表1实施例1的液晶组合物LC-1的组分配比
化合物通式 液晶结构式 质量份
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
表2实施例2的液晶组合物LC-2的组分配比
化合物通式 液晶结构式 质量份
Ⅱ CC-3-V 35.0
III CCY-3-O3 10.0
III CCY-4-O2 10.0
Ⅱ CPP-1V-2 3.0
Ⅲ CPY-3-O2 10.0
Ⅲ COY-3-O2 10.0
I BH(S)-MAO-2OMA 0.1
Ⅱ PP-1-2V1 8.0
Ⅱ CC-2-3 9.0
Ⅲ PYP-2-3 5.0
表3实施例3的液晶组合物LC-3的组分配比
化合物通式 液晶结构式 质量份
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
表4实施例4的液晶组合物LC-4的组分配比
化合物通式 液晶结构式 质量份
Ⅱ CC-3-V 32.0
Ⅲ APY-3-O2 5.0
I B(S)-MAO-OMA 0.2
Ⅲ CCY-3-O2 8.0
Ⅲ CPY-3-O2 5.0
Ⅱ CPP-1-2V1 10.0
Ⅲ CY-3-O2 15.0
Ⅲ PGIY-3-O2 5.0
Ⅱ PP-1-5 5.0
IV CVCCY-V-O2 10.0
IV CVECPY-V-O4 5.0
表5实施例5的液晶介质LC-5的组分配比
化合物通式 液晶结构式 质量份
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
表6实施例6的液晶介质LC-6的组分配比
化合物通式 液晶结构式 质量份
Ⅱ CC-3-V 35.0
Ⅱ CCP-V-1 14.0
Ⅲ CY-3-O2 7.0
Ⅲ CCY-3-O2 8.0
I B(S)[CH 3,CH 3]-MAO-OMA 0.3
Ⅲ COY-3-O2 5.0
Ⅲ CPY-3-O2 5.0
IV CVCPY-3-O2 5.0
IV PVEPYP-1V-O2 5.0
Ⅲ PYY-3-O2 6.0
V PVEB-V-O2 5.0
V YVEB(S)-V-O2 5.0
表7实施例7的液晶介质LC-7的组分配比
Figure PCTCN2023071140-appb-000073
Figure PCTCN2023071140-appb-000074
表8实施例8的液晶介质LC-8的组分配比
化合物通式 液晶结构式 质量份
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
表9：对比例1的液晶介质C-01的组分配比
化合物通式 液晶结构式 质量份
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
  PG-MAO-OMA 0.1
Ⅱ PP-1-2V1 5.0
Ⅱ CLP-3-1 10.0
III PYP-2-3 8.0
表10：对比例2的液晶介质C-02的组分配比
化合物通式 液晶结构式 质量份
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
将前述制备的实施例以及对比例的液晶组合物填充于液晶显示器两基板间进行性能测试，得到的测试结果如下表所示。需要说明的是，对比例2中不含有聚合性单体，因此，没有进行聚合反应速率测试。
表11实施例以及对比例的液晶组合物的性能测试结果
Figure PCTCN2023071140-appb-000075
Figure PCTCN2023071140-appb-000076
如上述的表11所示，实施例1～8的液晶组合物与对比例1的液晶组合物相比，实施例1～8中的含有聚合性单体化合物的组合物经紫外线(UV)照射能量3J～9J后，其聚合反应速率均快于对比例1，可以缩短现有量产聚合物稳定排列制程时间。
进而，对在实施例1～实施例8中所获得的液晶显示器件中残存的聚合性化合物的量进行确认，结果残留量充分少。
另外，与比较例1相比，实施例1～8的液晶组合物显示出更优异的低温保存性。
根据以上确认到，本发明的液晶组合物在用于PS-VA液晶显示器件、PS-VA显示器件等时能够获得良好的低温保存性、较快的聚合速率。
进一步，实施例1～8的组合物的经紫外线(UV)照射后的VHR比含有现有技术中使用的聚合性单体化合物的对比例1的组合物更高，这也说明了实施例1～8的液晶组合物具有高电压保持率等性能，具有较高的可靠性，不容易发生预倾角的变化导致的显示不良。
本发明虽未穷尽要求保护的所有液晶混合物，但是本领域技术人员可以预见的是，在已公开的上述实施例基础上，仅结合自身的专业尝试即能以类似的方法得到其他同类液晶材料而不需要付出创造性劳动。此处由于篇幅有限，仅列举代表性的实施方式。

Claims (12)

  1. 一种负介电各向异性液晶组合物，其特征在于，所述液晶组合物包含：
    至少一种式I所示化合物；
    至少一种式Ⅱ所示化合物；以及，
    至少一种式Ⅲ所示化合物；
    Figure PCTCN2023071140-appb-100001
    式I中，P 1、P 2各自独立地表示丙烯酸酯基、甲基丙烯酸酯基、乙基丙烯酸酯基、丙基丙烯酸酯基、丁基丙烯酸酯基、戊基丙烯酸酯基、氟代丙烯酸酯基、氟代甲基丙烯酸酯基、氟代乙基丙烯酸酯基、氟代丙基丙烯酸酯基、氟代丁基丙烯酸酯基或氟代戊基丙烯酸酯基；
    Z 1、Z 2各自独立地表示单键、碳原子数为1～8的直链亚烷基、碳原子数为1～8的直链亚烷氧基、碳原子数为2～8的直链亚烯基、或者碳原子数为2～8的直链亚烯氧基，其中一个或两个不相邻的-CH 2-任选被-O-取代，任意的H任选被F原子取代；
    Y 1、Y 2、Y 3、Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10各自独立地表示-H、-F、-CH 3、-CH 2F、-CHF 2、-CF 3、-C 2H 5、-OCH 3、-OCH 2F、-OCHF 2、-OCF 3或者-OC 2H 5；
    n表示0、1或2；
    式II中，R 3、R 4各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 3、R 4中任意碳原子上的H各自独立地任选被F取代；
    环C、环D各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5- 二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基；
    p表示0、1、2或3；
    式Ⅲ中，R 5、R 6各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；并且，R 5、R 6中任意碳原子上的H各自独立地任选被F取代；
    Z 3表示单键或-CH 2O-；
    q、r各自独立地表示0、1或2；
    环E、环F各自独立地选自下述的基团组成的组：1,4-亚环己基、环己烯-1,4-二基、1,4-亚苯基、2-氟-1,4-亚苯基、2,3-二氟-1,4-亚苯基、氧杂环己烷-2,5-二基、1,3-二氧杂环己烷-2,5-二基、1-甲基环己烷-1,4-二基、2-甲基环己烷-1,4-二基、2-甲基苯-1,4-二基。
  2. 根据权利要求1所述的负介电各向异性液晶组合物，其中，所述式I所示化合物选自下述的式I-1～I-57所示化合物组成的组，其中P 1、P 2、Z 1、Z 2定义与权利要求1中相同，
    Figure PCTCN2023071140-appb-100002
    Figure PCTCN2023071140-appb-100003
    Figure PCTCN2023071140-appb-100004
    Figure PCTCN2023071140-appb-100005
    Figure PCTCN2023071140-appb-100006
    Figure PCTCN2023071140-appb-100007
    Figure PCTCN2023071140-appb-100008
    Figure PCTCN2023071140-appb-100009
  3. 根据权利要求1或2所述的负介电各向异性液晶组合物，其中，所述式I所示化合物选自下述的式IA-1～IA-258所示化合物组成的组；
    Figure PCTCN2023071140-appb-100010
    Figure PCTCN2023071140-appb-100011
    Figure PCTCN2023071140-appb-100012
    Figure PCTCN2023071140-appb-100013
    Figure PCTCN2023071140-appb-100014
    Figure PCTCN2023071140-appb-100015
    Figure PCTCN2023071140-appb-100016
    Figure PCTCN2023071140-appb-100017
    Figure PCTCN2023071140-appb-100018
    Figure PCTCN2023071140-appb-100019
    Figure PCTCN2023071140-appb-100020
    Figure PCTCN2023071140-appb-100021
    Figure PCTCN2023071140-appb-100022
    Figure PCTCN2023071140-appb-100023
    Figure PCTCN2023071140-appb-100024
    Figure PCTCN2023071140-appb-100025
    Figure PCTCN2023071140-appb-100026
    Figure PCTCN2023071140-appb-100027
    Figure PCTCN2023071140-appb-100028
    Figure PCTCN2023071140-appb-100029
    Figure PCTCN2023071140-appb-100030
    Figure PCTCN2023071140-appb-100031
    Figure PCTCN2023071140-appb-100032
    Figure PCTCN2023071140-appb-100033
    Figure PCTCN2023071140-appb-100034
    Figure PCTCN2023071140-appb-100035
    Figure PCTCN2023071140-appb-100036
    Figure PCTCN2023071140-appb-100037
    Figure PCTCN2023071140-appb-100038
    Figure PCTCN2023071140-appb-100039
    Figure PCTCN2023071140-appb-100040
    Figure PCTCN2023071140-appb-100041
    Figure PCTCN2023071140-appb-100042
    Figure PCTCN2023071140-appb-100043
    Figure PCTCN2023071140-appb-100044
    Figure PCTCN2023071140-appb-100045
  4. 根据权利要求1～3的任一项所述的负介电各向异性液晶组合物，其中，所述式Ⅱ所示的化合物选自下述的式Ⅱ-1至Ⅱ-11所示化合物组成的组:
    Figure PCTCN2023071140-appb-100046
    Figure PCTCN2023071140-appb-100047
    R 3、R 4各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基；R 3、R 4中任意碳原子上的氢各自独立地任选被氟取代；
    (F)表示F或H。
  5. 根据权利要求1～4的任一项所述的负介电各向异性组合物，其中，所述式Ⅲ所示的化合物选自下述的式Ⅲ-1至Ⅲ-17所示化合物组成的组:
    Figure PCTCN2023071140-appb-100048
    Figure PCTCN2023071140-appb-100049
    R 5、R 6各自独立地表示碳原子数为1～5的烷基、碳原子数为1～5的烷氧基、碳原子数为2～5的烯基、或碳原子数为2～5的烯氧基，并且R 5、R 6中任 意碳原子上的H各自独立地任选被F取代。
  6. 根据权利要求1～5的任一项所述的负介电各向异性液晶组合物，其中，所述液晶组合物还包含一种或多种下述的式Ⅳ-1～Ⅳ-50所示的化合物：
    Figure PCTCN2023071140-appb-100050
    Figure PCTCN2023071140-appb-100051
    Figure PCTCN2023071140-appb-100052
    Figure PCTCN2023071140-appb-100053
    Figure PCTCN2023071140-appb-100054
    其中，R 1’表示H或者碳原子数为1～8的烷基或碳原子数为2～8的烯基,并且任选4个以下H被F取代；
    R 2’表示H或者碳原子数为1～8的烷基或碳原子数为2～8的烯基，其中一个或两个不相邻的-CH 2-任选被-O-所取代，并且任选4个以下H被F取代。
  7. 根据权利要求1～6的任一项所述的负介电各向异性液晶组合物，其中，所述液晶组合物还包含一种或多种下述的式Ⅴ-1～Ⅴ-78所示的化合物：
    Figure PCTCN2023071140-appb-100055
    Figure PCTCN2023071140-appb-100056
    Figure PCTCN2023071140-appb-100057
    Figure PCTCN2023071140-appb-100058
    Figure PCTCN2023071140-appb-100059
    Figure PCTCN2023071140-appb-100060
    Figure PCTCN2023071140-appb-100061
    Figure PCTCN2023071140-appb-100062
    Figure PCTCN2023071140-appb-100063
  8. 根据权利要求1～5的任一项所述的负介电各向异性液晶组合物，其中，相对于100质量份所述负介电各向异性液晶组合物，所述式I所示化合物为0.001～1质量份，所述式Ⅱ所示化合物为10～60质量份，所述式Ⅲ所示化合物为10～70质量份。
  9. 根据权利要求6所述的负介电各向异性液晶组合物，其中，相对于100质量份所述负介电各向异性液晶组合物，所述式I所示化合物为0.001～0.3质量份，所述式Ⅱ所示化合物为20～60质量份，所述式Ⅲ所示化合物为20～60质量份，所述式Ⅳ所示的化合物为1～20质量份。
  10. 根据权利要求7所述的负介电各向异性液晶组合物，其中，相对于100质量份所述负介电各向异性液晶组合物，所述式I所示化合物为0.001～0.3质量份，所述式Ⅱ所示化合物为20～60质量份，所述式Ⅲ所示化合物为20～60质量份，所述式Ⅳ所示的化合物为1～20质量份,所述式Ⅴ所示的化合物为1～10质量份。
  11. 一种光学各向异构体，其由权利要求1～10的任一项所述的负介电各向异性液晶组合物的聚合物构成。
  12. 一种液晶显示器件，其为使用权利要求1～10的任一项所述的负介电各向异性液晶组合物，使所述负介电各向异性液晶组合物中的聚合性化合物聚合而被赋予液晶取向性能的液晶显示器件。
PCT/CN2023/071140 2022-01-13 2023-01-08 负介电各向异性液晶组合物、光学各向异构体及液晶显示器件 WO2023134596A1 (zh)

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