WO2023134594A1 - 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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WO2023134594A1
WO2023134594A1 PCT/CN2023/071138 CN2023071138W WO2023134594A1 WO 2023134594 A1 WO2023134594 A1 WO 2023134594A1 CN 2023071138 W CN2023071138 W CN 2023071138W WO 2023134594 A1 WO2023134594 A1 WO 2023134594A1
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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
江德
冷雪
尹硕
赖育宏
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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13712—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy

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.
  • Liquid crystal display devices are widely used in televisions and the like, but have a problem in response speed compared with organic EL, plasma, and the like.
  • a liquid crystal display device it is common practice to make a pixel multi-domain to improve visual characteristics, thus providing a projection structure in a pixel to perform pixel division.
  • the protrusion when the protrusion is provided, there is a difference in pretilt angle between the portion near the protrusion and the separated portion, which causes a problem that the response speed of the separated portion decreases.
  • display devices are generally constructed by improving the alignment method without adjusting the structure.
  • PSA Polymer Sustained Alignment
  • PSVA Polymer Stabilized Vertical Alignment
  • 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 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.
  • a polymer that is a cured product of a polymerizable compound is flexible, when the same pattern is continuously displayed for a long time when a display device is formed, the structure of the polymer changes, and as a result, the pretilt angle changes.
  • a change in pretilt causes aging as it greatly affects response speed.
  • a polymerizable compound forming a polymer having a rigid structure in which the polymer structure does not change is effective, but the low-temperature storage of the liquid crystal composition deteriorates. Compatibility also needs to be improved.
  • An object of the present invention is to provide a liquid crystal composition which has excellent UV reactivity and is excellent in compatibility (storage stability) with a liquid crystal compound which is a component of the liquid crystal composition.
  • another object of the present invention is the storage stability of the composition when used in PSA, PSVA display devices, display properties, UV reactive polymer polymerized under short UV irradiation time or shorter irradiation energy, without Reaction of the polymer wherein the remaining amount is reduced.
  • 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 combining compounds having specific structures, and completed the present invention.
  • the present invention provides a kind of negative dielectric anisotropy liquid crystal composition, it 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 straight chain alkylene group having 1 to 8 carbon atoms, a straight chain alkyleneoxy group having 1 to 8 carbon atoms, a straight chain alkylene group having 2 to 8 carbon atoms
  • Straight-chain alkenylene, or straight-chain alkenyleneoxy with 2 to 8 carbon atoms wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is optionally substituted by F atom substitution;
  • Y 1 and Y 2 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 , when Y 1 is selected from H or F and Y 2 is selected from H or F, neither Z 1 nor Z 2 represent a single bond;
  • 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 anisotropic liquid crystal composition of the present invention has excellent UV reactivity, and when the negative dielectric anisotropic liquid crystal composition of the present invention is polymerized to impart liquid crystal orientation ability in a liquid crystal display device, the reliability and reliability of the liquid crystal display device will be improved. Productivity is improved.
  • the negative dielectric anisotropy liquid crystal composition of the present invention also has excellent storage stability as evaluated by precipitating or separating crystals during storage.
  • 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 and Y 2 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 when Y 1 is selected from H or F and Y 2 is selected from H or F, Z 1 , Z 2 Neither represents a single bond.
  • Y 1 and Y 2 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 , 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 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each independently represent -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 the formula I is preferably selected from the group consisting of the compounds represented by the following formulas I-1 to I-57, wherein P 1 , P 2 , Z 1 , Z 2 definition is 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-244.
  • 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.
  • the negative dielectric anisotropy liquid crystal composition of the present invention may also optionally contain one or more compounds represented by the following formulas V-1 to 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, One or more of them may be included.
  • 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 dielectric anisotropy 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 on the side of an irradiation surface 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 preparation method is a conventional method unless otherwise specified, and the raw materials used can be obtained from open commercial channels if not otherwise specified, and the percentages all refer to mass percentages, the temperature is degrees Celsius (°C), and the liquid crystal compound is also 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.
  • Table 9 The component distribution ratio of the liquid crystal medium LC-6 of embodiment 6
  • Table 10 The component distribution ratio of the liquid crystal medium LC-7 of embodiment 7
  • the VHR performance of the example after ultraviolet deterioration is better than that of Comparative Example 1 and Comparative Example 2, which shows that the liquid crystal composition of the example has high voltage retention and other properties, and has high reliability.
  • the polymerization reaction rates of the liquid crystal compositions of Examples are faster than those of Comparative Examples 1 and 2 after being irradiated with ultraviolet (UV) energy of 3J-9J. Therefore, the composition of the embodiment has the property of rapid polymerization, which can shorten the process time of mass-produced polymer stable alignment.
  • UV ultraviolet

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
液晶显示装置广泛用于电视等，但与有机EL、等离子体等相比，在响应速度方面存在问题。另一方面，在液晶显示器件中，通常的做法是将像素制成多畴以改善视觉特性，因此在像素中提供投影结构以执行像素分割。然而，当设置突起时，在突起附近的部分和分离的部分之间存在预倾角的差异，这导致分离部分的响应速度降低的问题。为了解决该问题，通常通过在不调整结构的情况下改进对准方法来构造显示装置。
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，不可聚合液晶组合物和可聚合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可聚合化合物聚合，并将液晶的取向状态储存在固化产物中。
这种液晶显示器件的问题仍然存在诸如当长时间持续相同显示时出现的“老化”等可靠性问题，存储稳定性和由制造工艺引起的生产率等问题。可靠性问题并不简单，它是由几个复杂因素引起，但特别是，(1)由于剩余的可聚合化合物，(2)液晶分子倾斜的变化(预倾角的变化)，(3)由于紫外线照射引起的液晶分子等的劣化等因素。
关于可靠性，在使用聚合引发剂的情况下，可聚合引发剂及其分解产物导致液晶显示器件的电压保持率降低和老化的原因。因此，需要含有可聚合化合物的液晶组合物，其在不使用光聚合引发剂的情况下以少量紫外光完成聚合。另外，还已知老化的发生是由含有可聚合化合物的液晶组合物中的液晶分子的预倾角的变化引起的。即，如果作为可聚合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的图案时，聚合物的结构改变，结果，预倾角改变。预倾角的变化会导致老化，因为它会极大地影响响应速度。由此，为了解决(2)，形成具有其中聚合物结构不改变的刚性结构的聚合物的可聚合化合物是有效的，但是液晶组合物的低温储存劣化。还需要改善兼容性。如果在所有环结构和可聚合官能团之间插入间隔基团以提高溶解度，则分子的刚性降低并且控制液晶分子倾斜的能力降低。因此，需要开发满足UV反应性，预倾角稳定性和溶解性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液晶组合物，其具有优异的UV反应性和与作为液晶组合物的组分的液晶化合物的相容性(储存稳定性)优异。另外，本发明的另一个目的是在PSA、PSVA显示器件中使用时组合物的储存稳定性，显示特性，在短的UV照射时间或更短的照射能量下聚合的UV反应性聚合物，未反应的聚合物其中剩余量的减少。
本发明人等为了解决上述课题而进行了深入研究，发现具有特定结构的化合物组合使用可以解决上述课题，由此完成了本发明。
一方面，本发明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 PCTCN2023071138-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、或者、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的直链亚烷基氧基、碳原子数为2～8的直链亚烯基、或者碳原子数为2～8的直链亚烯基氧基，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，当Y 1选自H或F并且Y 2选自H或F时，Z 1、Z 2均不表示单键；
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
本发明负介电各向异性液晶组合物具有优异的UV反应性，将本发明负介电各向异性液晶组合物聚合而赋予液晶取向能力的液晶显示器件中时，液晶显示器件的可靠性和生产率得到改善。
此外，其通过在储存期间沉淀或分离晶体来评价，本发明负介电各向异性液晶组合物还具有优异的储存稳定性。
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 PCTCN2023071138-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。
本发明的式I所示化合物的一些实施方式中，Y 1、Y 2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，当Y 1选自H或F并且Y 2选自H或F时，Z 1、Z 2均不表示单 键。优选地，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。
本发明的式I所示化合物的一些实施方式中，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。优选Y 3、Y 4、Y 5、Y 6、Y 7、Y 8、Y 9、Y 10各自独立地表示-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。
本发明的式I所示化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。
本发明的式I所示化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 PCTCN2023071138-appb-000003
Figure PCTCN2023071138-appb-000004
Figure PCTCN2023071138-appb-000005
Figure PCTCN2023071138-appb-000006
Figure PCTCN2023071138-appb-000007
Figure PCTCN2023071138-appb-000008
Figure PCTCN2023071138-appb-000009
Figure PCTCN2023071138-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-244所示化合物组成的组。
Figure PCTCN2023071138-appb-000011
Figure PCTCN2023071138-appb-000012
Figure PCTCN2023071138-appb-000013
Figure PCTCN2023071138-appb-000014
Figure PCTCN2023071138-appb-000015
Figure PCTCN2023071138-appb-000016
Figure PCTCN2023071138-appb-000017
Figure PCTCN2023071138-appb-000018
Figure PCTCN2023071138-appb-000019
Figure PCTCN2023071138-appb-000020
Figure PCTCN2023071138-appb-000021
Figure PCTCN2023071138-appb-000022
Figure PCTCN2023071138-appb-000023
Figure PCTCN2023071138-appb-000024
Figure PCTCN2023071138-appb-000025
Figure PCTCN2023071138-appb-000026
Figure PCTCN2023071138-appb-000027
Figure PCTCN2023071138-appb-000028
Figure PCTCN2023071138-appb-000029
Figure PCTCN2023071138-appb-000030
Figure PCTCN2023071138-appb-000031
Figure PCTCN2023071138-appb-000032
Figure PCTCN2023071138-appb-000033
Figure PCTCN2023071138-appb-000034
Figure PCTCN2023071138-appb-000035
Figure PCTCN2023071138-appb-000036
Figure PCTCN2023071138-appb-000037
Figure PCTCN2023071138-appb-000038
Figure PCTCN2023071138-appb-000039
Figure PCTCN2023071138-appb-000040
Figure PCTCN2023071138-appb-000041
Figure PCTCN2023071138-appb-000042
Figure PCTCN2023071138-appb-000043
Figure PCTCN2023071138-appb-000044
Figure PCTCN2023071138-appb-000045
Figure PCTCN2023071138-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 PCTCN2023071138-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 PCTCN2023071138-appb-000048
Figure PCTCN2023071138-appb-000049
(F)表示F或H。RRRA11HCHZCHCZ1ZRB2m22Rn112
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 PCTCN2023071138-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 PCTCN2023071138-appb-000051
Figure PCTCN2023071138-appb-000052
Figure PCTCN2023071138-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 PCTCN2023071138-appb-000054
Figure PCTCN2023071138-appb-000055
Figure PCTCN2023071138-appb-000056
Figure PCTCN2023071138-appb-000057
Figure PCTCN2023071138-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 PCTCN2023071138-appb-000059
Figure PCTCN2023071138-appb-000060
Figure PCTCN2023071138-appb-000061
Figure PCTCN2023071138-appb-000062
Figure PCTCN2023071138-appb-000063
Figure PCTCN2023071138-appb-000064
Figure PCTCN2023071138-appb-000065
Figure PCTCN2023071138-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、聚合引发剂，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。
本发明中，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。
[负介电各向异性液晶组合物]
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、对比例2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 PCTCN2023071138-appb-000067
Figure PCTCN2023071138-appb-000068
Figure PCTCN2023071138-appb-000069
表(二)：端基与链接基团的对应代码
Figure PCTCN2023071138-appb-000070
举例：
Figure PCTCN2023071138-appb-000071
按照下述的表1～11所示的配比，制备实施例1～9以及对比例1～2的液晶 组合物。
表1：对比例1的液晶组合物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 CPY-3-O2 10.0
III APY-3-O2 8.0
  B-MAO-OMA 0.1
Ⅱ CPP-5-2V1 8.0
Ⅱ CCP-3-1 7.0
III PYP-2-3 8.0
III CY-3-O2 14
表2：对比例2的液晶组合物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 CPY-3-O2 10.0
III APY-3-O2 8.0
  B[F,H]-MAO-OMA 0.1
Ⅱ CPP-5-2V1 8.0
Ⅱ CCP-3-1 7.0
III PYP-2-3 8.0
III CY-3-O2 14
表3：对比例3的液晶组合物C-03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 CPY-3-O2 10.0
III APY-3-O2 8.0
Ⅱ CPP-5-2V1 8.0
Ⅱ CCP-3-1 7.0
III PYP-2-3 8.0
III CY-3-O2 14
表4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 CPY-3-O2 10.0
III APY-3-O2 8.0
I B-MAO-3OMA 0.1
Ⅱ CPP-5-2V1 8.0
Ⅱ CCP-3-1 7.0
III PYP-2-3 8.0
III CY-3-O2 14
表5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-O2 10.0
III CPY-3-O2 10.0
III APY-3-O2 8.0
I B[F,H]-MAO-3OMA 0.1
Ⅱ CPP-5-2V1 8.0
Ⅱ CCP-3-1 7.0
III PYP-2-3 8.0
III CY-3-O2 14
表6实施例3的液晶组合物LC-3的组分配比
Figure PCTCN2023071138-appb-000072
表7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 28.0
Ⅱ CC-3-5 5.0
Ⅱ PGP-3-1 2.0
Ⅱ CPGP-3-2 2.0
Ⅲ CCY-2-O2 10.0
Ⅲ PGIY-3-O2 9.0
I BP-MAO-3OMA 0.1
Ⅱ CCP-3-1 6.0
Ⅲ CPY-3-O2 11.0
Ⅲ PGY-3-O2 9.0
Ⅱ PP-1-2V1 7.0
III CY-3-O2 11.0
表8实施例5的液晶组合物LC-5的组分配比
Figure PCTCN2023071138-appb-000073
表9：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 28.0
Ⅱ CC-5-V 8.0
I B[H,CH 3]-MAO-OMA 0.1
Ⅲ COY-3-O2 3.0
Ⅲ CPY-3-O2 5.0
Ⅱ PGP-3-2 6.0
Ⅱ PP-1-5 3.0
IV CVEY-V-O2 5.0
IV CVECY-V-O2 12.0
Ⅲ CY-3-O2 8.0
Ⅲ LPY-3-O2 10.0
V COBOIC-3-3 2.0
V B(S)[CF 3,F]OIC-3-2 3.0
Ⅱ CPGP-3-2 7.0
表10：实施例7的液晶介质LC-7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 CCP-3-O1 10.0
Ⅱ PPP-3-1 7.0
Ⅲ AY-3-O2 7.0
Ⅲ CLY-3-O2 5.0
I B[CF 3,CF 3]-MAO-OMA 0.3
Ⅲ COY-3-O2 5.0
IV PVCPY-V-O4 5.0
IV AVEPYP-1V-O2 5.0
IV CVOCCY-1V-O2 4.0
IV CVCY-V-O3 6.0
IV CVGY-V-O2 5.0
V LVEB-V-O2 4.0
V B[CF 3,F]OIC-3-2 5.0
表11：实施例8的液晶介质LC-8的组分配比
Figure PCTCN2023071138-appb-000074
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。测试结果示于下述的表12所示。需要说明的是，对比例3中由 于不含有可聚型单体，因此，没有进行聚合反应速率测试。
表12：实施例以及对比例的液晶组合物的性能测试结果
Figure PCTCN2023071138-appb-000075
如上述的表12所示，实施例的紫外线恶化后VHR表现优于对比例1、对比例2，这说明实施例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。
另外，实施例的液晶组合物与对比例1～2相比，经紫外线(UV)照射能量3J～9J后，其聚合反应速率皆快于对比例1、对比例2。因此实施例的组合物具有快速聚合性能,可以缩短现有量产聚合物稳定排列制程时间。
进而，与比较例1～3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。
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 PCTCN2023071138-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、或者、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的直链亚烷基氧基、碳原子数为2～8的直链亚烯基、或者碳原子数为2～8的直链亚烯基氧基，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，当Y 1选自H或F并且Y 2选自H或F时，Z 1、Z 2均不表示单键；
    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、或者、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的定义与权利要求1中相同，
    Figure PCTCN2023071138-appb-100002
    Figure PCTCN2023071138-appb-100003
    Figure PCTCN2023071138-appb-100004
    Figure PCTCN2023071138-appb-100005
    Figure PCTCN2023071138-appb-100006
    Figure PCTCN2023071138-appb-100007
    Figure PCTCN2023071138-appb-100008
    Figure PCTCN2023071138-appb-100009
  3. 根据权利要求1或2的任一项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-244所示化合物组成的组；
    Figure PCTCN2023071138-appb-100010
    Figure PCTCN2023071138-appb-100011
    Figure PCTCN2023071138-appb-100012
    Figure PCTCN2023071138-appb-100013
    Figure PCTCN2023071138-appb-100014
    Figure PCTCN2023071138-appb-100015
    Figure PCTCN2023071138-appb-100016
    Figure PCTCN2023071138-appb-100017
    Figure PCTCN2023071138-appb-100018
    Figure PCTCN2023071138-appb-100019
    Figure PCTCN2023071138-appb-100020
    Figure PCTCN2023071138-appb-100021
    Figure PCTCN2023071138-appb-100022
    Figure PCTCN2023071138-appb-100023
    Figure PCTCN2023071138-appb-100024
    Figure PCTCN2023071138-appb-100025
    Figure PCTCN2023071138-appb-100026
    Figure PCTCN2023071138-appb-100027
    Figure PCTCN2023071138-appb-100028
    Figure PCTCN2023071138-appb-100029
    Figure PCTCN2023071138-appb-100030
    Figure PCTCN2023071138-appb-100031
    Figure PCTCN2023071138-appb-100032
    Figure PCTCN2023071138-appb-100033
    Figure PCTCN2023071138-appb-100034
    Figure PCTCN2023071138-appb-100035
    Figure PCTCN2023071138-appb-100036
    Figure PCTCN2023071138-appb-100037
    Figure PCTCN2023071138-appb-100038
    Figure PCTCN2023071138-appb-100039
    Figure PCTCN2023071138-appb-100040
    Figure PCTCN2023071138-appb-100041
    Figure PCTCN2023071138-appb-100042
    Figure PCTCN2023071138-appb-100043
    Figure PCTCN2023071138-appb-100044
    Figure PCTCN2023071138-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 PCTCN2023071138-appb-100046
    Figure PCTCN2023071138-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 PCTCN2023071138-appb-100048
    Figure PCTCN2023071138-appb-100049
    Figure PCTCN2023071138-appb-100050
    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-64所示的化合物：
    Figure PCTCN2023071138-appb-100051
    Figure PCTCN2023071138-appb-100052
    Figure PCTCN2023071138-appb-100053
    Figure PCTCN2023071138-appb-100054
    Figure PCTCN2023071138-appb-100055
    Figure PCTCN2023071138-appb-100056
    Figure PCTCN2023071138-appb-100057
    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 PCTCN2023071138-appb-100058
    Figure PCTCN2023071138-appb-100059
    Figure PCTCN2023071138-appb-100060
    Figure PCTCN2023071138-appb-100061
    Figure PCTCN2023071138-appb-100062
    Figure PCTCN2023071138-appb-100063
    Figure PCTCN2023071138-appb-100064
    Figure PCTCN2023071138-appb-100065
    Figure PCTCN2023071138-appb-100066
  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/CN2023/071138 2022-01-17 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 WO2023134594A1 (zh)

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