WO2019001525A1 - 一种液晶组合物及其应用 - Google Patents

一种液晶组合物及其应用 Download PDF

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Publication number
WO2019001525A1
WO2019001525A1 PCT/CN2018/093430 CN2018093430W WO2019001525A1 WO 2019001525 A1 WO2019001525 A1 WO 2019001525A1 CN 2018093430 W CN2018093430 W CN 2018093430W WO 2019001525 A1 WO2019001525 A1 WO 2019001525A1
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Prior art keywords
liquid crystal
crystal composition
group
compound
formula
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PCT/CN2018/093430
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English (en)
French (fr)
Inventor
马文阳
王立威
徐海彬
韩文明
张文琦
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江苏和成显示科技有限公司
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Priority to US16/608,577 priority Critical patent/US11629291B2/en
Publication of WO2019001525A1 publication Critical patent/WO2019001525A1/zh

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    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
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    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • 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
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    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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    • 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
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122—Ph-Ph
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    • 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
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
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    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K2019/2078—Ph-COO-Ph-COO-Ph
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    • C09K19/3001—Cyclohexane rings
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    • 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
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    • C09K19/3001—Cyclohexane rings
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    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
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    • C09K2019/3016—Cy-Ph-Ph
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    • C09K19/3001—Cyclohexane rings
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    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3027—Compounds comprising 1,4-cyclohexylene and 2,3-difluoro-1,4-phenylene
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    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor

Definitions

  • the present invention relates to the field of liquid crystal materials, and in particular to a liquid crystal composition and application thereof.
  • LCDs Liquid crystal displays
  • PC phase change
  • TN tunnel nematic
  • STN super twisted nematic
  • ECB electrically controlled birefringence
  • OCB optical compensated bend
  • IPS in-plane switching
  • FFS far-field switching
  • VA vertical alignment
  • PSA polymer stable alignment
  • the PSA mode is to add a small amount (such as 0.3 wt%, more typically ⁇ 1 wt%) of one or more polymerizable compounds to the liquid crystal composition, and apply a voltage between the electrodes after charging the liquid crystal cell or In situ polymerization or cross-linking (usually by UV photopolymerization) without applying a voltage.
  • the polymerization is carried out at a temperature at which the liquid crystal composition exhibits a liquid crystal phase, usually at room temperature. It has been confirmed that addition of a polymerizable liquid crystal compound to a liquid crystal composition is particularly suitable.
  • PSA displays can operate as active matrix or passive matrix displays.
  • active matrix displays the individual pixels are typically addressed by integrated non-linear active components such as transistors, and in the case of passive matrix displays, the individual pixels are typically known in the art. Multiplexing methods for addressing.
  • P represents a polymerizable group, typically an acrylate or methacrylate group, as described in US 7,169,449.
  • liquid crystal composition + reactive mesogenic (RM) components are suitable for PSA displays because, for example, tilting cannot be established at all or sufficient tilt cannot be established.
  • prior art liquid crystal compositions and RMs still have some disadvantages when used in PSA displays. Therefore, not every RM known to be soluble in liquid crystal compositions is suitable for use in PSA displays.
  • a suitable selection criterion for RM it is often difficult to find a suitable selection criterion for RM. If it is desired to carry out the polymerization by means of UV light without adding a photoinitiator, the selection space of a suitable RM becomes smaller.
  • the combination of selected liquid crystal composition/RM should have as low a rotational viscosity as possible and as good electrical properties as possible, in particular it should have as high a VHR as possible.
  • a high VHR after irradiation with UV light is particularly desirable because UV exposure is an integral part of the display production process and is also a normal exposure during the operation of the finished display.
  • pretilt angle For PSA displays, it is preferred to produce a particularly small pretilt angle, where preferred materials should produce a pretilt angle that is less than the hitherto known materials during the same exposure time during polymerization, and/or The pretilt angles that can be obtained with known materials can also be achieved with shorter exposure times. In this way, the production time of the display can be shortened and the cost can be reduced. Since the pretilt angles generated by the materials at different positions are inconsistent, the position with a large pretilt angle is more likely to leak light, and the position with a small pretilt angle is less likely to leak light, which causes the liquid crystal display to show unevenness, which is called drop mura. Therefore, it is necessary to find LC materials that can make little difference in pretilt angles at different locations to solve this problem.
  • liquid crystal composition comprising:
  • At least one polymerizable compound of the formula II At least one polymerizable compound of the formula II
  • R 1 and R 2 each independently represent -H, -F, an alkyl or alkoxy group having 1 to 12 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 12 carbon atoms, -OR 5 OR 6 , Wherein the alkyl or alkoxy group and one or more H of the alkenyl or alkenyloxy group may be substituted by F, and at least one of R 1 and R 2 is -OR 5 OR 6 ;
  • R 5 and R 6 each independently represent an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms;
  • Z 1 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2 - or -CH 2 CH 2 -;
  • L 1 and L 2 each independently represent -F, -Cl, -CN or -NCS;
  • One or more -CH 2 - may be replaced by -O-, One or more H may be replaced by a halogen;
  • n 0, 1, 2 or 3, and when n is 2 or 3, the ring May be the same or different, Z 1 may be the same or different;
  • r 1 represents 1, 2 or 3;
  • r 2 and r 3 each independently represent a positive integer of 0-6;
  • r 4 and r 5 each independently represent 0, 1, 2, 3 or 4;
  • Y 1 and Y 2 each independently represent H, a halogen, an alkyl group having 1 to 3 C atoms or an alkoxy group.
  • the compound of formula I is selected from the group consisting of:
  • R 11 and R 21 each independently represent -H, -F, an alkyl or alkoxy group having 1 to 7 carbon atoms, an alkenyl group or an alkenyloxy group having 2 to 7 carbon atoms, -OR 51 OR 61 , Wherein the alkyl or alkoxy group and one or more H of the alkenyl or alkenyloxy group may be substituted by F, and at least one of R 11 and R 21 is -OR 51 OR 61 ;
  • R 51 and R 61 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms.
  • the compound of the I-1 is selected from the group consisting of the following compounds:
  • the compound of the I-2 is selected from the group consisting of the following compounds:
  • the compound of the I-3 is selected from the group consisting of the following compounds:
  • the compound of the formula I-4 is selected from the group consisting of the following compounds:
  • the compound of the formula I-5 is selected from the group consisting of the following compounds:
  • the compound of the I-6 is selected from the group consisting of the following compounds:
  • the compound of the formula I-7 is selected from the group consisting of the following compounds:
  • the compound of I-8 is selected from the group consisting of the following compounds:
  • the compound of the I-9 is selected from the group consisting of the following compounds:
  • the compound of I-10 is selected from the group consisting of the following compounds:
  • the compound of the formula I-11 is selected from the group consisting of the following compounds:
  • the compound of I-12 is selected from the group consisting of the following compounds:
  • the compound of I-13 is selected from the group consisting of the following compounds:
  • the compound of the formula I-14 is selected from the group consisting of the following compounds:
  • the compound of I-15 is selected from the group consisting of the following compounds:
  • P 1 and P 2 are each independently represented
  • the compound of formula II is selected from the group consisting of:
  • liquid crystal composition further comprises at least one compound of the formula III
  • R 3 and R 4 each independently represent -H, -F, an alkyl or alkoxy group having 1 to 12 carbon atoms, an alkenyl group or an alkenyloxy group having 2 to 12 carbon atoms, Wherein one or more of the alkyl or alkoxy group and the alkenyl or alkenyloxy group may be substituted by F;
  • Z 3 represents a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2 - or -CH 2 CH 2 -;
  • L 3 and L 4 each independently represent -F, -Cl, -CN or -NCS;
  • One or more -CH 2 - may be replaced by -O-, One or more H may be replaced by a halogen;
  • N1 represents 0, 1, 2 or 3, and when n1 is 2 or 3, the ring May be the same or different, Z 3 may be the same or different;
  • N2 represents 0 or 1.
  • the compound of formula III is selected from the group consisting of:
  • R 31 and R 41 each independently represent -H, -F, an alkyl group or alkoxy group having 1 to 7 carbon atoms, an alkenyl group or an alkenyloxy group having 2 to 7 carbon atoms, Wherein one or more of the alkyl or alkoxy group and the alkenyl or alkenyloxy group may be substituted by F.
  • liquid crystal composition further comprises at least one compound of the formula IV:
  • R 7 and R 8 each independently represent H, an alkyl or alkoxy group having 1 to 12 carbon atoms, an alkenyl group or an alkenyloxy group having 2 to 12 carbon atoms;
  • r represents 1, 2 or 3.
  • the compound of formula IV is selected from the group consisting of:
  • R 71 and R 81 each independently represent H, an alkyl group or alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group.
  • the compound of formula IV-1 is selected from the group consisting of:
  • the compound of formula IV-2 is selected from the group consisting of:
  • the compound of formula IV-3 is selected from the group consisting of:
  • the compound of formula IV-4 is selected from the group consisting of:
  • the compound of formula IV-5 is selected from the group consisting of:
  • the compound of formula IV-6 is selected from the group consisting of:
  • the compound of formula IV-7 is selected from the group consisting of:
  • the compound of formula IV-8 is selected from the group consisting of:
  • the compound of formula IV-9 is selected from the group consisting of:
  • the compound of formula IV-10 is selected from the group consisting of:
  • the compound of formula IV-11 is selected from the group consisting of:
  • the compound of formula IV-12 is selected from the group consisting of:
  • the compound of Formula I comprises from 1 to 30% by weight based on the total weight of the liquid crystal composition
  • the compound of Formula II comprises from 0.001% to 5% by weight based on the total weight of the liquid crystal composition.
  • the compound of the formula III accounts for 0 to 70% by weight based on the total weight of the liquid crystal composition
  • the compound of the formula IV accounts for 0 to 70% by weight based on the total weight of the liquid crystal composition.
  • the compound of the formula I accounts for 1 to 30% by weight of the total weight of the liquid crystal composition
  • the compound of the formula II accounts for 0.001 of the total weight of the liquid crystal composition.
  • the compound of the formula III accounts for 10 to 70% by weight based on the total weight of the liquid crystal composition
  • the compound of the formula IV accounts for 20 to 70% by weight based on the total weight of the liquid crystal composition.
  • the compound of Formula I comprises from 1% to 15% by weight based on the total weight of the liquid crystal composition
  • the compound of Formula II comprises the total weight of the liquid crystal composition.
  • the compound of the formula III accounts for 20 to 60% by weight based on the total weight of the liquid crystal composition
  • the compound of the formula IV accounts for 30 to 65% by weight based on the total weight of the liquid crystal composition.
  • liquid crystal composition further comprising one or more additives known to those skilled in the art and described in the literature.
  • a multicolor dye and/or a chiral dopant may be added in an amount of from 0 to 15% by weight based on the total weight of the liquid crystal composition.
  • the dopant accounts for 0 to 5% of the total weight of the liquid crystal composition; more preferably, the dopant accounts for 0-1% of the total weight of the liquid crystal composition.
  • Stabilizers which can be added, for example, to the mixture according to the invention are mentioned below.
  • the stabilizer is selected from the group consisting of stabilizers as shown below.
  • the stabilizer accounts for 0 to 5% of the total weight of the liquid crystal composition; more preferably, the stabilizer accounts for 0-1% of the total weight of the liquid crystal composition; Particularly preferably, the stabilizer comprises from 0 to 0.1% by weight based on the total weight of the liquid crystal composition.
  • Another aspect of the present invention also provides a liquid crystal display device comprising the above liquid crystal composition.
  • the liquid crystal composition provided by the present invention has suitable optical anisotropy, suitable dielectric anisotropy, and good pretilt angle consistency while maintaining a relatively high clearing point, and the drop mura performs well.
  • the liquid crystal composition is applied to a PSA type liquid crystal display, it has an excellent display effect.
  • nCCGF The structural formula is expressed by the code listed in Table 1, and can be expressed as: nCCGF, where n in the code represents the number of C atoms of the left-end alkyl group, for example, n is "3", that is, the alkyl group is -C 3 H 7 ; C in the code represents a cyclohexane group, G represents 2-fluoro-1,4-phenylene, and F represents fluorine.
  • Optical anisotropy was measured using an Abbe refractometer under a sodium light (589 nm) light source at 25 ° C;
  • ⁇ ⁇ ⁇ - ⁇ ⁇ , where ⁇ ⁇ is the dielectric constant parallel to the molecular axis, ⁇ ⁇ is the dielectric constant perpendicular to the molecular axis, test conditions: 25 ° C, 1 KHz, test box is TN90 type, box thickness 7 ⁇ m.
  • Drop mura test The LCD panel uses a opaque plate with a transmittance of 8%, 4%, and 2% to observe the uniformity of the panel under 48 gray scales. When the drop mura is observed, it is marked as "Yes”; if the drop mura is not observed, it is marked as "None”; the opacity of the different transmittances is observed to be easy to sort: 8%>4%>2% .
  • the components used in the following examples can be synthesized by a known method or obtained commercially. These synthetic techniques are conventional, and each of the obtained liquid crystal compounds has been tested to meet the standards of electronic compounds.
  • a liquid crystal composition was prepared in accordance with the ratio of each liquid crystal composition specified in the following examples.
  • the preparation of the liquid crystal composition is carried out according to a conventional method in the art, such as heating, ultrasonic wave, suspension, etc., in a predetermined ratio.
  • liquid crystal composition given in the following examples was prepared and studied.
  • the composition of each liquid crystal composition and the test results of its performance parameters are shown below.
  • the liquid crystal composition of Comparative Example 1 was prepared according to each compound and weight percentage listed in Table 2, and was filled between the two substrates of the liquid crystal display for performance test.
  • the polymerizable component in Table 3 was added to 100 parts by weight of the above liquid crystal composition:
  • the content and composition of the polymerizable component were the same as in Comparative Example 1.
  • Component code Weight percentage 3CWO2 6 5CWO2 8 2CPWO2 7 3CPWO4 9 3CWO4 7 3CCWO2 14 1O3OCCWO2 5 3CPO2 9 3CPP2 6 3CC2 20 4CC3 9 total 100
  • the content and composition of the polymerizable component were the same as in Comparative Example 1.
  • Example 3CWO2 and 4CCWO2 in Comparative Example 1 were replaced with 3CWO4O1 and 1O3OCCWO2, respectively, to prepare a liquid crystal composition of Example 3, as shown in Table 9, which was filled between two substrates of a liquid crystal display for performance test.
  • the content and composition of the polymerizable component were the same as in Comparative Example 1.
  • the drop mura containing the liquid crystal composition of the formula I of the present invention is more excellent in performance.
  • the liquid crystal composition of Comparative Example 2 was prepared according to each compound and weight percentage listed in Table 11, and was filled between the two substrates of the liquid crystal display for performance test.
  • Component code Weight percentage 3CC2 twenty three 4CC3 3 5PP1 11 3PWO2 10 5CC3 4 3C1OWO2 4 3CCP1 3
  • 3CPP2 15 3CPWO2 9 2CC1OWO2 7 3CC1OWO2 11 total 100
  • the polymerizable component in Table 12 was added to 100 parts by weight of the above liquid crystal composition:
  • Example 4 3PWO2 and 3C1OWO2 in Comparative Example 2 were replaced with 3PWO3O1 and 3C1OWO4O1, respectively, to prepare a liquid crystal composition of Example 4, as shown in Table 14, which was filled between two substrates of a liquid crystal display for performance test.
  • Component code Weight percentage 3CC2 twenty three 4CC3 3 5PP1 11 3PWO3O1 10 5CC3 4 3C1OWO4O1 4 3CCP1 3 3CPP2 15 3CPWO2 9 2CC1OWO2 7
  • the content and composition of the polymerizable component are the same as in Comparative Example 2.
  • Component code Weight percentage 3CC2 twenty three 4CC3 3 5PP1 11 3PWO2 10 5CC3 4 3C1OWO2 4 3CCP1 3 3CPP2 15 3CPWO3O1 9 2CC1OWO2 7 3CC1OWO2 11 total 100
  • the content and composition of the polymerizable component were the same as in Example 1.
  • Component code Weight percentage 3CC2 twenty three 4CC3 3 5PP1 11 3PWO2 10 5CC3 4 3C1OWO4O1 4 3CCP1 3 3CPP2 15 3CPWO3O1 9 2CC1OWO2 7 3CC1OWO2 11 total 100
  • the content and composition of the polymerizable component were the same as in Example 1.
  • the drop mura containing the liquid crystal composition of the formula I of the present invention is more excellent in performance.
  • liquid crystal composition according to the present invention can be applied to the field of liquid crystals.

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Abstract

本发明公开了一种液晶组合物及其应用，所述液晶组合物包含：至少一种通式Ⅰ的化合物以及至少一种通式Ⅱ的可聚合化合物。本发明提供的液晶组合物具有适合的光学各向异性、适合的介电各向异性以及在维持相对高的清亮点的同时，还具有较好的预倾角一致性，drop mura表现良好。所述液晶组合物应用于PSA型液晶显示器时，具有优异的显示效果。

Description

一种液晶组合物及其应用 技术领域
本发明涉及液晶材料领域，具体涉及一种液晶组合物及其应用。
背景技术
液晶显示器(Liquid Crystal Display，LCD)因其体积小、重量轻、功耗低且显示质量优异而获得了飞速发展，特别在便携式电子信息产品中获得广泛的应用。根据显示模式的类型分为PC(phase change，相变)、TN(twist nematic，扭曲向列)、STN(super twisted nematic，超扭曲向列)、ECB(electrically controlled birefringence，电控双折射)、OCB(optically compensated bend，光学补偿弯曲)、IPS(in-plane switching，共面转变)、FFS(fringe field switching，边缘场切换)、VA(vertical alignment，垂直配向)及PSA(polymer stable alignment，聚合物稳定配向)等类型。
其中，PSA模式是将少量(如0.3wt％，较典型的＜1wt％)的一种或多种可聚合化合物添加到液晶组合物中，并在充入液晶盒之后在电极之间施加电压或不施加电压的情况下，使其原位聚合或交联(通常通过UV光聚合)。聚合在液晶组合物显示出液晶相的温度下进行，通常在室温下进行。已证实将可聚合的液晶化合物添加到液晶组合物中是特别适宜的。
同时，PSA原理正用在各种传统的液晶显示器中，诸如已知的PSA-VA、PSA-OCB、PSA-IPS、PSA-FFS和PSA-TN显示器。如常规的液晶显示器一样，PSA显示器能作为有源矩阵或无源矩阵显示器来操作。就有源矩阵显示器的情况而言，各个像素通常通过集成的非线性有源元件如晶体管来进行寻址，而就无源矩阵显示器的情况而言，各个像素通常根据现有技术中已知的多路传输方法来进行寻址。
现有技术中，已经使用了下式的可聚合化合物：
Figure PCTCN2018093430-appb-000001
其中，P表示可聚合基团，通常是丙烯酸酯基或甲基丙烯酸酯基，如US7169449中描述的一样。
然而不是所有液晶组合物+可聚合组分(reactive mesogenic，RM)组成的组合都适用于PSA显示器，因为例如根本不能建立倾斜或不能建立充分的倾斜。此外，还发现当用于PSA显示器中时，现有已知的液晶组合物和RM仍有一些缺点。因此，不是每一种已知可溶于液晶组合物的RM都适用于PSA显示器中。此外，除了直接测量PSA显示器中的预倾角外，对于RM通常很难发现合适的选择标准。如果期望通过UV光而不添加光引 发剂的方式进行聚合，则适合的RM的选择空间就变得更小。
另外，选择的液晶组合物/RM的组合应当具有尽可能低的旋转粘度和尽可能好的电性质，尤其是它应当具有尽可能高的VHR。在PSA显示器中，尤其需要在用UV光辐照之后的高VHR，因为UV曝光是显示器生产过程中必不可少的部分，同时也是制成的显示器运行期间的正常曝光。
对于PSA显示器来说，比较好的是产生特别小的预倾角，在此，优选的材料在聚合期间应当在相同的曝光时间下能产生比迄今已知的材料更小的预倾角，和/或在较短的曝光时间下也能实现已知的材料所能获得的预倾角。这样，显示器的生产时间就能缩短，成本也就可以降低。由于不同位置的材料产生的预倾角不一致，预倾角偏大的位置更容易发生漏光，预倾角偏小的位置更不容易漏光，使得液晶显示器出现显示不均的现象，被称为drop mura。因此，需要找到可以在不同位置预倾角差异不大的LC材料来解决这一问题。
发明内容
发明目的：针对现有技术的缺陷，本发明的目的在于提供一种预倾角一致性高，drop mura表现良好的液晶组合物，以及包含所述液晶组合物的液晶显示元件。
本发明的技术方案：
本发明的一个方面提供一种液晶组合物，包含：
至少一种通式Ⅰ的化合物
Figure PCTCN2018093430-appb-000002
以及
至少一种通式Ⅱ的可聚合化合物
Figure PCTCN2018093430-appb-000003
其中，
R 1和R 2各自独立的表示-H、-F、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基、-OR 5OR 6、
Figure PCTCN2018093430-appb-000004
其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代，且R 1和R 2中至少一个为-OR 5OR 6；
R 5和R 6各自独立的表示含有1-12个碳原子的烷基或含有2-12个碳原子的烯基；
Z 1表示单键、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH 2CH 2-；
L 1和L 2各自独立的表示-F、-Cl、-CN或-NCS；
环
Figure PCTCN2018093430-appb-000005
表示
Figure PCTCN2018093430-appb-000006
其中，
Figure PCTCN2018093430-appb-000007
中一个或多个-CH 2-可被-O-替代，
Figure PCTCN2018093430-appb-000008
中一个或多个H可以被卤素取代；
n表示0、1、2或3，且当n为2或3时，环
Figure PCTCN2018093430-appb-000009
可以相同或不同，Z 1可以相同或不同；
P 1和P 2各自独立的表示
Figure PCTCN2018093430-appb-000010
Figure PCTCN2018093430-appb-000011
Figure PCTCN2018093430-appb-000012
或-SH；
r 1表示1、2或3；
r 2和r 3各自独立的表示0～6的正整数；
r 4和r 5各自独立的表示0、1、2、3或4；
Z 2表示单键、-CH 2CH 2-、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH＝CH-COO-；
Z p1和Z p2相同或不同，各自独立的选自由单键、-O-、-S-、-NH-、-NHCOO-、-OCONH-、-CF 2O-、-OCF 2-、-CF 2S-、-SCF 2-、-CH 2CH 2-、-CF 2CH 2-、-CH 2CF 2-、-CF 2CF 2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH 2-、-OCH 2-、-SCH 2-、-CH 2S-、-CH＝CH-、-C≡C-、-CH＝CH-COO-和-OCO-CH＝CH-组成的组；
Y 1和Y 2各自独立的表示H、卤素、C原子数为1～3的烷基或烷氧基。
优选的，所述通式Ⅰ的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000013
Figure PCTCN2018093430-appb-000014
Figure PCTCN2018093430-appb-000015
以及
Figure PCTCN2018093430-appb-000016
其中，R 11和R 21各自独立的表示-H、-F、含有1-7个碳原子的烷基或烷氧基、含有2-7个碳原子的烯基或烯氧基、-OR 51OR 61、
Figure PCTCN2018093430-appb-000017
其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代，且R 11和R 21中至少一个为-OR 51OR 61；
R 51和R 61各自独立的表示含有1-10个碳原子的烷基或含有2-10个碳原子的烯基。
再进一步的，所述Ⅰ-1的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000018
Figure PCTCN2018093430-appb-000019
以及
Figure PCTCN2018093430-appb-000020
所述Ⅰ-2的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000021
Figure PCTCN2018093430-appb-000022
以及
Figure PCTCN2018093430-appb-000023
所述Ⅰ-3的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000024
Figure PCTCN2018093430-appb-000025
以及
Figure PCTCN2018093430-appb-000026
所述Ⅰ-4的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000027
所述Ⅰ-5的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000028
Figure PCTCN2018093430-appb-000029
以及
Figure PCTCN2018093430-appb-000030
所述Ⅰ-6的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000031
Figure PCTCN2018093430-appb-000032
所述Ⅰ-7的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000033
所述Ⅰ-8的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000034
所述Ⅰ-9的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000035
所述Ⅰ-10的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000036
所述Ⅰ-11的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000037
所述Ⅰ-12的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000038
所述Ⅰ-13的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000039
Figure PCTCN2018093430-appb-000040
Figure PCTCN2018093430-appb-000041
以及
Figure PCTCN2018093430-appb-000042
所述Ⅰ-14的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000043
Figure PCTCN2018093430-appb-000044
以及
Figure PCTCN2018093430-appb-000045
所述Ⅰ-15的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000046
Figure PCTCN2018093430-appb-000047
以及
Figure PCTCN2018093430-appb-000048
优选的，通式Ⅱ中，P 1和P 2各自独立的表示
Figure PCTCN2018093430-appb-000049
再进一步优选的，所述通式Ⅱ的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000050
Figure PCTCN2018093430-appb-000051
Figure PCTCN2018093430-appb-000052
Figure PCTCN2018093430-appb-000053
Figure PCTCN2018093430-appb-000054
Figure PCTCN2018093430-appb-000055
以及
Figure PCTCN2018093430-appb-000056
进一步的，所述液晶组合物还包括至少一种通式Ⅲ的化合物
Figure PCTCN2018093430-appb-000057
R 3和R 4各自独立的表示-H、-F、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基、 其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代；
Z 3表示单键、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH 2CH 2-；
L 3和L 4各自独立的表示-F、-Cl、-CN或-NCS；
环
Figure PCTCN2018093430-appb-000059
表示
Figure PCTCN2018093430-appb-000060
其中，
Figure PCTCN2018093430-appb-000061
中一个或多个-CH 2-可被-O-替代，
Figure PCTCN2018093430-appb-000062
中一个或多个H可以被卤素取代；
n1表示0、1、2或3，且当n1为2或3时，环
Figure PCTCN2018093430-appb-000063
可以相同或不同，Z 3可以相同或不同；
n2表示0或1。
进一步优选的，所述通式Ⅲ的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000064
Figure PCTCN2018093430-appb-000065
Figure PCTCN2018093430-appb-000066
以及
Figure PCTCN2018093430-appb-000067
其中，
R 31和R 41各自独立的表示-H、-F、含有1-7个碳原子的烷基或烷氧基、含有2-7个碳原子的烯基或烯氧基、
Figure PCTCN2018093430-appb-000068
其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代。
进一步的，所述液晶组合物还包括至少一种通式Ⅳ的化合物：
Figure PCTCN2018093430-appb-000069
其中，
R 7和R 8各自独立的表示H、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基；
环
Figure PCTCN2018093430-appb-000070
和环
Figure PCTCN2018093430-appb-000071
各自独立的表示
Figure PCTCN2018093430-appb-000072
r表示1、2或3。
优选的，所述通式Ⅳ的化合物选自如下化合物组成的组：
Figure PCTCN2018093430-appb-000073
Figure PCTCN2018093430-appb-000074
Figure PCTCN2018093430-appb-000075
以及
Figure PCTCN2018093430-appb-000076
其中，R 71及R 81各自独立的表示H、含有1-7个碳原子的烷基或烷氧基、含有2-7个碳原子的烯基或烯氧基。
在本发明的一些实施方案中，优选的，所述通式Ⅳ-1的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000077
以及
Figure PCTCN2018093430-appb-000078
所述通式Ⅳ-2的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000079
Figure PCTCN2018093430-appb-000080
以及
Figure PCTCN2018093430-appb-000081
所述通式Ⅳ-3的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000082
Figure PCTCN2018093430-appb-000083
Figure PCTCN2018093430-appb-000084
以及
Figure PCTCN2018093430-appb-000085
所述通式Ⅳ-4的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000086
Figure PCTCN2018093430-appb-000087
以及
Figure PCTCN2018093430-appb-000088
所述通式Ⅳ-5的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000089
Figure PCTCN2018093430-appb-000090
Figure PCTCN2018093430-appb-000091
以及
Figure PCTCN2018093430-appb-000092
所述通式Ⅳ-6的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000093
Figure PCTCN2018093430-appb-000094
以及
Figure PCTCN2018093430-appb-000095
所述通式Ⅳ-7的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000096
Figure PCTCN2018093430-appb-000097
以及
Figure PCTCN2018093430-appb-000098
所述通式Ⅳ-8的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000099
以及
Figure PCTCN2018093430-appb-000100
所述通式Ⅳ-9的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000101
Figure PCTCN2018093430-appb-000102
Figure PCTCN2018093430-appb-000103
以及
Figure PCTCN2018093430-appb-000104
所述通式Ⅳ-10的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000105
Figure PCTCN2018093430-appb-000106
Figure PCTCN2018093430-appb-000107
以及
Figure PCTCN2018093430-appb-000108
所述通式Ⅳ-11的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000109
Figure PCTCN2018093430-appb-000110
Figure PCTCN2018093430-appb-000111
以及
Figure PCTCN2018093430-appb-000112
所述通式Ⅳ-12的化合物选自由如下化合物组成的组：
Figure PCTCN2018093430-appb-000113
Figure PCTCN2018093430-appb-000114
Figure PCTCN2018093430-appb-000115
以及
Figure PCTCN2018093430-appb-000116
在本发明的一些实施方案中，所述通式Ⅰ的化合物占所述液晶组合物总重量的1～30％，所述通式Ⅱ的化合物占所述液晶组合物总重量的0.001～5％，所述通式Ⅲ的化合物占所述液晶组合物总重量的0～70％，所述通式Ⅳ的化合物占所述液晶组合物总重量的0～70％。
进一步的，在本发明的一些实施方案中，所述通式Ⅰ的化合物占所述液晶组合物总重量的1～30％，所述通式Ⅱ的化合物占所述液晶组合物总重量的0.001～5％，所述通式Ⅲ的化合物占所述液晶组合物总重量的10～70％，所述通式Ⅳ的化合物占所述液晶组合物总重量的20～70％。
再进一步的，在本发明的一些实施方案中，所述通式Ⅰ的化合物占所述液晶组合物总重量的1～15％，所述通式Ⅱ的化合物占所述液晶组合物总重量的0.001～1％，所述通式Ⅲ的化合物占所述液晶组合物总重量的20～60％，所述通式Ⅳ的化合物占所述液晶组合物总重量的30～65％。
通过大量的实验发现，将上述液晶组合物应用于液晶显示器中时，在面板中不同位置具有更好的预倾角一致性，drop mura表现良好。
本发明另一方面提供一种液晶组合物，还包含本领域技术人员已知和文献中描述的一种或多种添加剂。例如，可以加入占所述液晶组合物总重量的0-15％的多色染料和/或手性掺杂剂。
如下显示优选加入到根据本发明的混合物中的可能掺杂剂。
Figure PCTCN2018093430-appb-000117
Figure PCTCN2018093430-appb-000118
Figure PCTCN2018093430-appb-000119
以及
Figure PCTCN2018093430-appb-000120
在本发明的实施方案中，优选所述掺杂剂占所述液晶组合物总重量的0-5％；更优地，所述掺杂剂占所述液晶组合物总重量的0-1％。
如下提及例如可以加入到根据本发明的混合物中的稳定剂。
Figure PCTCN2018093430-appb-000121
Figure PCTCN2018093430-appb-000122
Figure PCTCN2018093430-appb-000123
优选地，所述稳定剂选自如下所示的稳定剂。
Figure PCTCN2018093430-appb-000124
在本发明的实施方案中，优选所述稳定剂占所述液晶组合物总重量的0-5％；更优地，所述稳定剂占所述液晶组合物总重量的0-1％；作为特别优选方案，所述稳定剂占所述液晶组合物总重量的0-0.1％。
本发明另一方面还提供一种包含上述液晶组合物的液晶显示器件。
有益效果：
本发明提供的液晶组合物具有适合的光学各向异性、适合的介电各向异性以及在维持相对高的清亮点的同时，还具有较好的预倾角一致性，drop mura表现良好。所述液晶组合物应用于PSA型液晶显示器时，具有优异的显示效果。
具体实施方式
以下将结合具体实施方案来说明本发明。需要说明的是，下面的实施例为本发明的示例，仅用来说明本发明，而不用来限制本发明。在不偏离本发明主旨或范围的情况下，可进行本发明构思内的其他组合和各种改良。
为便于表达，以下各实施例中，液晶组合物的基团结构用表1所列的代码表示：
表1 液晶化合物的基团结构代码
Figure PCTCN2018093430-appb-000125
Figure PCTCN2018093430-appb-000126
以如下结构式的化合物为例：
Figure PCTCN2018093430-appb-000127
该结构式如用表1所列代码表示，则可表达为：nCCGF，代码中的n表示左端烷基的C原子数，例如n为“3”，即表示该烷基为-C 3H 7；代码中的C代表环己烷基，G代表2-氟-1,4-亚苯基，F代表氟。
以下实施例中测试项目的简写代号如下：
Cp(℃)         清亮点(向列-各向同性相转变温度)
Δn            光学各向异性(589nm，25℃)
Δε           介电各向异性(1KHz，25℃)
其中，
光学各向异性使用阿贝折光仪在钠光灯(589nm)光源下、25℃测试得到；
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℃、1KHz、测试盒为TN90型，盒厚7μm。
Drop mura测试：液晶面板在48灰阶下，分别使用透过率为8％、4％、2％的遮光板进行观察面板的均匀性。观察到drop mura，则记为“有”；观察不到drop mura，则记为“无”；不同透过率的遮光板观察到drop mura的容易度排序为：8％＞4％＞2％。
在以下的实施例中所采用的各成分，均可以通过公知的方法进行合成，或者通过商业途径获得。这些合成技术是常规的，所得到各液晶化合物经测试符合电子类化合物标准。
按照以下实施例规定的各液晶组合物的配比，制备液晶组合物。所述液晶组合物的制备是按照本领域的常规方法进行的，如采取加热、超声波、悬浮等方式按照规定比例混合制得。
制备并研究下列实施例中给出的液晶组合物。下面显示了各液晶组合物的组成和其性能参数测试结果。
对比例1
按表2中所列的各化合物及重量百分数配制成对比例1的液晶组合物，其填充于液晶显示器两基板之间进行性能测试。
表2 液晶组合物配方
组分代码 重量百分数
3CWO2 6
5CWO2 8
2CPWO2 7
3CPWO4 9
3CWO4 7
3CCWO2 14
4CCWO2 5
3CPO2 9
3CPP2 6
3CC2 20
4CC3 9
总计 100
于上述液晶组合物100重量份中添加表3中可聚合组分：
表3 可聚合组分
Figure PCTCN2018093430-appb-000128
所得组合物的性能参数测试结果如下表4：
表4 性能参数测试
Δn 0.094
Δε -3.1
Cp 73.7
Drop mura观察(8％) 有
Drop mura观察(4％) 有
Drop mura观察(2％) 有
实施例1
将对比例1中的3CWO2替换为3CWO4O1配制成实施例1的液晶组合物，如表5所示，其填充于液晶显示器两基板之间进行性能测试。
表5 液晶组合物配方
组分代码 重量百分数
3CWO4O1 6
5CWO2 8
2CPWO2 7
3CPWO4 9
3CWO4 7
3CCWO2 14
4CCWO2 5
3CPO2 9
3CPP2 6
3CC2 20
4CC3 9
总计 100
可聚合组分的含量及组分同对比例1。
所得组合物的性能参数测试结果如下表6：
表6 性能参数测试
Δn 0.093
Δε -3.0
Cp 72.6
Drop mura观察(8％) 有
Drop mura观察(4％) 有
Drop mura观察(2％) 无
实施例2
将对比例1中的4CCWO2替换为1O3OCCWO2配制成实施例2的液晶组合物，如表7所示，其填充于液晶显示器两基板之间进行性能测试。
表7 液晶组合物配方
组分代码 重量百分数
3CWO2 6
5CWO2 8
2CPWO2 7
3CPWO4 9
3CWO4 7
3CCWO2 14
1O3OCCWO2 5
3CPO2 9
3CPP2 6
3CC2 20
4CC3 9
总计 100
可聚合组分的含量及组分同对比例1。
所得组合物的性能参数测试结果如下表8：
表8 性能参数测试
Δn 0.093
Δε -3.1
Cp 73.5
Drop mura观察(8％) 有
Drop mura观察(4％) 有
Drop mura观察(2％) 无
实施例3
将对比例1中的3CWO2、4CCWO2分别替换为3CWO4O1、1O3OCCWO2配制成实施例3的液晶组合物，如表9所示，其填充于液晶显示器两基板之间进行性能测试。
表9 液晶组合物配方
组分代码 重量百分数
3CWO4O1 6
5CWO2 8
2CPWO2 7
3CPWO4 9
3CWO4 7
3CCWO2 14
1O3OCCWO2 5
3CPO2 9
3CPP2 6
3CC2 20
4CC3 9
总计 100
可聚合组分的含量及组分同对比例1。
所得组合物的性能参数测试结果如下表10：
表10 性能参数测试
Δn 0.094
Δε -3.1
Cp 73.7
Drop mura观察(8％) 有
Drop mura观察(4％) 无
Drop mura观察(2％) 无
由上述对比例1和实施例1-3比较可知，含有本发明通式I的液晶组合物的drop mura表现更加优异。
对比例2
按表11中所列的各化合物及重量百分数配制成对比例2的液晶组合物，其填充于液晶显示器两基板之间进行性能测试。
表11 液晶组合物配方
组分代码 重量百分数
3CC2 23
4CC3 3
5PP1 11
3PWO2 10
5CC3 4
3C1OWO2 4
3CCP1 3
3CPP2 15
3CPWO2 9
2CC1OWO2 7
3CC1OWO2 11
总计 100
于上述液晶组合物100重量份中添加表12中可聚合组分：
表12 可聚合组分
Figure PCTCN2018093430-appb-000129
所得组合物的性能参数测试结果如下表13：
表13 性能参数测试
Δn 0.109
Δε -3.2
Cp 75.6
Drop mura观察(8％) 有
Drop mura观察(4％) 有
Drop mura观察(2％) 无
实施例4
将对比例2中的3PWO2、3C1OWO2分别替换为3PWO3O1、3C1OWO4O1配制成实施例4的液晶组合物，如表14所示，其填充于液晶显示器两基板之间进行性能测试。
表14 液晶组合物配方
组分代码 重量百分数
3CC2 23
4CC3 3
5PP1 11
3PWO3O1 10
5CC3 4
3C1OWO4O1 4
3CCP1 3
3CPP2 15
3CPWO2 9
2CC1OWO2 7
3CC1OWO2 11
总计 100
可聚合组分的含量及组分同对比例2。
所得组合物的性能参数测试结果如下表15：
表15 性能参数测试
Δn 0.109
Δε -3.2
Cp 75.6
Drop mura观察(8％) 无
Drop mura观察(4％) 无
Drop mura观察(2％) 无
实施例5
将对比例2中的3CPWO2分别替换为3CPWO3O1配制成实施例5的液晶组合物，如表16所示，其填充于液晶显示器两基板之间进行性能测试。
表16 液晶组合物配方
组分代码 重量百分数
3CC2 23
4CC3 3
5PP1 11
3PWO2 10
5CC3 4
3C1OWO2 4
3CCP1 3
3CPP2 15
3CPWO3O1 9
2CC1OWO2 7
3CC1OWO2 11
总计 100
可聚合组分的含量及组分同实施例1。
所得组合物的性能参数测试结果如下表17：
表17 性能参数测试
Δn 0.1085
Δε -3.2
Cp 74.2
Drop mura观察(8％) 无
Drop mura观察(4％) 无
Drop mura观察(2％) 无
实施例6
将对比例2中的3C1OWO2、3CPWO2分别替换为3C1OWO4O1、3CPWO3O1配制成实施例6的液晶组合物，如表18所示，其填充于液晶显示器两基板之间进行性能测试。
表18 液晶组合物配方
组分代码 重量百分数
3CC2 23
4CC3 3
5PP1 11
3PWO2 10
5CC3 4
3C1OWO4O1 4
3CCP1 3
3CPP2 15
3CPWO3O1 9
2CC1OWO2 7
3CC1OWO2 11
总计 100
可聚合组分的含量及组分同实施例1。
所得组合物的性能参数测试结果如下表19：
表19 性能参数测试
Δn 0.107
Δε -3.0
Cp 73.9
Drop mura观察(8％) 无
Drop mura观察(4％) 无
Drop mura观察(2％) 无
由上述对比例2和实施例4-6比较可知，含有本发明通式I的液晶组合物的drop mura表现更加优异。
以上实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人了解本发明内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所做的等效变化或修饰，都应涵盖在本发明的保护范围内。
工业实用性
本发明所涉及的液晶组合物可以应用于液晶领域。

Claims (10)

  1. 一种液晶组合物，其特征在于，所述液晶组合物包含：
    至少一种通式Ⅰ的化合物
    Figure PCTCN2018093430-appb-100001
    以及
    至少一种通式Ⅱ的可聚合化合物
    Figure PCTCN2018093430-appb-100002
    其中，
    R 1和R 2各自独立的表示-H、-F、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基、-OR 5OR 6、
    Figure PCTCN2018093430-appb-100003
    其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代，且R 1和R 2中至少一个为-OR 5OR 6；
    R 5和R 6各自独立的表示含有1-12个碳原子的烷基或含有2-12个碳原子的烯基；
    Z 1表示单键、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH 2CH 2-；
    L 1和L 2各自独立的表示-F、-Cl、-CN或-NCS；
    Figure PCTCN2018093430-appb-100004
    表示
    Figure PCTCN2018093430-appb-100005
    其中，
    Figure PCTCN2018093430-appb-100006
    中一个或多个-CH 2-可被-O-替代，
    Figure PCTCN2018093430-appb-100007
    中一个或多个H可以被卤素取代；
    n表示0、1、2或3，且当n为2或3时，
    Figure PCTCN2018093430-appb-100008
    可以相同或不同，Z 1可以相同或不同；
    P 1和P 2各自独立的表示
    Figure PCTCN2018093430-appb-100009
    Figure PCTCN2018093430-appb-100010
    Figure PCTCN2018093430-appb-100011
    或-SH；
    r 1表示1、2或3；
    r 2和r 3各自独立的表示0～6的正整数；
    r 4和r 5各自独立的表示0、1、2、3或4；
    Z 2表示单键、-CH 2CH 2-、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH＝CH-COO-；
    Z p1和Z p2相同或不同，各自独立的选自由单键、-O-、-S-、-NH-、-NHCOO-、-OCONH-、-CF 2O-、-OCF 2-、-CF 2S-、-SCF 2-、-CH 2CH 2-、-CF 2CH 2-、-CH 2CF 2-、-CF 2CF 2-、-CF＝CH-、-CH＝CF-、-CF＝CF-、-CO-、-COO-、-OCO-、-OCOO-、-CH 2-、-OCH 2-、-SCH 2-、-CH 2S-、-CH＝CH-、-C≡C-、-CH＝CH-COO-和-OCO-CH＝CH-组成的组；
    Y 1和Y 2各自独立的表示H、卤素、C原子数为1～3的烷基或烷氧基。
  2. 根据权利要求1所述的液晶组合物，其特征在于，所述通式Ⅰ的化合物选自如下化合物组成的组：
    Figure PCTCN2018093430-appb-100012
    Figure PCTCN2018093430-appb-100013
    Figure PCTCN2018093430-appb-100014
    以及
    Figure PCTCN2018093430-appb-100015
    其中，
    R 11和R 21各自独立的表示-H、-F、含有1-7个碳原子的烷基或烷氧基、含有2-7个碳原子的烯基或烯氧基、-OR 51OR 61、
    Figure PCTCN2018093430-appb-100016
    其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代，且R 11和R 21中至少一个为-OR 51OR 61；
    R 51和R 61各自独立的表示含有1-10个碳原子的烷基或含有2-10个碳原子的烯基。
  3. 根据权利要求1所述的液晶组合物，其特征在于，通式Ⅱ中，P 1和P 2各自独立的表示
    Figure PCTCN2018093430-appb-100017
  4. 根据权利要求3所述的液晶组合物，其特征在于，所述通式Ⅱ的化合物选自如下化合物组成的组：
    Figure PCTCN2018093430-appb-100018
    Figure PCTCN2018093430-appb-100019
    Figure PCTCN2018093430-appb-100020
    Figure PCTCN2018093430-appb-100021
    Figure PCTCN2018093430-appb-100022
    Figure PCTCN2018093430-appb-100023
    Figure PCTCN2018093430-appb-100024
    以及
    Figure PCTCN2018093430-appb-100025
  5. 根据权利要求1所述的液晶组合物，其特征在于，所述液晶组合物还包括至少一种通式Ⅲ的化合物
    Figure PCTCN2018093430-appb-100026
    R 3和R 4各自独立的表示-H、-F、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基、
    Figure PCTCN2018093430-appb-100027
    其中所述烷基或烷氧基和所述烯基或烯氧基中的一个或多个H可以被F取代；
    Z 3表示单键、-COO-、-OCO-、-CH 2O-、-OCH 2-或-CH 2CH 2-；
    L 3和L 4各自独立的表示-F、-Cl、-CN或-NCS；
    Figure PCTCN2018093430-appb-100028
    表示
    Figure PCTCN2018093430-appb-100029
    其中，
    Figure PCTCN2018093430-appb-100030
    中一个或多个-CH 2-可被-O-替代，
    Figure PCTCN2018093430-appb-100031
    中一个或多个H可以被卤素取代；
    n1表示0、1、2或3，且当n1为2或3时，
    Figure PCTCN2018093430-appb-100032
    可以相同或不同，Z 3可以相同或不同；
    n2表示0或1。
  6. 根据权利要求1或5所述的液晶组合物，其特征在于，所述液晶组合物还包括至少一种通式Ⅳ的化合物：
    Figure PCTCN2018093430-appb-100033
    其中，
    R 7和R 8各自独立的表示H、含有1-12个碳原子的烷基或烷氧基、含有2-12个碳原子的烯基或烯氧基；
    Figure PCTCN2018093430-appb-100034
    各自独立的表示
    Figure PCTCN2018093430-appb-100035
    Figure PCTCN2018093430-appb-100036
    r表示1、2或3。
  7. 根据权利要求6所述的液晶组合物，其特征在于，所述通式Ⅳ的化合物选自如下化合物组成的组：
    Figure PCTCN2018093430-appb-100037
    Figure PCTCN2018093430-appb-100038
    Figure PCTCN2018093430-appb-100039
    以及
    Figure PCTCN2018093430-appb-100040
    其中，R 71及R 81各自独立的表示H、含有1-7个碳原子的烷基或烷氧基、含有2-7个碳原子的烯基或烯氧基。
  8. 根据权利要求6所述的液晶组合物，其特征在于，所述通式Ⅰ的化合物占所述液晶组合物总重量的1～30％，所述通式Ⅱ的化合物占所述液晶组合物总重量的0.001～5％，所述通式Ⅲ的化合物占所述液晶组合物总重量的0～70％，所述通式Ⅳ的化合物占所述液晶组合物总重量的0～70％。
  9. 根据权利要求8所述的液晶组合物，其特征在于，所述通式Ⅰ的化合物占所述液晶组合物总重量的1～30％，所述通式Ⅱ的化合物占所述液晶组合物总重量的0.001～5％，所述通式Ⅲ的化合物占所述液晶组合物总重量的10～70％，所述通式Ⅳ的化合物占所述液晶组合物总重量的20～70％。
  10. 一种包含权利要求1～9任一项所述液晶组合物的液晶显示器件。
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