WO2022057532A1 - 液晶组合物及其液晶显示器件 - Google Patents

液晶组合物及其液晶显示器件 Download PDF

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WO2022057532A1
WO2022057532A1 PCT/CN2021/112260 CN2021112260W WO2022057532A1 WO 2022057532 A1 WO2022057532 A1 WO 2022057532A1 CN 2021112260 W CN2021112260 W CN 2021112260W WO 2022057532 A1 WO2022057532 A1 WO 2022057532A1
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liquid crystal
crystal composition
compound
general formula
carbon atoms
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PCT/CN2021/112260
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English (en)
French (fr)
Inventor
刘云云
贺笛
徐爽
徐海彬
姚利芳
杨亚非
周振婷
潘帝可
赵飞
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江苏和成显示科技有限公司
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Application filed by 江苏和成显示科技有限公司 filed Critical 江苏和成显示科技有限公司
Priority to US18/026,456 priority Critical patent/US20240026223A1/en
Priority to JP2023511873A priority patent/JP2023541355A/ja
Publication of WO2022057532A1 publication Critical patent/WO2022057532A1/zh

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    • 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
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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
    • C09K19/3048—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon double bonds
    • C09K2019/3051—Cy-CH=CH-Cy-Ph
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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
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C09K2019/3063—Cy-Ph-C≡C-Ph
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    • 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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • C09K2019/3071—Cy-Cy-COO-Cy
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    • 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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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    • C09K2019/3074—Cy-Cy-COO-Cy-Cy, or more Cy rings
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    • C09K2019/3075—Cy-COO-Ph
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    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
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    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
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    • C09K2019/3077—Cy-Cy-COO-Ph
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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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    • C09K2019/3078—Cy-Cy-COO-Ph-Cy
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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
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
    • C09K2019/3083—Cy-Ph-COO-Ph

Definitions

  • the present invention relates to the field of liquid crystal, in particular to a liquid crystal composition and a liquid crystal display device comprising the liquid crystal composition.
  • the liquid crystal display element can be used in various household appliances including clocks and electronic calculators, measuring equipment, panels for automobiles, word processors, personal computers, printers, televisions, and the like.
  • liquid crystal display elements can be divided into PC (phase change, phase change), TN (twist nematic, twisted nematic), STN (super twisted nematic, super twisted nematic), ECB (electrically controlled birefringence, electrical control birefringence), OCB (optically compensated bend, optical compensation bending), IPS (in-plane switching, coplanar transition), VA (vertical alignment, vertical alignment) and other types.
  • the liquid crystal display element can be divided into PM (passive matrix, passive matrix) type and AM (active matrix, active matrix) type.
  • PM is divided into static (static) and multiplex (multiplex) and other types.
  • AM is divided into TFT (thin film transistor, thin film transistor), MIM (metal insulator metal, metal-insulator-metal) and other types.
  • Types of TFTs include amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process.
  • liquid crystal display elements can be classified into a reflective type using natural light, a transmissive type using background light, and a transflective type using both natural light and backlight.
  • the liquid crystal display element contains a liquid crystal composition having a nematic phase, and the composition has appropriate characteristics. By improving the properties of the composition, an AM device having good properties can be obtained.
  • Table 1 The correlation of composition properties and AM device properties is summarized in Table 1 below.
  • contrast ratio In the application of liquid crystal display device, the influence of contrast ratio on visual effect is very critical. Generally speaking, the larger the contrast, the clearer and more striking the image, and the brighter and brighter the color; and if the contrast is small, the whole picture will be gray. High contrast is very helpful for image clarity, detail performance, and grayscale performance. High-contrast products have advantages in black and white contrast, sharpness, and integrity. Contrast also has a great influence on the display effect of dynamic video. Since the transition between light and dark in dynamic images is relatively fast, the higher the contrast, the easier it is for human eyes to distinguish such a transition process.
  • T r ⁇
  • T r represents the transmittance
  • ⁇ represents the “inverse proportional” relationship
  • ⁇ represents the dielectric anisotropy
  • ⁇ ⁇ represents the perpendicular to the molecule
  • the dielectric constant in the axial direction if you want to improve the transmittance of the liquid crystal medium, you can try to reduce the ⁇ of the liquid crystal medium, but generally the adjustment range of the driving voltage of the same product is limited.
  • the liquid crystal molecules will tilt to the Z-axis direction, resulting in a change in its optical anisotropy.
  • contrast ratio (CR) and brightness (L) are as follows:
  • L 255 is the on-state brightness
  • L 0 is the off-state brightness. It can be seen that it should be the change in L0 that significantly affects CR. In the off state, L 0 has nothing to do with the dielectric properties of the liquid crystal molecules, but is related to the LC Scattering of the liquid crystal material itself; the smaller the LC Scattering, the smaller the L 0 , and the CR will also be significantly improved.
  • the common ways to improve the contrast and transmittance can be considered from the following two aspects: (1) Keep the dielectric anisotropy ⁇ of the liquid crystal composition unchanged, by increasing ⁇ ⁇ can effectively improve the transmittance (2) Increase the value of the average elastic constant Kave of the liquid crystal composition, so that the order of the liquid crystal molecules is better, the light leakage is less, and the transmittance is improved.
  • the purpose of the present invention is to provide a liquid crystal composition, which has a relatively high level of clearing point, proper optical anisotropy and proper absolute value of dielectric anisotropy under the condition of maintaining proper clearing point, proper optical anisotropy and proper absolute value of dielectric anisotropy. Larger vertical dielectric ( ⁇ ⁇ ), larger ratio of vertical dielectric to absolute value of dielectric ( ⁇ ⁇ /
  • Another object of the present invention is to provide a liquid crystal display device comprising the above-mentioned liquid crystal composition.
  • the present invention provides a liquid crystal composition
  • the liquid crystal composition comprises:
  • R 1 represents a straight-chain or branched alkenyl group containing 2-12 carbon atoms, or a straight-chain or branched alkenyloxy group containing 2-11 carbon atoms;
  • R 2 represents a linear or branched alkyl group containing 1-12 carbon atoms,
  • R 3 and R 4 each independently represent a linear or branched alkoxy group containing 1-11 carbon atoms
  • L 1 , L 2 , L 3 and L 4 each independently represent -F, -Cl, -CF 3 , -OCF 3 or -CHF 2 ;
  • n 1 0 or 1.
  • both L 1 and L 2 are -F.
  • R 2 represents a linear or branched alkyl group containing 1-10 carbon atoms, a linear or branched alkoxy group containing 1-9 carbon atoms, Or a straight-chain or branched alkenyl group containing 2-10 carbon atoms; further preferably, R 2 represents a straight-chain or branched alkyl group containing 1-8 carbon atoms, an alkyl group containing 1-7 carbon atoms Linear or branched alkoxy, or linear or branched alkenyl containing 2 to 8 carbon atoms.
  • the compound of general formula I is selected from the group consisting of:
  • a represents an integer from 0 to 4.
  • b represents an integer of 1-4.
  • the compound of formula I accounts for 0.1%-50% by weight of the liquid crystal composition, for example, 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8% , 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32 %, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%; preferably, the compound of formula I accounts for 0.5% by weight of the liquid crystal composition -40%.
  • the liquid crystal composition comprises at least two compounds of formula I.
  • the liquid crystal composition comprises at least one compound of formula I-1 and/or compound of formula I-2.
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • ), larger Kave value and higher transmittance, preferably contains at least one compound of the general formula I-2; particularly preferably contains at least one a 0 The compound of general formula I-2.
  • L 3 and L 4 are both -F.
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the compound of formula II accounts for 0.1%-60% by weight of the liquid crystal composition, for example, 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8% , 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32 %, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 50%, 52%, 54%, 56%, 58%, 60%;
  • the compound of general formula II accounts for 0.5%-40% by weight of the liquid crystal composition.
  • liquid crystal compositions of the present invention further comprise at least one compound of general formula M
  • ring ring and ring represent independently in One or more of the -CH 2 - in the ring may be replaced by -O-, and, in one or more of the rings, the single bond may be replaced by a double bond, At most one of the -Hs may be substituted by halogen;
  • the alkenyl group in the present invention is preferably selected from the group represented by any one of formula (V1) to formula (V9), particularly preferably formula (V1), formula (V2), formula (V8) or formula ( V9).
  • the groups represented by formula (V1) to formula (V9) are as follows:
  • * represents a carbon atom in the bonded ring structure.
  • the alkenyloxy group in the present invention is preferably selected from the group represented by any one of formula (OV1) to formula (OV9), particularly preferably formula (OV1), formula (OV2), formula (OV8) or formula (OV9).
  • the groups represented by formula (OV1) to formula (OV9) are as follows:
  • * represents a carbon atom in the bonded ring structure.
  • the compound of general formula M is selected from the group consisting of:
  • the compound of general formula M accounts for 1%-80% by weight of the liquid crystal composition, for example, 1%, 2%, 4%, 6%, 8%, 10%, 11% , 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35 %, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%; preferably, the compound of general formula M accounts for 20%-70% by weight of the liquid crystal composition.
  • the liquid crystal composition in order to obtain a larger vertical dielectric ( ⁇ ⁇ ), a larger vertical dielectric and a larger absolute value of the dielectric with the absolute value of the dielectric anisotropy at the same or approximately horizontal level ratio ( ⁇ ⁇ /
  • the content of the compound of general formula M must depend on solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, burn-in, dielectric anisotropy Make appropriate adjustments according to the required performance.
  • the lower limit value is preferably higher and the upper limit value is higher;
  • the lower limit value is preferably high and the upper limit value is high;
  • the absolute value of is large, it is preferable that the lower limit value is lower and the upper limit value is lower.
  • R M1 and R M2 are preferably each independently a linear or branched alkyl group containing 1-10 carbon atoms, a linear or branched alkyl group containing 1-9 carbon atoms Alkoxy, or straight-chain or branched alkenyl containing 2-10 carbon atoms; R M1 and R M2 are further preferably each independently a straight-chain or branched alkyl group containing 1-8 carbon atoms, A straight-chain or branched alkoxy group containing 1-7 carbon atoms, or a straight-chain or branched alkenyl group containing 2-8 carbon atoms; R M1 and R M2 are further preferably each independently containing 1 - Linear or branched alkyl of 5 carbon atoms, linear or branched alkoxy of 1 to 4 carbon atoms, or linear or branched alkenyl of 2 to 5 carbon atoms .
  • R M1 and R M2 are preferably each independently a straight-chain alkenyl group containing 2-8 carbon atoms; further preferably each independently is a straight-chain alkenyl group containing 2-5 carbon atoms alkenyl.
  • either one of R M1 and R M2 is a straight-chain alkenyl group containing 2-5 carbon atoms, and the other is a straight-chain alkenyl group containing 1-5 carbon atoms straight chain alkyl.
  • R M1 and R M2 are preferably each independently a straight-chain alkyl group containing 1-8 carbon atoms, or a straight-chain alkoxy group containing 1-7 carbon atoms; further Preferably, each independently is a straight-chain alkyl group having 1 to 5 carbon atoms, or a straight-chain alkoxy group having 1 to 4 carbon atoms.
  • either one of R M1 and R M2 is a straight-chain alkyl group containing 1-5 carbon atoms, and the other is a linear alkyl group containing 1-5 carbon atoms A straight-chain alkyl group, or a straight-chain alkoxy group containing 1-4 carbon atoms; further preferably, both R M1 and R M2 are each independently a straight-chain alkane containing 1-5 carbon atoms base.
  • both R M1 and R M2 when emphasis is placed on reliability, it is preferred that both R M1 and R M2 are alkyl; when emphasis is placed on reducing the volatility of the compound, it is preferred that both R M1 and R M2 are alkoxy; When emphasis is placed on viscosity reduction, at least one of R M1 and R M2 is preferably an alkenyl group.
  • liquid crystal compositions of the present invention further comprise at least one compound of general formula III:
  • R 5 and R 6 each independently represent a straight or branched chain alkyl group containing 1-12 carbon atoms,
  • T 1 , T 2 , T 3 , T 4 , T 5 , and T 6 each independently represent -H, an alkyl group containing 1-3 carbon atoms, or a halogen;
  • the compound of general formula III is selected from the group consisting of:
  • R 5 and R 6 each independently represent a linear or branched alkyl group containing 1-10 carbon atoms, a linear or branched alkyl group containing 1-9 carbon atoms Chain alkoxy, or straight-chain or branched alkenyl containing 2-10 carbon atoms; further preferably, R 5 and R 6 each independently represent a straight-chain or branched chain containing 1-8 carbon atoms The alkyl group, the straight-chain or branched alkoxy group containing 1-7 carbon atoms, or the straight-chain or branched alkenyl group containing 2-8 carbon atoms; further preferably, R 5 and R 6 Each independently represents a straight-chain or branched alkyl group containing 1-5 carbon atoms, a straight-chain or branched alkoxy group containing 1-4 carbon atoms, or a straight-chain chain containing 2-5 carbon atoms or branched alkenyl.
  • the compound of formula III accounts for 0%-30% by weight of the liquid crystal composition, for example, 0%, 0.1%, 1%, 2%, 4%, 6%, 8% , 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%; preferred Typically, the compound of the general formula III accounts for 0.1%-25% by weight of the liquid crystal composition.
  • liquid crystal compositions of the present invention further comprise at least one compound of general formula N
  • R N1 and R N2 each independently represent a linear or branched alkyl group containing 1 to 12 carbon atoms,
  • L N1 and L N2 each independently represent -F, -Cl, -CF 3 , -OCF 3 or -CHF 2 ;
  • L N3 and L N4 each independently represent -H, an alkyl group containing 1-3 carbon atoms or a halogen
  • n N1 0, 1, 2 or 3
  • n N2 represents 0 or 1
  • 0 ⁇ n N1 +n N2 ⁇ 3 wherein when n N1 2 or 3, the ring Can be the same or different, Z N1 can be the same or different;
  • R N1 is not alkenyl or alkenyloxy
  • the compound of the general formula N is not a terphenyl structure.
  • the compound of general formula N is selected from the group consisting of:
  • R N1 ' and R N2 ' each independently represent a straight-chain or branched alkyl group containing 1-8 carbon atoms, or a straight-chain or branched alkenyl group containing 2-8 carbon atoms;
  • R N1 "represents a linear or branched alkyl group containing 1-8 carbon atoms, or a linear or branched alkoxy group containing 1-7 carbon atoms.
  • the compound of general formula N accounts for 0.1%-60% by weight of the liquid crystal composition, for example, 0.1%, 1%, 2%, 4%, 6%, 8%, 10% , 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34 %, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%; preferably, the general formula N The compound accounts for 1%-55% by weight of the liquid crystal composition.
  • the lower limit value and the upper limit value of the content of the compound of general formula N are lower;
  • the lower limit value of the content of the compound of the general formula N is preferably lower and the upper limit value is lower; in addition, in order to When the absolute value of the dielectric anisotropy is increased while keeping the driving voltage low, it is preferable to increase the lower limit value and the upper limit value of the content of the compound of the general formula N higher.
  • R N1 and R N2 each independently represent a linear or branched alkyl group containing 1-10 carbon atoms, a linear or branched alkyl group containing 1-9 carbon atoms Chain alkoxy, or straight-chain or branched alkenyl containing 2-10 carbon atoms; further preferably, R N1 and R N2 each independently represent a straight-chain or branched chain containing 1-8 carbon atoms alkyl, straight-chain or branched alkoxy containing 1-7 carbon atoms, or straight-chain or branched alkenyl containing 2-8 carbon atoms; further preferably, R N1 and R N2 Each independently represents a straight-chain or branched alkyl group containing 1-5 carbon atoms, a straight-chain or branched alkoxy group containing 1-4 carbon atoms, or a straight-chain chain containing 2-5 carbon atoms or branched alkenyl.
  • liquid crystal composition of the present invention further comprises at least one compound of general formula A-1 and/or compound of general formula A-2:
  • R A1 and R A2 each independently represent a linear or branched alkyl group containing 1 to 12 carbon atoms,
  • One or more -Hs in can be independently replaced by -F or -Cl respectively;
  • L A11 , L A12 , L A13 , L A21 and L A22 each independently represent -H, an alkyl group containing 1-3 carbon atoms or a halogen;
  • X A1 and X A2 each independently represent halogen, haloalkyl or haloalkoxy containing 1 to 5 carbon atoms, haloalkenyl or haloalkenyloxy containing 2 to 5 carbon atoms;
  • the compound of general formula A-1 is selected from the group consisting of:
  • R v and R w each independently represent -CH 2 - or -O-;
  • L A11 , L A12 , L A11 ′, L A12 ′, L A14 , L A15 and L A16 each independently represent -H or -F;
  • L A13 and L A13 ' each independently represent -H or -CH 3 ;
  • X A1 represents -F, -CF 3 or -OCF 3 ;
  • v and w each independently represent 0 or 1.
  • the compound of general formula A-1 accounts for 0%-50% by weight of the liquid crystal composition, for example, 0%, 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30% , 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%.
  • the lower limit is preferably slightly lower and the upper limit is preferably The value is slightly lower; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to make the lower limit value slightly lower and the upper limit value slightly lower; Further, in order to keep the driving voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable to make the lower limit value slightly higher and the upper limit value slightly higher.
  • the compound of general formula A-2 is selected from the group consisting of:
  • L A21 , L A22 , L A23 , L A24 and L A25 each independently represent -H or -F;
  • the compound of general formula A-2 accounts for 0%-50% by weight of the liquid crystal composition, for example, 0%, 0.1%, 1%, 2%, 4%, 6%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30% , 32%, 34%, 35%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%.
  • the lower limit is preferably slightly lower and the upper limit is preferably is slightly lower; further, when the clearing point of the liquid crystal composition of the present invention is kept high and the temperature stability is good, it is preferable to make the lower limit value slightly lower and the upper limit value slightly lower; furthermore, In order to keep the driving voltage low and to increase the absolute value of the dielectric anisotropy, it is preferable to make the lower limit value slightly higher and the upper limit value slightly higher.
  • liquid crystal composition of the present invention may also contain general nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, dopants, antioxidants, ultraviolet absorbers, infrared absorbers, polymerizable monomers or Light stabilizers, etc.
  • the dopant accounts for 0%-5% by weight of the liquid crystal composition; preferably, the dopant accounts for 0.01%-1% by weight of the liquid crystal composition.
  • additives such as antioxidants and light stabilizers used in the liquid crystal composition of the present invention are preferably the following:
  • n a positive integer from 1 to 12.
  • the light stabilizer is selected from the following light stabilizers:
  • the light stabilizer accounts for 0%-5% of the total weight of the liquid crystal composition; preferably, the light stabilizer accounts for 0.01%-1% of the total weight of the liquid crystal composition; more preferably Typically, the light stabilizer accounts for 0.01%-0.1% of the total weight of the liquid crystal composition.
  • the present invention also provides a liquid crystal display device comprising the above-mentioned liquid crystal composition.
  • the liquid crystal composition of the present invention also has a larger vertical dielectric ( ⁇ ) under the condition of maintaining a proper clearing point, proper optical anisotropy and proper absolute value of dielectric anisotropy.
  • ⁇ a larger ratio of the vertical dielectric to the absolute value of the dielectric ( ⁇ ⁇ /
  • nCCGF n in the code represents the number of C atoms of the left-terminal alkyl group, for example, n is "3", which means that the alkyl group is -C 3 H 7 ;
  • C in the code stands for 1,4-cyclohexylene, G stands for 2-fluoro-1,4-phenylene, and F stands for fluorine.
  • ⁇ n measured at 25° C. using an Abbe refractometer under a sodium lamp (589 nm) light source.
  • ⁇ ⁇ ⁇ - ⁇ ⁇ , where ⁇ ⁇ is the dielectric constant parallel to the molecular axis, ⁇ ⁇ is the dielectric constant perpendicular to the molecular axis; test conditions: VA type at 25°C, 1KHz, cell thickness 6 ⁇ m test box.
  • Tr DMS 505 photoelectric comprehensive tester is used to test the VT curve of the dimming device, and the maximum transmittance on the VT curve is taken as the transmittance of the liquid crystal.
  • the test cell is a negative IPS type with a cell thickness of 3.5 ⁇ m.
  • the components used in the following examples can be synthesized by known methods or obtained through commercial channels. These synthesis techniques are conventional, and each of the resulting liquid crystal compounds has been tested to meet electronic compound standards.
  • the liquid crystal compositions were prepared according to the proportions of the liquid crystal compositions specified in the following examples.
  • the preparation of the liquid crystal composition is carried out according to the conventional methods in the art, such as heating, ultrasonic wave, suspension, etc., by mixing according to the proportion.
  • the liquid crystal composition of Comparative Example 1 was prepared according to the compounds listed in Table 3 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 1 The liquid crystal composition of Example 1 was prepared according to the compounds listed in Table 4 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • the liquid crystal composition of Comparative Example 2 was formulated according to the compounds listed in Table 5 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 2 The liquid crystal composition of Example 2 was prepared according to the compounds listed in Table 6 and their weight percentages, and was filled between the two substrates of the liquid crystal display for performance testing.
  • Example 3 The liquid crystal composition of Example 3 was prepared according to the compounds listed in Table 7 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 4 The liquid crystal composition of Example 4 was prepared according to the compounds listed in Table 8 and their weight percentages, and was filled between the two substrates of the liquid crystal display for performance testing.
  • Example 5 The liquid crystal composition of Example 5 was prepared according to the compounds listed in Table 9 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 6 According to each compound listed in Table 10 and its weight percentage, the liquid crystal composition of Example 6 was prepared, and it was filled between the two substrates of the liquid crystal display for performance testing.
  • Example 7 The liquid crystal composition of Example 7 was prepared according to the compounds listed in Table 11 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 8 The liquid crystal composition of Example 8 was prepared according to the compounds listed in Table 12 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 9 The liquid crystal composition of Example 9 was prepared according to the compounds listed in Table 13 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 10 The liquid crystal composition of Example 10 was prepared according to the compounds listed in Table 14 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • Example 11 The liquid crystal composition of Example 11 was prepared according to the compounds listed in Table 15 and their weight percentages, and was filled between two substrates of a liquid crystal display for performance testing.
  • the liquid crystal composition of the present invention also has a relatively large vertical dielectric ( ⁇ ⁇ ), relatively Larger ratio of vertical dielectric to absolute value of dielectric ( ⁇ ⁇ /
  • the performance improvement is more significant, and the liquid crystal display device comprising the liquid crystal composition of the present invention has better contrast ratio, faster response speed and better threshold voltage under the condition of maintaining a proper usable temperature range and proper threshold voltage. transmittance.
  • the liquid crystal composition of the present invention can be applied to the field of liquid crystal.

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Abstract

液晶组合物及其液晶显示器件，所述液晶组合物包含至少一种通式I的化合物和至少一种通式II的化合物。该液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，使得包含其的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下，具有较好的对比度、较快的响应速度和较好的透过率。

Description

液晶组合物及其液晶显示器件 技术领域
本发明涉及液晶领域，具体涉及液晶组合物和包含所述液晶组合物的液晶显示器件。
背景技术
液晶显示元件可以在钟表、电子计算器为代表的各种家庭用电器、测定机器、汽车用面板、文字处理机、电脑、打印机、电视等中使用。根据显示模式的类型，液晶显示元件可以分为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)、VA(vertical alignment，垂直配向)等类型。根据元件的驱动方式，液晶显示元件可以分为PM(passive matrix，被动矩阵)型和AM(active matrix，主动矩阵)型。PM分为静态(static)和多路(multiplex)等类型。AM分为TFT(thin film transistor，薄膜晶体管)、MIM(metal insulator metal，金属-绝缘层-金属)等类型。TFT的类型包含非晶硅(amorphous silicon)和多晶硅(polycrystal silicon)。后者根据制造工艺分为高温型和低温型。根据光源的类型，液晶显示元件可以分为利用自然光的反射型、利用背景光的透过型、以及利用自然光和背光两种光源的半透过型。
液晶显示元件含有具有向列相的液晶组合物，该组合物具有适当的特性。借由提高该组合物的特性，可获得具有良好特性的AM元件。组合物特性和AM元件特性的关联归纳于下表1中。
表1.组合物的特性与AM元件的特性
编号 组合物的特性 AM元件的特性
1 向列相的温度范围广 可使用的温度范围广
2 粘度小 响应时间短
3 光学各向异性适当 对比度大
4 正或负的介电各向异性的绝对值大 阈值电压低、消耗电力小、对比度大
5 比电阻大 电压保持率大、对比率大
6 对紫外线及热稳定 寿命长
7 弹性常数大 对比度大、响应时间短
在液晶显示器件的应用中，对比度对视觉效果的影响非常关键。一般来说，对比度越大，图像越清晰醒目，色彩也越鲜明艳丽；而如果对比度小，则整个画面都灰蒙蒙的。高对比度对于图像的清晰度、细节表现、灰度层次表现都有很大的帮助。高对比度产品在黑白反差、清晰度、完整性等方面都具有优势。对比度对于动态视频显示效果的影响也较大，由于动态图像中明暗转换比较快，因此对比度越高，人的眼睛越容易分辨出这样的转换过 程。
根据IPS模式的透过率公式T r∝|Δε|/ε ⊥(其中,T r表示透过率，“∝”表示“反比例”关系，Δε表示介电各向异性，ε ⊥表示垂直于分子轴方向的介电常数)，若要提高液晶介质的透过率，可以试图降低液晶介质的Δε，但一般同一款产品的驱动电压的调整范围有限。另外，液晶分子在边缘电场垂直分量的作用下会向Z轴方向发生倾斜，导致其光学各向异性发生变化，根据公式
Figure PCTCN2021112260-appb-000001
(其中，χ即为液晶层光轴与偏光片光轴之间的夹角，Δn为光学各向异性，d为液晶盒的间距，λ为波长)可知，有效Δn*d会影响T r，若要提升液晶的透过率，也可以考虑增大Δn*d，但每款产品的延迟量设计都是固定的。
另一方面，本领域技术人员基于传统的IPS-LCD漏光性能测试发现，造成液晶显示器件漏光问题的主要原因是：光散射(LC scattering)、摩擦均匀性(rubbing uniformity)、彩色滤光膜漏光(CF/TFT scattering)以及极化能力(polarize ability)，其中，光散射在漏光性能的影响因素中占比达63％。
根据如下关系式：
Figure PCTCN2021112260-appb-000002
(其中，d表示液晶盒的间距，Δn表示光学各向异性，n e表示非寻常光折射率，n o表示寻常光折射率，K ave表示平均弹性常数
Figure PCTCN2021112260-appb-000003
K 11为斜展弹性常数，K 22为扭曲弹性常数，K 33为弯曲弹性常数)。由该关系式可知，LC Scattering与K ave成反比关系，在提高K ave的情况下，可以降低液晶材料的漏光。
此外，对比度(CR)与亮度(L)的关系式如下：
CR＝L 255/L 0×100％，
其中，L 255为开态亮度，L 0为关态亮度。可以看出，显著影响CR的应该是L 0的变化。在关态下，L 0与液晶分子的介电性能无关，而与液晶材料本身的LC Scattering相关；LC Scattering愈小，L 0也愈小，CR从而也就会显著提高。
鉴于上述情况，常见的用来提高对比度和透过率的方式可以从如下两方面考虑：(1)保持液晶组合物的介电各向异性Δε不变，通过提高ε ⊥可以有效地提高透过率；(2)提高液晶组合物的平均弹性常数K ave的值，使液晶分子的有序度更好、漏光更少，从而使透过率提高。
从液晶材料的制备角度出发，液晶材料的各项性能互相牵制影响，某项性能指标的提升可能会使其他性能发生变化。因此，制备各方面性能都合适的液晶材料往往需要创造性劳动。
发明内容
发明目的：本发明的目的在于提供一种液晶组合物，所述液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率。
本发明的目的还在于提供一种包含上述液晶组合物的液晶显示器件。
技术方案：为了实现以上发明目的，本发明提供一种液晶组合物，所述液晶组合物包含：
至少一种通式I的化合物
Figure PCTCN2021112260-appb-000004
至少一种通式II的化合物
Figure PCTCN2021112260-appb-000005
其中，
R 1表示含有2-12个碳原子的直链或支链的烯基、或含有2-11个碳原子的直链或支链的烯氧基；
R 2表示含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000006
所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
R 3和R 4各自独立地表示含有1-11个碳原子的直链或支链的烷氧基；
L 1、L 2、L 3和L 4各自独立地表示-F、-Cl、-CF 3、-OCF 3或-CHF 2；并且
n 1表示0或1。
在本发明的一些实施方案中，L 1和L 2均为-F。
在本发明的一些实施方案中，优选地，R 2表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基；进一步优选地，R 2表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基。
在本发明的一些实施方案中，通式I的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000007
Figure PCTCN2021112260-appb-000008
Figure PCTCN2021112260-appb-000009
以及
Figure PCTCN2021112260-appb-000010
其中，
a表示0-4的整数；并且
b表示1-4的整数。
在本发明的一些实施方案中，通式I的化合物占液晶组合物的重量百分比为0.1％-50％，例如，0.1％、0.5％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％；优选地，通式I的化合物占液晶组合物的重量百分比为0.5％-40％。
在本发明的一些实施方案中，液晶组合物包含至少两种通式I的化合物。
在本发明的一些实施方案中，液晶组合物包含至少一种通式I-1的化合物和/或通式I-2的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种通式I-2的化合物；特别优选包含至少一种a＝0的通式I-2的化合物。
在本发明的一些实施方案中，L 3和L 4均为-F。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少两种通式II的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种n 1表示0的通式II的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种a表示0的通式I-2的化合物和至少一种n 1表示0的通式II的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种n 1表示1的通式II的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种a表示0的通式I-2的化合物和至少一种n 1表示1的通式II的化合物。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种n 1表示0的通式II的化合物和至少一种n 1表示1的通式II的化合物。
在本发明的一些实施方案中，通式II的化合物占液晶组合物的重量百分比为0.1％-60％，例如，0.1％、0.5％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％、50％、52％、54％、56％、58％、60％；优选地，通式II的化合物占液晶组合物的重量百分比为0.5％-40％。
在本发明的一些实施方案中，本发明的液晶组合物还包含至少一种通式M的化合物
Figure PCTCN2021112260-appb-000011
其中，
R M1和R M2各自独立地表示含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000012
Figure PCTCN2021112260-appb-000013
所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
环
Figure PCTCN2021112260-appb-000014
环
Figure PCTCN2021112260-appb-000015
和环
Figure PCTCN2021112260-appb-000016
各自独立地表示
Figure PCTCN2021112260-appb-000017
Figure PCTCN2021112260-appb-000018
其中
Figure PCTCN2021112260-appb-000019
中的一个或更多个-CH 2-可被-O-替代，并且，一个或更多个环中单键可被双键替代，
Figure PCTCN2021112260-appb-000020
中的至多一个-H可被卤素取代；
Z M1和Z M2各自独立地表示单键、-CO-O-、-O-CO-、-CH 2O-、-OCH 2-、-C≡C-、-CH＝CH-、-CH 2CH 2-或-(CH 2) 4-；并且
n M表示0、1或2，其中当n M＝2时，环
Figure PCTCN2021112260-appb-000021
可以相同或不同，Z M2可以相同或不同。
本发明中的烯基优选地选自式(V1)至式(V9)中的任一者所表示的基团，特别优选为式(V1)、式(V2)、式(V8)或式(V9)。式(V1)至式(V9)所表示的基团如下所示：
Figure PCTCN2021112260-appb-000022
其中，*表示所键结的环结构中的碳原子。
本发明中的烯氧基优选地选自式(OV1)至式(OV9)中的任一者所表示的基团，特别优选为式(OV1)、式(OV2)、式(OV8)或式(OV9)。式(OV1)至式(OV9)所表示的基团如下所示：
Figure PCTCN2021112260-appb-000023
其中，*表示所键结的环结构中的碳原子。
在本发明的一些实施方案中，通式M的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000024
Figure PCTCN2021112260-appb-000025
Figure PCTCN2021112260-appb-000026
Figure PCTCN2021112260-appb-000027
以及
Figure PCTCN2021112260-appb-000028
在本发明的一些实施方案中，通式M的化合物占液晶组合物的重量百分比为1％-80％，例如，1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％、52％、54％、56％、58％、60％、62％、64％、66％、68％、70％、72％、74％、76％、78％、80％；优选地，通式M的化合物占液晶组合物的重量百分比为20％-70％。
在本发明的一些实施方案中，在介电各向异性绝对值处于相同或近似水平的情况下，为了获得较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，液晶组合物优选包含至少一种一侧端基为烯基的通式M-12的化合物。
在本发明的一些实施方案中，通式M的化合物的含量必须视低温下的溶解性、转变温度、电可靠性、双折射率、工艺适应性、滴下痕迹、烧屏、介电各向异性等所需的性能而适当进行调整。
关于通式M的化合物的含量，在需要保持本发明的液晶组合物的粘度较低、且响应时间较短时，优选其下限值较高且上限值较高；进一步地，在需要保持本发明的液晶组合物的清亮点较高、且温度稳定性良好时，优选其下限值较高且上限值较高；在为了将驱动电压保持为较低、且使介电各向异性的绝对值较大时，优选其下限值变低且上限值变低。
在本发明的一些实施方案中，R M1和R M2优选各自独立地为含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基；R M1和R M2进一步优选各自独立地为含有1-8个碳原子的直链或支链的烷基、 含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基；R M1和R M2再进一步优选各自独立地为含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中，R M1和R M2优选各自独立地为含有2-8个碳原子的直链的烯基；进一步优选各自独立地为含有2-5个碳原子的直链的烯基。
在本发明的一些实施方案中，优选地，R M1和R M2中的任一者为含有2-5个碳原子的直链的烯基，而另一者为含有1-5个碳原子的直链的烷基。
在本发明的一些实施方案中，R M1和R M2优选各自独立地为含有1-8个碳原子的直链的烷基、或含有1-7个碳原子的直链的烷氧基；进一步优选各自独立地为含有1-5个碳原子的直链的烷基、或含有1-4个碳原子的直链的烷氧基。
在本发明的一些实施方案中，优选地，R M1和R M2中的任一者为含有1-5个碳原子的直链的烷基，而另一者为含有1-5个碳原子的直链的烷基、或含有1-4个碳原子的直链的烷氧基；进一步优选地，R M1和R M2两者均各自独立地为含有1-5个碳原子的直链的烷基。
在本发明的一些实施方案中，在重视可靠性时，优选R M1和R M2均为烷基；在重视降低化合物的挥发性的情形时，优选R M1和R M2均为烷氧基；在重视粘度降低的情形时，优选R M1和R M2中至少一者为烯基。
在本发明的一些实施方案中，本发明的液晶组合物还包含至少一种通式III的化合物：
Figure PCTCN2021112260-appb-000029
其中，
R 5和R 6各自独立地表示含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000030
Figure PCTCN2021112260-appb-000031
所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
T 1、T 2、T 3、T 4、T 5和T 6各自独立地表示-H、含有1-3个碳原子的烷基或卤素；并且
通式III的化合物含有至少一个环结构
Figure PCTCN2021112260-appb-000032
在本发明的一些实施方案中，通式III的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000033
Figure PCTCN2021112260-appb-000034
Figure PCTCN2021112260-appb-000035
以及
Figure PCTCN2021112260-appb-000036
在本发明的一些实施方案中，优选地，R 5和R 6各自独立地表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基；进一步优选地，R 5和R 6各自独立地表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基；再进一步优选地，R 5和R 6各自独立地表示含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中，通式III的化合物占液晶组合物的重量百分比为0％-30％，例如，0％、0.1％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％；优选地，通式III的化合物占液晶组合物的重量百分比为0.1％-25％。
在本发明的一些实施方案中，本发明的液晶组合物还包含至少一种通式N的化合物
Figure PCTCN2021112260-appb-000037
其中，
R N1和R N2各自独立地表示含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000038
Figure PCTCN2021112260-appb-000039
所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
环
Figure PCTCN2021112260-appb-000040
和环
Figure PCTCN2021112260-appb-000041
各自独立地表示
Figure PCTCN2021112260-appb-000042
其中
Figure PCTCN2021112260-appb-000043
中的一个或更多个-CH 2-可被-O-替代，一个或更多个环中单键可被双键替代，其中
Figure PCTCN2021112260-appb-000044
中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代，一个或更多个环中-CH＝可被-N＝替代；
Z N1和Z N2各自独立地表示单键、-CO-O-、-O-CO-、-CH 2O-、-OCH 2-、-CH＝CH-、-C≡C-、-CH 2CH 2-、-CF 2CF 2-、-(CH 2) 4-、-CF 2O-或-OCF 2-；
L N1和L N2各自独立地表示-F、-Cl、-CF 3、-OCF 3或-CHF 2；
L N3和L N4各自独立地表示-H、含有1-3个碳原子的烷基或卤素；
n N1表示0、1、2或3，n N2表示0或1，且0≤n N1+n N2≤3，其中当n N1＝2或3时，环
Figure PCTCN2021112260-appb-000045
可以相同或不同，Z N1可以相同或不同；
当n N1+n N2＝0时，或者n N1+n N2＝1，且通式N的化合物为双联苯结构时，R N1和R N2不为烷氧基；
当n N1表示2，n N2表示0，且通式N的化合物中存在双联苯结构时，R N1不为烯基或烯氧基；并且
当n N1+n N2＝3时，通式N的化合物不为三联苯结构。
在本发明的一些实施方案中，通式N的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000046
Figure PCTCN2021112260-appb-000047
Figure PCTCN2021112260-appb-000048
Figure PCTCN2021112260-appb-000049
以及
Figure PCTCN2021112260-appb-000050
其中，
R N1’和R N2’各自独立的表示含有1-8个碳原子的直链或支链的烷基、或含有2-8个碳原子的直链或支链的烯基；并且
R N1”表示含有1-8个碳原子的直链或支链的烷基、或含有1-7个碳原子的直链或支链的烷氧基。
在本发明的一些实施方案中，通式N的化合物占液晶组合物的重量百分比为0.1％-60％，例如，0.1％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％、52％、54％、56％、58％、60％；优选地，通式N的化合物占液晶组合物的重量百分比为1％-55％。
在本发明的一些实施方案中，在需要保持本发明的液晶组合物粘度较低、且响应时间较短时，优选通式N的化合物的含量的下限值较低且上限值较低；进一步地，在需要保持本发明的液晶组合物的清亮点较高、且温度稳定性良好时，优选通式N的化合物的含量的下限值较低且上限值较低；另外，在为了将驱动电压保持为较低、而使介电各向异性的绝对值变大时，优选使通式N的化合物的含量的下限值变高且上限值变高。
在本发明的一些实施方案中，优选地，R N1和R N2各自独立地表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的 直链或支链的烯基；进一步优选地，R N1和R N2各自独立地表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基；再进一步优选地，R N1和R N2各自独立地表示含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中，本发明的液晶组合物还包含至少一种通式A-1的化合物和/或通式A-2的化合物：
Figure PCTCN2021112260-appb-000051
其中，
R A1和R A2各自独立地表示含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000052
Figure PCTCN2021112260-appb-000053
所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，并且所述含有1-12个碳原子的直链或支链的烷基、
Figure PCTCN2021112260-appb-000054
中的一个或更多个-H可分别独立地被-F或-Cl取代；
环
Figure PCTCN2021112260-appb-000055
环
Figure PCTCN2021112260-appb-000056
环
Figure PCTCN2021112260-appb-000057
和环
Figure PCTCN2021112260-appb-000058
各自独立地表示
Figure PCTCN2021112260-appb-000059
其中
Figure PCTCN2021112260-appb-000060
Figure PCTCN2021112260-appb-000061
中的一个或更多个-CH 2-可被-O-替代，一个或更多个环中单键可被双键替代，其中
Figure PCTCN2021112260-appb-000062
中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代，一个或更多个环中-CH＝可被-N＝替代；
Z A11、Z A21和Z A22各自独立地表示单键、-CH 2CH 2-、-CF 2CF 2-、-CO-O-、-O-CO-、-O-CO-O-、-CH＝CH-、-CF＝CF-、-CH 2O-或-OCH 2-；
L A11、L A12、L A13、L A21和L A22各自独立地表示-H、含有1-3个碳原子的烷基或卤素；
X A1和X A2各自独立地表示卤素、含有1-5个碳原子的卤代烷基或卤代烷氧基、含有2-5个碳原子的卤代烯基或卤代烯氧基；
n A11表示0、1、2或3，其中当n A11＝2或3时，环
Figure PCTCN2021112260-appb-000063
可以相同或不同，Z A11 可以相同或不同；
n A12表示1或2，其中当n A12＝2时，环
Figure PCTCN2021112260-appb-000064
可以相同或不同；并且
n A2表示0、1、2或3，其中当n A2＝2或3时，环
Figure PCTCN2021112260-appb-000065
可以相同或不同，Z A21可以相同或不同。
在本发明的一些实施方案中，通式A-1的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000066
Figure PCTCN2021112260-appb-000067
Figure PCTCN2021112260-appb-000068
以及
Figure PCTCN2021112260-appb-000069
其中，
R A1表示含有1-8个碳原子的直链或支链的烷基，所述含有1-8个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，并且存在于这些基团中的一个或更多个-H可分别独立地被-F或-Cl取代；
R v和R w各自独立地表示-CH 2-或-O-；
L A11、L A12、L A11’、L A12’、L A14、L A15和L A16各自独立地表示-H或-F；
L A13和L A13’各自独立地表示-H或-CH 3；
X A1表示-F、-CF 3或-OCF 3；并且
v和w各自独立地表示0或1。
在本发明的一些实施方案中，通式A-1的化合物占液晶组合物的重量百分比为0％-50％，例如，0％、0.1％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％。
关于通式A-1的化合物的优选含量，在将本发明的液晶组合物的粘度保持为较低、且响应速度较快的情况下，优选使其下限值略低、且使其上限值略低；进一步地，在将本发明的液晶组合物的清亮点保持为较高、且温度稳定性良好的情况下，优选使其下限值略低、且使其上限值略低；此外，为了将驱动电压保持为较低、而欲增大介电各向异性绝对值时，优选使其下限值略高、且使上限值略高。
在本发明的一些实施方案中，通式A-2的化合物选自由如下化合物组成的组：
Figure PCTCN2021112260-appb-000070
Figure PCTCN2021112260-appb-000071
Figure PCTCN2021112260-appb-000072
Figure PCTCN2021112260-appb-000073
以及
Figure PCTCN2021112260-appb-000074
其中，
R A2表示含有1-8个碳原子的直链或支链的烷基，所述含有1-8个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代，并且存在于这些基团中的一个或更多个-H可分别独立地被-F或-Cl取代；
L A21、L A22、L A23、L A24和L A25各自独立地表示-H或-F；并且
X A2表示-F、-CF 3、-OCF 3或-CH 2CH 2CH＝CF 2。
在本发明的一些实施方案中，通式A-2的化合物占液晶组合物的重量百分比为0％-50％，例如，0％、0.1％、1％、2％、4％、6％、8％、10％、11％、12％、13％、14％、15％、16％、17％、18％、20％、22％、24％、25％、26％、28％、30％、32％、34％、35％、36％、38％、40％、42％、44％、46％、48％、50％。
关于通式A-2的化合物的优选含量，在将本发明的液晶组合物的粘度保持为较低、且响应速度快的情况下，优选使其下限值略低、且使其上限值略低；进一步地，在将本发明的液晶组合物的清亮点保持为较高、且温度稳定性良好的情况下，优选使其下限值略低、且使上限值略低；此外，为了将驱动电压保持为较低、而欲增大介电各向异性的绝对值时，优选使其下限值略高、且使其上限值略高。
除上述化合物以外，本发明的液晶组合物也可含有通常的向列型液晶、近晶型液晶、胆固醇型液晶、掺杂剂、抗氧化剂、紫外线吸收剂、红外线吸收剂、聚合性单体或光稳定 剂等。
如下显示优选加入到根据本发明的液晶组合物中的可能的掺杂剂：
Figure PCTCN2021112260-appb-000075
Figure PCTCN2021112260-appb-000076
以及
Figure PCTCN2021112260-appb-000077
在本发明的一些实施方案中，掺杂剂占液晶组合物的重量百分比为0％-5％；优选地，掺杂剂占液晶组合物的重量百分比为0.01％-1％。
另外，本发明的液晶组合物所使用的抗氧化剂、光稳定剂等添加剂优选以下物质：
Figure PCTCN2021112260-appb-000078
Figure PCTCN2021112260-appb-000079
Figure PCTCN2021112260-appb-000080
其中，n表示1-12的正整数。
优选地，光稳定剂选自如下所示的光稳定剂：
Figure PCTCN2021112260-appb-000081
在本发明的一些实施方案中，光稳定剂占液晶组合物的总重量百分比为0％-5％；优选地，光稳定剂占液晶组合物的总重量百分比为0.01％-1％；更优选地，光稳定剂占液晶组合物的总重量百分比为0.01％-0.1％。
在再一方面，本发明还提供一种液晶显示器件，所述液晶显示器件包含上述液晶组合物。
有益效果：
与现有技术相比，本发明的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，使得包含其的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下，具有较好的对比度、较快的响应速度和较好的透过率。
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，各化合物的基团结构用表2所列的代码表示：
表2.化合物的基团结构代码
Figure PCTCN2021112260-appb-000082
以如下结构式的化合物为例：
Figure PCTCN2021112260-appb-000083
该结构式如用表2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1,4-亚环己基，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(向列相-各向同性相的转变温度，℃)
Δn          光学各向异性(589nm，25℃)
ε ⊥         垂直介电
Δε         介电各向异性(1KHz，25℃)
ε ⊥/|Δε|  垂直介电与介电绝对值的比值
K ave         平均弹性常数(20℃)
T r           透过率(％)(20℃)
其中，
Cp：通过熔点仪测试获得。
Δn：使用阿贝折光仪在钠光灯(589nm)光源下、在25℃测试得到。
Δε：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、盒厚6μm的VA型测试盒。
T r：使用DMS 505光电综合测试仪测试调光器件的V-T曲线，全部取V-T曲线上透过率的最大值来作为液晶的透过率，测试盒为负性IPS型，盒厚3.5μm。
K ave：
Figure PCTCN2021112260-appb-000084
其中K 11、K 22和K 33是使用LCR仪和VA测试盒测试液晶材料的C-V曲线并且进行计算所得，测试条件：20℃，盒厚6μm的VA测试盒，V＝0.1-20V。
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，所得到的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。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、悬浮等方式按照比例混合制得。
对比例1
按表3中所列的各化合物及其重量百分数配制成对比例1的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表3.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000085
实施例1
按表4中所列的各化合物及其重量百分数配制成实施例1的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表4.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000086
由对比例1和实施例1的对比可知，相较于仅包含本发明通式I的化合物的液晶组合物，包含本发明通式I的化合物和通式II的化合物的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率。
对比例2
按表5中所列的各化合物及其重量百分数配制成对比例2的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表5.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000087
实施例2
按表6中所列的各化合物及其重量百分数配制成实施例2的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表6.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000088
由对比例2和实施例2的对比可知，相较于仅包含本发明通式II的化合物的液晶组合物，包含本发明通式I的化合物和通式II的化合物的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率。
实施例3
按表7中所列的各化合物及其重量百分数配制成实施例3的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表7.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000089
实施例4
按表8中所列的各化合物及其重量百分数配制成实施例4的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表8.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000090
实施例5
按表9中所列的各化合物及其重量百分数配制成实施例5的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表9.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000091
实施例6
按表10中所列的各化合物及其重量百分数配制成实施例6的液晶组合物，并且将其 填充于液晶显示器两基板之间进行性能测试。
表10.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000092
实施例7
按表11中所列的各化合物及其重量百分数配制成实施例7的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表11.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000093
实施例8
按表12中所列的各化合物及其重量百分数配制成实施例8的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表12.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000094
实施例9
按表13中所列的各化合物及其重量百分数配制成实施例9的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表13.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000095
实施例10
按表14中所列的各化合物及其重量百分数配制成实施例10的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表14.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000096
实施例11
按表15中所列的各化合物及其重量百分数配制成实施例11的液晶组合物，并且将其填充于液晶显示器两基板之间进行性能测试。
表15.液晶组合物的配方及性能参数测试结果
Figure PCTCN2021112260-appb-000097
综上，本发明的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下，还具有较大的垂直介电(ε ⊥)、较大的垂直介电与介电绝对值的比值(ε ⊥/|Δε|)、较大的K ave值和较高的透过率，尤其是，当液晶组合物中含有通式I-2的化合物时，性能提升更显著，包含本发明液晶组合物的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下，具有较好的对比度、较快的响应速度和较好的透过率。
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 PCTCN2021112260-appb-100001
    至少一种通式II的化合物
    Figure PCTCN2021112260-appb-100002
    其中，R 1表示含有2-12个碳原子的直链或支链的烯基、或含有2-11个碳原子的直链或支链的烯氧基；
    R 2表示含有1-12个碳原子的直链或支链的烷基、
    Figure PCTCN2021112260-appb-100003
    所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
    R 3和R 4各自独立地表示含有1-11个碳原子的直链或支链的烷氧基；
    L 1、L 2、L 3和L 4各自独立地表示-F、-Cl、-CF 3、-OCF 3或-CHF 2；并且
    n 1表示0或1。
  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的化合物选自由如下化合物组成的组：
    Figure PCTCN2021112260-appb-100004
    Figure PCTCN2021112260-appb-100005
    以及
    Figure PCTCN2021112260-appb-100006
    其中，a表示0-4的整数；并且b表示1-4的整数。
  3. 根据权利要求2所述的液晶组合物，其特征在于，所述液晶组合物包含至少一种通式I-2的化合物。
  4. 根据权利要求1所述的液晶组合物，其特征在于，所述液晶组合物包含至少两种 通式II的化合物。
  5. 根据权利要求4所述的液晶组合物，其特征在于，所述液晶组合物包含至少一种n 1表示1的通式II的化合物。
  6. 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含至少一种通式M的化合物
    Figure PCTCN2021112260-appb-100007
    其中，R M1和R M2各自独立地表示含有1-12个碳原子的直链或支链的烷基、
    Figure PCTCN2021112260-appb-100008
    Figure PCTCN2021112260-appb-100009
    所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
    环
    Figure PCTCN2021112260-appb-100010
    环
    Figure PCTCN2021112260-appb-100011
    和环
    Figure PCTCN2021112260-appb-100012
    各自独立地表示
    Figure PCTCN2021112260-appb-100013
    Figure PCTCN2021112260-appb-100014
    其中
    Figure PCTCN2021112260-appb-100015
    中的一个或更多个-CH 2-可被-O-替代，并且一个或更多个环中单键可被双键替代，
    Figure PCTCN2021112260-appb-100016
    中的至多一个-H可被卤素取代；
    Z M1和Z M2各自独立地表示单键、-CO-O-、-O-CO-、-CH 2O-、-OCH 2-、-C≡C-、-CH＝CH-、-CH 2CH 2-或-(CH 2) 4-；并且
    n M表示0、1或2，其中当n M＝2时，环
    Figure PCTCN2021112260-appb-100017
    可以相同或不同，Z M2可以相同或不同。
  7. 根据权利要求6所述的液晶组合物，其特征在于，所述液晶组合物还包含至少一种通式III的化合物
    Figure PCTCN2021112260-appb-100018
    其中，
    R 5和R 6各自独立地表示含有1-12个碳原子的直链或支链的烷基、
    Figure PCTCN2021112260-appb-100019
    Figure PCTCN2021112260-appb-100020
    所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
    T 1、T 2、T 3、T 4、T 5和T 6各自独立地表示-H、含有1-3个碳原子的烷基或卤素；并且所述通式III的化合物含有至少一个环结构
    Figure PCTCN2021112260-appb-100021
  8. 根据权利要求7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的重量百分比为0.1％-50％；所述通式II的化合物占所述液晶组合物的重量百分比为0.1％-60％；所述通式M的化合物占液晶组合物的重量百分比为1％-80％；并且所述通式III的化合物占所述液晶组合物的重量百分比为0.1％-30％。
  9. 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含至少一种通式N的化合物
    Figure PCTCN2021112260-appb-100022
    其中，
    R N1和R N2各自独立地表示含有1-12个碳原子的直链或支链的烷基、
    Figure PCTCN2021112260-appb-100023
    Figure PCTCN2021112260-appb-100024
    所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH 2-可分别独立地被-CH＝CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代；
    环
    Figure PCTCN2021112260-appb-100025
    和环
    Figure PCTCN2021112260-appb-100026
    各自独立地表示
    Figure PCTCN2021112260-appb-100027
    其中
    Figure PCTCN2021112260-appb-100028
    中的一个或更多个-CH 2-可被-O-替代，一个或更多个环中单键可被双键替代，其中
    Figure PCTCN2021112260-appb-100029
    中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代，一个或更多个环中-CH＝可被-N＝替代；
    Z N1和Z N2各自独立地表示单键、-CO-O-、-O-CO-、-CH 2O-、-OCH 2-、-CH＝CH-、-C≡C-、-CH 2CH 2-、-CF 2CF 2-、-(CH 2) 4-、-CF 2O-或-OCF 2-；
    L N1和L N2各自独立地表示-F、-Cl、-CF 3、-OCF 3或-CHF 2；
    L N3和L N4各自独立地表示-H、含有1-3个碳原子的烷基或卤素；
    n N1表示0、1、2或3，n N2表示0或1，且0≤n N1+n N2≤3，其中当n N1＝2或3时，环
    Figure PCTCN2021112260-appb-100030
    可以相同或不同，Z N1可以相同或不同；
    当n N1+n N2＝0时，或者n N1+n N2＝1，且所述通式N的化合物为双联苯结构时，R N1和R N2不为烷氧基；
    当n N1表示2，n N2表示0，且所述通式N的化合物中存在双联苯结构时，R N1不为烯基或烯氧基；并且
    当n N1+n N2＝3时，所述通式N的化合物不为三联苯结构。
  10. 一种包含权利要求1-9中任一项所述的液晶组合物的液晶显示器件。
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