WO2020248299A1 - Liquid crystal composition having negative dielectric constant, and application thereof - Google Patents

Liquid crystal composition having negative dielectric constant, and application thereof Download PDF

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WO2020248299A1
WO2020248299A1 PCT/CN2019/092472 CN2019092472W WO2020248299A1 WO 2020248299 A1 WO2020248299 A1 WO 2020248299A1 CN 2019092472 W CN2019092472 W CN 2019092472W WO 2020248299 A1 WO2020248299 A1 WO 2020248299A1
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liquid crystal
alkenyl
alkoxy
carbon atoms
group
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PCT/CN2019/092472
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French (fr)
Chinese (zh)
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李珊珊
陆嘉文
陈新华
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晶美晟光电材料（南京）有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

Definitions

  • the invention relates to the field of liquid crystal materials, in particular to a liquid crystal composition and its application.
  • Liquid crystal displays can be divided into passive matrix (also called passive matrix or simple matrix) and active matrix (also called active matrix) two driving methods.
  • the active matrix liquid crystal display changes the arrangement of liquid crystal compounds by applying voltage, thereby changing the light emission intensity emitted by the backlight to form an image. It has high resolution, high contrast, low power, thin surface and light weight. The characteristics of it are becoming more and more popular.
  • Active matrix liquid crystal displays can be divided into two types according to active devices: MOS (metal oxide semiconductor) or other diodes on the silicon chip as the substrate; thin film transistors on the glass plate as the substrate Transistor-TFT), among them, the fastest growing thin film transistor liquid crystal display (TFT-LCD) has been well applied in display devices such as mobile phones, computers, LCD TVs and cameras, and has become the mainstream of the current LCD market product.
  • MOS metal oxide semiconductor
  • TFT thin film transistors on the glass plate as the substrate Transistor-TFT
  • TFT-LCD the fastest growing thin film transistor liquid crystal display
  • the mainstream wide viewing angle technology mainly includes VA vertical orientation technology, IPS in-plane switching technology and FFS fringe field switching technology. Both require higher light transmittance and smaller color shift.
  • VA vertical orientation technology IPS in-plane switching technology
  • FFS fringe field switching technology because an in-plane electric field is generated between the electrodes when a voltage is applied, the light penetration in this area is limited, which will increase energy consumption and affect the display effect.
  • Liquid crystal compounds perform better in terms of color shift and being affected by vertical electric fields. Compared with positive materials, they exhibit higher light transmittance and are therefore widely used.
  • the purpose of the present invention is to provide a liquid crystal composition with a negative dielectric constant, which is conducive to adjusting the optical anisotropy value of the system, improving the temperature range of the liquid crystal display, thereby increasing the response speed and improving the liquid crystal display Operating temperature range.
  • Another object of the present invention is to provide applications of the above-mentioned liquid crystal composition.
  • a liquid crystal composition which includes at least one liquid crystal compound having the general formula I, at least one liquid crystal compound having the general formula II, and At least one liquid crystal compound having the general formula III,
  • R and R' are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, where H can be cyclopentyl Group or F, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 may not be substituted by O at the same time; or, the R and R′ are each independently selected from cyclopentyl, Oxycyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Group-substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said R and R'are each independently selected from cyclopentenyl, oxo
  • a is selected from 0, 1 or 2;
  • the general formula includes two which is Appears twice in the general formula, each time Each independently selected from Any one of the formed groups;
  • R 1 and R 1 ' are each independently selected from C1-C7 alkyl or C2-C7 alkenyl, wherein H may be substituted by cyclopentyl or F, and CH 2 may be substituted by cyclopentyl, O or F , And two adjacent CH 2 cannot be replaced by O at the same time;
  • R 2 and R 2 ' are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, wherein H or CH 2 may be substituted by cyclopentyl or F; or, each of R 2 and R 2 'is independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl;
  • the liquid crystal composition of the present invention is beneficial to adjust the optical anisotropy value of the system, improve the temperature range of the liquid crystal display, and further can increase the response speed and increase the use temperature range of the liquid crystal display.
  • a liquid crystal composition comprising at least one liquid crystal compound having the general formula I, at least one liquid crystal compound having the general formula II, and at least one Liquid crystal compound of general formula III.
  • R and R' are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, where H can be cyclopentyl Group or F, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 may not be substituted by O at the same time; or, the R and R′ are each independently selected from cyclopentyl, Oxycyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Group-substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said R and R'are each independently selected from cyclopentenyl, oxo
  • a is selected from 0, 1 or 2;
  • the general formula includes two which is Appears twice in the general formula, each time Each independently selected from Any one of the formed groups;
  • R 1 and R 1 ' are each independently selected from C1-C7 alkyl or C2-C7 alkenyl, wherein H may be substituted by cyclopentyl or F, and CH 2 may be substituted by cyclopentyl, O or F , And two adjacent CH 2 cannot be replaced by O at the same time;
  • R 2 and R 2 ' are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, wherein H or CH 2 may be substituted by cyclopentyl or F; or, each of R 2 and R 2 'is independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl
  • the liquid crystal compound with the general formula I is white in the state of pure substance, and it is a liquid crystal compound with negative dielectric anisotropy.
  • the liquid crystal molecules tend to be distributed along the direction perpendicular to the electric field, and the negative liquid crystal materials are arranged on a horizontal plane under fringe electric fields, and the pretilt angle distribution is more uniform than that of positive materials. It exhibits high light transmittance and wide viewing angle, and is especially suitable for preparing VA, PSVA, IPS and FFS type liquid crystal materials with high transmittance and wide viewing angle; in addition, the addition of liquid crystal compounds with negative dielectric constant can improve the system
  • the bending elasticity coefficient K 33 can improve the light transmittance and contrast of the entire system, which is conducive to energy saving, and can improve the image display quality to better meet the performance requirements of liquid crystal displays.
  • the liquid crystal compound with the general formula II is white in the pure state, has a higher optical anisotropy ⁇ n value and a wider nematic phase temperature range.
  • anisotropic materials when light enters anisotropic materials, it is generally divided into two waves with mutually perpendicular vibration directions and different propagation speeds. They respectively have two refracted rays to form the so-called birefringence. Polarizers are used to separate them. Obtain the refractive index of the material for parallel light and perpendicular light, and the difference is the value of optical anisotropy ⁇ n.
  • the refractive index is closely related to the arrangement of charges. The tighter the arrangement of charges, the greater the refractive index.
  • the compound of general formula II is a conjugated terphenyl compound.
  • the conjugated structure of the benzene ring will hybridize with the lone pair of electrons carried by the adjacent tail chain O atom to form a larger electron cloud overlap, which has a larger overlap than the pure terphenyl compound.
  • the conjugated structure which has a greater refractive index, but also increases the nematic temperature range of the liquid crystal molecules.
  • the value of optical path difference d ⁇ n is preset, the higher the value of ⁇ n, the lower the value of d, and the response speed is inversely proportional to the value of d, so high ⁇ n is conducive to rapid production Responsive liquid crystal display device.
  • the liquid crystal compound of the general formula III is white or transparent colloidal in the pure state, and is a weakly polar or non-polar liquid crystal compound.
  • the liquid crystal compound of the general formula III is characterized by a low rotational viscosity, and Lower melting point, so it has better mutual solubility when mixed with other types of liquid crystal compounds and improves the viscosity of liquid crystal materials and low temperature reliability.
  • liquid crystal compound of the general formula I with the liquid crystal compound of the general formula II and the general formula III can not only retain the advantage of the high negative dielectric constant of the negative liquid crystal material, but also improve its refractive index, viscosity and liquid crystal Insufficient width, so as to obtain a lower driving voltage, wider operating temperature and faster response speed of liquid crystal materials.
  • alkyl group includes not only linear alkyl groups but also corresponding branched chain alkyl groups.
  • the liquid crystal compound with negative dielectric constant of the general formula I is a negative liquid crystal compound with formulas I1 to I34, and the liquid crystal compound with low rotational viscosity of the general formula III preferably has Liquid crystal compounds of formula III1 to III3.
  • Y and Y' are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H can be Cyclopentyl or F is substituted, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 cannot be substituted by O at the same time; or, each of the Y and Y'is independently selected from cyclopentyl Group, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkene Alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said Y and Y'are each independently selected from cyclopenty
  • Y 2 and Y 2 ' are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H or CH 2 may be substituted by cyclopentyl or F; alternatively, Y 2 and Y 2 'are each independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl.
  • the characteristics of the liquid crystal composition with a negative dielectric constant can be adjusted in a wider range, so as to meet the requirements of more liquid crystal materials. Performance requirements.
  • the liquid crystal composition of the present invention has better mutual solubility when mixed with other types of liquid crystal compounds, and has fewer restrictions on the types of other liquid crystal compounds used in combination, and can be applied to various liquid crystal materials corresponding to the purpose, and is particularly advantageous Improve the comprehensive properties of liquid crystal materials.
  • the liquid crystal composition has good UV, light and thermal stability.
  • the liquid crystal composition having a negative dielectric constant of the present invention can be prepared according to a conventional method. Usually, the required amount of components is dissolved in a lower amount of the components constituting the main component at high temperature; the solution of each component can also be mixed into an organic solvent, such as acetone, chloroform or methanol, and then removed again after thorough mixing The solvent is, for example, removed by distillation.
  • an organic solvent such as acetone, chloroform or methanol
  • liquid crystal compounds contained in the liquid crystal composition having a negative dielectric constant of the present invention are not limited, and any type of liquid crystal compound can be selected according to the purpose to form a liquid crystal mixture with the liquid crystal compound of the present invention, or as required Add other additives in the technical field.
  • a polymerizable compound, an optically active component and/or a stabilizer may be added in a mass content of 0-20%.
  • -T1 and -T2 are represented independently Or epoxy
  • —W 1 — and —W 2 — each independently represent a single bond or an alkyl group having 1 to 8 carbon atoms;
  • —X 1 — and —X 2 — each independently represent a single bond, —O—, —CO—, —COO— or —OCO—;
  • i 0, 1 or 2;
  • optically active component is preferably:
  • R is a halogenated or unsubstituted alkyl, alkoxy or alkenyl group having 1 to 7 carbon atoms.
  • the above-mentioned stabilizer is preferably one or more of the compounds represented by the general formulae VI1 to VI5.
  • R 9 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyl group having 1 to 7 carbon atoms.
  • the halogenated alkyl group, the halogenated alkoxy group having 1 to 7 carbon atoms or the halogenated alkenyl group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group and the alkenyl group are linear or branched Chain alkyl, alkoxy and alkenyl;
  • the above-mentioned liquid crystal composition further includes at least one polar compound and/or at least one non-polar compound.
  • the polar compound is a positive polarity compound and/or a negative polarity compound, preferably a negative polarity compound
  • the positive polarity compound is selected from one or more of the compounds represented by formulas X1 to X105
  • the negative polarity compound is selected From one or more of the compounds represented by formulas IV1 to IV63
  • the non-polar compound is selected from one or more of the compounds represented by formulas V1 to V33,
  • the positive polarity compounds having X1 to X105 are:
  • R 7 is H, an alkyl group, alkoxy group, alkenyl group, or alkenyl alkoxy group having 1 to 7 carbon atoms, wherein H or CH 2 may be substituted by cyclopentyl or F; R 7 can also be cyclopentyl or cyclopentyl substituted with 1 to 7 carbon atoms alkyl, alkoxy or alkenyl; R 8 is H, F, CN, NCS, Cl, OCF 3 , having 1 to Alkyl, alkoxy, alkenyl or alkenyl alkoxy of 7 carbon atoms, where H or CH2 can be substituted by cyclopentyl or F; R 8 can also be cyclopentyl or an alkane with 1 to 7 carbon atoms Cyclopentyl substituted by alkoxy, alkoxy or alkenyl; the alkyl group having 1 to 7 carbon atoms is preferably: -CH 3 , -C 2
  • the above-mentioned polar liquid crystal compounds X1 to X105 have positive dielectric anisotropy, and can be combined with the above-mentioned liquid crystal composition to form a positive dielectric liquid crystal mixture or a liquid crystal mixture with a negative dielectric, which can be used to adjust the dielectric constant of the system , Refractive index, rotational viscosity, elastic coefficient and clearing point temperature and other parameters.
  • the addition of positive dielectric liquid crystal compounds with large structural differences on the basis of the above composition is beneficial to lower the melting point and improve the low temperature reliability of the liquid crystal mixture, thereby reducing the lower limit temperature of the liquid crystal medium and widening the working temperature range of the liquid crystal medium.
  • the negative polarity compounds with IV1 to IV63 are:
  • R 3 and R 4 are each independently H, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms Or an alkene alkoxy group having 2 to 7 carbon atoms, or an alkyl group having 1 to 7 carbon atoms, or an alkoxy group having 1 to 7 carbon atoms in which H or CH 2 is substituted by cyclopentyl or F , Alkenyl with 2-7 carbon atoms or alkenyl alkoxy with 2-7 carbon atoms, or cyclopentyl, oxocyclopentyl Oxymethylcyclopentyl Oxyethylcyclopentyl Or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopen
  • the alkoxy group of 7 is preferably -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 or -OC 7 H 15 ; the carbon
  • the above-mentioned polar liquid crystal compounds IV1 to IV63 have negative dielectric anisotropy.
  • the characteristic of negative dielectric constant liquid crystal compounds is that they have a large dipole effect in the direction perpendicular to the long axis of the molecule, so the corresponding dielectric constant is vertical
  • the direction component is relatively large, that is, it has a high vertical dielectric constant ⁇ ⁇ .
  • the liquid crystal molecules tend to be distributed along the direction perpendicular to the electric field, and the negative liquid crystal materials are arranged on the horizontal plane under the fringe electric field, and the pretilt angle distribution
  • the more positive type material is uniform, so it exhibits higher light transmittance and wide viewing angle;
  • the addition of a liquid crystal compound with a negative dielectric constant can increase the bending elastic coefficient K 33 of the system, thereby improving the light transmittance of the entire system , Is conducive to energy saving, and is conducive to improve contrast.
  • the addition of different types of liquid crystal compounds is also beneficial to improve the low-temperature reliability of the liquid crystal medium, reduce the lower limit temperature of the liquid crystal medium, and broaden the working temperature range of the liquid crystal medium.
  • non-polar liquid crystal compound is selected from one or more of the compounds represented by formulas V1 to V33; wherein, formulas V1 to V33 are as follows:
  • R 5 and R 6 are each independently selected from H, F, alkyl groups having 1 to 7 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, and 2 carbon atoms. ⁇ 7 alkenyl or C 2-7 alkenyl alkoxy, or H or CH 2 is substituted by cyclopentyl or F with C 1-7 alkyl, C 1 ⁇ The alkoxy group of 7, the alkenyl group having 2 to 7 carbon atoms, or the alkenyl group having 2 to 7 carbon atoms, or the cyclopentyl group, or the alkyl group having 1 to 7 carbon atoms, An alkoxy group having 1 to 7 carbon atoms or a cyclopentyl group substituted with an alkenyl group having 2 to 7 carbon atoms; the alkyl group having 1 to 7 carbon atoms is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C
  • the above-mentioned non-polar liquid crystal compounds V1 to V6 have a lower rotational viscosity ⁇ 1 , and their response time is proportional to the rotational viscosity ⁇ 1 , indicating that the lower the rotational viscosity ⁇ 1 value, the lower the response time, and the faster the response speed.
  • the liquid crystal mixture having the above-mentioned non-polar liquid crystal compounds V1 to V6 is used to manufacture a fast-response liquid crystal medium.
  • the aforementioned non-polar liquid crystal compounds V7 to V17 have higher clearing point temperatures, and are mainly used to adjust the T NI value of the system, so that the liquid crystal mixtures with the aforementioned non-polar liquid crystal compounds V7 to V17 are beneficial to increase the upper limit temperature of the liquid crystal medium. , Broaden the working temperature range of the liquid crystal medium.
  • non-polar liquid crystal compounds V18 to V24 have terphenyl structure, and V25 to V30 have alkynylbenzene structure, all of which are compounds of large conjugated system, which are beneficial to increase the optical anisotropy of the system ⁇ n value, usually optical path difference d ⁇
  • ⁇ n is predetermined, the higher the value of ⁇ n, the lower the value of d, and the response speed is inversely proportional to the value of d, so that the response speed of the liquid crystal mixture with the non-polar liquid crystal compounds V18 to V30 is more ideal Value.
  • the above-mentioned non-polar liquid crystal compounds V31 to V33 have larger elastic coefficients, and the response time is inversely proportional to the elastic coefficient, indicating that the higher the elastic coefficient value and the lower the response time, the faster the response speed. Therefore, the above-mentioned non-polar liquid crystal compounds
  • the liquid crystal mixture of V31 to V33 has an ideal response speed.
  • the outstanding feature of the liquid crystal composition of the present invention is that the general formula I and the general formula II can be added in a smaller amount to obtain suitable dielectric constant and optical properties, so the overall viscosity of the liquid crystal composition can be reduced and the response speed can be increased.
  • at least one low-viscosity non-polar liquid crystal compound of structural formula III1 is added to the liquid crystal composition to obtain a low-viscosity liquid crystal composition and improve the response speed.
  • III1 is more preferably a compound in which Y 2 is a propyl group and Y 2 ′ is a vinyl group.
  • the liquid crystal composition is preferably applied to vertical alignment display (VA), polymer stabilized vertical alignment (PSVA) or fringe field switching (FFS) liquid crystal display modes.
  • the content of the liquid crystal compound in the liquid crystal composition can be adjusted according to the performance requirements of the liquid crystal material.
  • the weight content of the liquid crystal compound having the general formula I in the liquid crystal composition is 0.1-75%, preferably 0.1-50%, more preferably 0.1-30%;
  • the weight content of the liquid crystal compound of II is 0.1 to 75%, preferably 0.1 to 50%, more preferably 0.1 to 30%;
  • the weight content of the liquid crystal compound having the general formula III is 0.1 to 75%, and more preferably 0.1 to 50%.
  • the remaining ingredients can be added according to the above teachings of the present invention.
  • the mass fraction of the polar liquid crystal compound is preferably 0-50%, and the mass fraction of the non-polar liquid crystal compound is preferably 0-50%. In short, the sum of the percentage content of each component is 100%.
  • an application of the above-mentioned liquid crystal composition in a liquid crystal display device is provided.
  • Application of the liquid crystal composition of the present invention in the preparation of liquid crystal display materials or liquid crystal display devices can significantly improve the performance of the liquid crystal display materials or liquid crystal display devices.
  • T NI clearing point
  • ⁇ n optical anisotropy
  • ⁇ ⁇ dielectric anisotropy
  • ⁇ ⁇ rotational viscosity (measurement temperature 25°C)
  • T NI is measured by DSC
  • ⁇ n is measured by abbe refractometer
  • ⁇ and ⁇ 1 are measured by CV.
  • the main chain of the liquid crystal molecule is named: cyclohexyl Expressed by the letter C; benzene ring Represented by the letter P; cyclohexenyl Expressed by A; positive dielectric difluorobenzene Expressed by Y; Tetrahydropyran Expressed by J; Methoxy bridge -CH 2 O- Expressed by B; Difluoromethoxy bridge -CF 2 O- Expressed by Q; Alkynyl -C ⁇ C- Expressed by G; Monofluorobenzene Expressed by the letter H1; negative dielectric difluorobenzene Expressed as W; difluorodibenzofuran Expressed by the letter X1; methyl monofluorobenzene It is represented by the letter K1.
  • Each compound branch is converted into a chemical formula according to Table 2 below, the left branch is represented by Ra, and the right branch is represented by Rb.
  • the groups C n H 2n+1 and C m H 2m+1 are linear alkyl groups having n and m carbon atoms, respectively, and Cp represents cyclopentyl C n H 2n+1 Cp represents a cyclopentyl group with a linear alkyl group of n carbon atoms.
  • the main chain and the branch are separated by "-", such as Expressed as WW-2OO2; Expressed as CCBW-3O2; Expressed as PW-3O2; Expressed as X1-3O2; Expressed as X1-CpOO2; Expressed as W-CpOO4; Expressed as PH1P-2Cp; Expressed as PWP-1OO2; Expressed as PGW-3O2; Expressed in CC-3V.
  • liquid crystal compound Expressed as VHHP1; Expressed as CC31D1; Expressed as PH1P-F3.
  • Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 6 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial numbers 7 to 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial number 9 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1-7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9-10 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1-7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9-10 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 8 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial number 9 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial numbers 10 to 12 are liquid crystal compounds with general formula III .
  • Liquid crystal compounds with serial numbers 1 to 2 are liquid crystal compounds with general formula I
  • liquid crystal compounds with serial numbers 3 to 4 are liquid crystal compounds with general formula II
  • liquid crystal compounds with serial number 5 are liquid crystal compounds with general formula III .
  • liquid crystal composition composed of general formula I, general formula II and general formula III When the liquid crystal composition composed of general formula I, general formula II and general formula III is mixed with other different kinds of liquid crystal compounds, it can be obtained with suitable optical anisotropy, dielectric anisotropy, high-definition bright spots, lower viscosity and higher Liquid crystal mixtures with elastic coefficients, especially when III1 is further preferably a compound in which Y 2 is propyl and Y 2 ′ is vinyl, a low-viscosity liquid crystal mixture can be obtained, which can be used to produce a fast-response liquid crystal medium.
  • the above measurement parameters are related to the physical and chemical properties of all liquid crystal compounds constituting the liquid crystal medium, and the liquid crystal composition of the present invention is mainly used to adjust the liquid crystal parameters of the system.
  • Example 5 and Comparative Example 1 Through the comparison between Example 5 and Comparative Example 1, and the comparison between Example 6 and Comparative Example 2, it can be found that when the liquid crystal compound of general formula II is combined with general formula I and general formula III, the dielectric anisotropy is similar In this case, a liquid crystal composition with relatively high optical anisotropy and high clearing point can be obtained, that is, the combination of the liquid crystal compound of the general formula I with the general formula II and the general formula III can obtain a faster response speed and a wider use temperature.
  • the liquid crystal composition

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Abstract

Provided are a liquid crystal composition having a negative dielectric constant, and an application thereof. The liquid crystal composition comprises liquid crystal compounds as represented by general formula I, general formula II and general formula III. The general formula I is />, and the liquid crystal composition especially facilitates adjustment of an optical anisotropy value of a system, facilitates improvement of the range of temperature shown by liquid crystals, and especially facilitates production of liquid crystal display devices having fast response.

Description

一种负介电常数的液晶组合物及其应用Liquid crystal composition with negative dielectric constant and its application 技术领域Technical field
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。The invention relates to the field of liquid crystal materials, in particular to a liquid crystal composition and its application.
背景技术Background technique
20世纪60年代，RCA公司首次发现用电刺激会改变液晶的透光方式，并随后应用该性质发布了液晶显示技术后，液晶才逐渐引起人们的高度重视，并迅速发展至各个领域。1966年，杜邦公司利用芳族聚酰胺液晶合成了Kevlar纤维后，液晶材料开始了工业化进程。经过几十年的迅速发展，液晶材料凭借其特殊的性能已广泛应用于显示技术、光学存储设备和太阳能电池等众多领域，研究范围更是遍及化学、生物及信息科学等众多领域，成为当今社会上备受青睐、不可或缺的新型材料之一。In the 1960s, RCA first discovered that electrical stimulation would change the light transmission mode of liquid crystals, and after applying this property to release liquid crystal display technology, liquid crystals gradually attracted people's attention and quickly developed into various fields. In 1966, after DuPont used aramid liquid crystal to synthesize Kevlar fiber, the liquid crystal material began the industrialization process. After decades of rapid development, liquid crystal materials have been widely used in many fields such as display technology, optical storage devices, and solar cells due to their special properties. The research scope covers many fields such as chemistry, biology and information science. One of the most popular and indispensable new materials on the market.
液晶显示器可分为无源矩阵(又称为被动矩阵或简单矩阵)和有源矩阵(又称为主动矩阵)两种驱动方式。其中，有源矩阵液晶显示器是通过施加电压来改变液晶化合物的排列方式，从而改变背光源发出的光发射强度来形成图像，其由于具有高分辨率、高对比度、低功率、面薄以及质轻的特点越来越受到人们的青睐。有源矩阵液晶显示器根据有源器件可以分为两种类型：在作为衬底的硅芯片上的MOS(金属氧化物半导体)或其它二极管；在作为衬底的玻璃板上的薄膜晶体管(Thin Film Transistor-TFT)，其中，目前发展最迅速的是薄膜晶体管液晶显示器(TFT-LCD)，其已在手机、电脑、液晶电视和相机等显示设备上得到了良好的应用，成为目前液晶市场的主流产品。Liquid crystal displays can be divided into passive matrix (also called passive matrix or simple matrix) and active matrix (also called active matrix) two driving methods. Among them, the active matrix liquid crystal display changes the arrangement of liquid crystal compounds by applying voltage, thereby changing the light emission intensity emitted by the backlight to form an image. It has high resolution, high contrast, low power, thin surface and light weight. The characteristics of it are becoming more and more popular. Active matrix liquid crystal displays can be divided into two types according to active devices: MOS (metal oxide semiconductor) or other diodes on the silicon chip as the substrate; thin film transistors on the glass plate as the substrate Transistor-TFT), among them, the fastest growing thin film transistor liquid crystal display (TFT-LCD) has been well applied in display devices such as mobile phones, computers, LCD TVs and cameras, and has become the mainstream of the current LCD market product.
随着TFT-LCD的不断发展，宽视角模式已成为行业内追求的目标，目前主流的宽视角技术主要有VA垂直取向技术、IPS面内开关技术及FFS边缘场开关技术等技术，这类技术都要求更高的光穿透率及较小的色偏。其中，对于IPS面内开关技术及FFS边缘场开关技术，由于施加电压时电极间会产生面内电场，使该区域内光穿透受到限制，这样会增加能耗及影响显示效果，而负型液晶化合物在色偏及受垂直电场影响方面表现较为出色，比起正型材料，其表现出更高的光穿透率，因而受到广泛应用。但目前市场上通用型的负型液晶材料的粘度一般较高，不利于响应速度的提高，因此开发具有低粘度、高负介电常数的液晶材料成为目前负性液晶材料的主要研究方向。With the continuous development of TFT-LCD, the wide viewing angle mode has become the goal pursued in the industry. At present, the mainstream wide viewing angle technology mainly includes VA vertical orientation technology, IPS in-plane switching technology and FFS fringe field switching technology. Both require higher light transmittance and smaller color shift. Among them, for IPS in-plane switching technology and FFS fringe field switching technology, because an in-plane electric field is generated between the electrodes when a voltage is applied, the light penetration in this area is limited, which will increase energy consumption and affect the display effect. Liquid crystal compounds perform better in terms of color shift and being affected by vertical electric fields. Compared with positive materials, they exhibit higher light transmittance and are therefore widely used. However, the current general-purpose negative liquid crystal materials on the market generally have relatively high viscosity, which is not conducive to the improvement of response speed. Therefore, the development of liquid crystal materials with low viscosity and high negative dielectric constant has become the main research direction of negative liquid crystal materials.
随着液晶显示器的广泛应用，对其性能的要求也在不断的提高，要求更广的工作温度、更快的响应速度和更高的对比度，这些性能的提高都离不开液晶材料的改善。With the widespread application of liquid crystal displays, the requirements for its performance are constantly improving, requiring wider operating temperatures, faster response speeds and higher contrast. The improvement of these performances is inseparable from the improvement of liquid crystal materials.
发明内容Summary of the invention
本发明的目的是提供一种具有负介电常数的液晶组合物，该液晶组合物有利于调节体系的光学各向异性值，改善液晶显示的温度范围，进而可以提高响应速度、提高液晶显示的使用温度范围。The purpose of the present invention is to provide a liquid crystal composition with a negative dielectric constant, which is conducive to adjusting the optical anisotropy value of the system, improving the temperature range of the liquid crystal display, thereby increasing the response speed and improving the liquid crystal display Operating temperature range.
本发明的另一目的是提供上述液晶组合物的应用。Another object of the present invention is to provide applications of the above-mentioned liquid crystal composition.
技术方案：为了实现上述目的，根据本发明的一个方面，提供了一种液晶组合物，该液晶组合物包括至少一种具有通式I的液晶化合物、至少一种具有通式 II的液晶化合物和至少一种具有通式III的液晶化合物，Technical Solution: In order to achieve the above objective, according to one aspect of the present invention, a liquid crystal composition is provided, which includes at least one liquid crystal compound having the general formula I, at least one liquid crystal compound having the general formula II, and At least one liquid crystal compound having the general formula III,
所述通式I为：The general formula I is:
Figure PCTCN2019092472-appb-000001
Figure PCTCN2019092472-appb-000001
其中，among them,
R和R’各自独立地选自H、F、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代；或者，所述R和R’各自独立地选自环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；或者，所述R和R’各自独立地选自环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基； R and R'are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, where H can be cyclopentyl Group or F, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 may not be substituted by O at the same time; or, the R and R′ are each independently selected from cyclopentyl, Oxycyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Group-substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said R and R'are each independently selected from cyclopentenyl, oxocyclopentenyl, Oxymethylcyclopentenyl, oxyethylcyclopentenyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy substituted Cyclopentenyl, oxocyclopentenyl, oxymethylcyclopentenyl, oxyethylcyclopentenyl;
a选自0、1或2；a is selected from 0, 1 or 2;
Figure PCTCN2019092472-appb-000002
选自
Figure PCTCN2019092472-appb-000003
Figure PCTCN2019092472-appb-000004
Figure PCTCN2019092472-appb-000005
组成的组中的任一种；
Figure PCTCN2019092472-appb-000002
Selected from
Figure PCTCN2019092472-appb-000003
Figure PCTCN2019092472-appb-000004
Figure PCTCN2019092472-appb-000005
Any one of the formed groups;
当a为1时，
Figure PCTCN2019092472-appb-000006
选自
Figure PCTCN2019092472-appb-000007
Figure PCTCN2019092472-appb-000008
Figure PCTCN2019092472-appb-000009
组成的组中的任一种； When a is 1,
Figure PCTCN2019092472-appb-000006
Selected from
Figure PCTCN2019092472-appb-000007
Figure PCTCN2019092472-appb-000008
Figure PCTCN2019092472-appb-000009
Any one of the formed groups;
当a为2时，通式中包括两个
Figure PCTCN2019092472-appb-000010
即
Figure PCTCN2019092472-appb-000011
在通式中出现两次，在每次出现时
Figure PCTCN2019092472-appb-000012
各自独立地选自
Figure PCTCN2019092472-appb-000013
Figure PCTCN2019092472-appb-000014
Figure PCTCN2019092472-appb-000015
组成的组中的任一种； When a is 2, the general formula includes two
Figure PCTCN2019092472-appb-000010
which is
Figure PCTCN2019092472-appb-000011
Appears twice in the general formula, each time
Figure PCTCN2019092472-appb-000012
Each independently selected from
Figure PCTCN2019092472-appb-000013
Figure PCTCN2019092472-appb-000014
Figure PCTCN2019092472-appb-000015
Any one of the formed groups;
所述通式II为：The general formula II is:
Figure PCTCN2019092472-appb-000016
和/或
Figure PCTCN2019092472-appb-000016
and / or
Figure PCTCN2019092472-appb-000017
和/或
Figure PCTCN2019092472-appb-000017
and / or
Figure PCTCN2019092472-appb-000018
Figure PCTCN2019092472-appb-000018
其中，R 1和R 1’各自独立地选自C1～C7的烷基或C2～C7的烯基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代； Wherein, R 1 and R 1 'are each independently selected from C1-C7 alkyl or C2-C7 alkenyl, wherein H may be substituted by cyclopentyl or F, and CH 2 may be substituted by cyclopentyl, O or F , And two adjacent CH 2 cannot be replaced by O at the same time;
所述通式III为：
Figure PCTCN2019092472-appb-000019
The general formula III is:
Figure PCTCN2019092472-appb-000019
其中，R 2和R 2’各自独立地选自H、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H或CH 2可被环戊基或F取代；或者，所述R 2和R 2’各自独立地选自环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基； Wherein, R 2 and R 2 'are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, wherein H or CH 2 may be substituted by cyclopentyl or F; or, each of R 2 and R 2 'is independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl;
Figure PCTCN2019092472-appb-000020
各自独立地选自
Figure PCTCN2019092472-appb-000021
Figure PCTCN2019092472-appb-000022
组成的组中的任一种。
Figure PCTCN2019092472-appb-000020
Each independently selected from
Figure PCTCN2019092472-appb-000021
Figure PCTCN2019092472-appb-000022
Any one of the formed groups.
根据本发明的另一方面，提供了一种上述的液晶组合物在液晶显示材料或液晶显示设备中的应用。According to another aspect of the present invention, there is provided an application of the above-mentioned liquid crystal composition in a liquid crystal display material or a liquid crystal display device.
有益效果：本发明的液晶组合物有利于调节体系的光学各向异性值，改善液晶显示的温度范围，进而可以提高响应速度、提高液晶显示的使用温度范围。Beneficial effects: The liquid crystal composition of the present invention is beneficial to adjust the optical anisotropy value of the system, improve the temperature range of the liquid crystal display, and further can increase the response speed and increase the use temperature range of the liquid crystal display.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other if there is no conflict. Hereinafter, the present invention will be described in detail in conjunction with embodiments.
在本发明一种典型的实施方式中，提供了一种液晶组合物，该液晶组合物包括至少一种具有通式I的液晶化合物、至少一种具有通式II的液晶化合物和至少一种具有通式III的液晶化合物。In a typical embodiment of the present invention, a liquid crystal composition is provided, the liquid crystal composition comprising at least one liquid crystal compound having the general formula I, at least one liquid crystal compound having the general formula II, and at least one Liquid crystal compound of general formula III.
所述通式I为：The general formula I is:
Figure PCTCN2019092472-appb-000023
Figure PCTCN2019092472-appb-000023
其中，among them,
R和R’各自独立地选自H、F、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代；或者，所述R和R’各自独立地选自环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；或者，所述R和R’各自独立地选自环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基； R and R'are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, where H can be cyclopentyl Group or F, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 may not be substituted by O at the same time; or, the R and R′ are each independently selected from cyclopentyl, Oxycyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Group-substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said R and R'are each independently selected from cyclopentenyl, oxocyclopentenyl, Oxymethylcyclopentenyl, oxyethylcyclopentenyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy substituted Cyclopentenyl, oxocyclopentenyl, oxymethylcyclopentenyl, oxyethylcyclopentenyl;
a选自0、1或2；a is selected from 0, 1 or 2;
Figure PCTCN2019092472-appb-000024
选自
Figure PCTCN2019092472-appb-000025
Figure PCTCN2019092472-appb-000026
Figure PCTCN2019092472-appb-000027
组成的组中的任一种；
Figure PCTCN2019092472-appb-000024
Selected from
Figure PCTCN2019092472-appb-000025
Figure PCTCN2019092472-appb-000026
Figure PCTCN2019092472-appb-000027
Any one of the formed groups;
当a为1时，
Figure PCTCN2019092472-appb-000028
选自
Figure PCTCN2019092472-appb-000029
Figure PCTCN2019092472-appb-000030
Figure PCTCN2019092472-appb-000031
组成的组中的任一种； When a is 1,
Figure PCTCN2019092472-appb-000028
Selected from
Figure PCTCN2019092472-appb-000029
Figure PCTCN2019092472-appb-000030
Figure PCTCN2019092472-appb-000031
Any one of the formed groups;
当a为2时，通式中包括两个
Figure PCTCN2019092472-appb-000032
即
Figure PCTCN2019092472-appb-000033
在通式中出现两次，在每次出现时
Figure PCTCN2019092472-appb-000034
各自独立地选自
Figure PCTCN2019092472-appb-000035
Figure PCTCN2019092472-appb-000036
Figure PCTCN2019092472-appb-000037
组成的组中的任一种； When a is 2, the general formula includes two
Figure PCTCN2019092472-appb-000032
which is
Figure PCTCN2019092472-appb-000033
Appears twice in the general formula, each time
Figure PCTCN2019092472-appb-000034
Each independently selected from
Figure PCTCN2019092472-appb-000035
Figure PCTCN2019092472-appb-000036
Figure PCTCN2019092472-appb-000037
Any one of the formed groups;
所述通式II为：The general formula II is:
Figure PCTCN2019092472-appb-000038
和/或
Figure PCTCN2019092472-appb-000038
and / or
Figure PCTCN2019092472-appb-000039
和/或
Figure PCTCN2019092472-appb-000039
and / or
Figure PCTCN2019092472-appb-000040
Figure PCTCN2019092472-appb-000040
其中，R 1和R 1’各自独立地选自C1～C7的烷基或C2～C7的烯基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代； Wherein, R 1 and R 1 'are each independently selected from C1-C7 alkyl or C2-C7 alkenyl, wherein H may be substituted by cyclopentyl or F, and CH 2 may be substituted by cyclopentyl, O or F , And two adjacent CH 2 cannot be replaced by O at the same time;
所述通式III为：
Figure PCTCN2019092472-appb-000041
The general formula III is:
Figure PCTCN2019092472-appb-000041
其中，R 2和R 2’各自独立地选自H、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H或CH 2可被环戊基或F取代；或者，所述R 2和R 2’各自独立地选自环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基； Wherein, R 2 and R 2 'are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, wherein H or CH 2 may be substituted by cyclopentyl or F; or, each of R 2 and R 2 'is independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl
Figure PCTCN2019092472-appb-000042
各自独立地选自
Figure PCTCN2019092472-appb-000043
Figure PCTCN2019092472-appb-000044
组成的组中的任一种。
Figure PCTCN2019092472-appb-000042
Each independently selected from
Figure PCTCN2019092472-appb-000043
Figure PCTCN2019092472-appb-000044
Any one of the formed groups.
具有通式I的液晶化合物在纯物质状态下是白色的，为具有负介电各向异性的液晶化合物，负介电常数的液晶化合物的特点是在垂直于分子长轴方向上具有较大的偶极作用，因而相对应的介电常数在垂直方向的分量相对较大，即具有较高的垂直介电常数ε ⊥，因此介电各向异性△ε＝ε //-ε ⊥表现为负值。由于具有较高的垂直介电常数ε ⊥，液晶分子倾向于沿垂直于电场方向分布，且负型液晶材料在边缘电场下都是在水平平面上排列，预倾角分布较正型材料均匀，因而表现出较高的的光穿透率及宽视角，特别适用于制备高穿透率宽视角的VA、PSVA、IPS及FFS型液晶材料；另外负介电常数的液晶化合物的加入可以提高体系的弯曲弹性系数K 33，从而可以改善光在整个体系的穿透率及对比度，有利于节能，并且可以改善图像显示质量，以更好地满足液晶显示的性能要求。 The liquid crystal compound with the general formula I is white in the state of pure substance, and it is a liquid crystal compound with negative dielectric anisotropy. The liquid crystal compound with negative dielectric constant is characterized by having a larger value in the direction perpendicular to the long axis of the molecule. Dipole action, so the corresponding dielectric constant component in the vertical direction is relatively large, that is, it has a higher vertical dielectric constant ε ⊥ , so the dielectric anisotropy △ε=ε // -ε ⊥ is negative value. Due to the high vertical permittivity ε ⊥ , the liquid crystal molecules tend to be distributed along the direction perpendicular to the electric field, and the negative liquid crystal materials are arranged on a horizontal plane under fringe electric fields, and the pretilt angle distribution is more uniform than that of positive materials. It exhibits high light transmittance and wide viewing angle, and is especially suitable for preparing VA, PSVA, IPS and FFS type liquid crystal materials with high transmittance and wide viewing angle; in addition, the addition of liquid crystal compounds with negative dielectric constant can improve the system The bending elasticity coefficient K 33 can improve the light transmittance and contrast of the entire system, which is conducive to energy saving, and can improve the image display quality to better meet the performance requirements of liquid crystal displays.
具有通式II的液晶化合物在纯物质状态下是白色的，具有较高的光学各向异性Δn值及较宽的向列相温度范围。一般来说，光进入各向异性的材料时，一般都要分为振动方向相互垂直、传播速度不等的两个波，它们分别有两条折射光线，构成所谓的双折射，利用偏振片分别得到材料对平行光与对垂直光的折射率，取其差值即为光学各向异性Δn值。而折射率和电荷的排列密切相关，电荷排列越紧密，则折射率越大。通式II的化合物为共轭三联苯化合物，苯环的共轭结构会与相邻尾链O原子所带孤对电子杂化形成更大的电子云重叠，其具有比单纯三联苯化合物更大的共轭结构，因而具有更大的折射率，同时也增加液晶分子的向列相温度范围。在LCD显示中，光程差d·△n的值是预先设定好的，则△n值越高，d值越低，而响应速度与d值成反比，因而高△n有利于制作快速响应的液晶显示器件。The liquid crystal compound with the general formula II is white in the pure state, has a higher optical anisotropy Δn value and a wider nematic phase temperature range. Generally speaking, when light enters anisotropic materials, it is generally divided into two waves with mutually perpendicular vibration directions and different propagation speeds. They respectively have two refracted rays to form the so-called birefringence. Polarizers are used to separate them. Obtain the refractive index of the material for parallel light and perpendicular light, and the difference is the value of optical anisotropy Δn. The refractive index is closely related to the arrangement of charges. The tighter the arrangement of charges, the greater the refractive index. The compound of general formula II is a conjugated terphenyl compound. The conjugated structure of the benzene ring will hybridize with the lone pair of electrons carried by the adjacent tail chain O atom to form a larger electron cloud overlap, which has a larger overlap than the pure terphenyl compound. The conjugated structure, which has a greater refractive index, but also increases the nematic temperature range of the liquid crystal molecules. In LCD display, the value of optical path difference d·△n is preset, the higher the value of △n, the lower the value of d, and the response speed is inversely proportional to the value of d, so high △n is conducive to rapid production Responsive liquid crystal display device.
具有通式III的液晶化合物在纯物质状态下是白色的或透明胶状，为具有弱极性或非极性的液晶化合物，通式III的液晶化合物的特点是具有较低的旋转粘度，及较低的熔点，因此与其他种类液晶化合物混合时具有较好的互溶性及对液晶材料粘度及低温可靠性的改善。The liquid crystal compound of the general formula III is white or transparent colloidal in the pure state, and is a weakly polar or non-polar liquid crystal compound. The liquid crystal compound of the general formula III is characterized by a low rotational viscosity, and Lower melting point, so it has better mutual solubility when mixed with other types of liquid crystal compounds and improves the viscosity of liquid crystal materials and low temperature reliability.
因此，将通式I的液晶化合物与通式II和通式III的液晶化合物组合在一起，既可以保留负型液晶材料负介电常数高的优势，又可以改善其在折射率、粘度及液晶宽度方面的不足，从而可以获得更低的驱动电压、更宽的工作温度及更快响应速度的液晶材料。Therefore, combining the liquid crystal compound of the general formula I with the liquid crystal compound of the general formula II and the general formula III can not only retain the advantage of the high negative dielectric constant of the negative liquid crystal material, but also improve its refractive index, viscosity and liquid crystal Insufficient width, so as to obtain a lower driving voltage, wider operating temperature and faster response speed of liquid crystal materials.
此外，本领域技术人员应该清楚的，上述烷基不仅包括直链烷基也包括相应的支链烷基。In addition, it should be clear to those skilled in the art that the above-mentioned alkyl group includes not only linear alkyl groups but also corresponding branched chain alkyl groups.
为了获得更为合适的液晶宽度、较高的介电各向异性值、较小的旋转粘度及适宜的弹性系数K，更有利于提高液晶材料的响应速度，降低阈值电压，改善液晶材料的互溶性，在本申请一种优选的实施例中，上述通式I的负介电常数的液晶化合物为具有式I1至I34的负极性液晶化合物，通式III的低旋转粘度的液晶化合物优选为具有式III1至III3的液晶化合物。In order to obtain a more suitable liquid crystal width, a higher dielectric anisotropy value, a smaller rotational viscosity and a suitable elastic coefficient K, it is more conducive to increase the response speed of the liquid crystal material, reduce the threshold voltage, and improve the mutual Solubility, in a preferred embodiment of the present application, the liquid crystal compound with negative dielectric constant of the general formula I is a negative liquid crystal compound with formulas I1 to I34, and the liquid crystal compound with low rotational viscosity of the general formula III preferably has Liquid crystal compounds of formula III1 to III3.
上述具有通式I1至I34的化合物通式如下：The general formulas of the above compounds having general formulas I1 to I34 are as follows:
Figure PCTCN2019092472-appb-000045
Figure PCTCN2019092472-appb-000045
Figure PCTCN2019092472-appb-000046
Figure PCTCN2019092472-appb-000046
其中，Y和Y’各自独立地选自H、F、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代；或者，所述Y和Y’各自独立地选自环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；或者，所述Y和Y’各自独立地选自环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基。 Wherein, Y and Y'are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H can be Cyclopentyl or F is substituted, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 cannot be substituted by O at the same time; or, each of the Y and Y'is independently selected from cyclopentyl Group, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkene Alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said Y and Y'are each independently selected from cyclopentenyl, oxocyclopentene Group, oxymethylcyclopentenyl, oxyethylcyclopentenyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Substituted cyclopentenyl, oxocyclopentenyl, oxymethylcyclopentenyl, and oxyethylcyclopentenyl.
上述具有通式III1至III3的化合物通式如下：The general formulas of the above compounds having general formulas III1 to III3 are as follows:
Figure PCTCN2019092472-appb-000047
Figure PCTCN2019092472-appb-000047
其中，Y 2和Y 2’各自独立地选自H、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H或CH 2可被环戊基或F取代；或者，所述Y 2和Y 2’各自独立地选自环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基。 Wherein, Y 2 and Y 2 'are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H or CH 2 may be substituted by cyclopentyl or F; alternatively, Y 2 and Y 2 'are each independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl.
本发明的液晶组合物与其他种类液晶化合物组合形成具有负介电常数的液晶混合物时，该具有负介电常数的液晶组合物特性可在较宽的范围进行调节，从而满足更多液晶材料的性能要求。并且，本发明的液晶组合物与其他种类液晶化合物混合时具有较好的互溶性，对于并用的其它液晶化合物等的种类限制较少，可适用于与目的相应的各种液晶材料，特别有利于改善液晶材料的综合性质。另外，该液晶组合物具有良好的UV、光及热稳定性。When the liquid crystal composition of the present invention is combined with other types of liquid crystal compounds to form a liquid crystal mixture with a negative dielectric constant, the characteristics of the liquid crystal composition with a negative dielectric constant can be adjusted in a wider range, so as to meet the requirements of more liquid crystal materials. Performance requirements. In addition, the liquid crystal composition of the present invention has better mutual solubility when mixed with other types of liquid crystal compounds, and has fewer restrictions on the types of other liquid crystal compounds used in combination, and can be applied to various liquid crystal materials corresponding to the purpose, and is particularly advantageous Improve the comprehensive properties of liquid crystal materials. In addition, the liquid crystal composition has good UV, light and thermal stability.
本发明的具有负介电常数的液晶组合物可按照常规的方法来制备。通常于高温下将所需量的组分以较低量溶于构成主成分的组分；还可以将各组分的溶液混入有机溶剂，例如混入丙酮、氯仿或甲醇中，充分混合之后再次除去溶剂，例如通过蒸馏除去溶剂。The liquid crystal composition having a negative dielectric constant of the present invention can be prepared according to a conventional method. Usually, the required amount of components is dissolved in a lower amount of the components constituting the main component at high temperature; the solution of each component can also be mixed into an organic solvent, such as acetone, chloroform or methanol, and then removed again after thorough mixing The solvent is, for example, removed by distillation.
本发明的具有负介电常数的液晶组合物中包含的现有的液晶化合物的种类并没有限制，可根据目的选择任意种类的液晶化合物与本发明的液晶化合物一起构成液晶混合物，也可根据需要加入所属技术领域的其它添加剂。例如，可添加质量含量为0～20％的可聚合化合物、旋光活性组分和/或稳定剂。The types of existing liquid crystal compounds contained in the liquid crystal composition having a negative dielectric constant of the present invention are not limited, and any type of liquid crystal compound can be selected according to the purpose to form a liquid crystal mixture with the liquid crystal compound of the present invention, or as required Add other additives in the technical field. For example, a polymerizable compound, an optically active component and/or a stabilizer may be added in a mass content of 0-20%.
上述可聚合化合物通式如下：The general formula of the above polymerizable compound is as follows:
Figure PCTCN2019092472-appb-000048
Figure PCTCN2019092472-appb-000048
其中，among them,
—T1和—T2各自独立地表示
Figure PCTCN2019092472-appb-000049
或环氧基； -T1 and -T2 are represented independently
Figure PCTCN2019092472-appb-000049
Or epoxy;
—W 1—和—W 2—各自独立地表示单键或碳原子数为1～8的烷基； —W 1 — and —W 2 — each independently represent a single bond or an alkyl group having 1 to 8 carbon atoms;
—X 1—和—X 2—各自独立地表示单键、—O—、—CO—、—COO—或—OCO—； —X 1 — and —X 2 — each independently represent a single bond, —O—, —CO—, —COO— or —OCO—;
i为0、1或2；i is 0, 1 or 2;
当i为1时，—Z 1—表示单键、—O—、—CO—、—COO—、—OCO—、—CH 2O—、—OCH 2—、—C 2H 4—、—CF 2O—、—OCF 2—、-C≡C-、—CH＝CH—、
Figure PCTCN2019092472-appb-000050
When i is 1, —Z 1 — represents a single bond, —O—, —CO—, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —C 2 H 4 —, —CF 2 O—, —OCF 2 —, -C≡C-, —CH=CH—,
Figure PCTCN2019092472-appb-000050
当i为2时，—Z 1—在通式中出现两次，—Z 1—每次出现时各自独立地表示单键、—O—、—CO—、—COO—、—OCO—、—CH 2O—、—OCH 2—、—C 2H 4—、—CF 2O—、—OCF 2—、-C≡C-、—CH＝CH—、
Figure PCTCN2019092472-appb-000051
When i is 2, —Z 1 — appears twice in the general formula, and —Z 1 — each time it appears independently represents a single bond, —O—, —CO—, —COO—, —OCO—, — CH 2 O—, —OCH 2 —, —C 2 H 4 —, —CF 2 O—, —OCF 2 —, -C≡C-, —CH=CH—,
Figure PCTCN2019092472-appb-000051
Figure PCTCN2019092472-appb-000052
表示
Figure PCTCN2019092472-appb-000053
其中环己基上的—CH 2—可被O取代，或表示
Figure PCTCN2019092472-appb-000054
其中苯环上的＝CH—可被N取代，苯环上的H可被F取代，或表示
Figure PCTCN2019092472-appb-000055
Figure PCTCN2019092472-appb-000052
Means
Figure PCTCN2019092472-appb-000053
The —CH 2 — on the cyclohexyl group can be substituted by O, or it means
Figure PCTCN2019092472-appb-000054
Wherein the =CH- on the benzene ring can be substituted by N, and the H on the benzene ring can be substituted by F, or
Figure PCTCN2019092472-appb-000055
当i为1时，
Figure PCTCN2019092472-appb-000056
表示
Figure PCTCN2019092472-appb-000057
其中环己基上的—CH 2—可被O取代，或表示
Figure PCTCN2019092472-appb-000058
其中苯环上的＝CH—可被N取代，苯环上的H可被F取代，或表示
Figure PCTCN2019092472-appb-000059
When i is 1,
Figure PCTCN2019092472-appb-000056
Means
Figure PCTCN2019092472-appb-000057
The —CH 2 — on the cyclohexyl group can be substituted by O, or it means
Figure PCTCN2019092472-appb-000058
Wherein the =CH- on the benzene ring can be substituted by N, and the H on the benzene ring can be substituted by F, or
Figure PCTCN2019092472-appb-000059
当i为2时，通式中包括两个
Figure PCTCN2019092472-appb-000060
即
Figure PCTCN2019092472-appb-000061
在通式中出现两次，
Figure PCTCN2019092472-appb-000062
在每次出现时各自独立地为
Figure PCTCN2019092472-appb-000063
其中环己基上的—CH 2—可被O取代，或为
Figure PCTCN2019092472-appb-000064
其中苯环上的＝CH—可被N取代，苯环上的H可被F取代，或为
Figure PCTCN2019092472-appb-000065
When i is 2, the general formula includes two
Figure PCTCN2019092472-appb-000060
which is
Figure PCTCN2019092472-appb-000061
Appears twice in the general formula,
Figure PCTCN2019092472-appb-000062
Each appears independently for
Figure PCTCN2019092472-appb-000063
Wherein —CH 2 — on the cyclohexyl group can be substituted by O, or
Figure PCTCN2019092472-appb-000064
Wherein the =CH- on the benzene ring can be substituted by N, and the H on the benzene ring can be substituted by F, or
Figure PCTCN2019092472-appb-000065
上述旋光活性组分优选为：The above-mentioned optically active component is preferably:
Figure PCTCN2019092472-appb-000066
Figure PCTCN2019092472-appb-000066
其中，R为具有1到7个碳原子的卤化或未取代的烷基、烷氧基或烯基。Wherein, R is a halogenated or unsubstituted alkyl, alkoxy or alkenyl group having 1 to 7 carbon atoms.
上述稳定剂优选为具有通式VI1～VI5所示化合物中的一种或多种。The above-mentioned stabilizer is preferably one or more of the compounds represented by the general formulae VI1 to VI5.
Figure PCTCN2019092472-appb-000067
Figure PCTCN2019092472-appb-000067
Figure PCTCN2019092472-appb-000068
Figure PCTCN2019092472-appb-000068
式VI1～VI5中，R 9为具有1～7个碳原子的烷基、具有1～7个碳原子的烷氧基、具有2～7个碳原子的烯基、具有1～7个碳原子的卤化烷基、具有1～7个碳原子的卤化烷氧基或具有2～7个碳原子的卤化烯基；所述烷基、所述烷氧基和所述烯基为直链或支链的烷基、烷氧基和烯基； In formulas VI1 to VI5, R 9 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyl group having 1 to 7 carbon atoms. The halogenated alkyl group, the halogenated alkoxy group having 1 to 7 carbon atoms or the halogenated alkenyl group having 2 to 7 carbon atoms; the alkyl group, the alkoxy group and the alkenyl group are linear or branched Chain alkyl, alkoxy and alkenyl;
Figure PCTCN2019092472-appb-000069
选自
Figure PCTCN2019092472-appb-000070
Figure PCTCN2019092472-appb-000071
组成的组中的任一种。
Figure PCTCN2019092472-appb-000069
Selected from
Figure PCTCN2019092472-appb-000070
Figure PCTCN2019092472-appb-000071
Any one of the formed groups.
在本申请一种优选的实施例中，上述液晶组合物还包括至少一种极性化合物和/或至少一种非极性化合物。所述极性化合物为正极性化合物和/或负极性化合物，优选为负极性化合物，所述正极性化合物选自式X1～X105所示化合物中的一种或多种，所述负极性化合物选自式IV1～IV63所示化合物中的一种或多种，所述非极性化合物选自式V1～V33所示化合物中的一种或多种，In a preferred embodiment of the present application, the above-mentioned liquid crystal composition further includes at least one polar compound and/or at least one non-polar compound. The polar compound is a positive polarity compound and/or a negative polarity compound, preferably a negative polarity compound, the positive polarity compound is selected from one or more of the compounds represented by formulas X1 to X105, and the negative polarity compound is selected From one or more of the compounds represented by formulas IV1 to IV63, the non-polar compound is selected from one or more of the compounds represented by formulas V1 to V33,
其中，所述具有X1至X105的正极性化合物分别为：Wherein, the positive polarity compounds having X1 to X105 are:
Figure PCTCN2019092472-appb-000072
Figure PCTCN2019092472-appb-000072
Figure PCTCN2019092472-appb-000073
Figure PCTCN2019092472-appb-000073
Figure PCTCN2019092472-appb-000074
Figure PCTCN2019092472-appb-000074
Figure PCTCN2019092472-appb-000075
Figure PCTCN2019092472-appb-000075
Figure PCTCN2019092472-appb-000076
Figure PCTCN2019092472-appb-000076
所述式X1至X105中，R 7为H、具有1到7个碳原子的烷基、烷氧基、烯基或烯烷氧基，其中H或CH 2可被环戊基或F取代；R 7也可为环戊基或者为1到7个碳原子烷基、烷氧基或烯基取代的环戊基；R 8为H、F、CN、NCS、Cl、OCF 3、具有1到7个碳原子的烷基、烷氧基、烯基或烯烷氧基，其中H或CH2可被环戊基或F取代；R 8也可为环戊基或者为1到7个碳原子烷基、烷氧基或烯基取代的环戊基；所述具有1到7个碳原子烷基优选为：-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 6H 13或-C 7H 15；所述具有1到7个碳原子的烯基优选为：-CH＝CH 2、-CH＝CHCH 3、-CH＝CHC 2H 5、-CH＝CHC 3H 7、-C 2H 4CH＝CH 2、-C 2H 4CH＝CHCH 3、-C 3H 6CH＝CH 2或-C 3H 6CH＝CHCH 3；所述具有1到7个碳原子的烷氧基优选为：-OCH 3、-OC 2H 5、-OC 3H 7、-OC 4H 9、-OC 5H 11、-OC 6H 13或-OC 7H 15；所述具有1到7个碳原子的烯烷氧基优选为：-OCH＝CH 2、-OCH 2CH＝CH 2、-OCH 2CH＝CHCH 3或-OCH 2CH＝CHC 2H 5；X 9及X 10各自独立地选自H或F。 In the formulas X1 to X105, R 7 is H, an alkyl group, alkoxy group, alkenyl group, or alkenyl alkoxy group having 1 to 7 carbon atoms, wherein H or CH 2 may be substituted by cyclopentyl or F; R 7 can also be cyclopentyl or cyclopentyl substituted with 1 to 7 carbon atoms alkyl, alkoxy or alkenyl; R 8 is H, F, CN, NCS, Cl, OCF 3 , having 1 to Alkyl, alkoxy, alkenyl or alkenyl alkoxy of 7 carbon atoms, where H or CH2 can be substituted by cyclopentyl or F; R 8 can also be cyclopentyl or an alkane with 1 to 7 carbon atoms Cyclopentyl substituted by alkoxy, alkoxy or alkenyl; the alkyl group having 1 to 7 carbon atoms is preferably: -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 or -C 7 H 15 ; the alkenyl group having 1 to 7 carbon atoms is preferably: -CH=CH 2 , -CH=CHCH 3 , -CH=CHC 2 H 5 , -CH=CHC 3 H 7 , -C 2 H 4 CH=CH 2 , -C 2 H 4 CH=CHCH 3 , -C 3 H 6 CH=CH 2 or -C 3 H 6 CH=CHCH 3 ; The alkoxy having 1 to 7 carbon atoms is preferably: -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 Or -OC 7 H 15 ; The alkenyl alkoxy group having 1 to 7 carbon atoms is preferably: -OCH=CH 2 , -OCH 2 CH=CH 2 , -OCH 2 CH=CHCH 3 or -OCH 2 CH =CHC 2 H 5 ; X 9 and X 10 are each independently selected from H or F.
上述极性液晶化合物X1～X105具有正介电各向异性，与上述液晶组合物即可组合成正介电液晶混合物，也可以组合成具有负介电的液晶混合物，可用于调节体系的介电常数、折射系数、旋转粘度、弹性系数及清亮点温度等参数。且在上述组合物基础上加入结构差别较大的正介电液晶化合物，有利于降低熔点，改善液晶混合物的低温可靠性，从而降低液晶介质的使用下限温度，拓宽液晶介质的工作温度范围。The above-mentioned polar liquid crystal compounds X1 to X105 have positive dielectric anisotropy, and can be combined with the above-mentioned liquid crystal composition to form a positive dielectric liquid crystal mixture or a liquid crystal mixture with a negative dielectric, which can be used to adjust the dielectric constant of the system , Refractive index, rotational viscosity, elastic coefficient and clearing point temperature and other parameters. In addition, the addition of positive dielectric liquid crystal compounds with large structural differences on the basis of the above composition is beneficial to lower the melting point and improve the low temperature reliability of the liquid crystal mixture, thereby reducing the lower limit temperature of the liquid crystal medium and widening the working temperature range of the liquid crystal medium.
所述具有IV1至IV63的负极性化合物分别为：The negative polarity compounds with IV1 to IV63 are:
Figure PCTCN2019092472-appb-000077
Figure PCTCN2019092472-appb-000077
Figure PCTCN2019092472-appb-000078
Figure PCTCN2019092472-appb-000078
Figure PCTCN2019092472-appb-000079
Figure PCTCN2019092472-appb-000079
式IV1～IV63中，R 3和R 4各自独立地为H、碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为H或CH 2被环戊基或F取代的碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为环戊基、氧环戊基
Figure PCTCN2019092472-appb-000080
氧甲基环戊基
Figure PCTCN2019092472-appb-000081
氧乙基环戊基
Figure PCTCN2019092472-appb-000082
或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；所述碳原子数为1～7的烷基为-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 6H 13或-C 7H 15；所述碳原子数为2～7的烯基优选为-CH＝CH 2、-CH＝CHCH 3、-CH＝CHC 2H 5、-CH＝CHC 3H 7、-C 2H 4CH＝CH 2、-C 2H 4CH＝CHCH 3、-C 3H 6CH＝CH 2或-C 3H 6CH＝CHCH 3；所述碳原子数为1～7的烷氧基优选为-OCH 3、-OC 2H 5、-OC 3H 7、-OC 4H 9、-OC 5H 11、-OC 6H 13或-OC 7H 15；所述碳原子数为2～7的烯烷氧基优选为-OCH＝CH 2、-OCH 2CH＝CH 2、-OCH 2CH＝CHCH 3或-OCH 2CH＝CHC 2H 5。 In formulas IV1 to IV63, R 3 and R 4 are each independently H, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an alkenyl group having 2 to 7 carbon atoms Or an alkene alkoxy group having 2 to 7 carbon atoms, or an alkyl group having 1 to 7 carbon atoms, or an alkoxy group having 1 to 7 carbon atoms in which H or CH 2 is substituted by cyclopentyl or F , Alkenyl with 2-7 carbon atoms or alkenyl alkoxy with 2-7 carbon atoms, or cyclopentyl, oxocyclopentyl
Figure PCTCN2019092472-appb-000080
Oxymethylcyclopentyl
Figure PCTCN2019092472-appb-000081
Oxyethylcyclopentyl
Figure PCTCN2019092472-appb-000082
Or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, Oxyethyl cyclopentyl; the alkyl group having 1 to 7 carbon atoms is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 or -C 7 H 15 ; the alkenyl group having 2 to 7 carbon atoms is preferably -CH=CH 2 , -CH=CHCH 3 , -CH=CHC 2 H 5 , -CH=CHC 3 H 7. -C 2 H 4 CH=CH 2 , -C 2 H 4 CH=CHCH 3 , -C 3 H 6 CH=CH 2 or -C 3 H 6 CH=CHCH 3 ; the number of carbon atoms is 1～ The alkoxy group of 7 is preferably -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 or -OC 7 H 15 ; the carbon The alkenyloxy group having 2 to 7 atoms is preferably -OCH=CH 2 , -OCH 2 CH=CH 2 , -OCH 2 CH=CHCH 3 or -OCH 2 CH=CHC 2 H 5 .
上述极性液晶化合物IV1～IV63具有负介电各向异性，负介电常数液晶化合物的特点是在垂直于分子长轴方向上具有较大的偶极作用，因而相对应的介电常数在垂直方向的分量相对较大，即具有较高的垂直介电常数ε ⊥，液晶分子倾向于沿垂直于电场方向分布，且负型液晶材料在边缘电场下都是在水平平面上排列， 预倾角分布较正型材料均匀，因而表现出较高的光穿透率及宽视角；另外负介电常数的液晶化合物的加入可以提高体系的弯曲弹性系数K 33，从而改善光在整个体系的穿透率，有利于节能，并且有利于提高对比度。另外不同种类液晶化合物的加入还有利于改善液晶介质的低温可靠性，降低液晶介质的使用下限温度，拓宽液晶介质的工作温度范围。 The above-mentioned polar liquid crystal compounds IV1 to IV63 have negative dielectric anisotropy. The characteristic of negative dielectric constant liquid crystal compounds is that they have a large dipole effect in the direction perpendicular to the long axis of the molecule, so the corresponding dielectric constant is vertical The direction component is relatively large, that is, it has a high vertical dielectric constant ε ⊥ . The liquid crystal molecules tend to be distributed along the direction perpendicular to the electric field, and the negative liquid crystal materials are arranged on the horizontal plane under the fringe electric field, and the pretilt angle distribution The more positive type material is uniform, so it exhibits higher light transmittance and wide viewing angle; in addition, the addition of a liquid crystal compound with a negative dielectric constant can increase the bending elastic coefficient K 33 of the system, thereby improving the light transmittance of the entire system , Is conducive to energy saving, and is conducive to improve contrast. In addition, the addition of different types of liquid crystal compounds is also beneficial to improve the low-temperature reliability of the liquid crystal medium, reduce the lower limit temperature of the liquid crystal medium, and broaden the working temperature range of the liquid crystal medium.
上述非极性液晶化合物选自式V1～V33所示化合物中的一种或多种；其中，式V1～V33如下：The aforementioned non-polar liquid crystal compound is selected from one or more of the compounds represented by formulas V1 to V33; wherein, formulas V1 to V33 are as follows:
Figure PCTCN2019092472-appb-000083
Figure PCTCN2019092472-appb-000083
所述式V1～V33中，R 5、R 6各自独立地选自H、F、碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为H或CH 2被环戊基或F取代的碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为环戊基，或者为被碳原子数为1～7的烷基、碳原子数为1～7的烷氧基或碳原子数为2～7的烯基取代的环戊基；所述碳原子数为1～7的烷基为-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 6H 13或-C 7H 15；所述碳原子数为2～7的烯基优选为-CH＝CH 2、-CH＝CHCH 3、-CH＝CHC 2H 5、-CH＝CHC 3H 7、-C 2H 4CH＝CH 2、-C 2H 4CH＝CHCH 3、-C 3H 6CH＝CH 2或-C 3H 6CH＝CHCH 3；所述碳原子数为1～7的烷氧基优选为-OCH 3、-OC 2H 5、-OC 3H 7、-OC 4H 9、-OC 5H 11、-OC 6H 13或-OC 7H 15；所述碳原子数为2～7的烯烷氧基优选为-OCH＝CH 2、-OCH 2CH＝CH 2、-OCH 2CH＝CHCH 3或-OCH 2CH＝CHC 2H 5。 In the formulas V1 to V33, R 5 and R 6 are each independently selected from H, F, alkyl groups having 1 to 7 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, and 2 carbon atoms. ～7 alkenyl or C 2-7 alkenyl alkoxy, or H or CH 2 is substituted by cyclopentyl or F with C 1-7 alkyl, C 1～ The alkoxy group of 7, the alkenyl group having 2 to 7 carbon atoms, or the alkenyl group having 2 to 7 carbon atoms, or the cyclopentyl group, or the alkyl group having 1 to 7 carbon atoms, An alkoxy group having 1 to 7 carbon atoms or a cyclopentyl group substituted with an alkenyl group having 2 to 7 carbon atoms; the alkyl group having 1 to 7 carbon atoms is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 or -C 7 H 15 ; the alkenyl group having 2-7 carbon atoms is preferably -CH=CH 2 , -CH=CHCH 3 , -CH=CHC 2 H 5 , -CH=CHC 3 H 7 , -C 2 H 4 CH=CH 2 , -C 2 H 4 CH=CHCH 3 , -C 3 H 6 CH= CH 2 or -C 3 H 6 CH=CHCH 3 ; the alkoxy group having 1 to 7 carbon atoms is preferably -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 or -OC 7 H 15 ; the alkene alkoxy having 2-7 carbon atoms is preferably -OCH=CH 2 , -OCH 2 CH=CH 2 , -OCH 2 CH=CHCH 3 or -OCH 2 CH=CHC 2 H 5 .
上述非极性液晶化合物V1至V6具有较低的旋转粘度γ 1，其响应时间与旋转粘度γ 1成正比，说明旋转粘度γ 1值越低，响应时间越低，则响应速度越快，可将具有上述非极性液晶化合物V1至V6的液晶混合物用于制造快速响应的液晶介质。上述非极性液晶化合物V7至V17具有较高的清亮点温度，主要用于调节体系的T NI值，从而具有上述非极性液晶化合物V7至V17的液晶混合物有利于提高液晶介质的使用上限温度，拓宽液晶介质的工作温度范围。上述非极性液晶化合物V18至V24具有三联苯结构，V25至V30具有炔基苯结构，均为大共轭体系化合物，有利于增加体系的光学各向异性△n值，通常光程差d·△n的值是预先规定的，则△n值越高，d值越低，而响应速度与d值成反比，从而具有上述非极性液晶化合物V18至V30的液晶混合物的响应速度具有更理想的值。上述非极性液晶化合物V31至V33具有较大的弹性系数，响应时间与弹性系数成反比，说明弹性系数值越高，响应时间越低，则响应速度越快，因此具有上述非极性液晶化合物V31至V33的液晶混合物具有较为理想的响应速度。 The above-mentioned non-polar liquid crystal compounds V1 to V6 have a lower rotational viscosity γ 1 , and their response time is proportional to the rotational viscosity γ 1 , indicating that the lower the rotational viscosity γ 1 value, the lower the response time, and the faster the response speed. The liquid crystal mixture having the above-mentioned non-polar liquid crystal compounds V1 to V6 is used to manufacture a fast-response liquid crystal medium. The aforementioned non-polar liquid crystal compounds V7 to V17 have higher clearing point temperatures, and are mainly used to adjust the T NI value of the system, so that the liquid crystal mixtures with the aforementioned non-polar liquid crystal compounds V7 to V17 are beneficial to increase the upper limit temperature of the liquid crystal medium. , Broaden the working temperature range of the liquid crystal medium. The above-mentioned non-polar liquid crystal compounds V18 to V24 have terphenyl structure, and V25 to V30 have alkynylbenzene structure, all of which are compounds of large conjugated system, which are beneficial to increase the optical anisotropy of the system △n value, usually optical path difference d· The value of △n is predetermined, the higher the value of △n, the lower the value of d, and the response speed is inversely proportional to the value of d, so that the response speed of the liquid crystal mixture with the non-polar liquid crystal compounds V18 to V30 is more ideal Value. The above-mentioned non-polar liquid crystal compounds V31 to V33 have larger elastic coefficients, and the response time is inversely proportional to the elastic coefficient, indicating that the higher the elastic coefficient value and the lower the response time, the faster the response speed. Therefore, the above-mentioned non-polar liquid crystal compounds The liquid crystal mixture of V31 to V33 has an ideal response speed.
本发明中的液晶组合物的突出特点通式I和通式II以较少量加入即可获得合适的介电常数及光学特性，因此可以降低液晶组合物的整体粘度，增加响应速度。优选液晶组合物中至少加入一种结构式为III1的低粘度非极性液晶化合物，以获得低粘度的液晶组合物，提高响应速度。III1进一步优选为Y 2为丙基，Y 2’为乙烯基的化合物。该液晶组合物优选应用于垂直取向显示(VA)、聚合物稳定的垂直排列(PSVA)或边缘场开关(FFS)型液晶显示模式中。 The outstanding feature of the liquid crystal composition of the present invention is that the general formula I and the general formula II can be added in a smaller amount to obtain suitable dielectric constant and optical properties, so the overall viscosity of the liquid crystal composition can be reduced and the response speed can be increased. Preferably, at least one low-viscosity non-polar liquid crystal compound of structural formula III1 is added to the liquid crystal composition to obtain a low-viscosity liquid crystal composition and improve the response speed. III1 is more preferably a compound in which Y 2 is a propyl group and Y 2 ′ is a vinyl group. The liquid crystal composition is preferably applied to vertical alignment display (VA), polymer stabilized vertical alignment (PSVA) or fringe field switching (FFS) liquid crystal display modes.
上述液晶组合物中的液晶化合物的含量可以根据液晶材料的性能需求进行调整。为了获得更为合适的液晶宽度、较高的介电各向异性值、较小的旋转粘度及适宜的弹性系数K，更有利于提高液晶材料的响应速度，降低阈值电压，改善液晶材料的互溶性，在本发明一种优选的实施例中，上述液晶组合物中具有通式I的液晶化合物的重量含量为0.1～75％，优选0.1～50％，进一步优选0.1～30％；具有通式II的液晶化合物的重量含量为0.1～75％，优选0.1～50％，进一步优选0.1～30％；具有通式III的液晶化合物的重量含量为0.1～75％，进一步优选为0.1～50％。其余成分可以根据本发明上述的教导进行添加。所述极性液晶化合物的质量分数优选为0～50％，所述非极性液晶化合物的质量分数优选为0～50％。总之，各成分的百分比含量之和为100％。The content of the liquid crystal compound in the liquid crystal composition can be adjusted according to the performance requirements of the liquid crystal material. In order to obtain a more suitable liquid crystal width, a higher dielectric anisotropy value, a smaller rotational viscosity and a suitable elastic coefficient K, it is more conducive to increase the response speed of the liquid crystal material, reduce the threshold voltage, and improve the mutual Solubility, in a preferred embodiment of the present invention, the weight content of the liquid crystal compound having the general formula I in the liquid crystal composition is 0.1-75%, preferably 0.1-50%, more preferably 0.1-30%; The weight content of the liquid crystal compound of II is 0.1 to 75%, preferably 0.1 to 50%, more preferably 0.1 to 30%; the weight content of the liquid crystal compound having the general formula III is 0.1 to 75%, and more preferably 0.1 to 50%. The remaining ingredients can be added according to the above teachings of the present invention. The mass fraction of the polar liquid crystal compound is preferably 0-50%, and the mass fraction of the non-polar liquid crystal compound is preferably 0-50%. In short, the sum of the percentage content of each component is 100%.
在本申请一种典型的实施方式中，提供了一种上述液晶组合物在液晶显示设备中的应用。将本发明的液晶组合物应用在制备液晶显示材料或液晶显示设备中，能够显著改善液晶显示材料或液晶显示设备的性能。In a typical embodiment of the present application, an application of the above-mentioned liquid crystal composition in a liquid crystal display device is provided. Application of the liquid crystal composition of the present invention in the preparation of liquid crystal display materials or liquid crystal display devices can significantly improve the performance of the liquid crystal display materials or liquid crystal display devices.
以下将结合实施例和对比例，进一步说明本发明的有益效果。The following examples and comparative examples will further illustrate the beneficial effects of the present invention.
下列实施例是用于解释本发明而非限制它。实施例中涉及百分比均为质量百分比，温度用摄氏度表示。所测物化参数表示如下：T NI表示清亮点；△n表示光学各向异性(△n＝n e-n o，589nm，测量温度25℃)；△ε表示介电各向异性(△ε＝ε ‖-ε ⊥，25℃)；γ 1表示旋转粘度(测量温度25℃)，且采用DSC测量T NI；采用abbe折射仪测量△n；采用CV测量△ε和γ 1。 The following examples are used to explain the present invention but not to limit it. The percentages involved in the examples are all mass percentages, and the temperature is expressed in degrees Celsius. The physical and chemical parameters measured is expressed as follows: T NI represents clearing point; △ n denotes optical anisotropy (△ n = n e -n o , 589nm, measured temperature 25 ℃); △ ε denotes the dielectric anisotropy (△ ε = ε ‖ -ε ⊥ , 25°C); γ 1 represents rotational viscosity (measurement temperature 25°C), and T NI is measured by DSC; Δn is measured by abbe refractometer; Δε and γ 1 are measured by CV.
在本发明的各实施例中，液晶分子主链命名：环己基
Figure PCTCN2019092472-appb-000084
以字母C表示；苯环
Figure PCTCN2019092472-appb-000085
以字母P表示；环己烯基
Figure PCTCN2019092472-appb-000086
以A表示；正介电二氟苯
Figure PCTCN2019092472-appb-000087
以Y表示；四氢吡喃
Figure PCTCN2019092472-appb-000088
以J表示；甲氧基桥-CH 2O-以B表示；二氟甲氧基桥-CF 2O-以Q表示；炔基-C≡C-以G表示；单氟苯
Figure PCTCN2019092472-appb-000089
以字母H1表示；负介电二氟苯
Figure PCTCN2019092472-appb-000090
以W表示；二氟二苯并呋喃
Figure PCTCN2019092472-appb-000091
以字母X1表示；甲基单氟苯
Figure PCTCN2019092472-appb-000092
以字母K1表示。 In each embodiment of the present invention, the main chain of the liquid crystal molecule is named: cyclohexyl
Figure PCTCN2019092472-appb-000084
Expressed by the letter C; benzene ring
Figure PCTCN2019092472-appb-000085
Represented by the letter P; cyclohexenyl
Figure PCTCN2019092472-appb-000086
Expressed by A; positive dielectric difluorobenzene
Figure PCTCN2019092472-appb-000087
Expressed by Y; Tetrahydropyran
Figure PCTCN2019092472-appb-000088
Expressed by J; Methoxy bridge -CH 2 O- Expressed by B; Difluoromethoxy bridge -CF 2 O- Expressed by Q; Alkynyl -C≡C- Expressed by G; Monofluorobenzene
Figure PCTCN2019092472-appb-000089
Expressed by the letter H1; negative dielectric difluorobenzene
Figure PCTCN2019092472-appb-000090
Expressed as W; difluorodibenzofuran
Figure PCTCN2019092472-appb-000091
Expressed by the letter X1; methyl monofluorobenzene
Figure PCTCN2019092472-appb-000092
It is represented by the letter K1.
具体基团结构的对应代码如表1所示。The corresponding codes for specific group structures are shown in Table 1.
表1Table 1
Figure PCTCN2019092472-appb-000093
Figure PCTCN2019092472-appb-000093
Figure PCTCN2019092472-appb-000094
Figure PCTCN2019092472-appb-000094
各化合物支链根据下文表2来转化成化学式，左侧支链以Ra表示，右侧支链以Rb表示。其中，基团C nH 2n+1和C mH 2m+1是分别具有n和m个碳原子的直链烷基，Cp表示环戊基
Figure PCTCN2019092472-appb-000095
C nH 2n+1Cp表示带n个碳原子直链烷基的环戊基。命名时主链在前，支链在后，主链与支链之间以“-”隔开，如
Figure PCTCN2019092472-appb-000096
以WW-2OO2表示；
Figure PCTCN2019092472-appb-000097
以CCBW-3O2表示；
Figure PCTCN2019092472-appb-000098
以PW-3O2表示；
Figure PCTCN2019092472-appb-000099
以X1-3O2表示；
Figure PCTCN2019092472-appb-000100
以X1-CpOO2表示；
Figure PCTCN2019092472-appb-000101
以 W-CpOO4表示；
Figure PCTCN2019092472-appb-000102
以PH1P-2Cp表示；
Figure PCTCN2019092472-appb-000103
以PWP-1OO2表示；
Figure PCTCN2019092472-appb-000104
以PGW-3O2表示；
Figure PCTCN2019092472-appb-000105
以CC-3V表示。 Each compound branch is converted into a chemical formula according to Table 2 below, the left branch is represented by Ra, and the right branch is represented by Rb. Among them, the groups C n H 2n+1 and C m H 2m+1 are linear alkyl groups having n and m carbon atoms, respectively, and Cp represents cyclopentyl
Figure PCTCN2019092472-appb-000095
C n H 2n+1 Cp represents a cyclopentyl group with a linear alkyl group of n carbon atoms. When naming, the main chain is in front and the branch is in the back. The main chain and the branch are separated by "-", such as
Figure PCTCN2019092472-appb-000096
Expressed as WW-2OO2;
Figure PCTCN2019092472-appb-000097
Expressed as CCBW-3O2;
Figure PCTCN2019092472-appb-000098
Expressed as PW-3O2;
Figure PCTCN2019092472-appb-000099
Expressed as X1-3O2;
Figure PCTCN2019092472-appb-000100
Expressed as X1-CpOO2;
Figure PCTCN2019092472-appb-000101
Expressed as W-CpOO4;
Figure PCTCN2019092472-appb-000102
Expressed as PH1P-2Cp;
Figure PCTCN2019092472-appb-000103
Expressed as PWP-1OO2;
Figure PCTCN2019092472-appb-000104
Expressed as PGW-3O2;
Figure PCTCN2019092472-appb-000105
Expressed in CC-3V.
表2Table 2
代码Code RaRa RbRb
nmnm C nH 2n+1 C n H 2n+1 C mH 2m+1 C m H 2m+1
nHnH C nH 2n+1 C n H 2n+1 HH
nOHnOH OC nH 2n+1 OC n H 2n+1 HH
nOmnOm C nH 2n+1 C n H 2n+1 OC mH 2m+1 OC m H 2m+1
nOOmnOOm OC nH 2n+1 OC n H 2n+1 OC mH 2m+1 OC m H 2m+1
nCpnCp C nH 2n+1 C n H 2n+1 CpCp
nmCpnmCp C nH 2n+1 C n H 2n+1 C mH 2m+1Cp C m H 2m+1 Cp
nFnF C nH 2n+1 C n H 2n+1 FF
nOTFnOTF C nH 2n+1 C n H 2n+1 OCF 3 OCF 3
CpmCpm CpCp C mH 2m+1 C m H 2m+1
CpHCpH CpCp HH
CpOHCpOH OCpOCp HH
CpOmCpOm CpCp OC mH 2m+1 OC m H 2m+1
CpOOmCpOOm OCpOCp OC mH 2m+1 OC m H 2m+1
CpFCpF CpCp FF
nCpmnCpm C nH 2n+1Cp C n H 2n+1 Cp C mH 2m+1 C m H 2m+1
nCpHnCpH C nH 2n+1Cp C n H 2n+1 Cp HH
nCpOmnCpOm C nH 2n+1Cp C n H 2n+1 Cp OC mH 2m+1 OC m H 2m+1
nCpOOmnCpOOm OC nH 2n+1Cp OC n H 2n+1 Cp OC mH 2m+1 OC m H 2m+1
nCpFnCpF C nH 2n+1Cp C n H 2n+1 Cp FF
nVnV C nH 2n+1 C n H 2n+1 -CH＝CH 2 -CH=CH 2
另外，液晶化合物
Figure PCTCN2019092472-appb-000106
以VHHP1表示；
Figure PCTCN2019092472-appb-000107
以CC31D1表示；
Figure PCTCN2019092472-appb-000108
以PH1P-F3表示。 In addition, the liquid crystal compound
Figure PCTCN2019092472-appb-000106
Expressed as VHHP1;
Figure PCTCN2019092472-appb-000107
Expressed as CC31D1;
Figure PCTCN2019092472-appb-000108
Expressed as PH1P-F3.
实施例1Example 1
实施例1的液晶混合物组成、及测量参数见表3。The composition and measurement parameters of the liquid crystal mixture of Example 1 are shown in Table 3.
表3table 3
Figure PCTCN2019092472-appb-000109
Figure PCTCN2019092472-appb-000109
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～11的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
实施例2Example 2
实施例2的液晶混合物组成、及测量参数见表4。The composition and measurement parameters of the liquid crystal mixture of Example 2 are shown in Table 4.
表4Table 4
Figure PCTCN2019092472-appb-000110
Figure PCTCN2019092472-appb-000110
Figure PCTCN2019092472-appb-000111
Figure PCTCN2019092472-appb-000111
注：序号为1～6的液晶化合物为具有通式I的液晶化合物，序号为7～8的液晶化合物为具有通式II的液晶化合物，序号为9的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 6 are liquid crystal compounds with general formula I, liquid crystal compounds with serial numbers 7 to 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial number 9 are liquid crystal compounds with general formula III .
实施例3Example 3
实施例3的液晶混合物组成、及测量参数见表5。The composition and measurement parameters of the liquid crystal mixture of Example 3 are shown in Table 5.
表5table 5
Figure PCTCN2019092472-appb-000112
Figure PCTCN2019092472-appb-000112
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～11的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
实施例4Example 4
实施例4的液晶混合物组成、及测量参数见表6。The composition and measurement parameters of the liquid crystal mixture of Example 4 are shown in Table 6.
表6Table 6
Figure PCTCN2019092472-appb-000113
Figure PCTCN2019092472-appb-000113
Figure PCTCN2019092472-appb-000114
Figure PCTCN2019092472-appb-000114
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～11的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
实施例5Example 5
实施例5的液晶混合物组成、及测量参数见表7。The composition and measurement parameters of the liquid crystal mixture of Example 5 are shown in Table 7.
表7Table 7
Figure PCTCN2019092472-appb-000115
Figure PCTCN2019092472-appb-000115
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～10的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1-7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9-10 are liquid crystal compounds with general formula III .
实施例6Example 6
实施例6的液晶混合物组成、及测量参数见表8。The composition and measurement parameters of the liquid crystal mixture of Example 6 are shown in Table 8.
表8Table 8
Figure PCTCN2019092472-appb-000116
Figure PCTCN2019092472-appb-000116
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～11的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
实施例7Example 7
实施例7的液晶混合物组成、及测量参数见表9。The composition and measurement parameters of the liquid crystal mixture of Example 7 are shown in Table 9.
表9Table 9
Figure PCTCN2019092472-appb-000117
Figure PCTCN2019092472-appb-000117
Figure PCTCN2019092472-appb-000118
Figure PCTCN2019092472-appb-000118
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～10的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1-7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9-10 are liquid crystal compounds with general formula III .
实施例8Example 8
实施例8的液晶混合物组成、及测量参数见表10。The composition and measurement parameters of the liquid crystal mixture of Example 8 are shown in Table 10.
表10Table 10
Figure PCTCN2019092472-appb-000119
Figure PCTCN2019092472-appb-000119
注：序号为1～7的液晶化合物为具有通式I的液晶化合物，序号为8的液晶化合物为具有通式II的液晶化合物，序号为9～11的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 7 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 8 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 9 to 11 are liquid crystal compounds with general formula III .
实施例9Example 9
实施例9的液晶混合物组成、及测量参数见表11。The composition and measurement parameters of the liquid crystal mixture of Example 9 are shown in Table 11.
表11Table 11
Figure PCTCN2019092472-appb-000120
Figure PCTCN2019092472-appb-000120
Figure PCTCN2019092472-appb-000121
Figure PCTCN2019092472-appb-000121
注：序号为1～8的液晶化合物为具有通式I的液晶化合物，序号为9的液晶化合物为具有通式II的液晶化合物，序号为10～12的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 8 are liquid crystal compounds with general formula I, liquid crystal compounds with serial number 9 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial numbers 10 to 12 are liquid crystal compounds with general formula III .
实施例10Example 10
实施例10的液晶混合物组成、及测量参数见表12。The composition and measurement parameters of the liquid crystal mixture of Example 10 are shown in Table 12.
表12Table 12
Figure PCTCN2019092472-appb-000122
Figure PCTCN2019092472-appb-000122
注：序号为1～2的液晶化合物为具有通式I的液晶化合物，序号为3～4的液晶化合物为具有通式II的液晶化合物，序号为5的液晶化合物为具有通式III的液晶化合物。Note: Liquid crystal compounds with serial numbers 1 to 2 are liquid crystal compounds with general formula I, liquid crystal compounds with serial numbers 3 to 4 are liquid crystal compounds with general formula II, and liquid crystal compounds with serial number 5 are liquid crystal compounds with general formula III .
对比例1Comparative example 1
对比例1的液晶混合物组成、及测量参数见表13。The composition and measurement parameters of the liquid crystal mixture of Comparative Example 1 are shown in Table 13.
表13Table 13
Figure PCTCN2019092472-appb-000123
Figure PCTCN2019092472-appb-000123
对比例2Comparative example 2
对比例2的液晶混合物组成、及测量参数见表14。The composition and measurement parameters of the liquid crystal mixture of Comparative Example 2 are shown in Table 14.
表14Table 14
Figure PCTCN2019092472-appb-000124
Figure PCTCN2019092472-appb-000124
Figure PCTCN2019092472-appb-000125
Figure PCTCN2019092472-appb-000125
其中，对比例1中以液晶化合物
Figure PCTCN2019092472-appb-000126
代替了实施例5中的通式II的化合物及对比例2中以液晶化合物
Figure PCTCN2019092472-appb-000127
代替了实施例6中的通式II的化合物。 Among them, the liquid crystal compound in Comparative Example 1
Figure PCTCN2019092472-appb-000126
Instead of the compound of Formula II in Example 5 and the liquid crystal compound in Comparative Example 2,
Figure PCTCN2019092472-appb-000127
Instead of the compound of formula II in Example 6.
从上述实施例可以发现，通式I、通式II及通式III的组合有利于组成具有高光学各向异性值及高清亮点的液晶组合物，并且可以改善体系粘度、调节体系介电常数值，有利于改善响应速度、增加液晶组合物使用上限温度。当通式I、通式II及通式III组成的液晶组合物与其他不同种类液晶化合物混合时，可以得到具有合适光学各向异性、介电各向异性、高清亮点、较低粘度及较高弹性系数的液晶混合物，尤其是III1进一步优选为Y 2为丙基，Y 2’为乙烯基的化合物时，能够得到低粘度的液晶混合物，可用于制造快速响应的液晶介质。上述测量参数与组成液晶介质的所有液晶化合物的物化性质有关，本发明的液晶组合物主要用于调节体系的液晶参数。 From the above examples, it can be found that the combination of general formula I, general formula II and general formula III is beneficial to form a liquid crystal composition with high optical anisotropy value and high-definition bright spots, and can improve the viscosity of the system and adjust the dielectric constant value of the system. It is beneficial to improve the response speed and increase the upper limit temperature of the liquid crystal composition. When the liquid crystal composition composed of general formula I, general formula II and general formula III is mixed with other different kinds of liquid crystal compounds, it can be obtained with suitable optical anisotropy, dielectric anisotropy, high-definition bright spots, lower viscosity and higher Liquid crystal mixtures with elastic coefficients, especially when III1 is further preferably a compound in which Y 2 is propyl and Y 2 ′ is vinyl, a low-viscosity liquid crystal mixture can be obtained, which can be used to produce a fast-response liquid crystal medium. The above measurement parameters are related to the physical and chemical properties of all liquid crystal compounds constituting the liquid crystal medium, and the liquid crystal composition of the present invention is mainly used to adjust the liquid crystal parameters of the system.
通过实施例5和对比例1的对比以及实施例6和对比例2的对比可以发现，当以通式II的液晶化合物与通式I及通式III组合时，在介电各向异性近似的情况下，可以得到具有相对较高光学各向异性、较高清亮点的液晶组合物，即通式I的液晶化合物与通式II及通式III组合可以得到具有更快响应速度、更宽使用温度的液晶组合物。Through the comparison between Example 5 and Comparative Example 1, and the comparison between Example 6 and Comparative Example 2, it can be found that when the liquid crystal compound of general formula II is combined with general formula I and general formula III, the dielectric anisotropy is similar In this case, a liquid crystal composition with relatively high optical anisotropy and high clearing point can be obtained, that is, the combination of the liquid crystal compound of the general formula I with the general formula II and the general formula III can obtain a faster response speed and a wider use temperature. The liquid crystal composition.
本发明虽未穷尽要求保护的所有液晶组合物，但是本领域技术人员可以预见的是，在已公开的上述实施例基础上，仅结合自身的专业尝试即能以类似的方法得到其他同类液晶材料而不需要付出创造性劳动。此处由于篇幅有限，仅列举代表性的实施方式。Although the present invention does not exhaust all the claimed liquid crystal compositions, those skilled in the art can foresee that on the basis of the disclosed above-mentioned embodiments, only by combining their own professional attempts, other similar liquid crystal materials can be obtained by similar methods. Without creative work. Due to limited space, only representative implementations are listed here.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The foregoing descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc., made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

  1. 一种具有负介电常数的液晶组合物，其特征在于，所述液晶组合物包括至少一种具有通式I的液晶化合物、至少一种具有通式II的液晶化合物和至少一种具有通式III的液晶化合物，A liquid crystal composition with a negative dielectric constant, characterized in that the liquid crystal composition comprises at least one liquid crystal compound with general formula I, at least one liquid crystal compound with general formula II, and at least one liquid crystal compound with general formula II. III liquid crystal compound,
    所述通式I为：The general formula I is:
    Figure PCTCN2019092472-appb-100001
    Figure PCTCN2019092472-appb-100001
    其中，among them,
    R和R’各自独立地选自H、F、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代；或者，所述R和R’各自独立地选自环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；或者，所述R和R’各自独立地选自环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基； R and R'are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, where H can be cyclopentyl Group or F, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 may not be substituted by O at the same time; or, the R and R′ are each independently selected from cyclopentyl, Oxycyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Group-substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said R and R'are each independently selected from cyclopentenyl, oxocyclopentenyl, Oxymethylcyclopentenyl, oxyethylcyclopentenyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy substituted Cyclopentenyl, oxocyclopentenyl, oxymethylcyclopentenyl, oxyethylcyclopentenyl;
    a选自0、1或2；a is selected from 0, 1 or 2;
    Figure PCTCN2019092472-appb-100002
    选自
    Figure PCTCN2019092472-appb-100003
    Figure PCTCN2019092472-appb-100004
    Figure PCTCN2019092472-appb-100005
    组成的组中的任一种；
    Figure PCTCN2019092472-appb-100002
    Selected from
    Figure PCTCN2019092472-appb-100003
    Figure PCTCN2019092472-appb-100004
    Figure PCTCN2019092472-appb-100005
    Any one of the formed groups;
    当a为1时，
    Figure PCTCN2019092472-appb-100006
    选自
    Figure PCTCN2019092472-appb-100007
    Figure PCTCN2019092472-appb-100008
    Figure PCTCN2019092472-appb-100009
    组成的组中的任一种；     When a is 1,
    Figure PCTCN2019092472-appb-100006
    Selected from
    Figure PCTCN2019092472-appb-100007
    Figure PCTCN2019092472-appb-100008
    Figure PCTCN2019092472-appb-100009
    Any one of the formed groups;
    当a为2时，通式中包括两个
    Figure PCTCN2019092472-appb-100010
    即
    Figure PCTCN2019092472-appb-100011
    在通式中出现两次，在每次出现时
    Figure PCTCN2019092472-appb-100012
    各自独立地选自
    Figure PCTCN2019092472-appb-100013
    Figure PCTCN2019092472-appb-100014
    Figure PCTCN2019092472-appb-100015
    组成的组中的任一种；     When a is 2, the general formula includes two
    Figure PCTCN2019092472-appb-100010
    which is
    Figure PCTCN2019092472-appb-100011
    Appears twice in the general formula, each time
    Figure PCTCN2019092472-appb-100012
    Each independently selected from
    Figure PCTCN2019092472-appb-100013
    Figure PCTCN2019092472-appb-100014
    Figure PCTCN2019092472-appb-100015
    Any one of the formed groups;
    所述通式II为：The general formula II is:
    Figure PCTCN2019092472-appb-100016
    Figure PCTCN2019092472-appb-100016
    其中，R 1和R 1’各自独立地选自C1～C7的烷基或C2～C7的烯基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代； Wherein, R 1 and R 1 'are each independently selected from C1-C7 alkyl or C2-C7 alkenyl, wherein H may be substituted by cyclopentyl or F, and CH 2 may be substituted by cyclopentyl, O or F , And two adjacent CH 2 cannot be replaced by O at the same time
    所述通式III为：
    Figure PCTCN2019092472-appb-100017
    The general formula III is:
    Figure PCTCN2019092472-appb-100017
    其中，R 2和R 2’各自独立地选自H、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H或CH 2可被环戊基或F取代；或者，所述R 2和R 2’各自独立地选自环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基； Wherein, R 2 and R 2 'are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy, wherein H or CH 2 may be substituted by cyclopentyl or F; or, each of R 2 and R 2 'is independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl;
    Figure PCTCN2019092472-appb-100018
    各自独立地选自
    Figure PCTCN2019092472-appb-100019
    Figure PCTCN2019092472-appb-100020
    组成的组中的任一种。
    Figure PCTCN2019092472-appb-100018
    Each independently selected from
    Figure PCTCN2019092472-appb-100019
    Figure PCTCN2019092472-appb-100020
    Any one of the formed groups.
  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为The liquid crystal composition according to claim 1, wherein the general formula I is
    Figure PCTCN2019092472-appb-100021
    Figure PCTCN2019092472-appb-100021
    Figure PCTCN2019092472-appb-100022
    Figure PCTCN2019092472-appb-100022
    其中，Y和Y’各自独立地选自H、F、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H可被环戊基或F取代，CH 2可被环戊基、O或F取代，且相邻的两个CH 2不可以同时被O取代；或者，所述Y和Y’各自独立地选自环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基，或者为 C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；或者，所述Y和Y’各自独立地选自环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊烯基、氧环戊烯基、氧甲基环戊烯基、氧乙基环戊烯基。 Wherein, Y and Y'are each independently selected from H, F, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H can be Cyclopentyl or F is substituted, CH 2 may be substituted by cyclopentyl, O or F, and two adjacent CH 2 cannot be substituted by O at the same time; or, each of the Y and Y'is independently selected from cyclopentyl Group, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkene Alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, oxyethylcyclopentyl; or, said Y and Y'are each independently selected from cyclopentenyl, oxocyclopentene Group, oxymethylcyclopentenyl, oxyethylcyclopentenyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy Substituted cyclopentenyl, oxocyclopentenyl, oxymethylcyclopentenyl, oxyethylcyclopentenyl.
  3. 根据权利要求1所述的液晶组合物，其特征在于，所述通式III为：The liquid crystal composition of claim 1, wherein the general formula III is:
    Figure PCTCN2019092472-appb-100023
    Figure PCTCN2019092472-appb-100023
    其中，Y 2和Y 2’各自独立地选自H、C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基，其中H或CH 2可被环戊基或F取代；或者，所述Y 2和Y 2’各自独立地选自环戊基，或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基。 Wherein, Y 2 and Y 2 'are each independently selected from H, C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyloxy, wherein H or CH 2 may be substituted by cyclopentyl or F; alternatively, Y 2 and Y 2 'are each independently selected from cyclopentyl, or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 Alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl.
  4. 根据权利要求1所述的液晶组合物，其特征在于，所述通式III为III1。The liquid crystal composition of claim 1, wherein the general formula III is III1.
  5. 根据权利要求1至4中任一项所述的液晶组合物，其特征在于，所述液晶组合物还包括至少一种极性化合物和/或至少一种非极性化合物。The liquid crystal composition according to any one of claims 1 to 4, wherein the liquid crystal composition further comprises at least one polar compound and/or at least one non-polar compound.
  6. 根据权利要求1所述的液晶组合物，其特征在于，所述液晶组合物中所述具有通式I的液晶化合物的重量含量为0.1～75％，优选为0.1～50％，进一步优选为0.1～30％；所述具有通式II的液晶化合物的重量含量为0.1～75％，优选为0.1～50％，进一步优选为0.1～30％；所述具有通式III的液晶化合物的重量含量为0.1～75％，进一步优选为0.1～50％。The liquid crystal composition according to claim 1, wherein the weight content of the liquid crystal compound having the general formula I in the liquid crystal composition is 0.1 to 75%, preferably 0.1 to 50%, and more preferably 0.1 ~30%; the weight content of the liquid crystal compound having the general formula II is 0.1 to 75%, preferably 0.1 to 50%, more preferably 0.1 to 30%; the weight content of the liquid crystal compound having the general formula III is 0.1 to 75%, more preferably 0.1 to 50%.
  7. 根据权利要求5所述的液晶组合物，其特征在于，所述极性化合物为正极性化合物和/或负极性化合物，优选为负极性化合物，所述负极性化合物选自式IV1～IV63所示化合物中的一种或多种，所述非极性化合物选自式V1～V33所示化合物中的一种或多种，The liquid crystal composition according to claim 5, wherein the polar compound is a positive polarity compound and/or a negative polarity compound, preferably a negative polarity compound, and the negative polarity compound is selected from formula IV1 to IV63. One or more of the compounds, and the non-polar compound is selected from one or more of the compounds represented by formulas V1 to V33,
    式IV1～IV63分别如下：The formulas IV1 to IV63 are as follows:
    Figure PCTCN2019092472-appb-100024
    Figure PCTCN2019092472-appb-100024
    Figure PCTCN2019092472-appb-100025
    Figure PCTCN2019092472-appb-100025
    Figure PCTCN2019092472-appb-100026
    Figure PCTCN2019092472-appb-100026
    式IV1～IV63中，R 3和R 4各自独立地为H、F、碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为H或CH 2被环戊基或F取代的碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为环戊基、氧环戊基
    Figure PCTCN2019092472-appb-100027
    氧甲基环戊基
    Figure PCTCN2019092472-appb-100028
    氧乙基环戊基
    Figure PCTCN2019092472-appb-100029
    或者为C1～C7的烷基、C1～C7的烷氧基、C2～C7的烯基或C2～C7的烯烷氧基取代的环戊基、氧环戊基、氧甲基环戊基、氧乙基环戊基；所述碳原子数为1～7的烷基为-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 6H 13或-C 7H 15；所述碳原子数为2～7的烯基优选为-CH＝CH 2、-CH＝CHCH 3、-CH＝CHC 2H 5、-CH＝CHC 3H 7、-C 2H 4CH＝CH 2、-C 2H 4CH＝CHCH 3、-C 3H 6CH＝CH 2或-C 3H 6CH＝CHCH 3；所述碳原子数为1～7的 烷氧基优选为-OCH 3、-OC 2H 5、-OC 3H 7、-OC 4H 9、-OC 5H 11、-OC 6H 13或-OC 7H 15；所述碳原子数为2～7的烯烷氧基优选为-OCH＝CH 2、-OCH 2CH＝CH 2、-OCH 2CH＝CHCH 3或-OCH 2CH＝CHC 2H 5。     In the formulas IV1 to IV63, R 3 and R 4 are each independently H, F, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and one having 2 to 7 carbon atoms. Alkenyl or alkenyl alkoxy having 2 to 7 carbon atoms, or an alkyl having 1 to 7 carbon atoms in which H or CH 2 is substituted by cyclopentyl or F, or an alkyl having 1 to 7 carbon atoms An oxy group, an alkenyl group having 2 to 7 carbon atoms or an alkenyl alkoxy group having 2 to 7 carbon atoms, or a cyclopentyl group or an oxocyclopentyl group
    Figure PCTCN2019092472-appb-100027
    Oxymethylcyclopentyl
    Figure PCTCN2019092472-appb-100028
    Oxyethylcyclopentyl
    Figure PCTCN2019092472-appb-100029
    Or C1-C7 alkyl, C1-C7 alkoxy, C2-C7 alkenyl or C2-C7 alkenyl alkoxy substituted cyclopentyl, oxocyclopentyl, oxymethylcyclopentyl, Oxyethyl cyclopentyl; the alkyl group having 1 to 7 carbon atoms is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 or -C 7 H 15 ; the alkenyl group having 2 to 7 carbon atoms is preferably -CH=CH 2 , -CH=CHCH 3 , -CH=CHC 2 H 5 , -CH=CHC 3 H 7. -C 2 H 4 CH=CH 2 , -C 2 H 4 CH=CHCH 3 , -C 3 H 6 CH=CH 2 or -C 3 H 6 CH=CHCH 3 ; the number of carbon atoms is 1～ The alkoxy group of 7 is preferably -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 or -OC 7 H 15 ; the carbon The alkenyloxy group having 2 to 7 atoms is preferably -OCH=CH 2 , -OCH 2 CH=CH 2 , -OCH 2 CH=CHCH 3 or -OCH 2 CH=CHC 2 H 5 .
    所述式V1～V33分别为：The formulas V1 to V33 are:
    Figure PCTCN2019092472-appb-100030
    Figure PCTCN2019092472-appb-100030
    所述式V1～V33中，R 5、R 6各自独立地选自H、F、碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为H或CH 2被环戊基或F取代的碳原子数为1～7的烷基、碳原子数为1～7的烷氧基、碳原子数为2～7的烯基或碳原子数为2～7的烯烷氧基，或者为环 戊基，或者为被碳原子数为1～7的烷基、碳原子数为1～7的烷氧基或碳原子数为2～7的烯基取代的环戊基；所述碳原子数为1～7的烷基为-CH 3、-C 2H 5、-C 3H 7、-C 4H 9、-C 5H 11、-C 6H 13或-C 7H 15；所述碳原子数为2～7的烯基优选为-CH＝CH 2、-CH＝CHCH 3、-CH＝CHC 2H 5、-CH＝CHC 3H 7、-C 2H 4CH＝CH 2、-C 2H 4CH＝CHCH 3、-C 3H 6CH＝CH 2或-C 3H 6CH＝CHCH 3；所述碳原子数为1～7的烷氧基优选为-OCH 3、-OC 2H 5、-OC 3H 7、-OC 4H 9、-OC 5H 11、-OC 6H 13或-OC 7H 15；所述碳原子数为2～7的烯烷氧基优选为-OCH＝CH 2、-OCH 2CH＝CH 2、-OCH 2CH＝CHCH 3或-OCH 2CH＝CHC 2H 5。 In the formulas V1 to V33, R 5 and R 6 are each independently selected from H, F, alkyl groups having 1 to 7 carbon atoms, alkoxy groups having 1 to 7 carbon atoms, and 2 carbon atoms. ～7 alkenyl or C 2-7 alkenyl alkoxy, or H or CH 2 is substituted by cyclopentyl or F with C 1-7 alkyl, C 1～ The alkoxy group of 7, the alkenyl group having 2 to 7 carbon atoms, or the alkenyl group having 2 to 7 carbon atoms, or the cyclopentyl group, or the alkyl group having 1 to 7 carbon atoms, An alkoxy group having 1 to 7 carbon atoms or a cyclopentyl group substituted with an alkenyl group having 2 to 7 carbon atoms; the alkyl group having 1 to 7 carbon atoms is -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -C 6 H 13 or -C 7 H 15 ; the alkenyl group having 2-7 carbon atoms is preferably -CH=CH 2 , -CH=CHCH 3 , -CH=CHC 2 H 5 , -CH=CHC 3 H 7 , -C 2 H 4 CH=CH 2 , -C 2 H 4 CH=CHCH 3 , -C 3 H 6 CH= CH 2 or -C 3 H 6 CH=CHCH 3 ; the alkoxy group having 1 to 7 carbon atoms is preferably -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , -OC 5 H 11 , -OC 6 H 13 or -OC 7 H 15 ; the alkene alkoxy having 2-7 carbon atoms is preferably -OCH=CH 2 , -OCH 2 CH=CH 2 , -OCH 2 CH=CHCH 3 or -OCH 2 CH=CHC 2 H 5 .
    优选地，所述液晶组合物中所述极性液晶化合物的质量分数为0～50％，所述非极性液晶化合物的质量分数为0～50％。Preferably, the mass fraction of the polar liquid crystal compound in the liquid crystal composition is 0-50%, and the mass fraction of the non-polar liquid crystal compound is 0-50%.
  8. 根据权利要求1～7任意一项所述的液晶组合物，其特征在于，所述液晶组合物中还包含质量分数为0～20％的可聚合化合物，所述可聚合化合物通式如下：7. The liquid crystal composition according to any one of claims 1 to 7, wherein the liquid crystal composition further comprises a polymerizable compound with a mass fraction of 0-20%, and the general formula of the polymerizable compound is as follows:
    Figure PCTCN2019092472-appb-100031
    Figure PCTCN2019092472-appb-100031
    其中among them
    —T 1和—T 2各自独立地表示
    Figure PCTCN2019092472-appb-100032
    或环氧基；     -T 1 and -T 2 are expressed independently
    Figure PCTCN2019092472-appb-100032
    Or epoxy;
    —W 1—和—W 2—各自独立地表示单键或碳原子数为1～8的烷基； —W 1 — and —W 2 — each independently represent a single bond or an alkyl group having 1 to 8 carbon atoms;
    —X 1—和—X 2—各自独立地表示单键、—O—、—CO—、—COO—或—OCO—； —X 1 — and —X 2 — each independently represent a single bond, —O—, —CO—, —COO— or —OCO—;
    —Z 1—选自单键、—O—、—CO—、—COO—、—OCO—、—CH 2O—、—OCH 2—、—C 2H 4—、—CF 2O—、—OCF 2—、-C≡C-、—CH＝CH—、
    Figure PCTCN2019092472-appb-100033
    Figure PCTCN2019092472-appb-100034
    组成的组中的一种或两种；     —Z 1 —Selected from single bond, —O—, —CO—, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —C 2 H 4 —, —CF 2 O—, — OCF 2 —, -C≡C-, —CH=CH—,
    Figure PCTCN2019092472-appb-100033
    Figure PCTCN2019092472-appb-100034
    One or two of the formed groups;
    i为0、1或2；i is 0, 1 or 2;
    Figure PCTCN2019092472-appb-100035
    每次出现时各自独立地表示未被取代或亚环己基上的—CH 2—被O取代的
    Figure PCTCN2019092472-appb-100036
    未被取代或亚苯环上的＝CH—被N取代的
    Figure PCTCN2019092472-appb-100037
    环上的H被F取代的
    Figure PCTCN2019092472-appb-100038
    Figure PCTCN2019092472-appb-100035
    Each occurrence of each independently represents unsubstituted or —CH 2 — on the cyclohexylene group substituted by O
    Figure PCTCN2019092472-appb-100036
    Unsubstituted or the =CH on the phenylene ring-substituted by N
    Figure PCTCN2019092472-appb-100037
    The H on the ring is replaced by F
    Figure PCTCN2019092472-appb-100038
  9. 根据权利要求1～7中任意一项所述的具有负介电常数的液晶组合物，其特征在于，所述液晶组合物中还包含质量分数为0～20％的稳定剂，优选地，所述稳定剂为具有通式VI1～VI5所示的化合物中的一种或多种：The liquid crystal composition having a negative dielectric constant according to any one of claims 1 to 7, wherein the liquid crystal composition further contains a stabilizer with a mass fraction of 0-20%, preferably, The stabilizer is one or more of the compounds represented by the general formula VI1 to VI5:
    Figure PCTCN2019092472-appb-100039
    Figure PCTCN2019092472-appb-100039
    其中，R 9为具有1～7个碳原子的烷基、具有1～7个碳原子的烷氧基、具有2～7个碳原子的烯基、具有1～7个碳原子的卤化烷基、具有1～7个碳原子的卤化烷氧基或具有2～7个碳原子的卤化烯基；所述烷基、所述烷氧基和所述烯基为直链或支链的烷基、烷氧基和烯基； Among them, R 9 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and a halogenated alkyl group having 1 to 7 carbon atoms , Halogenated alkoxy having 1-7 carbon atoms or halogenated alkenyl having 2-7 carbon atoms; the alkyl group, the alkoxy group and the alkenyl group are linear or branched alkyl groups , Alkoxy and alkenyl;
    Figure PCTCN2019092472-appb-100040
    选自
    Figure PCTCN2019092472-appb-100041
    Figure PCTCN2019092472-appb-100042
    组成的组中的任一种。
    Figure PCTCN2019092472-appb-100040
    Selected from
    Figure PCTCN2019092472-appb-100041
    Figure PCTCN2019092472-appb-100042
    Any one of the formed groups.
  10. 权利要求1至9中任一项所述的液晶组合物在液晶显示材料或液晶显示设备中的应用，优选为在负型显示模式中的应用，所述负型显示模式优选为VA、PSVA或FFS等显示模式。The application of the liquid crystal composition of any one of claims 1 to 9 in a liquid crystal display material or a liquid crystal display device is preferably an application in a negative display mode, and the negative display mode is preferably VA, PSVA or Display modes such as FFS.
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