CN108728118A - Liquid crystal media and its application - Google Patents
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 227
- 150000001875 compounds Chemical class 0.000 claims abstract description 397
- 230000004044 response Effects 0.000 claims abstract description 28
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 125000003342 alkenyl group Chemical group 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000006005 fluoroethoxy group Chemical group 0.000 abstract description 5
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical group FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 68
- 230000000694 effects Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- -1 2,3-difluorobenzene structure compound Chemical class 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- UVZUFUGNHDDLRQ-LLHZKFLPSA-N cholesteryl benzoate Chemical compound O([C@@H]1CC2=CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)C(=O)C1=CC=CC=C1 UVZUFUGNHDDLRQ-LLHZKFLPSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 0 *C(CC1)CCC1c(ccc(*)c1F)c1F Chemical compound *C(CC1)CCC1c(ccc(*)c1F)c1F 0.000 description 1
- 239000005148 Cholesterol Benzoate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- C09K19/00—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
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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
- C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
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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
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- 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
- C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
- C09K2019/0437—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being an optically active chain used as linking group between rings or as end group
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Abstract
本发明涉及液晶显示领域，尤其涉及一种液晶介质及其应用，该液晶介质至少包含一种通式I所代表的化合物：以及至少一种通式II所代表的化合物；其中，通式I所代表的化合物为三环含有2，3‑二氟苯类结构化合物，该结构具有较大的负介电各向异性和高的清亮点；本发明所提供的通式II所代表的化合物为两环含有2，3‑二氟苯类结构的化合物，该结构为负介电各向异性液晶化合物，其在末端采用氟代乙氧基结构，大幅提升液晶化合物的介电各向异性。本发明所提供的液晶介质具有低的旋转粘度、良好的低温互溶性以及快的响应时间，适用于VA/MVA/PVA/PSVA等VA类液晶显示装置以及IPS、FFS模式液晶显示装置，对于改善液晶显示器的响应时间非常有效。 The present invention relates to the field of liquid crystal display, in particular to a liquid crystal medium and its application, the liquid crystal medium at least comprises a compound represented by general formula I: and at least one compound represented by general formula II; wherein, represented by general formula I The representative compound is a tricyclic compound containing 2,3-difluorobenzene structure, which has relatively large negative dielectric anisotropy and high clearing point; the compound represented by the general formula II provided by the present invention is two The ring contains a compound of 2,3-difluorobenzene structure, which is a liquid crystal compound with negative dielectric anisotropy, and adopts a fluoroethoxy structure at the end to greatly increase the dielectric anisotropy of the liquid crystal compound. The liquid crystal medium provided by the present invention has low rotational viscosity, good low-temperature miscibility and fast response time, and is suitable for VA liquid crystal display devices such as VA/MVA/PVA/PSVA and IPS and FFS mode liquid crystal display devices, for improving The response time of the LCD is very efficient.
Description
技术领域technical field
本发明涉及一种液晶介质，具体地说是一种向列相液晶组合物，确切地说本发明所提供的液晶组合物具有负的介电各向异性，更确切地说本发明所提供的液晶组合物中含有氟代乙氧基结构的液晶化合物。属于液晶材料及其应用领域。The present invention relates to a kind of liquid crystal medium, specifically a kind of nematic phase liquid crystal composition, exactly the liquid crystal composition provided by the present invention has negative dielectric anisotropy, more precisely the liquid crystal composition provided by the present invention The liquid crystal composition contains a liquid crystal compound with a fluoroethoxy structure. The invention belongs to the field of liquid crystal material and its application.
背景技术Background technique
目前，液晶在信息显示领域得到了广泛应用，同时在光通讯中的应用也取得了一定的进展(S.T.Wu，D.K.Yang.Reflective Liquid Crystal Displays.Wiley，2001)。近几年，液晶化合物的应用领域已经显著拓宽到各类显示器件、电光器件、电子元件、传感器等，向列型液晶化合物已经在平板显示器中得到最为广泛的应用，特别是用于TFT有源矩阵的系统中。At present, liquid crystals have been widely used in the field of information display, and at the same time, some progress has been made in the application in optical communication (S.T.Wu, D.K.Yang. Reflective Liquid Crystal Displays. Wiley, 2001). In recent years, the application fields of liquid crystal compounds have been significantly expanded to various display devices, electro-optic devices, electronic components, sensors, etc. Nematic liquid crystal compounds have been most widely used in flat panel displays, especially for TFT active matrix system.
液晶显示伴随液晶的发现经历了漫长的发展道路。1888年奥地利植物学家Friedrich Reinitzer发现了第一种液晶材料安息香酸胆固醇(cholesteryl benzoate)。1917年Manguin发明了摩擦定向法，用以制作单畴液晶和研究光学各向异性。1909年E.Bose建立了攒动(Swarm)学说，并得到L.S.Ormstein及F.Zernike等人的实验支持(1918年)，后经De Gennes论述为统计性起伏。G.W.Oseen和H.Zocher在1933年创立连续体理论，并得到F.C.Frank完善(1958年)。M.Born(1916年)和K.Lichtennecker(1926年)发现并研究了液晶的介电各向异性。1932年，W.Kast据此将向列相分为正、负性两大类。1927年，V.Freedericksz和V.Zolinao发现向列相液晶在电场或磁场作用下，发生形变并存在电压阈值(Freederichsz转变)。这一发现为液晶显示器的制作提供了依据。Liquid crystal display has experienced a long development path with the discovery of liquid crystal. In 1888, the Austrian botanist Friedrich Reinitzer discovered the first liquid crystal material, cholesterol benzoate (cholesteryl benzoate). In 1917, Manguin invented the rubbing orientation method to make monodomain liquid crystals and study optical anisotropy. In 1909, E.Bose established the theory of Swarm, which was supported by the experiments of L.S.Ormstein and F.Zernike et al. (1918), and was later discussed as statistical fluctuation by De Gennes. G.W.Oseen and H.Zocher founded the continuum theory in 1933, and it was perfected by F.C.Frank (1958). M.Born (1916) and K.Lichtennecker (1926) discovered and studied the dielectric anisotropy of liquid crystals. In 1932, W.Kast divided the nematic phase into two categories, positive and negative. In 1927, V.Freedericksz and V.Zolinao discovered that the nematic liquid crystal was deformed and had a voltage threshold (Freederichsz transition) under the action of an electric field or a magnetic field. This finding provides a basis for the production of liquid crystal displays.
1968年美国RCA公司R.Williams发现向列相液晶在电场作用下形成条纹畴，并有光散射现象。G.H.Heilmeir随即将其发展成动态散射显示模式，并制成世界上第一个液晶显示器(LCD)。七十年代初，Helfrich及Schadt发明了TN原理，人们利用TN光电效应和集成电路相结合，将其做成显示器件(TN-LCD)，为液晶的应用开拓了广阔的前景。七十年代以来，由于大规模集成电路和液晶材料的发展，液晶在显示方面的应用取得了突破性的发展，1983～1985年T.Scheffer等人先后提出超扭曲向列相(SuperTwisred Nematic：STN)模式以及P.Brody在1972年提出的有源矩阵(Active matrix：AM)方式被重新采用。传统的TN-LCD技术已发展为STN-LCD及TFT-LCD技术，尽管STN的扫描线数可达768行以上，但是当温度升高时仍然存在着响应速度、视角以及灰度等问题，因此大面积、高信息量、彩色显示大多采用有源矩阵显示方式。TFT-LCD已经广泛用于直视型电视、大屏幕投影电视、计算机终端显示和某些军用仪表显示，相信TFT-LCD技术具有更为广阔的应用前景。In 1968, R.Williams of RCA Company in the United States discovered that the nematic liquid crystal forms stripe domains under the action of an electric field, and has light scattering phenomenon. G.H.Heilmeir then developed it into a dynamic scattering display mode and made it the world's first liquid crystal display (LCD). In the early 1970s, Helfrich and Schadt invented the TN principle. People combined the TN photoelectric effect with integrated circuits to make it into a display device (TN-LCD), which opened up broad prospects for the application of liquid crystals. Since the 1970s, due to the development of large-scale integrated circuits and liquid crystal materials, the application of liquid crystals in display has achieved breakthrough development. From 1983 to 1985, T. Scheffer and others successively proposed super twisted nematic phase (SuperTwisred Nematic: STN ) mode and the active matrix (Active matrix: AM) method proposed by P.Brody in 1972 were re-adopted. The traditional TN-LCD technology has been developed into STN-LCD and TFT-LCD technology. Although the number of scanning lines of STN can reach more than 768 lines, there are still problems such as response speed, viewing angle and gray scale when the temperature rises. Therefore, Most of the large-area, high-information, and color displays use active matrix display. TFT-LCD has been widely used in direct-view TV, large-screen projection TV, computer terminal display and some military instrument display. It is believed that TFT-LCD technology has a broader application prospect.
其中“有源矩阵”包括两种类型：1、在作为基片的硅晶片上的OMS(金属氧化物半导体)或其它二极管。2、在作为基片的玻璃板上的薄膜晶体管(TFT)。The "active matrix" includes two types: 1. OMS (Metal Oxide Semiconductor) or other diodes on a silicon wafer as a substrate. 2. A thin film transistor (TFT) on a glass plate as a substrate.
单晶硅作为基片材料限制了显示尺寸，因为各部分显示器件甚至模块组装在其结合处出现许多问题。因而，第二种薄膜晶体管是具有前景的有源矩阵类型，所利用的光电效应通常是TN效应。TFT包括化合物半导体，如Cdse，或以多晶或无定形硅为基础的TFT。Monocrystalline silicon as a substrate material limits the size of the display, because there are many problems in the combination of various display devices and even module assembly. Thus, the second thin-film transistor is a promising active-matrix type, where the photoelectric effect used is usually the TN effect. TFTs include compound semiconductors, such as Cdse, or TFTs based on polycrystalline or amorphous silicon.
负性液晶最早于上世纪80年代末提出，其主要用于VA模式，其主要优点在于对比度高，主要缺点是视角小，响应时间慢。随着显示技术的发展，MVA、PVA、PSVA等技术相继出现，解决了响应时间和视角的问题。近年来，随着触摸屏成为移动设备市场主流，IPS和FFS类硬屏显示器有着先天的优势，IPS和FFS类显示器既可以使用正性液晶，也可以使用负性液晶，由于该类显示器中存在的弯曲电场，正性液晶沿着电场线方向排列，从而导致分子弯曲，以及于透过率下降；负性液晶垂直于电场线方向排列，因而透过率会大幅提升，是目前提升透过率、降低背光功耗最好的方法。但负性液晶存在的响应时间问题是目前遇到的重大难题，利用负性液晶的FFS显示器相对于正性液晶的FFS显示器响应时间慢50％或更多。因此，如何提升负性液晶的响应时间成为目前的核心问题。Negative liquid crystal was first proposed in the late 1980s. It is mainly used in VA mode. Its main advantage is high contrast, and its main disadvantages are small viewing angle and slow response time. With the development of display technology, MVA, PVA, PSVA and other technologies have emerged one after another, which solve the problems of response time and viewing angle. In recent years, as touch screens have become the mainstream of the mobile device market, IPS and FFS hard-screen displays have inherent advantages. IPS and FFS displays can use both positive and negative liquid crystals. In the bending electric field, the positive liquid crystals are arranged along the direction of the electric field lines, which causes the molecules to bend and the transmittance decreases; the negative liquid crystals are arranged perpendicular to the direction of the electric field lines, so the transmittance will be greatly increased. The best way to reduce backlight power consumption. However, the problem of response time of negative liquid crystals is a major problem encountered at present, and the response time of FFS displays using negative liquid crystals is 50% or more slower than that of positive liquid crystals. Therefore, how to improve the response time of the negative liquid crystal has become a core issue at present.
发明内容Contents of the invention
由于液晶显示器的响应时间取决于(d^2γ1)/Keff(d为液晶层厚度，γ1为液晶旋转粘度，Keff为有效弹性常数)，因此，降低旋转粘度、降低液晶层厚度和提升弹性常数均可以达到改善响应时间的目的，液晶层厚度取决于液晶显示器的设计；而对于液晶组合物，降低旋转粘度最有效。本发明提供了一种全新的液晶介质(下文也可成为液晶组合物)，其具有低的旋转粘度，可有效地降低液晶显示器的响应时间。Since the response time of the liquid crystal display depends on (d^2γ1)/Keff (d is the thickness of the liquid crystal layer, γ1 is the rotational viscosity of the liquid crystal, and Keff is the effective elastic constant), therefore, reducing the rotational viscosity, reducing the thickness of the liquid crystal layer and improving the elastic constant are all The purpose of improving the response time can be achieved, the thickness of the liquid crystal layer depends on the design of the liquid crystal display; and for the liquid crystal composition, reducing the rotational viscosity is the most effective. The present invention provides a brand-new liquid crystal medium (hereinafter also referred to as a liquid crystal composition), which has a low rotational viscosity and can effectively reduce the response time of a liquid crystal display.
具体而言，本发明所述的液晶介质，其至少包含一种通式I所代表的化合物：Specifically, the liquid crystal medium of the present invention comprises at least one compound represented by general formula I:
其中，R1代表C1～C12的直链烷基、直链烷氧基或C2～C12的直链烯基；Z1代表CH2O或CH2CH2。Wherein, R 1 represents C 1 -C 12 linear alkyl, linear alkoxy or C 2 -C 12 linear alkenyl; Z 1 represents CH 2 O or CH 2 CH 2 .
以及至少一种通式II所代表的化合物：And at least one compound represented by general formula II:
其中，R2代表C1～C12的直链烷基、直链烷氧基或C2～C12的直链烯基；A1代表反式1，4-环己基或1，4-亚苯基。Among them, R 2 represents C 1 ~ C 12 straight-chain alkyl, straight-chain alkoxy or C 2 ~ C 12 straight-chain alkenyl; A 1 represents trans 1,4-cyclohexyl or 1,4-ethylene phenyl.
本发明提供的通式I所代表的化合物为含有2，3-二氟苯结构的液晶化合物，端基采用氟代乙氧基(-OCH2CH2F)后，大幅提升了该结构的负介电各向异性，所以具有大的负介电各向异性和高的清亮点。用于本发明所述的液晶介质中可有效地提升液晶介质的负介电各向异性，降低极性单体使用，增加低粘度单体使用，降低液晶介质的旋转粘度，改善液晶显示器的响应时间。The compound represented by the general formula I provided by the present invention is a liquid crystal compound containing a 2,3-difluorobenzene structure. After the terminal group adopts a fluoroethoxy group (-OCH 2 CH 2 F), the negative structure of the structure is greatly improved. Dielectric anisotropy, so it has large negative dielectric anisotropy and high clearing point. Used in the liquid crystal medium of the present invention can effectively improve the negative dielectric anisotropy of the liquid crystal medium, reduce the use of polar monomers, increase the use of low-viscosity monomers, reduce the rotational viscosity of the liquid crystal medium, and improve the response of liquid crystal displays time.
本发明提供的液晶介质中，在其所有组分的质量总和为100％的情况下，通式I所述化合物在介质中的含量在5～70％为宜，优选为8～60％或13～65％；更优选8～35％、25～60％、10～53％、53～57％或16～39％；或者，通式I所述化合物在介质中的含量在10～60％，优选为10～42％、16～39％或53～57％；更优选14～35％或19～33％；此时更有利于实现降低液晶显示器响应时间的目的。In the liquid crystal medium provided by the present invention, when the mass sum of all its components is 100%, the content of the compound described in general formula I in the medium is preferably 5-70%, preferably 8-60% or 13% ～65%; More preferably 8～35%, 25～60%, 10～53%, 53～57% or 16～39%; Or, the content of the compound described in general formula I in medium is 10～60%, Preferably it is 10-42%, 16-39% or 53-57%; more preferably 14-35% or 19-33%; at this time, it is more beneficial to achieve the purpose of reducing the response time of the liquid crystal display.
具体而言，理想的通式I所代表的化合物选自式IA～式IB所代表的化合物的一种或几种：Specifically, the ideal compound represented by general formula I is selected from one or more of the compounds represented by formula IA to formula IB:
其中，R1代表C1～C7的直链烷基、C2～C7的直链烯基；Among them, R 1 represents C 1 ~ C 7 straight chain alkyl, C 2 ~ C 7 straight chain alkenyl;
优选的，通式I所代表的化合物选自式IA1～IA8、IB1～IB8所代表的化合物的一种或几种：Preferably, the compound represented by general formula I is selected from one or more of the compounds represented by formula IA1～IA8, IB1～IB8:
其中，当通式I所代表的化合物选择IA2、IA3、IA4、IA5、IA6、IA7、IB2及IB3时，在本发明所述液晶介质中的应用效果尤为突出。Among them, when IA2, IA3, IA4, IA5, IA6, IA7, IB2 and IB3 are selected as the compound represented by the general formula I, the application effect in the liquid crystal medium of the present invention is particularly prominent.
本发明所述的液晶介质还包括了至少一种通式II所代表的化合物，所述通式II所代表的的化合物为两环具有2,3-二氟-1,4-苯基的液晶化合物，末端采用氟代乙氧基结构(-OCH2CH2F)，大幅提升液晶化合物的介电各向异性，用于本发明所述的液晶介质中可改善液晶介质的互溶性和提升液晶介质的负介电各向异性，降低极性组分使用，增加中性低粘度组分使用，实现降低液晶介质的旋转黏度，提升液晶显示器响应时间的目的，同时拓宽液晶介质的低温相转变温度，改善液晶介质的低温互溶性。The liquid crystal medium of the present invention also includes at least one compound represented by general formula II, which is a liquid crystal having two rings of 2,3-difluoro-1,4-phenyl The compound adopts a fluoroethoxy structure (-OCH 2 CH 2 F) at the end, which greatly improves the dielectric anisotropy of the liquid crystal compound, and can improve the mutual solubility of the liquid crystal medium and enhance the liquid crystal when used in the liquid crystal medium of the present invention. The negative dielectric anisotropy of the medium reduces the use of polar components and increases the use of neutral low-viscosity components to achieve the purpose of reducing the rotational viscosity of liquid crystal media and improving the response time of liquid crystal displays, while broadening the low-temperature phase transition temperature of liquid crystal media , to improve the low-temperature miscibility of liquid crystal media.
本发明提供的液晶介质中，在其所有组分的质量总和为100％的情况下，通式II所述化合物在介质中的含量在1～40％为宜，优选为3～35％；更优选5～29％、10～35％、3～20％、15～29％或13～30％；或者，通式II所述化合物在介质中的含量在5～29％，优选为15～24％、5～29％、23～24％或5～23％；更优选23～24％或8～20％此时更有利于液晶介质的低温互溶性和低的旋转粘度。In the liquid crystal medium provided by the present invention, when the mass sum of all its components is 100%, the content of the compound described in the general formula II in the medium is preferably 1-40%, preferably 3-35%; more preferably Preferably 5-29%, 10-35%, 3-20%, 15-29% or 13-30%; or, the content of the compound described in the general formula II in the medium is 5-29%, preferably 15-24% %, 5-29%, 23-24% or 5-23%; more preferably 23-24% or 8-20%, which is more conducive to the low-temperature miscibility and low rotational viscosity of liquid crystal media.
具体而言，理想的通式II所代表的化合物选自IIA或IIB中的一种或多种：Specifically, the ideal compound represented by general formula II is selected from one or more of IIA or IIB:
其中，R2代表C1～C7的直链烷基或C2～C7的直链烯基。Wherein, R 2 represents a straight-chain alkyl group of C 1 to C 7 or a straight-chain alkenyl group of C 2 to C 7 .
优选地，通式II的化合物选自IIA1～IIA8、IIB1～IIB6中的一种或多种：Preferably, the compound of general formula II is selected from one or more of IIA1～IIA8, IIB1～IIB6:
其中，当通式III所代表的化合物选择IIA2、IIA4、IIA5、IIB2及IIB4时，在本发明所述液晶介质中的应用效果尤为突出。Among them, when IIA2, IIA4, IIA5, IIB2 and IIB4 are selected as the compound represented by the general formula III, the application effect in the liquid crystal medium of the present invention is particularly prominent.
此外，本发明所提供的的液晶介质还可以进一步包含一种或多种通式III所代表的化合物：In addition, the liquid crystal medium provided by the present invention may further comprise one or more compounds represented by the general formula III:
其中，R3、R4各自独立地代表C1～C12的直链烷基、直链烷氧基或C2～C12的直链烯基；A2、A3各自独立地代表反式1,4-环己基或1,4亚苯基。Among them, R 3 and R 4 each independently represent a straight-chain alkyl group of C 1 to C 12 , a straight-chain alkoxy group or a straight-chain alkenyl group of C 2 to C 12 ; A 2 and A 3 each independently represent a trans 1,4-cyclohexyl or 1,4-phenylene.
本发明提供的通式III所代表的化合物为双环结构，其加入到液晶介质中有助于配合本发明所述通式I及通式II所代表的化合物，进一步降低液晶介质的旋转黏度和增加互溶性，改善液晶显示器的响应时间和拓宽液晶显示器的低温工作温度。The compound represented by the general formula III provided by the present invention has a bicyclic structure, and its addition to the liquid crystal medium helps to coordinate the compounds represented by the general formula I and the general formula II of the present invention, further reducing the rotational viscosity of the liquid crystal medium and increasing the Miscibility, improve the response time of LCD and broaden the low temperature working temperature of LCD.
本发明提供的液晶介质中，在其所有组分的质量总和为100％的情况下，通式III所述化合物在介质中的含量在5～70％为宜，优选为10～60％；更优选13～56％、22～56％、10～53％、13～49％、30～60％或13～35％；或者，当液晶介质中包括所述通式III所述化合物时，其在介质中的含量在13～56％，优选为19～32％、22～56％、13～15％或22～50％；更优选30～50％或16～43％；此时更有利于改善液晶显示器的响应时间和拓宽液晶显示器的工作温度。In the liquid crystal medium provided by the present invention, when the mass sum of all its components is 100%, the content of the compound described in the general formula III in the medium is preferably 5-70%, preferably 10-60%; more preferably Preferably 13～56%, 22～56%, 10～53%, 13～49%, 30～60% or 13～35%; Or, when the compound described in the general formula III is included in the liquid crystal medium, it is in The content in the medium is 13-56%, preferably 19-32%, 22-56%, 13-15% or 22-50%; more preferably 30-50% or 16-43%; this time is more conducive to improving LCD response time and broaden the operating temperature of the LCD.
具体而言，理想的通式III所代表的化合物选自如下化合物的一种或多种：Specifically, the ideal compound represented by general formula III is selected from one or more of the following compounds:
其中，R3代表C1～C7的直链烷基；R4代表C1～C7的直链烷基、直链烷氧基或C2～C7的直链烯基。Wherein, R 3 represents a C 1 -C 7 linear alkyl group; R 4 represents a C 1 -C 7 linear alkyl group, a linear alkoxy group or a C 2 -C 7 linear alkenyl group.
优选的，通式III所代表的化合物选自式IIIA1～IIIA34、IIIB1～IIIB24、IIIC1～IIIC24所代表的化合物的一种或几种：Preferably, the compound represented by the general formula III is selected from one or more of the compounds represented by the formulas IIIA1~IIIA34, IIIB1~IIIB24, IIIC1~IIIC24:
其中，当通式III所代表的化合物选择IIIA1、IIIA2、IIIA16、IIIA18、IIIA22、IIIA23、IIIB18、IIIB22、IIIC2、IIIC4、IIIC15及IIIC16时，在本发明所述液晶介质中的应用效果尤为突出。Wherein, when the compound represented by the general formula III is selected from IIIA1, IIIA2, IIIA16, IIIA18, IIIA22, IIIA23, IIIB18, IIIB22, IIIC2, IIIC4, IIIC15 and IIIC16, the application effect in the liquid crystal medium of the present invention is particularly prominent.
进一步地，本发明所提供的液晶介质还可以包含一种或多种选自通式IV所代表的化合物：Further, the liquid crystal medium provided by the present invention may also contain one or more compounds selected from the general formula IV:
R5、R6各自独立地代表C1～C12的直链烷基，其中一个或多个不相邻的CH2可以被O或CH＝CH取代。R 5 and R 6 each independently represent a C 1 -C 12 linear alkyl group, wherein one or more non-adjacent CH 2 may be substituted by O or CH═CH.
A4选自以下结构：A 4 is selected from the following structures:
本发明所述通式IV所代表的的化合物具有高的清亮点和大的弹性常数，用于本发明所述的液晶介质中可提升液晶介质的清亮点和弹性常数。本发明提供的液晶介质中，在其所有组分的质量总和为100％的情况下，通式IV所述化合物在介质中的含量在0～45％为宜，优选为0～35％；更优选4～30％、0～25％或1～35％；或者，当液晶介质中包括所述通式IV所述化合物时，其在介质中的含量在4～30％，优选为9～30％或4～23％；更优选12～28％或8～18％；此时更有利于适应液晶显示器的性能需求，降低液晶介质的旋转粘度，提升液晶显示器的响应时间；同时解决液晶显示器因弹性常数较小导致的品质问题，如残像恢复。The compound represented by the general formula IV of the present invention has a high clearing point and a large elastic constant, and can be used in the liquid crystal medium of the present invention to increase the clearing point and elastic constant of the liquid crystal medium. In the liquid crystal medium provided by the present invention, when the mass sum of all its components is 100%, the content of the compound described in the general formula IV in the medium is preferably 0-45%, preferably 0-35%; more preferably Preferably 4-30%, 0-25% or 1-35%; or, when the compound of the general formula IV is included in the liquid crystal medium, its content in the medium is 4-30%, preferably 9-30% % or 4 to 23%; more preferably 12 to 28% or 8 to 18%; at this time, it is more conducive to adapting to the performance requirements of liquid crystal displays, reducing the rotational viscosity of liquid crystal media, and improving the response time of liquid crystal displays; Quality problems caused by small elastic constants, such as afterimage recovery.
优选地，通式IV所代表的化合物选自式IVA～式IVC以下化合物的一种或多种：Preferably, the compound represented by general formula IV is selected from one or more of the following compounds of formula IVA to formula IVC:
其中，R5代表C2～C10的直链烷基或直链烯基；R6代表C1～C8的直链烷基。Wherein, R 5 represents a C 2 -C 10 straight-chain alkyl group or a straight-chain alkenyl group; R 6 represents a C 1 -C 8 straight-chain alkyl group.
更优选地，通式IV所代表化合物选自式IVA1～IVA18、IVB1～IVB22、IVC1～IVC30结构中的一种或多种：More preferably, the compound represented by general formula IV is selected from one or more of the structures of formulas IVA1-IVA18, IVB1-IVB22, and IVC1-IVC30:
其中，当通式IV所代表的化合物选择IVA1、IVA2、IVA8、IVA12、IVA16、IVB3、IVB12及IVB16时，在本发明所述液晶介质中的应用效果尤为突出。Among them, when IVA1, IVA2, IVA8, IVA12, IVA16, IVB3, IVB12 and IVB16 are selected as the compound represented by the general formula IV, the application effect in the liquid crystal medium of the present invention is particularly prominent.
进一步地，本发明所提供的液晶介质还可以包含一种或多种选自通式V的化合物：Further, the liquid crystal medium provided by the present invention may also contain one or more compounds selected from the general formula V:
其中，R7代表C1～C12的直链烷基或C2～C12的直链烯基；R8代表F、C1～C12的直链烷基、直链烷氧基C2～C12的直链烯基；L1、L2、L3各自独立地代表H或F。Among them, R 7 represents C 1 ~ C 12 straight chain alkyl or C 2 ~ C 12 straight chain alkenyl; R 8 represents F, C 1 ~ C 12 straight chain alkyl, straight chain alkoxy C 2 ~C 12 linear alkenyl; L 1 , L 2 , L 3 each independently represent H or F.
本发明所述通式V所代表的的化合物具有大的光学各向异性，用于本发明所述的液晶介质中可提升液晶介质的光学各向异性，降低提供液晶介质光学各向异性组分的使用，增加低粘度单体使用，实现降低液晶介质的旋转粘度，提升液晶显示器的响应时间。The compound represented by the general formula V of the present invention has a large optical anisotropy, used in the liquid crystal medium of the present invention can improve the optical anisotropy of the liquid crystal medium, and reduce the optical anisotropy component of the liquid crystal medium The use of low-viscosity monomers is increased to reduce the rotational viscosity of liquid crystal media and improve the response time of liquid crystal displays.
本发明提供的液晶介质中，在其所有组分的质量总和为100％的情况下，通式V所述化合物在介质中的含量在0～30％为宜，优选为0～20％或1～25％；更优选0～17％、0～6％或5～17％；或者，通式V所述化合物在介质中的含量在0～17％，优选为5～17％；更优选5～6％或8～15％；此时更有利于适应液晶显示器对液晶介质的性能需求，降低液晶介质的旋转粘度，改善液晶显示器的响应时间。In the liquid crystal medium provided by the present invention, when the mass sum of all its components is 100%, the content of the compound of general formula V in the medium is preferably 0-30%, preferably 0-20% or 1 ～25%; more preferably 0～17%, 0～6% or 5～17%; Or, the content of the compound described in general formula V in the medium is 0～17%, preferably 5～17%; More preferably 5 ~ 6% or 8 ~ 15%; at this time, it is more conducive to adapting to the performance requirements of the liquid crystal display for the liquid crystal medium, reducing the rotational viscosity of the liquid crystal medium, and improving the response time of the liquid crystal display.
优选地，通式V所代表的化合物选自以下结构中的一种或多种；Preferably, the compound represented by general formula V is selected from one or more of the following structures;
其中，R7代表C1～C7的直链烷基或C2～C7的直链烯基，R8代表C1～C7的直链烷基、直链烷氧基或C2～C7的直链烯基。Among them, R 7 represents C 1 ~ C 7 straight chain alkyl or C 2 ~ C 7 straight chain alkenyl, R 8 represents C 1 ~ C 7 straight chain alkyl, straight chain alkoxy or C 2 ~ C7 straight chain alkenyl.
更优选地，通式V所代表的化合物选自式VA1～VA4、VB1～VB24、VC1～VC14、VD1～VD24中的一种或多种：More preferably, the compound represented by the general formula V is selected from one or more of the formulas VA1-VA4, VB1-VB24, VC1-VC14, VD1-VD24:
其中，当通式V所代表的化合物选择VA3、VB14、VB21、VB22、VC3及VC4时，在本发明所述液晶介质中的应用效果尤为突出。Among them, when VA3, VB14, VB21, VB22, VC3 and VC4 are selected as the compound represented by the general formula V, the application effect in the liquid crystal medium of the present invention is particularly prominent.
为确保本发明所述介质中各组分之间实现更为显著的协同效应，以有效提高所述液晶材料的综合应用性能，本发明进一步对所述液晶材料的中各组分的用量进行了优选。In order to ensure a more significant synergistic effect between the components in the medium of the present invention, to effectively improve the comprehensive application performance of the liquid crystal material, the present invention further carried out the dosage of each component in the liquid crystal material preferred.
具体的而言，本发明所提供的液晶介质包括以下组分：Specifically, the liquid crystal medium provided by the present invention comprises the following components:
(1)5～70％通式I所代表的化合物；(1) 5-70% of the compound represented by general formula I;
(2)1～40％通式II所代表的化合物；(2) 1-40% of the compound represented by general formula II;
(3)5～70％通式III所代表的化合物；(3) 5-70% of the compound represented by general formula III;
(4)0～45％通式IV所代表的化合物；(4) 0～45% of the compound represented by general formula IV;
(5)0～30％通式V所代表的化合物。(5) 0 to 30% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～60％通式I所代表的化合物；(1) 8-60% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)10～60％通式III所代表的化合物；(3) 10-60% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～57％通式I所代表的化合物；(1) 10-57% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)13～56％通式III所代表的化合物；(3) 13-56% of the compound represented by general formula III;
(4)0～30％通式IV所代表的化合物；(4) 0-30% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～35％通式I所代表的化合物；(1) 8 to 35% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)18～60％通式III所代表的化合物；(3) 18-60% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～35％通式I所代表的化合物；(1) 10-35% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)22～56％通式III所代表的化合物；(3) 22-56% of the compound represented by general formula III;
(4)5～30％通式IV所代表的化合物；(4) 5-30% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)25～60％通式I所代表的化合物；(1) 25-60% of the compound represented by general formula I;
(2)3～30％通式II所代表的化合物；(2) 3-30% of the compound represented by general formula II;
(3)10～45％通式III所代表的化合物；(3) 10-45% of the compound represented by general formula III;
(4)0～25％通式IV所代表的化合物；(4) 0-25% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)25～57％通式I所代表的化合物；(1) 25-57% of the compound represented by general formula I;
(2)5～26％通式II所代表的化合物；(2) 5-26% of the compound represented by general formula II;
(3)13～43％通式III所代表的化合物；(3) 13-43% of the compound represented by general formula III;
(4)0～22％通式IV所代表的化合物；(4) 0～22% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)13～65％通式I所代表的化合物；(1) 13-65% of the compound represented by general formula I;
(2)15～35％通式II所代表的化合物；(2) 15-35% of the compound represented by general formula II;
(3)10～53％通式III所代表的化合物；(3) 10-53% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)16～57％通式I所代表的化合物；(1) 16-57% of the compound represented by general formula I;
(2)15～29％通式II所代表的化合物；(2) 15-29% of the compound represented by general formula II;
(3)13～49％通式III所代表的化合物；(3) 13-49% of the compound represented by general formula III;
(4)0～29％通式IV所代表的化合物；(4) 0～29% of the compound represented by general formula IV;
(5)0～14％通式V所代表的化合物。(5) 0 to 14% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～55％通式I所代表的化合物；(1) 8 to 55% of the compound represented by general formula I;
(2)3～20％通式II所代表的化合物；(2) 3-20% of the compound represented by general formula II;
(3)20～60％通式III所代表的化合物；(3) 20-60% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～53％通式I所代表的化合物；(1) 10-53% of the compound represented by general formula I;
(2)5～20％通式II所代表的化合物；(2) 5-20% of the compound represented by general formula II;
(3)22～56％通式III所代表的化合物；(3) 22-56% of the compound represented by general formula III;
(4)0～30％通式IV所代表的化合物；(4) 0-30% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)15～60％通式I所代表的化合物；(1) 15-60% of the compound represented by general formula I;
(2)10～35％通式II所代表的化合物；(2) 10-35% of the compound represented by general formula II;
(3)10～35％通式III所代表的化合物；(3) 10-35% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)16～57％通式I所代表的化合物；(1) 16-57% of the compound represented by general formula I;
(2)15～29％通式II所代表的化合物；(2) 15-29% of the compound represented by general formula II;
(3)13～35％通式III所代表的化合物；(3) 13-35% of the compound represented by general formula III;
(4)0～29％通式IV所代表的化合物；(4) 0～29% of the compound represented by general formula IV;
(5)0～14％通式V所代表的化合物。(5) 0 to 14% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～55％通式I所代表的化合物；(1) 8 to 55% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)30～60％通式III所代表的化合物；(3) 30-60% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～53％通式I所代表的化合物；(1) 10-53% of the compound represented by general formula I;
(2)5～28％通式II所代表的化合物；(2) 5-28% of the compound represented by general formula II;
(3)30～56％通式III所代表的化合物；(3) 30-56% of the compound represented by general formula III;
(4)0～30％通式IV所代表的化合物；(4) 0-30% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～45％通式I所代表的化合物；(1) 8 to 45% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)18～60％通式III所代表的化合物；(3) 18-60% of the compound represented by general formula III;
(4)1～35％通式IV所代表的化合物；(4) 1 to 35% of the compound represented by general formula IV;
(5)0～20％通式V所代表的化合物。(5) 0 to 20% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～42％通式I所代表的化合物；(1) 10-42% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)22～56％通式III所代表的化合物；(3) 22-56% of the compound represented by general formula III;
(4)4～30％通式IV所代表的化合物；(4) 4-30% of the compound represented by general formula IV;
(5)0～17％通式V所代表的化合物。(5) 0 to 17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)45～60％通式I所代表的化合物；(1) 45-60% of the compound represented by general formula I;
(2)13～30％通式II所代表的化合物；(2) 13-30% of the compound represented by general formula II;
(3)10～35％通式III所代表的化合物；(3) 10-35% of the compound represented by general formula III;
(4)0～10％通式V所代表的化合物。(4) 0 to 10% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)53～57％通式I所代表的化合物；(1) 53-57% of the compound represented by general formula I;
(2)15～24％通式II所代表的化合物；(2) 15-24% of the compound represented by general formula II;
(3)13～32％通式III所代表的化合物；(3) 13-32% of the compound represented by general formula III;
(4)0～6％通式V所代表的化合物。(4) 0 to 6% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)10～60％通式I所代表的化合物；(1) 10-60% of the compound represented by general formula I;
(2)3～30％通式II所代表的化合物；(2) 3-30% of the compound represented by general formula II;
(3)10～55％通式III所代表的化合物；(3) 10-55% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物；(4) 0～35% of the compound represented by general formula IV;
(5)1～25％通式V所代表的化合物。(5) 1 to 25% of the compound represented by the general formula V.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)16～57％通式I所代表的化合物；(1) 16-57% of the compound represented by general formula I;
(2)5～24％通式II所代表的化合物；(2) 5-24% of the compound represented by general formula II;
(3)13～50％通式III所代表的化合物；(3) 13-50% of the compound represented by general formula III;
(4)0～30％通式IV所代表的化合物；(4) 0-30% of the compound represented by general formula IV;
(5)5～17％通式V所代表的化合物。(5) 5-17% of the compound represented by the general formula V.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～60％通式I所代表的化合物；(1) 8-60% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)15～60％通式III所代表的化合物；(3) 15-60% of the compound represented by general formula III;
(4)0～35％通式IV所代表的化合物。(4) 0 to 35% of the compound represented by the general formula IV.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～57％通式I所代表的化合物；(1) 10-57% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)19～56％通式III所代表的化合物；(3) 19-56% of the compound represented by general formula III;
(4)0～30％通式IV所代表的化合物。(4) 0 to 30% of the compound represented by the general formula IV.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)8～45％通式I所代表的化合物；(1) 8 to 45% of the compound represented by general formula I;
(2)3～35％通式II所代表的化合物；(2) 3-35% of the compound represented by general formula II;
(3)20～60％通式III所代表的化合物；(3) 20-60% of the compound represented by general formula III;
(4)5～35％通式IV所代表的化合物。(4) 5-35% of the compound represented by the general formula IV.
更优选地，所述液晶介质包括以下组分：More preferably, the liquid-crystalline medium comprises the following components:
(1)10～42％通式I所代表的化合物；(1) 10-42% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)24～56％通式III所代表的化合物；(3) 24-56% of the compound represented by general formula III;
(4)9～30％通式IV所代表的化合物。(4) 9-30% of the compound represented by the general formula IV.
优选的，所述液晶介质包括以下组分：Preferably, the liquid crystal medium comprises the following components:
(1)13～43％通式I所代表的化合物；(1) 13-43% of the compound represented by general formula I;
(2)3～26％通式II所代表的化合物；(2) 3-26% of the compound represented by general formula II;
(3)18～55％通式III所代表的化合物；(3) 18-55% of the compound represented by general formula III;
(4)1～25％通式IV所代表的化合物；(4) 1-25% of the compound represented by general formula IV;
(5)1～20％通式V所代表的化合物。(5) 1 to 20% of the compound represented by the general formula V.
此外，在实践中发现，当本发明所述的液晶介质各组分含量选择以下范围时，应用性能尤为突出：In addition, it has been found in practice that when the content of each component of the liquid crystal medium of the present invention is selected from the following ranges, the application performance is particularly prominent:
(1)53～57％通式I所代表的化合物；(1) 53-57% of the compound represented by general formula I;
(2)15～24％通式II所代表的化合物；(2) 15-24% of the compound represented by general formula II;
(3)19～32％通式III所代表的化合物；(3) 19-32% of the compound represented by general formula III;
或：or:
(1)50～60％通式I所代表的化合物；(1) 50-60% of the compound represented by general formula I;
(2)23～24％通式II所代表的化合物；(2) 23-24% of the compound represented by general formula II;
(3)13～15％通式III所代表的化合物；(3) 13-15% of the compound represented by general formula III;
(4)5～6％通式V所代表的化合物；(4) 5-6% of the compound represented by general formula V;
或：or:
(1)10～42％通式I所代表的化合物；(1) 10-42% of the compound represented by general formula I;
(2)5～29％通式II所代表的化合物；(2) 5-29% of the compound represented by general formula II;
(3)22～56％通式III所代表的化合物；(3) 22-56% of the compound represented by general formula III;
(4)9～30％通式IV所代表的化合物；(4) 9-30% of the compound represented by general formula IV;
优选：Preferred:
(1)14～35％通式I所代表的化合物；(1) 14-35% of the compound represented by general formula I;
(2)10～26％通式II所代表的化合物；(2) 10-26% of the compound represented by general formula II;
(3)30～50％通式III所代表的化合物；(3) 30-50% of the compound represented by general formula III;
(4)12～28％通式IV所代表的化合物；(4) 12-28% of the compound represented by general formula IV;
或：or:
(1)16～39％通式I所代表的化合物；(1) 16-39% of the compound represented by general formula I;
(2)5～23％通式II所代表的化合物；(2) 5-23% of the compound represented by general formula II;
(3)22～50％通式III所代表的化合物；(3) 22-50% of the compound represented by general formula III;
(4)4～23％通式IV所代表的化合物；(4) 4-23% of the compound represented by general formula IV;
(5)5～17％通式V所代表的化合物；(5) 5-17% of the compound represented by general formula V;
优选：Preferred:
(1)19～33％通式I所代表的化合物；(1) 19-33% of the compound represented by general formula I;
(2)8～20％通式II所代表的化合物；(2) 8-20% of the compound represented by general formula II;
(3)26～43％通式III所代表的化合物；(3) 26-43% of the compound represented by general formula III;
(4)8～18％通式IV所代表的化合物；(4) 8-18% of the compound represented by general formula IV;
(5)8～15％通式V所代表的化合物。(5) 8-15% of the compound represented by the general formula V.
除特殊说明外，本发明所述液晶介质中各组分的总质量百分比之和均为100％。Unless otherwise specified, the sum of the total mass percentages of the components in the liquid crystal medium of the present invention is 100%.
本发明所提供的通式I所代表的化合物为三环含有甲氧基桥键的2，3-二氟苯类结构化合物，该结构为负介电各向异性液晶化合物，其在末端采用氟代乙氧基结构，通过研究发现，利用氟取代乙氧基后，该结构的负介电各向异性得到大幅提升，仅作示例的部分化合物测试结果如下：The compound represented by the general formula I provided by the present invention is a tricyclic 2,3-difluorobenzene structure compound containing a methoxy bridge bond. This structure is a liquid crystal compound with negative dielectric anisotropy, and the terminal uses Substituting the ethoxy group structure, through research, it is found that the negative dielectric anisotropy of the structure is greatly improved after the ethoxy group is replaced by fluorine. The test results of some compounds for example are as follows:
以上对比可以发现，本发明所提出的氟代乙氧基的化合物具有大的负介电各向异性，可有效提升液晶介质的负介电各向异性，减少极性单体使用，增加低粘度单体使用，降低体系的旋转粘度，提升响应时间；本发明所提供的通式II所代表的化合物为两环含有2，3-二氟苯类结构的化合物，该结构为负介电各向异性液晶化合物，其在末端采用氟代乙氧基结构，通过研究发现，利用氟取代乙氧基后，该结构的负介电各向异性得到大幅提升，仅作示例的部分化合物测试结果如下：From the above comparison, it can be found that the fluoroethoxy compound proposed by the present invention has a large negative dielectric anisotropy, which can effectively improve the negative dielectric anisotropy of the liquid crystal medium, reduce the use of polar monomers, and increase the low viscosity. The use of monomers reduces the rotational viscosity of the system and increases the response time; the compound represented by the general formula II provided by the present invention is a compound containing 2,3-difluorobenzene in two rings, and the structure is a negative dielectric anisotropy The anisotropic liquid crystal compound adopts a fluoroethoxy structure at the end. Through research, it is found that the negative dielectric anisotropy of the structure is greatly improved after the ethoxy group is replaced by fluorine. The test results of some compounds for example are as follows:
以上对比可以发现，本发明所提出的氟代乙氧基的化合物具有大的负介电各向异性，可有效提升液晶介质的负介电各向异性，减少极性单体使用，增加低粘度单体使用，降低体系的旋转粘度，提升响应时间；式III所代表的化合物为双环结构，具有低的旋转粘度和优良的互溶性特点，是快响应液晶显示必不可少的组分，通式IV所代表的化合物为非极性三环化合物，该类单体具有高的清亮点和大的弹性常数，有利于提高液晶介质的弹性常数；通式V所代表的化合物具有大的光学各向异性，对于提升液晶介质的介电各向异性非常有效。From the above comparison, it can be found that the fluoroethoxy compound proposed by the present invention has a large negative dielectric anisotropy, which can effectively improve the negative dielectric anisotropy of the liquid crystal medium, reduce the use of polar monomers, and increase the low viscosity. The use of monomers reduces the rotational viscosity of the system and increases the response time; the compound represented by formula III is a bicyclic structure with low rotational viscosity and excellent mutual solubility, and is an essential component of a fast-response liquid crystal display. The general formula The compound represented by IV is a non-polar tricyclic compound. This type of monomer has a high clearing point and a large elastic constant, which is conducive to improving the elastic constant of the liquid crystal medium; the compound represented by the general formula V has a large optical anisotropy Anisotropy, which is very effective for increasing the dielectric anisotropy of liquid crystal media.
上述五种液晶化合物按照上文所述的各种组合方式(其中，通式I和通式II所代表的化合物为必选组分，其余为可选组分)组合形成的液晶介质都能实现较为理想的应用效果。需要特别说明的是，当本发明所述的液晶介质为三组分组合物时，理想的组合为通式I+通式II+通式III所代表的化合物；当本发明所述的液晶介质为四组分组合物时，理想的组合为通式I+通式II+通式III+通式IV所代表的化合物或通式I+通式II+通式III+通式V所代表的化合物，以实现更理想的搭配协同效果。The liquid crystal medium formed by combining the above five liquid crystal compounds according to the above-mentioned various combinations (wherein, the compounds represented by the general formula I and the general formula II are mandatory components, and the rest are optional components) can realize Ideal application effect. It should be noted that when the liquid crystal medium of the present invention is a three-component composition, the ideal combination is a compound represented by general formula I+general formula II+general formula III; when the liquid crystal medium of the present invention is four In the composition of components, the ideal combination is the compound represented by the general formula I + the general formula II + the general formula III + the general formula IV or the compound represented by the general formula I + the general formula II + the general formula III + the general formula V, so as to achieve a more ideal combination synergistic effect.
本发明所述液晶组合物的制备方法无特殊限制，可采用常规方法将两种或多种化合物混合进行生产，如通过在高温下混合不同组分并彼此溶解的方法制备，其中，将液晶组合物溶解在用于该化合物的溶剂中并混合，然后在减压下蒸馏出该溶剂；或者本发明所述液晶组合物可按照常规的方法制备，如将其中含量较小的组分在较高的温度下溶解在含量较大的主要组分中，或将各所属组分在有机溶剂中溶解，如丙酮、氯仿或甲醇等，然后将溶液混合去除溶剂后得到。The preparation method of the liquid crystal composition of the present invention is not particularly limited, and it can be produced by mixing two or more compounds by a conventional method, such as by mixing different components at high temperature and dissolving each other, wherein the liquid crystal is combined The compound is dissolved in the solvent used for the compound and mixed, and then the solvent is distilled off under reduced pressure; or the liquid crystal composition of the present invention can be prepared according to a conventional method, such as adding a smaller component in a higher It can be obtained by dissolving in the main components with relatively large content at a certain temperature, or dissolving each component in an organic solvent, such as acetone, chloroform or methanol, etc., and then mixing the solutions to remove the solvent.
本发明所提供的液晶介质具有低的旋转粘度、良好的低温互溶性以及快的响应时间，适用于VA/MVA/PVA/PSVA等VA类液晶显示装置以及IPS、FFS模式液晶显示装置。对于改善液晶显示器的响应时间非常有效。The liquid crystal medium provided by the invention has low rotational viscosity, good low-temperature mutual solubility and fast response time, and is suitable for VA liquid crystal display devices such as VA/MVA/PVA/PSVA and IPS and FFS mode liquid crystal display devices. Very effective for improving the response time of LCD monitors.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
除非另有说明，本发明中百分比为重量百分比；温度单位为摄氏度；△n代表光学各向异性(25℃)；△ε代表介电各向异性(25℃，1000Hz)；V10代表阈值电压，是在相对透过率改变10％时的特征电压(V，25℃)；γ1代表旋转粘度(mPa.s，25℃)；Cp代表液晶组合物的清亮点(℃)；K11、K22、K33分别代表展曲、扭曲和弯曲弹性常数(pN，25℃)。Unless otherwise specified, percentages in the present invention are percentages by weight; temperature units are degrees Celsius; Δn represents optical anisotropy (25°C); Δε represents dielectric anisotropy (25°C, 1000Hz); V 10 represents threshold voltage , is the characteristic voltage when the relative transmittance changes by 10% (V, 25°C); γ1 represents the rotational viscosity (mPa.s, 25°C); Cp represents the clearing point of the liquid crystal composition (°C); K 11 , K 22 and K 33 respectively represent splay, torsion and bending elastic constants (pN, 25°C).
以下各实施例中，液晶化合物中基团结构用表1所示代码表示。In the following examples, the group structures in liquid crystal compounds are represented by the codes shown in Table 1.
表1：液晶化合物的基团结构代码Table 1: Group structure codes of liquid crystal compounds
以如下化合物结构为例：Take the following compound structure as an example:
表示为：3PWO2FExpressed as: 3PWO2F
表示为：3PGIWO2Expressed as: 3PGIWO2
以下各实施例中，液晶组合物的制备均采用热溶解方法，包括以下步骤：用天平按重量百分比称量液晶化合物，其中称量加入顺序无特定要求，通常以液晶化合物熔点由高到低的顺序依次称量混合，在60～100℃下加热搅拌使得各组分熔解均匀，再经过滤、旋蒸，最后封装即得目标样品。In each of the following examples, the preparation of the liquid crystal composition adopts the thermal dissolution method, including the following steps: use a balance to weigh the liquid crystal compound by weight percentage, wherein there is no specific requirement for the order of weighing and adding, and the melting point of the liquid crystal compound is usually measured from high to low. Sequentially weigh and mix, heat and stir at 60-100°C to make each component melt evenly, then filter, rotary evaporate, and finally package to obtain the target sample.
以下各实施例中，所涉及到的液晶组分，均为已知化合物，可通过市售购得，如可由北京八亿时空液晶科技股份有限公司提供。In the following examples, the liquid crystal components involved are all known compounds, which can be purchased from the market, for example, provided by Beijing Bayi Shikong Liquid Crystal Technology Co., Ltd.
以下各实施例中，液晶组合物中各组分的重量百分比及液晶组合物的性能参数见下述表格。In the following examples, the weight percentage of each component in the liquid crystal composition and the performance parameters of the liquid crystal composition are shown in the following tables.
实施例1Example 1
表2：液晶组合物中各组分的重量百分比及性能参数Table 2: Weight percent and performance parameters of each component in the liquid crystal composition
实施例2Example 2
表3：液晶组合物中各组分的重量百分比及性能参数Table 3: Weight percent and performance parameters of each component in the liquid crystal composition
实施例3Example 3
表4：液晶组合物中各组分的重量百分比及性能参数Table 4: Weight percent and performance parameters of each component in the liquid crystal composition
实施例4Example 4
表5：液晶组合物中各组分的重量百分比及性能参数Table 5: Weight percent and performance parameters of each component in the liquid crystal composition
实施例5Example 5
表6：液晶组合物中各组分的重量百分比及性能参数Table 6: Weight percent and performance parameters of each component in the liquid crystal composition
实施例6Example 6
表7：液晶组合物中各组分的重量百分比及性能参数Table 7: Weight percent and performance parameters of each component in the liquid crystal composition
实施例7Example 7
表8：液晶组合物中各组分的重量百分比及性能参数Table 8: Weight percent and performance parameters of each component in the liquid crystal composition
实施例8Example 8
表9：液晶组合物中各组分的重量百分比及性能参数Table 9: Weight percent and performance parameters of each component in the liquid crystal composition
实施例9Example 9
表10：液晶组合物中各组分的重量百分比及性能参数Table 10: Weight percent and performance parameters of each component in the liquid crystal composition
实施例10Example 10
表11：液晶组合物中各组分的重量百分比及性能参数Table 11: Weight percent and performance parameters of each component in the liquid crystal composition
实施例11Example 11
表12：液晶组合物中各组分的重量百分比及性能参数Table 12: Weight percent and performance parameters of each component in the liquid crystal composition
实施例12Example 12
表13：液晶组合物中各组分的重量百分比及性能参数Table 13: Weight percent and performance parameters of each component in the liquid crystal composition
实施例13Example 13
表14：液晶组合物中各组分的重量百分比及性能参数Table 14: Weight percent and performance parameters of each component in the liquid crystal composition
实施例14Example 14
表15：液晶组合物中各组分的重量百分比及性能参数Table 15: Weight percent and performance parameters of each component in the liquid crystal composition
实施例15Example 15
表16：液晶组合物中各组分的重量百分比及性能参数Table 16: Weight percent and performance parameters of each component in the liquid crystal composition
实施例16Example 16
表17：液晶组合物中各组分的重量百分比及性能参数Table 17: Weight percent and performance parameters of each component in the liquid crystal composition
实施例17Example 17
表18：液晶组合物中各组分的重量百分比及性能参数Table 18: Weight percent and performance parameters of each component in the liquid crystal composition
实施例18Example 18
表19：液晶组合物中各组分的重量百分比及性能参数Table 19: Weight percent and performance parameters of each component in the liquid crystal composition
实施例19Example 19
表20：液晶组合物中各组分的重量百分比及性能参数Table 20: Weight percent and performance parameters of each component in the liquid crystal composition
实施例20Example 20
表21：液晶组合物中各组分的重量百分比及性能参数Table 21: Weight percent and performance parameters of each component in the liquid crystal composition
实施例21Example 21
表22：液晶组合物中各组分的重量百分比及性能参数Table 22: Weight percent and performance parameters of each component in the liquid crystal composition
实施例22Example 22
表23：液晶组合物中各组分的重量百分比及性能参数Table 23: Weight percent and performance parameters of each component in the liquid crystal composition
实施例23Example 23
表24：液晶组合物中各组分的重量百分比及性能参数Table 24: Weight percent and performance parameters of each component in the liquid crystal composition
实施例24Example 24
表25：液晶组合物中各组分的重量百分比及性能参数Table 25: Weight percent and performance parameters of each component in the liquid crystal composition
实施例25Example 25
表26：液晶组合物中各组分的重量百分比及性能参数Table 26: Weight percent and performance parameters of each component in the liquid crystal composition
实施例26Example 26
表27：液晶组合物中各组分的重量百分比及性能参数Table 27: Weight percent and performance parameters of each component in the liquid crystal composition
实施例27Example 27
表28：液晶组合物中各组分的重量百分比及性能参数Table 28: Weight percent and performance parameters of each component in the liquid crystal composition
实施例28Example 28
表29：液晶组合物中各组分的重量百分比及性能参数Table 29: Weight percent and performance parameters of each component in the liquid crystal composition
实施例29Example 29
表30：液晶组合物中各组分的重量百分比及性能参数Table 30: Weight percent and performance parameters of each component in the liquid crystal composition
实施例30Example 30
表31：液晶组合物中各组分的重量百分比及性能参数Table 31: Weight percent and performance parameters of each component in the liquid crystal composition
实施例31Example 31
表32：液晶组合物中各组分的重量百分比及性能参数Table 32: Weight percent and performance parameters of each component in the liquid crystal composition
实施例32Example 32
表33：液晶组合物中各组分的重量百分比及性能参数Table 33: Weight percent and performance parameters of each component in the liquid crystal composition
实施例33Example 33
表34：液晶组合物中各组分的重量百分比及性能参数Table 34: Weight percent and performance parameters of each component in the liquid crystal composition
实施例34Example 34
表35：液晶组合物中各组分的重量百分比及性能参数Table 35: Weight percent and performance parameters of each component in the liquid crystal composition
实施例35Example 35
表36：液晶组合物中各组分的百分比及性能参数Table 36: The percentage and performance parameters of each component in the liquid crystal composition
实施例36Example 36
表37：液晶组合物中各组分的重量百分比及性能参数Table 37: Weight percent and performance parameters of each component in the liquid crystal composition
实施例37Example 37
表38：液晶组合物中各组分的重量百分比及性能参数Table 38: Weight percent and performance parameters of each component in the liquid crystal composition
实施例38Example 38
表39：液晶组合物中各组分的重量百分比及性能参数Table 39: Weight percent and performance parameters of each component in the liquid crystal composition
实施例39Example 39
表40：液晶组合物中各组分的重量百分比及性能参数Table 40: Weight percent and performance parameters of each component in the liquid crystal composition
实施例40Example 40
表41：液晶组合物中各组分的重量百分比及性能参数Table 41: Weight percent and performance parameters of each component in the liquid crystal composition
实施例41Example 41
表42：液晶组合物中各组分的重量百分比及性能参数Table 42: Weight percent and performance parameters of each component in the liquid crystal composition
实施例42Example 42
表43：液晶组合物中各组分的重量百分比及性能参数Table 43: Weight percent and performance parameters of each component in the liquid crystal composition
实施例43Example 43
表44：液晶组合物中各组分的重量百分比及性能参数Table 44: Weight percent and performance parameters of each component in the liquid crystal composition
实施例44Example 44
表45：液晶组合物中各组分的重量百分比及性能参数Table 45: Weight percent and performance parameters of each component in the liquid crystal composition
实施例45Example 45
表46：液晶组合物中各组分的重量百分比及性能参数Table 46: Weight percent and performance parameters of each component in the liquid crystal composition
实施例46Example 46
表47：液晶组合物中各组分的重量百分比及性能参数Table 47: Weight percent and performance parameters of each component in the liquid crystal composition
实施例47Example 47
表48：液晶组合物中各组分的重量百分比及性能参数Table 48: Weight percent and performance parameters of each component in the liquid crystal composition
对比例1Comparative example 1
表49：液晶组合物中各组分的重量百分比及性能参数Table 49: Weight percent and performance parameters of each component in the liquid crystal composition
将实施例1与对比例1所得液晶组合物的各性能参数值进行汇总比较，参见表50。The values of various performance parameters of the liquid crystal compositions obtained in Example 1 and Comparative Example 1 were summarized and compared, see Table 50.
表50：液晶组合物的性能参数比较Table 50: Comparison of performance parameters of liquid crystal compositions
经比较可知：与对比例1相比，实施例1提供的液晶组合物具有低的旋转粘度，即具有更快的的响应时间。It can be seen from comparison that: compared with Comparative Example 1, the liquid crystal composition provided by Example 1 has a low rotational viscosity, that is, has a faster response time.
由以上实施例可知，本发明所提供的液晶组合物具有低粘度、高电阻率、适合的光学各向异性、良好的低温互溶性、大的弹性常数以及优异的光稳定性和热稳定性，可降低液晶显示器的响应时间，从而解决液晶显示器响应速度慢的问题。因此，本发明所提供的液晶组合物适用于VA/MVA/PVA/PSVA等VA显示模式以及IPS及FFS型TFT液晶显示装置。It can be seen from the above examples that the liquid crystal composition provided by the present invention has low viscosity, high resistivity, suitable optical anisotropy, good low temperature miscibility, large elastic constant and excellent light stability and thermal stability, The response time of the liquid crystal display can be reduced, thereby solving the problem of the slow response speed of the liquid crystal display. Therefore, the liquid crystal composition provided by the present invention is suitable for VA display modes such as VA/MVA/PVA/PSVA and IPS and FFS type TFT liquid crystal display devices.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.
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