CN101698802A - Liquid crystal mixture with low negative dielectric - Google Patents

Liquid crystal mixture with low negative dielectric Download PDF

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CN101698802A
CN101698802A CN200910035888A CN200910035888A CN101698802A CN 101698802 A CN101698802 A CN 101698802A CN 200910035888 A CN200910035888 A CN 200910035888A CN 200910035888 A CN200910035888 A CN 200910035888A CN 101698802 A CN101698802 A CN 101698802A
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liquid crystal
compounds
general formula
compound
negative dielectric
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CN101698802B (en
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谭玉东
雷艳蓉
马德文
胡彪
朱霞
韩文明
阮群奇
张宏伟
靳灿辉
孙仲猛
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Jiangsu Hecheng Display Technology Co Ltd
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JIANGSU HECHENG CHEMICAL MATERIALS CO Ltd
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Abstract

The invention relates to a liquid crystal mixture for a display, which comprises the following compounds in percentage by weight: 70 to 90 percent of compound in a general formula I, 0 to 20 percent of compound in a general formula II, 5 to 25 percent of compound in a general formula III, 0 to 10 percent of compound in a general formula IV and 1 to 15 percent of compound in a formula V. Through optimal combination and optical proportioning, the anisotropyenergy of the negative dielectric of the liquid crystal mixture reaches -9.5, a clearing point is between 95 and 110DEG C, the driving voltage is very low, the energy consumption can be effectively reduced, and a liquid crystal display (hereinafter referred to as LCD) powered by a battery is powered more durably. The mixture has good intersolubility between monomers, and the solubility of the mixture for dichroic dyes is good; and various single dichroic dyes with different colors can be added to the liquid crystal mixture, so the liquid crystal mixture has good absorbance and dichroic ratio to well realize darker dark state and greatly improve display contrast in the displaying process.

Description

Liquid crystal compound with low negative dielectric
Technical field
The present invention relates to be used for the liquid crystal compound of display device liquid crystal cell and the guest-host type liquid crystal compound after wherein adding dyestuff (guest-host liquid-crystal compostion), the guest-host type liquid-crystal composition after particularly having the liquid crystal compound of low negative dielectric and adding dyestuff.
Background technology
Liquid crystal material is a kind of mesomorphic phase material between solid phase and liquid phase, and its phase can roughly be divided into nematic phase, smectic phase and cholesteric phase, in display element, and nematic being most widely used.Liquid crystal compound is because of the characteristic of its inherent optical anisotropy (Δ n) and dielectric anisotropy (Δ ε), be widely used at present the making of device liquid crystal display device such as robot calculator, meter device, automobile dashboard, electronic memo, mobile telephone, computer, televisor, its range of application is also in expansion year by year.Classify by the liquid-crystal display mode, liquid crystal compound can be divided into dynamic scattering mode (DS type), guest-host type (GH type), twisted nematic (TN type), super-twist nematic (STN type), film transistor type (TFT type) and strong dielectricity types such as (FLC).
Liquid crystal display device all needs to use linear polarization to obtain polarized light mostly, and light utilization efficiency is lower.The dye liquid crystal mixture (being the guest-host type liquid crystal compound) that adds dichroic dye utilizes the dichroism of dichroic dye (promptly to showing as different absorbancys perpendicular to the polarized light with the extinction axle that is parallel to the dichroic dye molecule, also claim absorption anisotropy), adopt the liquid crystal display device of guest-host type liquid crystal compound also can realize monochrome or multicolor displaying in few usefulness or under without the situation of polarizer, higher brightness is arranged and show contrast gradient, the visual angle is wide, the energy color difference eliminating, particularly in the display element of the reflection-type pattern that does not have backlight, can realize luminous demonstration, light utilization efficiency is high.
Dichroic dye mostly is anthraquinone and azoic dye greatly, according to its substituting group difference visible spectrum is demonstrated different absorption characteristics; Single dichroic dye mainly absorbs the light of specific wavelength, and the color of demonstration is for seeing through the complementary color of all light, and the color that the dyestuff that for example main absorption is respectively red, yellow, green, blue light demonstrates is followed successively by indigo plant, purple, red, yellow.Homogencous dyes is difficult to realize black, thereby needs the mixing of a plurality of dyestuffs to make that the photoabsorption of visible-range is a constant, again according to the sensitivity of human eye to light, reach the 420-680nm wave band and evenly absorb, and just can be referred to as black.
When the direction of vibration of polarized light is consistent with the long axis direction of dye molecule, the absorption of light takes place, and this dyestuff is called positivity dyestuff (P type dye), when the direction of vibration of polarized light is consistent with the long axis direction of dye molecule, do not absorb, then this dyestuff is called negative dyes (N type dye).The dichroism of N type dye has only the P type dye about half, so general P type is in the majority.
As everyone knows, the required driving voltage of the liquid-crystal display that electro-optic threshold is low is low, can effectively cut down the consumption of energy, and what especially this index seemed in making battery-powered liquid crystal display device is particularly outstanding.In VA-LCD, in order to cut down the consumption of energy, a kind of method is to adopt lower pre-tilt to arrange in the making of indicating meter, but can make the contrast gradient of VA-LCD descend like this; Another kind method is to use the strong liquid crystal of dielectric anisotropy, but the nematic phase that is used for the liquid crystal of indicating meter at present mostly is positivity, and having only small part is the negativity nematic phase, and the nematic negative dielectric anisotropic of negativity can only reach-6.0.Therefore, develop the lower composition of negative dielectric anisotropic and could satisfy the requirement that cuts down the consumption of energy effectively.Because the various performance parameters optimization of mixed liquid crystal material is contradiction, mutual restriction and influence each other each other, liquid crystal will reach has extremely low negative dielectric to cut down the consumption of energy, has wide working temperature simultaneously, wide visual angle, high and contrast gradient uniformly, and require main body liquid crystal and dyestuff mutual solubility good, also have very big difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of liquid crystal compound with extremely low negative dielectric anisotropic, make the indicating meter driving voltage of making low, effectively cut down the consumption of energy, wide working temperature, wide visual angle, liquid crystal compound of the present invention also can have good mutual solubility with dyestuff, so that the interpolation dyestuff, host and guest's liquid-crystal display of making has high contrast gradient.
The liquid crystal compound that the present invention has low negative dielectric contains general formula I, II, III, IV, V compounds, and the weight of classes of compounds consists of: compound of Formula I 70%-90%, formula II compound 0-20%, compound of formula III 5-25%, general formula I V compound 0-10%, general formula V compound 1-15%; Each structural formula of compound is as follows:
The chemical structure of general formula of above-described five compounds is as follows:
Figure G2009100358881D0000021
Figure G2009100358881D0000031
Wherein,
R 1～R 10Be independently selected from C respectively nH 2n+1, C nH 2n-1, C nH 2n+1O or C nH 2n-1O, n are 1～7 integer;
Z be selected from singly-bound ,-COO-,-CH 2O-,-C 2H 4-or-C ≡ C-group ,-CH 2O-,-C 2H 4One or more H atoms in the-group can by halogen atom-F ,-Cl or-Br replaces;
L 1, L 2Represent independently respectively hydrogen atom, cyano group ,-F ,-Cl or-the Br atom;
Figure G2009100358881D0000032
Be selected from phenylene, cyclohexyl, dioxane base, cyclohexenyl, fluoro phenylene or two fluoro phenylenes respectively individually;
Figure G2009100358881D0000033
Be selected from phenylene, cyclohexyl, dioxane base, fluoro phenylene, cyanogen for phenylene, cyclohexenyl or
Figure G2009100358881D0000034
M is 1 or 2;
M1, m2, m3, m4 are independently selected from 0 or 1 respectively, and m1 and m2 are not 0 simultaneously, and m3 and m4 are not 0 simultaneously.
M5 is 0,1 or 2;
In the above general formula I compounds, each group optimum condition be:
Z be singly-bound ,-COO-or-C ≡ C-;
R 1, R 2Be selected from alkyl or alkoxyl group independently of one another;
L 1, L 2Be selected from-F or cyano group,
Figure G2009100358881D0000035
Be independently selected from phenylene, cyclohexyl or fluoro phenylene respectively, m1 is 1, and m2 is 0 or 1, and m1 and m2 are not 0 simultaneously.
Wherein be preferably one or more compounds of following Ia～Ip:
Figure G2009100358881D0000051
Wherein be more preferably one or more compounds among Ia, Ib, Ie, Ih, Ik, Im, Io, the Ip, most preferred is one or more compounds among Ia, Ih, Ik, Io, the Ip.
In the general formula I I compounds, the optimum condition of each group is:
R 3And R 4Be alkyl,
Figure G2009100358881D0000052
Be cyclohexyl, Z be singly-bound or-C 2H 4
Wherein the II compounds is preferably with one or more compounds among following formula IIa～IIc:
Figure G2009100358881D0000053
Wherein most preferably be at least a compound in the formula IIa class.
In the general formula III compounds, each group optimum condition be:
R 5And R 6Be independently selected from alkyl or alkoxyl group respectively;
Figure G2009100358881D0000061
Be independently selected from phenylene or cyclohexyl respectively;
Figure G2009100358881D0000062
Be phenylene; Z be selected from singly-bound ,-C 2H 4-or-C ≡ C-.
Wherein the III compounds is preferably one or more compounds among following formula III a～IIIg:
Figure G2009100358881D0000063
Wherein be more preferably at least a compound among IIIa, IIIb, IIIc, IIId, the IIIf; Most preferably be at least a compound among IIIa, IIIb, the IIIf, R wherein 5The expression alkyl.
The optimum condition of general formula I V compounds is:
R 7, R 8Be independently selected from alkyl or alkoxyl group respectively;
Figure G2009100358881D0000064
Be selected from cyclohexyl; Be selected from phenylene, cyclohexyl, fluoro phenylene, cyanogen for phenylene
Or
Figure G2009100358881D0000071
L 1, L 2For-F or cyano group;
Wherein the IV compounds is preferably one or more compounds among formula IVa～IVi:
Figure G2009100358881D0000072
Figure G2009100358881D0000081
One or more compounds among formula IVa, IVb, IVe, IVg, the IVh more preferably wherein;
One or more structural formulas during general formula V compounds is preferably below Va～Vb:
Figure G2009100358881D0000082
R wherein 9, R 10All be selected from alkyl.
The said liquid crystal compound with low negative dielectric of the present invention also contains the dichroism combination dyestuff by the dye monomer preparation of azo class or anthraquinone class, wherein, the weight ratio of liquid crystalline cpd and said dichroism combination dyestuff is 100: 0.5～10, be preferably 100: 0.8～and 8.
The monomer of liquid crystal compound of the present invention mostly has lower negative dielectric anisotropic, and the dielectric anisotropy that liquid-crystal composition is born is extremely low, and driving voltage is extremely low, can effectively cut down the consumption of energy, and makes more permanent supply of powered battery type liquid-crystal display (calling LCD in the following text).The present invention is by optimum combination and optimize proportioning, and the negative dielectric anisotropic of liquid crystal compound can reach-9.5, and clearing point is 95～110 ℃, has good mutual solubility between each monomer, and good to the solvability of dichroic dye; Multiple single dichroic dye is mixed with various optimized proportion, can make distinct colors such as purple, blueness, black, add in this liquid crystal compound, the solubleness height, have good absorbancy and dichroic ratio, thereby can realize well that in demonstration dark attitude is darker, improve the demonstration contrast gradient greatly.The dye liquid crystal indicating meter places-30 ℃ to preserve no crystalline polamer, still can embody good dichroism under the low temperature.Use this liquid crystal compound, can be backlight or the difference of display format according to VA-LCD (negative liquid crystal indicating meter), freely select the color of dye liquid crystal, wherein black dyes is a definite value in wide wavelength region internal absorption factor, aberration is little, color shows the contrast gradient height, and versicolor contrast gradient is roughly the same, and display effect is even.
The general negative liquid crystal of light transmission rate after adopting the VA-LCD of this dye liquid crystal mixture to power up is lower, thereby the good contrast gradient of performance in demonstration, except that being used for liquid-crystal display, also can be used as the liquid crystal cell in the light valve device, can be used for transmission-type (for example vehicle audio indicating meter) or reflective (for example automobile rearview mirror) display element.When being applied to automobile rear vision mirror with an automatic light meter, gray scale is adjustable, utilizes that dyestuff absorbs the light intensity that a large amount of light reduce specular reflection when powering up, and reaches antidinic effect, so that can see the things of back clearly clearly from minute surface under high light, avoids traffic accident.
Description of drawings
Fig. 1 represents the spectrum transmitting curve of various homogencous dyes.
Embodiment
Further confirm every performance of host and guest's liquid-crystal composition of being mixed with by liquid crystal compound of the present invention and dichroic dye below by specific examples.
Dyestuff in host and guest's liquid-crystal composition can be by the single dichroic dye (dyestuff of azo class or anthraquinone class, be outsourcing) be mixed with the combination dyestuff, and with liquid crystal compound of the present invention, below be several single dichroic dyes (dyestuff of azo or anthraquinone class is outsourcing):
Dichroic dye HB-I: Huang, azo class
Dichroic dye HB-II: red, the anthraquinone class
Dichroic dye HB-III: purple, anthraquinone class
Dichroic dye HB-IV: indigo plant, anthraquinone class
Dichroic dye HB-V: dark blue, the anthraquinone class
Above-mentioned each homogencous dyes is formulated in respectively in the parent liquid crystal compound, be poured in the testing cassete, test the transmitance of each dyestuff at the 380-780nm wave band to different wavelengths of light, each homogencous dyes spectrum transmitting curve is seen Fig. 1, and Fig. 1 has represented absorption bands and the receptivity of each homogencous dyes to the 380-780nm band of light.
As required, select wherein that some kinds of homogencous dyes are mixed with dichroic dye composition, take mode such as heating, ultrasonic wave, suspension and main body liquid crystal of the present invention to be mixed in proportion, to dissolve, obtain the dichroic dye liquid-crystal composition.
The indicating meter that is used to test liquid crystal property contains two substrates that are coated with transparency electrode, host and guest's liquid-crystal composition is filled between two substrates, electrode surface is coated with tilt angle can reach 70～95 ° special construction oriented layer, the surface can make liquid crystal molecule almost arrange perpendicular to glass substrate, and liquid crystal molecule forms 90 ° distortion under the situation of energising between two substrates.
Among each comparative example and the embodiment,, use the unit structure of the listed coded representation liquid crystalline cpd of table 1 below for ease of the expression of each liquid crystalline cpd:
The unit structure code of table 1 liquid crystalline cpd
Figure G2009100358881D0000101
Equally, for ease of explanation, each test event is represented with code name, is the corresponding respectively test event of each code name below:
The code name test event
TN-I (℃) clearing point (to row-isotropic phase transition temperature)
Visc. (mm 2S -1) kinetic viscosity (mm 2S -1, 20 ℃, except as otherwise noted)
The common specific refractory power of no (589nm, 20 ℃)
Δ n optical anisotropy (589nm, 20 ℃)
Δ ε dielectric anisotropy (1KHz, 25 ℃)
λ max maximum absorption wavelength (nm, 25 ℃)
Wherein,
The condition determination of dielectric anisotropy Δ ε: the mixed liquid crystal material is filled in the liquid-crystal display with the mode that vacuum sucks, and temperature is 25 ± 2 ℃, drives with sinusoidal wave (1KHz) and tests;
Kinetic viscosity Visc uses cone-and-plate viscometer to test;
Specific refractory power and specific refractory power anisotropy use Abbe refractometer under sodium lamp (589nm) light source, probe temperature is 20 ℃.
In the present invention if no special instructions, described ratio is weight ratio, and all temperature are degree celsius temperature.
Reference examples
This example is used for carrying out performance comparison with liquid-crystal composition of the present invention.The composition of its main body liquid crystalline cpd and the proportioning of dyestuff see Table 1-1, and the test result of performance test sees Table 1-2.
Table 1-1 reference examples is formed and proportioning
Liquid crystalline cpd (with coded representation) Weight part
??3AAEPA4 ??3
??3AAEPA3 ??3
??3AAEPA5 ??3
??3AAEA3 ??5
??4AAEA5 ??4
??3AMO2 ??14
??5AMO2 ??8
??2APMO2 ??11
??3AMO4 ??20
??5AAMO2 ??8
??4AAMO2 ??9
??3AAMO3 ??9
??4AA3 ??3
Dye composite ??1.5
Table 1-2 reference examples performance test data
Test event Data
??TN-I(℃) ??101
??Δn(589nm，20℃) ??0.096
??ne(589nm，20℃) ??1.574
??no(589nm，20℃) ??1.478
??Viscosity(mm 2·s -1，20℃) ??43.0
??Δε(1KHz，25℃) ??-6.0
??λmax(nm) ??590
Embodiment 1
Among the negativity main body liquid crystal 100g of the present invention, add the mixing purple dye-1 that the dichroic dye monomer is formed, form dye liquid crystal, it forms proportioning as table 2-1.
Mix consisting of of purple dye-1 (1.6g):
Dichroic dye HB-I:0.2000g
Dichroic dye HB-III:0.8000g
Dichroic dye HB-IV:0.6000g
The main body liquid crystal of table 2-1 embodiment 1 is formed and proportioning
Liquid crystalline cpd (with coded representation) Weight part
??3AAEMO2 ??6
??3AEMO1 ??20
??4AAEAA3 ??3
??5AAEAA3 ??3
??3AMO2 ??10
??2AMPO2 ??8
??3AMO4 ??9
??5AMO4 ??9
Liquid crystalline cpd (with coded representation) Weight part
??3AAMO2 ??7
??5AAMO2 ??6
??4AAMO2 ??7
??3AAMO3 ??6
??3AAM1 ??6
Mix purple dye-1 ??1.6
Dye liquid crystal is filled between the two substrates of liquid-crystal display, carries out performance test, data see Table 2-2.
Table 2-2 embodiment 1 performance test data
Test event Data
??TN-I(℃) ??100
??Δn(589nm，20℃) ??0.098
??ne(589nm，20℃) ??1.574
??no(589nm，20℃) ??1.476
??Viscosity(mm 2·s -1，20℃) ??53.0
??Δε(1KHz，25℃) ??-7.4
Color Purple
??λmax(nm) ??580
Embodiment 2
Among the negativity main body liquid crystal 100g of the present invention, add the mixing blue dyes of being made up of the dichroic dye monomer-2, form dye liquid crystal, it forms proportioning as table 3-1.
Mix consisting of of blue dyes-2 (1.9g):
Dichroic dye HB-I:0.2000g
Dichroic dye HB-III:0.2000g
Dichroic dye HB-IV:1.5000g
The main body liquid crystal of table 3-1 embodiment 2 is formed and proportioning
Liquid crystalline cpd (with coded representation) Weight part
??3AAEMO2 ??6
??3AEMO1 ??18
??4AAEAA3 ??2
??3AAEM1 ??7
??3AMO2 ??7
??2APMO2 ??5
??3AMPO2 ??5
??3PMP2 ??3
??3AMO4 ??6
??5AMO4 ??8
??3AW(5) ??8
??3AAMO2 ??7
??5AAMO2 ??6
??4AAMO2 ??6
??3AAMO3 ??6
Mix blue dyes-2 ??1.9
Dye liquid crystal is filled between the two substrates of liquid-crystal display and carries out performance test, data see Table 3-2.
Table 3-2 embodiment 2 performance test data
Test event Data
??TN-I(℃) ??98
??Δn(589nm，20℃) ??0.096
Test event Data
??ne(589nm，20℃) ??1.572
??no(589nm，20℃) ??1.476
??Viscosity(mm 2·s -1，20℃) ??62
??Δε(1KHz，25℃) ??-8.5
Color Blue
??λmax(nm) ??635
Embodiment 3
Among the negativity main body liquid crystal 100g of the present invention, add the mixing black dyes of being made up of the dichroic dye monomer-3, form dye liquid crystal, it forms proportioning as table 4-1.
Mix consisting of of black dyes-3 (2.0g):
Dichroic dye HB-I:0.4000g,
Dichroic dye HB-II:0.7500g,
Dichroic dye HB-IV:0.8500g;
The main body liquid crystal of table 4-1 embodiment 3 is formed and proportioning
Liquid crystalline cpd (with coded representation) Weight part
??3AAEMO2 ??8
??3AEMO1 ??13
??4AAEAA3 ??1
??5PTM3 ??3
??3AAEN1 ??5
??3PPEN2 ??4
??3AMO2 ??7
??2APMO2 ??5
??3AMPO2 ??5
Liquid crystalline cpd (with coded representation) Weight part
??3AMO4 ??8
??5AMO4 ??8
??3AW(5) ??8
??5AAMO2 ??8
??4AAMO2 ??8
??3AAMO3 ??9
Mix black dyes-3 ??2.0
Carry out performance test data between being filled into it between the two substrates of liquid-crystal display and see Table 4-2.
Table 4-2 embodiment 3 performance test data
Test event Data
?TN-I(℃) ??97
?Δn(589nm，20℃) ??0.098
?ne(589nm，20℃) ??1.573
?no(589nm，20℃) ??1.475
?Viscosity(mm 2·s -1，20℃) ??64
?Δε(1KHz，25℃) ??-9.2
Color Black
?λmax(nm) ??400～660
Embodiment 4
Among the negativity main body liquid crystal 100g of the present invention, add the mixing black dyes of being made up of the dichroic dye monomer-4, form dye liquid crystal, it forms proportioning as table 5-1.
Mix consisting of of black dyes-4 (2.255g):
Dichroic dye HB-I:0.4500g
Dichroic dye HB-II:0.8500g
Dichroic dye HB-V:0.9550g
The main body liquid crystal of table 5-1 embodiment 4 is formed and proportioning
Liquid crystalline cpd (with coded representation) Weight part
??3AAEMO2 ??6
??4AAEAA3 ??1
??3PPTM2 ??4
??3AEMO1 ??9
??3DAO1 ??3
??3GA3 ??2
??3AAEN1 ??5
??3PPEN2 ??4
??3AMO2 ??7
??2APMO2 ??5
??3AMPO2 ??5
??3AMO4 ??8
??5AMO4 ??8
??3AW(5) ??8
??5AAMO2 ??8
??4AAMO2 ??8
??3AAMO3 ??9
Mix black dyes-4 ??2.255
It is filled between the two substrates of liquid-crystal display carries out performance test, data see Table 4-2.
Table 5-2 embodiment 4 performance test data
Test event Data
??TN-I(℃) ??96
??Δn(589nm，20℃) ??0.094
??ne(589nm，20℃) ??1.571
??no(589nm，20℃) ??1.477
??Viscosity(mm 2·s -1，20℃) ??67
??Δε(1KHz，25℃) ??-9.5
Color Black
??λmax(nm) ??400～670
From the test data of above reference examples and each embodiment as seen, the negative dielectric anisotropic of dye liquid crystal composition of the present invention is all far below-6.0 of reference examples, and minimum reaching-9.5 reduced by 40% to 58% with respect to the dielectric of reference examples.Dye liquid crystal indicating meter of the present invention only needs the 1.2V driving voltage, can normally show, and the reference examples driving voltage needs 2.2V.Use the display element of dye liquid crystal of the present invention, greatly reduce to carrying out switching required driving voltage between the optical states in the liquid crystal cell.Effectively cut down the consumption of energy, this advantage is particularly outstanding in the powered battery escope, the battery durable, and can keep the contrast gradient height, and operating temperature range is wide, and response is fast, the every field that can be applied to show.
The one-tenth of liquid crystal compound that above embodiment is related and dichroism mixing colouring agent and proportioning only are used to illustrate the present invention, are not used in limiting the scope of the invention.

Claims (12)

1. the liquid crystal compound that has low negative dielectric is characterized in that containing general formula I, II, III, IV, V class liquid crystalline cpd, and the classes of compounds general structure is as follows:
Figure F2009100358881C0000011
Wherein, R 1～R 10Be selected from C independently of one another nH 2n+1, C nH 2n-1, C nH 2n+1O or C nH 2n-1O, n are 1～7 integer;
Z be selected from singly-bound ,-COO-,-CH 2O-,-C 2H 4-or-C ≡ C-group ,-CH 2O-,-C 2H 4One or more H atoms in the group can by halogen atom-F ,-Cl or-Br replaces;
L 1, L 2Represent independently of one another hydrogen atom, cyano group ,-F ,-Cl or-the Br atom;
Figure F2009100358881C0000012
Be selected from phenylene, cyclohexyl, dioxane base, cyclohexenyl, fluoro phenylene or two fluoro phenylenes respectively individually;
Figure F2009100358881C0000013
Be selected from phenylene, cyclohexyl, dioxane base, fluoro phenylene, cyanogen for phenylene, cyclohexenyl or
Figure F2009100358881C0000014
M is 1 or 2;
M1, m2, m3, m4 are selected from 0 or 1 independently of one another, and m1 and m2 are not 0 simultaneously, and m3 and m4 are not 0 simultaneously.
M5 is 0,1 or 2;
The weight percentage of classes of compounds is: compound of Formula I 70%-90%, formula II compound 0-20%, compound of formula III 5-25%, general formula I V compound 0-10%, general formula V compound 1-15%.
2. the liquid crystal compound with low negative dielectric according to claim 1 is characterized in that in the said general formula I compounds:
Z be singly-bound ,-COO-or-C ≡ C-;
R 1, R 2Be selected from alkyl or alkoxyl group independently of one another;
L 1, L 2Be selected from-F or cyano group,
Figure F2009100358881C0000021
Be selected from phenylene, cyclohexyl or fluoro phenylene independently of one another, m1 is 0 or 1, and m2 is 0 or 1, and m1 and m2 are not 0 simultaneously.
3. the liquid crystal compound with low negative dielectric according to claim 2 is characterized in that one or more compounds that said general formula I compounds is Ia～Ip:
Figure F2009100358881C0000022
Figure F2009100358881C0000031
4. the liquid crystal compound with low negative dielectric according to claim 3 is characterized in that said general formula I compounds is one or more compounds among formula Ia, Ib, Ie, Ih, Ik, Im, Io, the Ip; Be preferably the general formula I compounds and be one or more compounds among Ia, Ih, Ik, Io, the Ip.
5. the liquid crystal compound with low negative dielectric according to claim 1 is characterized in that said general formula I I compounds is one or more compounds among formula IIa～IIc:
Wherein be preferably at least a compound in the formula IIa class.
6. the liquid crystal compound with low negative dielectric according to claim 1 is characterized in that in the said general formula III compounds:
R 5And R 6Be independently selected from alkyl or alkoxyl group respectively;
Figure F2009100358881C0000042
Be independently selected from phenylene or cyclohexyl respectively;
Figure F2009100358881C0000043
Be phenylene; Z be selected from singly-bound ,-C 2H 4-or-C ≡ C-.
7. the liquid crystal compound with low negative dielectric according to claim 6 is characterized in that said general formula III compounds is one or more compounds among formula III a～IIIg:
Figure F2009100358881C0000044
Figure F2009100358881C0000051
8. the liquid crystal compound with low negative dielectric according to claim 7, it is characterized in that said general formula III compounds is at least a compound among IIIa, IIIb, IIIc, IIId, the IIIf, is preferably at least a compound among general formula III a, IIIb, the IIIf.
9. the liquid crystal compound with low negative dielectric according to claim 1 is characterized in that in the said general formula I V compounds:
R 7, R 8Be selected from alkyl or alkoxyl group independently of one another;
Figure F2009100358881C0000052
Be selected from cyclohexyl;
Figure F2009100358881C0000053
Be selected from phenylene, cyclohexyl, fluoro phenylene, cyanogen for phenylene or
Figure F2009100358881C0000054
L 1, L 2For-F or cyano group.
10. the liquid crystal compound with low negative dielectric according to claim 9 is characterized in that said general formula I V compounds is one or more compounds among formula IVa～IVi:
Figure F2009100358881C0000061
Figure F2009100358881C0000071
Wherein being preferably general formula I V compounds is one or more compounds among formula IVa, IVb, IVe, IVg, the IVh.
11., it is characterized in that said general formula V compounds is one or more compounds among formula Va, the Vb according to each described liquid crystal compound in the claim 1～10 with low negative dielectric:
R wherein 9, R 10All be selected from alkyl.
12. the liquid crystal compound with low negative dielectric according to claim 1, it is characterized in that containing dichroism combination dyestuff by the dye monomer preparation of azo class or anthraquinone class, the weight ratio of liquid crystalline cpd and said dichroism combination dyestuff is 100: 0.5～10, be preferably 100: 0.8～and 8.
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