CN100338506C - Multistable state liquid srystal material display and preparation method thereof - Google Patents

Multistable state liquid srystal material display and preparation method thereof Download PDF

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CN100338506C
CN100338506C CNB021007373A CN02100737A CN100338506C CN 100338506 C CN100338506 C CN 100338506C CN B021007373 A CNB021007373 A CN B021007373A CN 02100737 A CN02100737 A CN 02100737A CN 100338506 C CN100338506 C CN 100338506C
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CN1434331A (en
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姚乃燕
张智勇
康杰
邓友节
朱凯培
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Shijiazhuang Yongshenghuaqing Liquid Crystal Co Ltd
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Abstract

The present invention relates to a multistable state liquid crystal material display and a preparation method thereof, the multistable state liquid crystal material display has permanent memory character, and a helical pitch does not change following the variation of temperature. The multistable state liquid crystal material display comprises at least chiral composition (a first component) composed of chiral compounds represented by general formulas (I) to (III) and nematic liquid crystal composition (a second component) composed of liquid crystal compounds represented by general formulas (IV) to (XII) and a liquid crystal display produced by the multistable liquid crystal materials. The multistable liquid crystal material display has the advantages of low operating voltage and low viscosity; the helical pitch does not change following the variation of the temperature within the temperature range of a cholest phase state; the present invention has the permanent memory character, and can meet the development and the requirement of multistable liquid crystal display technology.

Description

Multistable Liquid Crystal Material Display And Preparation Method
What the present invention relates to is a kind of Multistable Liquid Crystal Material Display And Preparation Method, specifically, what the present invention relates to is a kind ofly to comprise chipal compounds and chiral composition thereof, have wide temperature, high birefringence rate, the multistable state liquid srystal material display of big dielectric anisotropy.
As everyone knows, multistable state liquid srystal material and display thereof have the advantages that displaying contents remains unchanged for a long time, energy consumption is extremely low under zero electric field, adopt the display of this material preparation can realize many continuous gray scale adjustings, high luminosity, high-contrast, wide visual angle (visual angle than STN-LCD and TN-LCD etc. is wide); The display that adopts described material preparation is that videoscanning shows, therefore is not subjected to the row, column numerical limitations, can realize that high density, high definition show; Also because the display of this kind form does not need polaroid, backlight and filter coating, make that this multistable display manufacture craft is simple, yield rate is high, production cost is low, so multistable state liquid srystal material is very well liquid crystal display materials of class market outlook.
The displaying principle of multistable state liquid srystal material and display thereof is disclosed among the Annual Reviews Materials Science 27:117-146 (1997); The indicating characteristic of multistable state liquid srystal material and display thereof is disclosed among Appl.Phys.Lett.64:1905 (1992), U.S. Pat 5889566, US5933203 and the Chinese patent CN1184534 (application number 96193977).
U.S. Pat 5933203, US5731859, US6061107, US5570216 disclose the performance of multistable state liquid srystal material.But multistable state liquid srystal material wherein all is nematic phase mixed liquid crystal and the chiral additives S811 that purchases from the market, and R1011 and CB15 modulation form.Because the restriction of chiral additives makes the spiral shell square of its liquid crystal material and spiral shell square thereof bigger with the change of temperature, operating voltage is mostly more than 35V, and the modulation of birefraction (Δ n) also is subjected to great restriction, can't satisfy the display technique demand for development.
Recently, Jap.P. JP11,323,342, JP11,305,187 and JP2000,129,261 also disclose multi-steady state liquid crystal display, have proposed requirement and preparation technique thereof to liquid crystal material from the angle of display technology research.But do not see the report of relevant multistable state liquid srystal material exploitation aspect.
Chinese patent CN1223657A and CN1257532A disclose chiral dopant and low viscosity liquid crystal material and other cholesteric liquid crystal, wherein relate to chiral nematic phase or cholesteric liquid-crystal composition or the material relevant or similar with multistable state liquid srystal, but all only be confined in a certain respect, preparation, combined method and the performance of multistable state liquid srystal material do not carried out system research and development.
The object of the present invention is to provide a kind of multistable state liquid srystal material display, described display adopts that operating voltage is low, viscosity is low, in cholesteric phase attitude temperature range (50 ℃-100 ℃), the spiral shell square is not formed with temperature change, multistable liquid crystal material composition with long-term memory characteristic, can satisfy the development and the requirement of multistable state liquid srystal display technique.
Another object of the present invention is to provide a kind of preparation method of described multistable state liquid srystal material display.
Purpose of the present invention can be achieved by mode once: a kind of multistable state liquid srystal material display, it is characterized in that described display employing has long-term memory characteristic, spiral shell square and do not prepare with the multistable liquid crystal material composition of temperature change, between 0.1500-0.2800, operating voltage is between 10-35V for its birefraction (Δ n); Described display is long-term displayed image or the content of keeping when zero electric field; Described display comprises:
A). the chipal compounds that is selected from least a general formula shown in the general formula (I)～(III) is first component, and described first components contents is the 5-40wt% of multistable liquid crystal material composition;
Figure C0210073700091
In general formula I～III:
R 1～R 3Be alkyl, alkenyl or the alkoxy with 1-13 carbon atom, the optional methylene in this alkyl or the alkene can be replaced by oxygen atom, but two or more methylene can not be replaced continuously by oxygen atom.
R 4, R 5Be the alkyl that has only 2-10 carbon atom, ring A～F structure is separate anti-form-1,4-cyclohexyl, 1,4-phenylene, pyrimidine-2,5-two bases.
Z 1～Z 4Be singly-bound ,-CO 2-or oxygen atom; X=F, CN or contain the alkyl of 1-5 carbon;
L 1～L 2Be respectively H or F atom;
M, n, l and k are respectively 0,1 or 2.
B) compound that is selected from least a general formula in the low viscosity shown in the general formula (IV)～(IX), the wide temperature liquid-crystal compounds is as second component, and described second components contents is 60-95wt%;
Figure C0210073700092
Among general formula I V～IX:
R 1-R 8Be alkyl or alkenyl with 1-12 carbon atom, or alkoxy; Ring A-F is respectively separate anti-form-1, the 4-cyclohexylidene,, 1,4-phenylene, pyrimidine-2.5-two bases, 1, the arbitrary group in the 3-dioxan base;
L 1-L 6Be respectively H, F or Cl; X and Y are respectively F, CN, NCS, CF 3, Cl, OCF 3, OCHF 2, C 1-C 7Straight chained alkyl or alkoxy; Z=CO 2, CH 2O ,-CH 2CH 2-or singly-bound ,-OCO-,-OCH 2-, m, n, l, q, j, r are respectively 1 or 2, k is 0 or 1.
Wherein said second component further comprises high birefringence rate shown at least a general formula X～XII or big dielectric anisotropy compound:
Figure C0210073700101
In general formula X～XII:
R 1-R 3Be 1-15 straight chained alkyl or alkenyl, wherein MU (methylene unit) can be replaced by oxygen atom, or the hydrogen atom on the methylene is replaced by fluorine atom; Z is CO 2,-CH 2CH 2-or singly-bound; L 1-L 7Independent respectively is H, F or Cl atom, ring A and C are independent respectively to be anti-form-1,4-two cyclohexylidenes, 1,4-phenylene or the phenylene, pyrimidine-2.5-two bases, 1 that have one or two hydrogen atom to be replaced by fluorine atom, 3-dioxan-2, a group in 5-two bases, ring B are respectively 1,4-phenylene or the phenylene, pyrimidine-2.5-two bases, 1 that have one or two hydrogen atom to be replaced by fluorine atom, 3-dioxan-2,5-two bases; M, n is respectively 0,1, and 2; K is 0 and 1; Y 1And Y 3Be respectively CN, F, NCS, OCF 3, CF 3, OC 2H 5, OCH 3, OC 3H 7, OCHF 2Deng; Y 2Be CN or NCS base.
Among the present invention, preferably the compound with at least two kinds of general formulas in the compound shown in the general formula (I)～(III) is first component; Two kinds of compounds can make up with arbitrary proportion, and for example every kind of compounds content is 5-95wt% (percentage by weight), and in selected scope, the total amount of two kinds of compounds is 100wt%, and described first components contents 5-40wt% that is liquid-crystal composition.
Also can be preferably be first component with the chipal compounds of each general formula shown in the general formula (I)～(III), selected each component composition is the ratio combination of content 1-95wt% by weight; The content of compound in first component that also can each class general formula is general formula (I): 5-55wt%; General formula (II): 5-45wt%; General formula (III): 5-65wt%; But ratio is in any case mixed, and the total amount of the composition that chipal compounds forms is 100%, and first components contents is the 5-40wt% of liquid-crystal composition.
The present invention finds, adopts first component of 3 represented category feature chipal compounds of at least a general formula (I)～(III) as chiral composition; Be generally the combination of 3 represented category feature chipal compounds of general formula (I)～(III) at least, at this moment the total content of each class general formula is (I): 5-55wt%; General formula (II): 5-45wt%; General formula (III): 5-65wt%.At least contain the chipal compounds among a kind of Ia-Ie of being selected from the chiral composition for example of the present invention, at least a chipal compounds that is selected among the IIa-IIc, and at least a chipal compounds that is selected from formula III a-IIIc.In preferred embodiments, at least aly be selected from the compound shown in the general formula (I), its content is 15-50%, at least a compound that is selected from general formula (II), its content is 15-50%, at least a compound that is selected from general formula (III), its content are 20-60%, and preferred 5-8 kind chipal compounds makes up.
In above-mentioned various embodiments, when comprising compound shown in the general formula (I) in first component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (I) in first component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (II) in first component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (II) in first component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (III) in the described liquid-crystal composition (first component), comprise the compound shown in 2 kinds of general formulas (III) in first component of described liquid-crystal composition at least.
Just when comprising compound shown in general formula I or II or the III in first component of described liquid-crystal composition, comprise 2 kinds in first component of described liquid-crystal composition at least and be selected from the compound shown in Ia-If or IIa-IIc or the IIIa-IIIc.
In addition, when comprising compound shown in general formula I or the III in first component of described liquid-crystal composition, comprise 3 kinds in first component of described liquid-crystal composition at least and be selected from the compound shown in formula Ia-If or the formula III a-IIIc.
In addition, when comprising compound shown in the general formula I in first component of described liquid-crystal composition, comprise at least in first component of described liquid-crystal composition that 4 kinds are selected from the compound shown in the formula Ia-Ief.
In addition, when comprising compound shown in the general formula I in first component of described liquid-crystal composition, comprise at least in first component of described liquid-crystal composition that 5 kinds are selected from the compound shown in the formula Ia-If.
In the general formula (I)～(III), described alkyl preferably has alkyl, the preferred separate anti-form-1 of ring A～F of 2-8 carbon atom, 4-cyclohexyl, 1,4-phenylene; L 1～L 2Be respectively H or F atom; Z 1～Z 4Preferred singly-bound or oxygen atom; The preferred F of X, CN or contain the alkyl of 3 carbon; M, n, l and k are respectively 0 or 1.
Wherein, first components contents is 5-40wt% in multistable state liquid srystal material display, preferred 10-30wt%, more preferably 10-25wt%.The described chipal compounds composition of its formula of (I)～(III) has certain spiral shell square, and its spiral shell square does not become with temperature change in the liquid crystal phase scope, be dp/dt＜0.01 μ m/ ℃ chiral composition, just first component of liquid-crystal composition of the present invention.
Among the present invention, the compound of at least two kinds of general formulas in the compound shown in preferred formula IV, V, VI, VII, the IX is second component; Two kinds of compounds can make up with arbitrary proportion, for example every kind of compounds content is 5-95wt% (percentage by weight), preferable range is 20-80wt%, more preferably scope is 40-60wt%, in selected scope, the total amount of two kinds of compounds is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, also the compound of at least three kinds of general formulas in the compound shown in preferred formula IV, V, VI, VII, the IX is second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, more preferably the compound of at least four kinds of general formulas in the compound shown in general formula I V, V, VI, VII, the IX is second component; The compound of four all general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, more preferably with general formula I Va～IVc, Va～Vm, VIa～VIk, VIIa～VIIk, the compound shown in each general formula is second component in the compound shown in IXa～IXw; Described compound can make up with arbitrary proportion, but the total amount of second component composition is 100wt%.Compounds content shown in the preferred formula IV is 3-25wt%, compounds content shown in the general formula V is 5-40wt%, compounds content shown in the general formula VI is 5-30wt%, and the compounds content shown in the general formula VII is 5-45wt%, and the compounds content shown in the general formula I X is 5-35wt%.
Among the present invention, can also with general formula I V, V, VI, VII, IX, X, XI, XII, shown in compound in the compound of at least three kinds of general formulas be second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, can also with general formula I V, V, VI, VII, IX, X, XI, XII, shown in compound in the compound of at least four kinds of general formulas be second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, can also with general formula I V, V, VI, VII, IX, X, XI, XII, shown in compound in the compound of at least five kinds of general formulas be second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, can also with general formula I V, V, VI, VII, IX, X, XI, XII, shown in compound in the compound of at least six kinds of general formulas be second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, can also with general formula I V, V, VI, VII, IX, X, XI, XII, shown in compound in the compound of at least seven kinds of general formulas be second component; The compound of three kinds of general formulas can make up with arbitrary proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is liquid-crystal composition.
Among the present invention, more preferably with IVa～IVc, Va～Vm, VIa～VIk, VIIa～VIIk, IXa～IXw, Xa～Xj, XIa～XIs, each compound of compound shown in XIIa～XIIw is second component; Described compound can make up with arbitrary proportion, but the total amount of second component composition is 100wt%.Compounds content shown in the preferred formula IV is 3-25wt%, compounds content shown in the general formula V is 5-40wt%, compounds content shown in the general formula VI is 5-30wt%, and the compounds content shown in the general formula VII is 5-45wt%, and the compounds content shown in the general formula I X is 5-35wt%.
Second components contents of the nematic phase liquid crystal composition that the low viscosity shown in the above-mentioned general formula (IV)～(IX), wide temperature liquid-crystal compounds are combined into is 60-95wt%.
In above-mentioned various embodiments, when comprising general formula compound shown in the general formula (IV) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (IV) in first component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising general formula compound shown in the general formula (V) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (V) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (VI) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (VI) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (VII) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (VII) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (IX) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (IX) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (X) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (X) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (XI) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (XI) in second component of described liquid-crystal composition at least.
In above-mentioned various embodiments, when comprising compound shown in the general formula (XII) in second component of described liquid-crystal composition, comprise the compound shown in 2 kinds of general formulas (XII) in second component of described liquid-crystal composition at least.
Just when comprising compound shown in general formula I V or V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 2 kinds are selected from the compound shown in IVa～IV or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
In addition, when comprising compound shown in general formula I V or V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 3 kinds are selected from the compound shown in IVa～IV or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
In addition, when comprising compound shown in general formula V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 4 kinds are selected from the compound shown in IVa～IVc or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
When comprising compound shown in general formula V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 5 kinds are selected from the compound shown in IVa～IVc or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
When comprising compound shown in general formula V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 6 kinds are selected from the compound shown in IVa～IVc or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
When comprising compound shown in general formula V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 7 kinds are selected from the compound shown in IVa～IVc or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
When comprising compound shown in general formula V or VI or VII or IX or X or XI or the XII in second component of described liquid-crystal composition, comprise at least in second component of described liquid-crystal composition that 8 kinds are selected from the compound shown in IVa～IVc or Va～Vm or VIa～Vik or VIIa～VIIk or IXa～Ixw or Xa～Xj or XIa～Xis or the XIIa～XIIw.
Among general formula I V, V, VI, VII, the IX, R 1-R 8The alkyl that preferably has 1-12 carbon atom; Ring A-F preferably is respectively separate anti-form-1,4-cyclohexylidene, 1,4-phenylene, pyrimidine-2.5-two bases, 1, appointing-group in the 3-dioxan base; L 1-L 5Be respectively H or F; X and Y preferably are respectively F, CN, NCS, CF 3, OCF 3, OCHF 2, C 1-C 7Straight chained alkyl or alkoxy; The preferred CO of Z 2, CH 2O ,-CH 2CH 2-or singly-bound-OCH 2-; M, n, l, q, j, r, k difference preferred 0 or 1.
R among general formula X, XI, the XII 1-R 3Be the 1-10 straight chained alkyl; Z is preferably CO 2,-CH 2CH 2-or singly-bound; L 1-L 7Preferably be respectively H or F, ring A and C are respectively anti-form-1,4-two cyclohexylidenes, 1,4-phenylene or the phenylene, pyrimidine-2.5-two bases, 1 that have one or two hydrogen atom to be replaced by fluorine atom, 3-dioxan-2, a group in 5-two bases, ring B are respectively 1,4-phenylene or the phenylene that has a hydrogen atom to be replaced by fluorine atom; M is preferably 1, and n preferably is respectively 0 or 1; K is preferably 0 and 1; Y 1Preferably be respectively CN, F, C 1-C 5Alkyl, OC 2H 5, OCH 3Or OC 3H 7Y 2Be preferably CN or NCS base; Y 3Preferably be respectively CN, F, NCS or OCHF 2
Among the present invention, the represented compound of 5-7 kind general formula in eight kinds of structures shown in preferred IV, V, VI, VII, IX, X, XI, the XII is combined as second component, but selected each general formula all has more than and is defined as a kind of structure, can change the compound that obtains for multiple substituting group; Preferred 12-24 kind combination of compounds.
Researchist of the present invention finds, the prerequisite of the described multistable state liquid srystal display material marketization is to widen operating temperature range, reduces its driving voltage, improves response speed, specifically: for yellowish green pattern showed, the Bragg reflection wavelength was 500～650nm; Contrast is higher than 20: 1, operating temperature range-10 ℃-+55 ℃; The temperature dependency of pitch little (dp/dT is little, less than 0.01 μ m/ ℃); Threshold voltage＜the 50V of homeotropic alignment (better being less than 30V, the thick 4-5 μ of box m); Line scan speed 4ms.Mixed liquid crystal can keep all even chemically stable of component for a long time, reach this target, and the selection of liquid crystal material is vital; Therefore, how optimization of C makes up, and makes the various aspects of performance of mixed liquid crystal all have best performance will be directly connected to the progress that multistable shows the marketization.To this, researchist of the present invention goes to consider the combination and the design of mixed liquid crystal from following seven aspects:
(1) liquid crystal operating temperature range and photoelectric properties are to Temperature Influence.In the multistable prescription, comprise of the last existence great negative effect of nearly about 20% the chiral material of total content to liquid crystal phase transition temperature.Therefore, at first must improve the high cleaning point of liquid crystal phase in the prescription and the problem of temperature performance, the cleaning point of nematic liquid crystal material is reached more than 90 ℃, thus do not cause that the cleaning point that adds the cholesteric liquid crystal prescription behind the chiral monomer falls too low and can't working.
(2) reduce Δ ε and the Vth value that liquid crystal material is filled a prescription.Reducing aspect the driving voltage, except reduce box thick, main dielectric anisotropy Δ ε by the raising liquid crystal material reduces Vth, thereby obtains lower driving voltage.It is better to fall the threshold voltage effect when Δ ε 〉=20, must use the high polarity liquid-crystal compounds for this reason.
(3) viscosity of reduction liquid crystal is to improve the key of the response speed of multi-steady state liquid crystal display.Because multistable shows response speed is had higher requirement, the viscosity of liquid crystal material is its major influence factors, and the rotary viscosity coefficient of chiral liquid crystal is bigger, therefore, when liquid crystal material is developed, also will quite pay close attention to the control of viscosity.According to viscosity relationship formula (log η=∑ c iLog η 1) as can be known: the viscosity logarithm and the content sum of products of the logarithm of mixed liquid crystal viscosity and each liquid-crystal compounds are linear, and the viscosity of liquid-crystal compounds is relevant with its molecular structure and molecular polarity.
(4) adjusting of refractive index.In order to satisfy the multistable display requirement, we must be adjusted to the refractive index of liquid crystal the numerical value about 0.15～0.250, to obtain wideer visible light reflection wavestrip, use the big liquid-crystal compounds of optical anisotropy, improve birefraction (the Δ n=n of liquid crystal material e-n o) help reflecting wideer visible light wavestrip.Therefore, under the situation of considering the viscosity factor, must use high index of refraction nematic liquid crystal compound.
(5) adjusting of multistable state liquid srystal material pitch is crucial.The principal feature that multistable state liquid srystal is different from nematic liquid crystal is to have added a large amount of chiral liquid crystals in the material, thereby make its pitch satisfy visible light the Bragg reflection takes place.According to Bragg reflection formula (λ=np) and the distortion of (Δ λ=Δ np) and chiral material can formula (p=[(HTP) Xc] -1, the HTP value is that the distortion of chiral liquid crystal can constant, Xc is its content), finally determine the addition of chiral liquid crystal.And the addition of chiral liquid crystal is related to the threshold value of system, and viscosity and cleaning point etc. are all multifactor, should be when guaranteeing the Bragg reflected colour addition of chiral liquid crystal is dropped to minimum, therefore, must use the big chiral liquid crystal of HTP value as adjuvant.
(6) the dp/dT value of adjusting liquid crystal material.For the pitch of avoiding liquid crystal changes with variation of temperature, cause the reflected colour difference of display device under the different temperatures, influence its display quality.Must control dp/dT value very little in operating temperature range, can guarantee that just naked eyes can not observe the change of display color under different temperatures.
(7) cryogenic property adjustment.In order to guarantee the low-temperature working temperature of multi-steady state liquid crystal display, the adjusting of liquid crystal material cryogenic property is very important.For this reason, when guaranteeing that various performance parameters satisfy the display technique requirement, select the low-melting point liquid crystal compound that solubility property is better, heat of solution is less for use, adopt multi-component system to reduce eutectic point, to enlarge operating temperature range.
Therefore, the present invention is by the formulated in combination to chipal compounds and liquid-crystal compounds, provide a kind of operating voltage to be lower than 35V (it is following to be preferably 25V) with practical value, low viscosity, birefraction (Δ n) is greater than 0.15 (being preferably 0.18～0.23), in cholesteric phase attitude temperature range (50 ℃-100 ℃), the spiral shell square is not with (dp/dT＜0.01 μ m/ degree) of temperature change, viscosity under 20 ℃ is preferably≤250mPa.s, ℃-60 ℃ preferably at least-20 of this cholesteric phase temperature ranges, multistable state liquid srystal material and preparation thereof or combined method are with development and the requirement of satisfying the multistable state liquid srystal display technique.It mainly is to be used on quick multi-steady state liquid crystal display (FM-LCD) or bistable liquid crystal display and other cholesteric liquid crystal displays (CH-LCD), comprise in the LCD of pbz polymer polymer film, the present main application of this display is to be generalized in e-book and the commercial advertisement, in mobile communication, videophone, military equipment instrument very big application prospect is arranged.
Multistable state liquid srystal material prescription of the present invention carries out from three aspects: the wide temperature nematic liquid crystal of (1) preparation; (2) the big chiral composition of preparation HTP value; (3) above-mentioned substance is mixed into multistable state liquid srystal material.
Composition of the present invention is a kind ofly to have long-term memory characteristic, spiral shell square not with the demonstration multistable state liquid srystal material of temperature change, and between 0.1500-0.2800, operating voltage is between 10-35V for its birefraction (Δ n).Wherein:
Wherein, be hybridly prepared into the multistable state liquid srystal material with cholesteric phase by a certain percentage as the chiral composition of first component with as the composition of second component, the total amount of multistable state liquid srystal material display is 100%.Wherein first components contents is the 5-40wt% of multistable state liquid srystal material display, and preferred content is 10-30wt%, and more preferably content is 10-20wt%.Pei Zhi multistable state liquid srystal material can be realized the display mode of different colours by the incident light of reflection different wave length in the manner described above.Described multistable state liquid srystal material display of the present invention has that operating voltage is low, viscosity is low, in cholesteric phase attitude temperature range, the spiral shell square not with temperature change, have long-term memory characteristic, can satisfy the development and the requirement of multistable state liquid srystal display technique.
The characteristic of long-term maintenance displayed image or content when having zero electric field when adopting the multistable state liquid srystal material of aforesaid way preparation to be used for LCD, its operating voltage can be controlled in the 35V.
The present invention finds that can reach above-mentioned purpose of the present invention by following mode, composition promptly of the present invention can adopt first component of 3 represented category feature chipal compounds of at least a general formula (I)～(III) as chiral composition; The preferably combination of the represented 3 category feature chipal compounds of general formula (I)～(III) at least, the total content of each class general formula is (I): 1-55wt%; General formula (II): 5-45wt%; General formula (III): 5-65wt%; Preferred 5-8 kind chipal compounds makes up.At least contain the chipal compounds among a kind of Ia-Ie of being selected from the chiral composition of the present invention, at least a chipal compounds that is selected among the IIa-IIc, and at least a chipal compounds that is selected from formula III a-IIIc.In its particularly preferred embodiment, at least a content that is selected from the general formula (I) is 5-15%, and at least a content that is selected from general formula (II) is 5-35%, and at least a content that is selected from general formula (III) is 15-45%.These chipal compounds are:
Figure C0210073700161
Figure C0210073700171
Above-mentioned general formula I a～If, among general formula I Ia～IId and the general formula III a～IIIc:
R 1-R 22Be the alkyl with 2-10 carbon atom, the optional methylene that has only in this alkyl can be replaced by oxygen atom.
L 1～L 2=H or F.
In the composition of the represented chipal compounds of general formula I a～If, general formula I Ia～IId and general formula III a～IIIc, the content combination by weight of selected each component composition, but ratio is in any case mixed, and the total amount of first composition that chipal compounds forms is 100%; They are combined into has certain spiral shell square, and its spiral shell square does not become the chiral composition (first component) of (dp/dt＜0.01 μ m/ ℃) with temperature change in the liquid crystal phase scope, and the content of described chiral composition in described multistable state liquid srystal material is respectively 5-95wt%, preferred 10-60wt%, preferred 10-25wt%.
The present invention relates to preferred second component is wide temperature nematic phase liquid crystal composition, in these liquid crystal combinations, at least preferably one or more wide temperature liquid-crystal compounds has IVa-IVc, Va～Vm, VIa～VIk, VIIa～VIIk, IXa～IXw, Xa～Xj, Xia～XIs, compound shown in XIIa～XIIw, the general formula of described compound is as follows:
Figure C0210073700172
Figure C0210073700181
Figure C0210073700191
Figure C0210073700201
Figure C0210073700211
Figure C0210073700221
Figure C0210073700231
Figure C0210073700241
In the composition of the liquid-crystal compounds of the represented high birefringence rate of general formula I V～XII (Δ n value big) and big each opposite sex of dielectric (Δ ε value greatly), at least comprise general formula I Va-IVc, Va～Vm, VIa～VIk, VIIa～VIIk, IXa～IXw, Xa～Xj, XIa～XIs, one or more liquid-crystal compoundss shown in XIIa～XIIw ratio of content 1-40wt% by weight make up as second component, preferred 5-25wt% content range combination; The content range of 5-15wt% more preferably.Particularly, the total content of each component is at least 3-25wt% among the general formula I V, the total content of each component is at least 5-40wt% at least among the general formula V, the total content of each component is at least 5-30wt% among the general formula VI, the total content of each component is at least 5-45wt% among the general formula VII, and the total content of each component is at least 5-35wt%. among the general formula I X
In second components composition of the present invention, further comprise shown in general formula X-XII high birefringence rate (Δ n value big) and the liquid-crystal compounds of big each opposite sex of dielectric (Δ ε value greatly), its total content is 1-75wt%.And the content of compound shown in the described X-XII is the 1-25wt% of second component, preferred 3-20wt%, and 4-15wt% most preferably, but no matter according to what kind of ratio mix, the total amount of the composition that the represented compound of IV～XII forms is 100%.Particularly, in second component, the content of general formula X is 1-20wt%, and the content of general formula X I is 5-25wt%, and the content of general formula X II is 5-25wt%.
In the present invention, the content of wide temperature nematic phase liquid crystal composition in described multistable state liquid srystal material display of being made up of IV～XII compound is 60-95wt%, preferred 70-90wt%, and preferred content is 75-85wt%.
Compound involved in the present invention all is known, but also without any single liquid-crystal compounds, or the liquid-crystal composition of these compounds is to be used in the multi-steady state liquid crystal display, in patent report in the past, these liquid-crystal compoundss all only are used in twisted-nematic phase (TN) type, supertwist nematic phase (STN) type, dynamic scattering mode (DS), in guest-host type (GH), thin film transistor (TFT) (TFT) type and high molecular polymer decentralized (PDLC) liquid crystal display, report is not used for multistable or bistable state, three-stable state LCD.
In implementation process of the present invention, described chipal compounds is used to reduce to be used for the spiral shell square of multistable state liquid srystal material display, the spiral shell square of chiral molecules is enough little for the practical application of most of liquid crystal, it roughly is inversely proportional to chipal compounds distortion power (HTP value) and concentration thereof, for multistable state liquid srystal material, it is desirable to obtain to have the chiral liquid crystal compounds of high HTP value, to reduce the amount of the needed chipal compounds of certain spiral shell square.
Multistable state liquid srystal material of the present invention wishes to have the liquid crystal compound of strong helically twisted performance and short spiral shell square, selected spiral shell square must make liquid crystal in the maximal value of the reflection wavelength of cholesteric phase attitude helical axis directions within visible-range.
Researchist of the present invention finds, can obtain short spiral shell square by dual mode: use the chipal compounds of high concentration or realize by the chipal compounds of high twist power (HTP value).
The represented HTP value that chiral liquid crystal compounds showed of existing general formula (II), (III) is lower, thereby makes the chipal compounds amount that needs more; But the increase of chipal compounds amount, to the phase transition temperature scope of mixed liquid crystal, Δ n value, Δ ε value, Vth value with and photoelectric properties such as cleaning point, viscosity, response speed certain influence is all arranged.
Therefore, the present invention selects the bigger left side of distortion power or dextrorotatory compound R-(+)-or S-(-)-styrene glycol, 1-methyl-alkylol-1 and chiral amyl alcohol are chiral center, the represented chipal compounds of general formula (I)～(III) that has synthesized the novel foundation HTP value of three series, wherein compound (I) shows bigger HTP value, and they are had the chiral composition (I component) that the formulated in combination of certain HTP value becomes to have certain HTP value by different proportion and performance requirement.These chiral compositions (I component) are added in the second component body hand of liquid-crystal composition, obtain having the multistable state liquid srystal material of cholesteric phase, and show the less spiral shell square and the dependence of temperature, reduced negative effect to the photoelectric properties of multistable state liquid srystal potpourri.
Chipal compounds of the present invention is usually with traditional synthetic method production, for example with various components when 80 ℃ of the temperature, the Hybrid Heating dissolving, each component that maybe will dissolve is dissolved in and makes it mixing in the organic solvent, decompression steams solvent then, and recrystallization, drying obtain target compound again.
In multistable mixed liquid crystal of the present invention, the first component thing that preferably contains the chipal compounds of at least a general formula (I) expression, they not only produce bigger HTP value therein, and to dependence on temperature bigger effect can be arranged to minimizing spiral shell square, reduction spiral shell square.
Usually, the chipal compounds of regulating general formula (II), (III) expression is to regulate the multistable mixed liquid crystal to suitable helical structure (being the spiral shell square) with to avoid the anti-twist effect to be produced as basic at the content of chiral composition.
Researchist of the present invention utilizes known wide temperature nematic phase, high Δ n value, categorical series liquid-crystal compoundss such as high Δ ε value liquid-crystal compounds Xa～XjXIa-XIs are prepared in the wide temperature nematic phase big Δ n value needs part, the wide temperature liquid-crystal compounds that can be used to liquid-crystal compounds has IVa-IVc, Va～Vm, VIa～VIk, VIIa～VIIk, IXa～IXw, Xa～Xj solves the wide temperature of mixed liquid crystal, high cleaning point part, utilize compounds X Ia-XIs, series such as XIIa-XIIw solve the high Δ ε value value part requirement of mixed liquid crystal, utilize Va～Vm, VIa～VIk solves the low viscous liquid-crystal compounds that needs; Thereby the liquid-crystal composition second component thing of the comprehensive wide temperature nematic phase of preparation performance, high Δ n value, high Δ ε value.Δ n 〉=0.150, Δ ε 〉=20, Vth≤3.0V, Von≤10V, Voff≤30V, phase transition temperature-30～80 ℃ are satisfied in the performance of these liquid-crystal compositions and requirement.In mixed liquid crystal combination, these liquid-crystal compoundss (IV-XII) optimal combination according to a certain percentage forms, and the weight of its component is independent of respectively than being about 1-20%.
Technical research personnel of the present invention are in conjunction with every performance requirement of multi-steady state liquid crystal display spare, with first component and second component and the cholesteric phase multistable state liquid srystal material of formulated low viscosity, short spiral shell square, Δ n 〉=0.150, Δ ε 〉=20 by a certain percentage, these materials have yellowish green, blue different colours along with the difference of chiral liquid crystal composition, and they are applied in the reflective multi-steady state liquid crystal display.
Below be embodiments of the invention, by following embodiment and in conjunction with the detailed description of instructions, can be expressly understood the present invention, in the embodiment of following composition, name these compounds according to listed regulation, with the carbon number of numeral straight chain end group.With (+) or (-) expression dextrorotation or left-handed chiral center, be connected to the number of chipal compounds of the present invention or liquid-crystal composition identical with shown in following examples.For example: compound (+)-6EM6 is general formula I Ia, wherein R 11, R 12Be respectively C 6H 13, L is a hydrogen atom: compound (+)-5BE6 is general formula I e, wherein R 9Be C 5H 11, R 10Be C 6H 13Compound (+)-2MCB is general formula III a, wherein R 15Be C 2H 5Compound (+)-60EM F6, (+)-70EM F6 and (+)-7EM FThe 6th, general formula I Ia and IIb, wherein R 13, R 14Be respectively C 6H 13, C 7H 15Other can the rest may be inferred.
Embodiment as chiral composition of the present invention (first component) is as follows:
Embodiment one
What present embodiment related to is the preparation of chiral composition, in the preparation of chiral composition (first component), and each composition preparation 5 gram.
The described compound method of present embodiment be with described chipal compounds in its ratio weighing and be placed into the 10ml quartz container, be heated to 60 ℃, constant temperature stirred 1 hour.Behind the cool to room temperature, these compositions are got 0.01 gram join in the 1 gram commodity liquid crystal " SLC-7611A " (commercially available standard liquid crystal), stirring and evenly mixing carries out the test of HTP value and dp/dT value and reflection wavelength thereof, and the experimental result that obtains is shown in Table 1.
Table 1: the preparation and the The performance test results of chiral composition (first component)
CH-001 CH-002 CH-003
Compound Weight % Compound Weight % Compound Weight %
(+)-6EM6 (+)-7EM6 (+)-8EM6 (+)-2MCB (+)-5HE5 (+)-5BE6 10 10 10 30 20 20 (+)-2MCB (+)-7HBE7 (+)-6EM6 (+)-8EM6 (+)-5BE5 60 10 10 10 10 (+)-5BE5 (+)-7HBE7 (+)-6EM6 (+)-8EM6 (+)-5HE5 (+)-7EM F6 5 15 25 25 5 25
HTP value: 16.2 phases: liquid (40 ℃) dp/dT value: 0.17nm/ ℃ (illustrated embodiments, better performances) HTP value: 12.0 phases: liquid (40 ℃) dp/dT value: 0.08nm/ ℃ (illustrated embodiments, better performances) HTP value: 14.2 phases: liquid (35 ℃) dp/dT value: 0.12nm/ ℃ (illustrated embodiments, better performances)
Continuous table 1-2: the preparation and the The performance test results of chiral composition (first component)
CH-004 CH-005 CH-006
Compound Weight % Compound Weight % Compound Weight %
(+)-6EM F6 (+)-7EM F6 (+)-6MCB (+)-2MBM (+)-5HHE5 (+)-5BE6 (+)-7HBE7 (+)-7HE7 15 15 15 5 15 10 20 5 (+)-2MCB (+)-7HBE7 (+)-5HBE5 (+)-6HBE6 (+)-5BE5 (+)-7BE6 (+)-60EM F6 (+)-70EM F6 (+)-7EM2 (+)-5HEM6 20 10 10 10 10 15 5 5 5 10 (+)-5BE5 (+)-7HE6 (+)-6HBE6 (+)-6EM F6 (+)-7HHE5 (+)-2MCB (+)-5MCB (+)-5HEBE5 (+)-70EM6 10 10 15 5 15 18 7 10 10
HTP value: 14.2 phases: liquid (40 ℃) dP/dT value: 0.11nm/ ℃ HTP value: 13.8 phases: liquid (40 ℃) dP/dT value: 0.09nm/ ℃ HTP value: 18.1 phases: liquid (40 ℃) dP/dT value: 0.15nm/ ℃
Continuous table 1-3: the preparation and the The performance test results of chiral composition (first component)
CH-007 CH-008 CH-009
Compound Weight % Compound Weight % Compound Weight %
(+)-2MCB (+)-7HBEM6 (+)-5HHE5 (+)-70EM F6 (+)-7EM F6 70 10 5 10 5 (+)-2MCB (+)-7HBE7 (+)-6EM6 94 5 1 (+)-5BE5 (+)-70EM6 (+)-7MOCB6 (+)-60EM F6 (+)-7HBE7 (+)-5HHE5 15 10 45 15 10 5
HTP value: 8.5 phases: liquid (40 ℃) dp/dT value: 0.12nm/ ℃ HTP value: 5.6 phases: liquid (50 ℃) dp/dT value: 0.18nm/ ℃ HTP value: 15.2 phases: liquid (35 ℃) dp/dT value: 0.08nm/ ℃
Continuous table 1-4: the preparation and the The performance test results of chiral composition (first component)
CH-010 CH-011 CH-012
Compound Weight % Compound Weight % Compound Weight %
(+)-3BBE2 (+)-12HBE6 (+)-2HHE3 (+)-4BBE3 50 1 4 45 (+)-9MOCB (+)-2MOCB (+)-10MCB (+)-8MBM 40 40 10 10 (+)-120EM F6 (+)-10EM F5 (+)-2EM F7 (+)-2MBM (+)-9MCB 85 1 5 5 4
HTP value: 7.5 phases: liquid (50 ℃) dp/dT value: 0.15nm/ ℃ HTP value: 3.6 phases: liquid (50 ℃) dp/dT value: 0.20nm/ ℃ HTP value: 14.1 phases: liquid (35 ℃) dp/dT value: 0.09nm/ ℃
Embodiment two
What present embodiment related to is wide temperature nematic phase liquid crystal composition preparation, and component, content and the physical property of the described wide temperature nematic phase liquid crystal composition of present embodiment (second component) are included in the table 2.
Table 2-1: composition, content and the physical property of wide temperature liquid-crystal composition (second component)
SLC-B-001 SLC-B-002 SLC-B-003
Compound Weight % Compound Weight % Compound Weight %
5HBO2 5HB(2F) 7HB(3F) 2BeB F(CNS) 4BeB F(CNS) 5BeB F(CNS) 2HB F(CN) 3HB F(CN) 3HHB(2F，NCS) 4HHB(2F，NCS) 5HHB(2F，NCS) 3HH2BB(2F) 5HH2BB(2F) 3HBBH3 5HBBH3 3HB FBH3 5HB FBH3 5HB FB(F) 4 5 5 6 6 6 7 6 8 5 7 5 5 3 3 5 5 9 3HB01 2BeB F(CNS) 3BeB F(CNS) 2BaB01 3HeB5(CN) 5HeB5(CN) 3HHB(2F，NCS) 5HHB(2F，NCS) 2HBB(2F，NCS) 3HBB(2F，NCS) 4HBB(2F，NCS) 5HBB(2F，NCS) 2HH2BB(2F) 3HH2BB(2F) 4HH2BB(2F) 5HH2BB(2F) 3PyB FB(F) 5PyB FB(F) 8 10 8 5 6 4 7 5 3 5 5 7 5 5 5 4 4 4 3HB01 3HB02 5HB02 4BeB F(CNS) 5BeB F(CNS) 4HHB(2F，NCS) 5HHB(2F，NCS) 3HBB(2F，NCS) 5HBB(2F，NCS) 4HBB(2F，NCS) 3PyB FB(F) 5PyB FB(F) 4HH2BB(2F) 5HH2BB(2F) 5HB FBH3 5HBBH3 4PyBB(2F) 5PyBB(2F) 7 8 8 4 4 3 3 5 5 6 7 7 5 5 5 5 5 8
Δ n value: 0.166＜n〉value: 1.588 Δ ε values :+21.0 Vth values: 1.13V Vsat value: 1.65V freezing point:＜-40 ℃ of clearing points: 90.0 ℃ of viscosity (20 ℃): 36mm2s -1 Δ n value: 0.150＜n〉value 1.58 Δ ε values :+15.0 Vth values: 1.39V Vsat value: 1.97V freezing point:＜-50 ℃ of clearing points: 100 ℃ of viscosity (20 ℃): 35mm2s -1(illustrated embodiments, better performances) Δ n value: 0.175＜n〉value 1.60 Δ ε values :+8.7 Vth values: 2.03V Vsat value: 2.81V freezing point:＜-50 ℃ of clearing points: 110 ℃ of viscosity (20 ℃): 30mm2s -1(illustrated embodiments, better performances)
Continuous table 2-2: composition, content and the physical property of wide temperature liquid-crystal composition (second component)
SLC-B-004 SLC-B-005 SLC-B-006
Compound Weight % Compound Weight % Compound Weight %
3HB02 5HB02 7HB((2F) 3BeB F(CNS) 5BeB F(CNS) 3HB F(CN) 3HBB(2F，NCS) 5HBB(2F，NCS) 3HH2BB(2F) 5HH2BB(2F) 3HBBH3 5HBBH3 3HB FBH3 5HB FBH3 3BBB(CN) 3BBB F(CN) 3HBB(CN，NCS) 5HBB(CN，NCS) 3PyBB(2F) 5PyBB(2F) 4 7 5 4 6 3 7 6 5 5 3 4 5 3 4 5 5 6 6 7 3HB(CN) 5BB(CN) 5HB(2F) 7HB(3F) 4BeB F(CNS) 5BeB F(CNS) 3HBeB F(CN) 5BaB04 3HBaB2 3HBaB(2F) 3HBB F(CN) 5HBB F(CN) 3HBB(2F，NCS) 5HBB(2F，NCS) 3HH2BB(2F) 5HH2BB(2F) 3PyB FB(F) 3PyB FB(2F) 3HB FBH3 5HB FBH3 5 5 7 5 4 6 5 4 4 3 5 7 5 5 5 4 5 8 5 3 3HBEB3 3HEBH3 3BB(2F) 5HeB F(CN) 5BeB F(CN) 3DB F(CN) 3DB(2F) 3HBB(2F，NCS) 5HBB(2F，NCS) 3HBB(F) 3PyB FB(F) 3BPyB2 4HH2BB(2F) 5HH2BB(2F) 5HB FBH3 5HBBH3 4PyBB(2F) 5PyB FB(F) 3BBB F(CN) 5 4 5 6 6 4 4 5 8 4 6 6 5 5 5 4 5 8 5
Δ n value: 0.186＜n〉value: 1.61 Δ ε values :+18.0 Vth values: 1.28V Vsat value: 1.75V freezing point:＜-40 ℃ of clearing points: 110.0 ℃ of viscosity (20 ℃): 37mm2s -1(illustrated embodiments, better performances) Δ n value: 0.168＜n〉value: 1.59 Δ ε values :+25.0 Vth values: 1.09V Vsat value: 1.57V freezing point:＜-40 ℃ of clearing points: 97.5 ℃ of viscosity (20 ℃): 42mm2s -1(illustrated embodiments, better performances) Δ n value: 0.185＜n〉value: 1.61 Δ ε values :+18.7 Vth values: 1.63V Vsat value: 2.11V freezing point:＜-40 ℃ of clearing points: 105 ℃ of viscosity (20 ℃): 53mm2s -1(illustrated embodiments, better performances)
Continuous table 2-3: component, content and the physical property of wide temperature liquid-crystal composition (second component)
SLC-B-007 SLC-B-008 SLC-B-009
Compound Weight % Compound Weight % Compound Weight %
5HB(3F) 4BeB F(CN) 5BeB F(CN) 2HB F(CN) 3HB F(CN) 2DB F(CN) 3DB F(CN) 3PyB F(CN) 5PyB F(CN) 2HBeB F(CN) 3HBeB F(CN) 3HB02 3HBEB3 3HBB(2F，NCS) 5HBB(2F，NCS) 3HH2BB(2F) 5HH2BB(2F) 5HBBH3 3HB FBH3 5HB FBH3 5HB FB(F) 5 5 5 4 4 5 5 5 5 5 3 6 6 6 5 5 4 4 4 4 5 3HB01 5HB(3F) 6HB(3F) 3BeB F(CN) 2BaB01 3HBaB(2F) 3HB FaB(F) 5HHB(2F，NCS) 3HBB(2F，NCS) 5HBB(2F，NCS) 3HH2BB(2F) 5HH2BB(2F) 3HB FBH3 5HB FBH3 3PyB FB(F) 5PyB FB(F) 3HPyB FB(2F) 4HPyB FB(2F) 5HPyB FB(2F) 5 10 5 5 6 4 4 4 5 6 6 6 8 5 4 4 5 4 4 3HBB F(CN) 5HB(CN) 5HB02 4BeB F(CN) 5BeB F(CN) 3BBB(CN) 5HBB F(CN) 3BB F(NCS) 5BB F(NCS) 5BB(CN) 9PyB(NCS) 10BB(NCS) 3PyB FB(F) 5PyB FB(F) 3HH2BB(2F) 5HH2BB(2F) 5HB FBH3 3PyBB(2F) 5PyBB(2F) 10 8 5 4 4 5 10 5 3 5 1 1 7 7 5 5 5 5 5
Δ n value: 0.176＜n〉value: 1.60 Δ ε values :+35.0 Vth values: 0.83V Vsat value: 1.15V freezing point:＜-40 ℃ of clearing points: 80.0 ℃ of viscosity (20 ℃): 46mm2s -1(illustrated embodiments, better performances) Δ n value: 0.175＜n〉value: 1.60 Δ ε values :+19.6 Vth values: 1.35V Vsat value: 1.75V freezing point:＜-40 ℃ of clearing points: 96.5 ℃ of viscosity (20 ℃): 31m2s -1(illustrated embodiments, better performances) Δ n value: 0.191＜n〉value: 1.62 Δ ε values :+22.7 Vth values: 1.03V Vsat value: 1.41V freezing point:＜-30 ℃ of clearing points: 95 ℃ of viscosity (20 ℃): 52mm2s -1(illustrated embodiments, better performances)
Continuous table 2-4: composition, content and the physical property of wide temperature liquid-crystal composition (second component)
SLC-B-010 SLC-B-011 SLC-B-012
Compound Weight % Compound Weight % Compound Weight %
3HPyBB(3F) 10BPyB(2F) 5BPyB(3F) 3HPyB(CN) 3HPB(CN) 5HHB(CN) 3BBB F(CN) 5BBB F(CN) 2HPyB FB(2F) 3HPyB F(CN) 10PyB FB2 2BPyB7 5 3 5 15 35 10 5 5 8 2 5 2 5HHB FBH3 5H2BB(F) 3HB FB(F) 2HHB FB(F) 3HHBB(CF 3) 3HHBB(OCF 3) 2HB10BB3 5HH2BB2 4HHB03 3HHB2 3HPyB FB(3F) 8HPyB FB(2F) 4HPyB F(CN) 10 5 2 5 5 15 6 10 25 5 2 5 5 3HHB FBH2 2HB FB(2F) 3HBEBH2 5HH10BH3 3B FBHH2 20B FBHH2 4B FBH2 2HPyBB(3F) 3HB FaB05 3HBaB(3F) 5BaB 9BaB(3F) 2BaB(2F) 10BaB(2F) 3HHeB F(CN) 10HBeB(NCS) 5HBB(NCS) 2HHB F(NCS) 4HeB F(CN) 2HeB F(NCS) 4H2BB(NCS) 3PyB(3F) 5HB(OCF 2) 5 5 10 5 10 7 10 5 3 3 2 3 1 2 7 5 5 1 5 3 1 1 1
Δ n value: 0.185＜n〉value: 1.58 Δ ε values :+18.5 Vth values: 1.38V Vsat value: 1.95V freezing point:＜-40 ℃ of clearing points: 100.0 ℃ of viscosity (20 ℃): 39mm2s -1 Δ n value: 0.168＜n〉value: 1.59 Δ ε values :+25.0 Vth values: 1.19V Vsat value: 1.47V freezing point:＜-40 ℃ of clearing points: 97.5 ℃ of viscosity (20 ℃): 38mm2s -1 Δ n value: 0.185＜n〉value: 1.61 Δ ε values :+19.7 Vth values: 1.23V Vsat value: 2.01V freezing point:＜-40 ℃ of clearing points: 105 ℃ of viscosity (20 ℃): 45mm2s -1
Continuous table 2-5: composition, content and the physical property of wide temperature liquid-crystal composition (second component)
SLC-B-013 SLC-B-014 SLC-B-015
Compound Weight % Compound Weight % Compound Weight %
2BEBH3 8HBEB03 9HB10BB2 3HH2BB2 30B FBH7 10HHB2 3HHB8 5HHB2 2HBB03 5HB3 2HHB03 1 7 15 15 25 10 5 5 8 4 5 2HHB FBH3 9HBBH2 2HB FBH2 10HB FBH5 3H2BB(F) 9H2BB(F) 9HB FB(F) 5HB FB(F) 5HHB FB(F) 9HHB FB(F) 7HPyB FB(3F) 2HPyB FB(2F) 5HPyB FB(2F) 1 9 6 10 10 5 6 10 14 6 7 10 6 11HH2BB(2F) 9HB FB(2F) 10HB FBH5 2HBBH10 12HBEBH5 2HH10BH11 50B FBH2 2HB12 30B FBH2 9B FBH2 10HPyBB(3F) 9BpyB5 2PyB FB10 12HPyB FB(2F) 5 7 7 8 5 5 5 6 5 10 10 10 7 10
Δ n value: 0.145＜n〉value: 1.26 Δ ε values :+16.5 Vth values: 1.22V Vsat value: 1.54V freezing point:＜-30 ℃ of clearing points: 88.0 ℃ of viscosity (20 ℃): 35mm2s -1 Δ n value: 0.134＜n〉value: 1.34 Δ ε values :+15.0 Vth values: 1.36V Vsat value: 1.28V freezing point:＜-40 ℃ of clearing points: 91.5 ℃ of viscosity (20 ℃): 36mm2s -1 Δ n value: 0.164＜n〉value: 1.88 Δ ε values :+17.7 Vth values: 1.56V Vsat value: 1.84V freezing point:＜-40 ℃ of clearing points: 93 ℃ of viscosity (20 ℃): 40mm2s -1
Embodiment three
What present embodiment related to is the preparation of multistable state liquid srystal material display, be specially, the wide temperature nematic phase liquid crystal composition of a certain proportion of second component SLC-B-001 to SLC-B-012 is hybridly prepared into multistable state liquid srystal material with the first component chiral composition CH-001 to CH-006 of certain ratio respectively, and its configuration proportion, photoelectric properties are shown in Table 3 respectively.
Table 3: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-001 SLC-FM-002 SLC-FM-003
Composition Weight % Composition Weight % Composition Weight %
CH-001 SLC-B-003 15 85 CH-002 SLC-B-001 23 77 CH-002 SLC-B-002 24 76
Δ ε value :+5.8 Vth values: 3.4V Von value: 25.1V Voff value: 29.5V freezing point:＜-30 ℃ of clearing points: 85.0 ℃ of maximum operating temperatures: 65.0 ℃ of viscosity (20 ℃): 189mm2s -1Reflection wavelength: 565nm dP/dT value:＜0.09nm/ ℃ Δ ε value :+18.5 Vth values: 2.56V Von value: 16.8V Voff value: 28.0V freezing point:＜-30 ℃ of clearing points: 70.0 ℃ of maximum operating temperatures: 55.0 ℃ of viscosity (20 ℃): 205mm2s -1Ejected wave is long: 555nm dP/dT value:＜0.08nm/ ℃ Δ ε value :+10.6 Vth values: 2.85V Von value: 18.4V Voff value: 31.2V freezing point:＜-35 ℃ of clearing points: 75.0 ℃ of maximum operating temperatures: 60.0 ℃ of viscosity (20 ℃): 195mm2s -1Reflection wavelength: 548nm dP/dT value:＜0.1nm/ ℃
Continuous table 3-2: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-004 SLC-FM-005 SLC-FM-006
Composition Weight % Composition Weight % Composition Weight %
CH-003 SLC-B-001 17 83 CH-004 SLC-B-003 20 80 CH-005 SLC-B-003 20 80
Δ ε value :+14.2 Vth values: 2.68V Von value: 19.5V Voff value: 25.6V freezing point:＜-40 ℃ of clearing points: 70 ℃ of maximum operating temperatures: 57.0 ℃ of viscosity (20 ℃): 215mm2s -1Reflection wavelength: 567nm dP/dT value:＜0.09nm/ ℃ Δ ε value :+5.3 Vth values: 3.50V Von value: 21.4V Voff value: 24.3V freezing point:＜-35 ℃ of clearing points: 80.4 ℃ of maximum operating temperatures: 62.5 ℃ of viscosity (20 ℃): 187mm2s -1Reflection wavelength: 575nm dP/dT value:＜0.1nm/ ℃ Δ ε value :+5.7 Vth values: 3.45V Von value: 20.4V Voff value: 25.5V freezing point:＜-40 ℃ of clearing points: 85.0 ℃ of maximum operating temperatures: 65.0 ℃ of viscosity (20 ℃): 181mm2s -1Reflection wavelength: 587nm dP/dT value:＜0.1nm/ ℃
Continuous table 3-3: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-007 5SLC-FM-008 SLC-FM-009
Composition Weight % Composition Weight % Composition Weight %
CH-001 SLC-B-006 20 80 CH-002 SLC-B-007 40 60 CH-002 SLC-B-008 23 77
Δ ε value :+26.7 Vth values: 2.0V Von value: 12.6V Voff value: 14.0V freezing point:＜-25 ℃ of clearing points: 65 ℃ of maximum operating temperatures: 55.0 ℃ of viscosity (20 ℃): 210mm2s -1Reflection wavelength: 570nm dP/dT value:＜0.09nm/ ℃ (illustrated embodiments, better performances) Δ ε value :+15.4 Vth values: 3.51V Von value: 16.8V Voff value: 28.0V freezing point:＜-30 ℃ of clearing points: 50.0 ℃ of maximum operating temperatures: 40.0 ℃ of viscosity (20 ℃): 196mm2s -1Reflection wavelength: 581nm dP/dT value:＜0.08nm/ ℃ (general embodiment, poor-performing) Δ ε value :+18.5 Vth values: 3.5V Von value: 18.4V Voff value: 25.2V freezing point:＜-30 ℃ of clearing points: 76.0 ℃ of maximum operating temperatures: 66.0 ℃ of viscosity (20 ℃): 185mm2s -1Reflection wavelength: 585nm dP/dT value:＜0.1nm/ ℃ (illustrated embodiments, better performances)
Continuous table 3-4: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-010 SLC-FM-011 SLC-FM-012
Composition Weight % Composition Weight % Composition Weight %
CH-002 SLC-B-004 24 76 CH-004 SLC-B-005 19.3 80.7 CH-005 SLC-B-006 20 80
Δ ε value :+16.5 Vth values: 3.1V Von value: 22.6V Voff value: 25.0V freezing point:＜-25 ℃ of clearing points: 75 ℃ of maximum operating temperatures: 65.0 ℃ of viscosity (20 ℃): 195mm2s -1Reflection wavelength: 560nm dP/dT value:＜0.09nm/ ℃ (illustrated embodiments, better performances) Δ ε value :+21.4 Vth values: 2.51V Von value: 19.8V Voff value: 22.0V freezing point:＜-20 ℃ of clearing points: 70.0 ℃ of maximum operating temperatures: 59.0 ℃ of viscosity (20 ℃): 206mm2s -1Reflection wavelength: 551nm dP/dT value:＜0.08nm/ ℃ (illustrated embodiments, better performances) Δ ε value :+16.4 Vth values: 3.8V Von value: 28.4V Voff value: 31.2V freezing point:＜-30 ℃ of clearing points: 76.0 ℃ of maximum operating temperatures: 66.0 ℃ of viscosity (20 ℃): 185mm2s -1Reflection wavelength: 565nm dP/dT value:＜0.1nm/ ℃ (illustrated embodiments, better performances)
Continuous table 3-5: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-013 SLC-FM-014 SLC-FM-015
Composition Weight % Composition Weight % Composition Weight %
CH-003 SLC-B-009 6 94 CH-004 SLC-B-010 40 60 CH-005 SLC-B-012 30 70
Δ ε value :+19.5 Vth values: 1.4V Von value: 22.6V Voff value: 25.0V freezing point:＜-35 ℃ of clearing points: 85 ℃ of maximum operating temperatures: 65.0 ℃ of viscosity (20 ℃): 195mm2s -1Reflection wavelength: 460nm dP/dT value:＜0.19nm/ ℃ (relatively poor property embodiment, poor-performing) Δ ε value :+16.4 Vth values: 2.51V Von value: 29.8V Voff value: 32.0V freezing point:＜-45 ℃ of clearing points: 50.0 ℃ of maximum operating temperatures: 39.0 ℃ of viscosity (20 ℃): 266mm2s -1Reflection wavelength: 501nm dP/dT value:＜0.18nm/ ℃ (general embodiment, poor-performing) Δ ε value :+17.4 Vth values: 2.8V Von value: 28.4V Voff value: 31.2V freezing point:＜-30 ℃ of clearing points: 56.0 ℃ of maximum operating temperatures: 45.0 ℃ of viscosity (20 ℃): 205mm2s -1Reflection wavelength: 565nm dP/dT value:＜0.10nm/ ℃ (preferred property embodiment, better performances)
Continuous table 3-6: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-016 SLC-FM-017 SLC-FM-018
Composition Weight % Composition Weight % Composition Weight %
CH-007 SLC-B-015 10 90 CH-008 SLC-B-013 38 62 CH-009 SLC-B-014 30 70
Δ ε value :+14.5 Vth values: 2.3V Von value: 15.5V Voff value: 23.0V freezing point:＜-35 ℃ of clearing points: 85 ℃ of maximum operating temperatures: 50.0 ℃ of viscosity (20 ℃): 188mm2s -1Reflection wavelength: 450nm dP/dT value:＜0.19nm/ ℃ (relatively poor property embodiment, poor-performing) Δ ε value :+13.5 Vth values: 1.8V Von value: 14.2V Voff value: 24.0V freezing point:＜-35 ℃ of clearing points: 70.0 ℃ of maximum operating temperatures: 45.0 ℃ of viscosity (20 ℃): 180mm2s -1Reflection wavelength: 475nm dP/dT value:＜0.15nm/ ℃ (general embodiment, poor-performing) Δ ε value :+13.2 Vth values: 1.9V Von value: 14.8V Voff value: 26.0V freezing point:＜-35 ℃ of clearing points: 50.0 ℃ of maximum operating temperatures: 50.0 ℃ of viscosity (20 ℃): 190mm2s -1Reflection wavelength: 495nm dP/dT value:＜0.14nm/ ℃ (general embodiment, poor-performing)
Continuous table 3-7: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-019 SLC-FM-020 SLC-FM-021
Composition Weight % Composition Weight % Composition Weight %
CH-010 SLC-B-014 30 70 CH-011 SLC-B-013 8 92 CH-012 SLC-B-011 36 64
Poor-performing Poor-performing Performance is general
Continuous table 3-7: the preparation of multistable state liquid srystal material and photoelectric properties result
SLC-FM-022 SLC-FM-023 SLC-FM-024
Composition Weight % Composition Weight % Composition Weight %
CH-006 SLC-B-011 30 70 CH-01 SLC-B-015 25 75 CH-012 SLC-B-003 36 64
Functional Functional Better performances

Claims (29)

1. LCD that multistable state liquid srystal material is made, described display adopts has long-term memory characteristic, spiral shell square not with the multistable liquid crystal material composition preparation of temperature change, its birefraction is between 0.1500-0.2800, and operating voltage is between 10-35V; Described display has the long-term characteristic that keeps displayed image or content when zero electric field; Described display comprises:
A). the chipal compounds that is selected from least a general formula shown in the general formula (I)～(III) is first component, the containing of described first component
Amount is the 5-40wt% of multistable state liquid srystal material total amount;
Figure C021007370002C1
In general formula I～III:
R 1～R 3Be alkyl, alkenyl or the alkoxy with 1-13 carbon atom, the optional methylene in this alkyl or the alkene can be replaced by oxygen atom, but two or more methylene can not be replaced continuously by oxygen atom;
R 4, R 5Be the alkyl that has only 2-10 carbon atom, ring A～F structure is separate anti-form-1,4-cyclohexyl, 1,4-phenylene, pyrimidine-2,5-two bases;
Z 1～Z 4Be singly-bound ,-CO 2-or oxygen atom; X=F, CN or contain the alkyl of 1-5 carbon;
L 1～L 2Be respectively H or F atom;
M, n, l and k are respectively 0,1 or 2;
B) compound that is selected from least a general formula in the low viscosity shown in the general formula (IV)～(IX), the wide temperature liquid-crystal compounds is as second component, and described second components contents is the 60-95wt% of multistable state liquid srystal material total amount;
Figure C021007370003C1
Among general formula I V～IX: R 1-R 8Be alkyl or alkenyl with 1-12 carbon atom, or alkoxy; Ring A-F is respectively separate anti-form-1,4-cyclohexylidene, 1,4-phenylene, pyrimidine-2,5-two bases, 1, the arbitrary group in the 3-dioxan base; L 1-L 5Be respectively H, F or Cl; X and Y are respectively F, CN, NCS, CF 3, Cl, OCF 3, OCHF 2, C 1-C 7Straight chained alkyl or alkoxy; Z=CO 2, CH 2O ,-CH 2CH 2-or singly-bound ,-OCO-,-OCH 2-, m, n, l, q, j, r are respectively 1 or 2, k is 0 or 1.
2. a kind of multistable state liquid srystal material according to claim 1 is made LCD, compound with at least two kinds of general formulas in the compound shown in the general formula (I)～(III) is first component, every kind of compounds content is the 5-95wt% of first composition weight, in selected scope, the total amount of two kinds of compounds is 100wt%.
3. a kind of multistable state liquid srystal material according to claim 1 and 2 is made LCD, chipal compounds with each general formula shown in the general formula (I)～(III) is first component, the ratio combination of the 5-95wt% that selected each component composition is first composition weight; But ratio is in any case mixed, the total amount of the composition that chipal compounds forms is 100wt%, and first components contents is the 5-40wt% of multistable state liquid srystal material display total amount, and the compounds content shown in the general formula (I) is the 5-55wt% of first composition weight; Compounds content shown in the general formula (II) is the 5-45wt% of first composition weight; Compounds content shown in the general formula (III) is the 5-65wt% of first composition weight.
4. a kind of multistable state liquid srystal material according to claim 3 is made LCD, chipal compounds with each general formula shown in the general formula (I)～(III) is first component, compounds content shown in the general formula (I) is the 15-50wt% of first composition weight, compounds content shown in the general formula (II) is the 15-50wt% of first composition weight, and the compounds content shown in the general formula (III) is the 20-60wt% of first composition weight.
5. a kind of multistable state liquid srystal material according to claim 1 is made LCD, at least comprise the compound shown in 2 kinds of general formulas (I) in wherein said first component, or comprise the compound shown in 2 kinds of general formulas (II) at least, or comprise the compound shown in 2 kinds of general formulas (III) at least.
6. a kind of multistable state liquid srystal material according to claim 1 is made LCD, comprises the compound shown in the 3-5 kind general formula (I) in wherein said first component at least, or is selected from the compound shown in formula Ia-If or the formula III a-IIIc.
In general formula I a～And if general formula III a～IIIc:
R 1-R 22Be the alkyl with 2-10 carbon atom, the optional methylene that has only in this alkyl can be replaced by oxygen atom.
L 1～L 2=H or F.
7. a kind of multistable state liquid srystal material according to claim 1 is made LCD, in its formula of (I)～(III), described alkyl is selected from alkyl, ring A～F with 2-8 carbon atom and is selected from separate anti-form-1,4-cyclohexyl, 1,4-phenylene; L 1～L 2Be respectively H or F atom; Z 1～Z 4Be selected from singly-bound or oxygen atom; X is selected from F, CN or contains the alkyl of 3 carbon; M, n, l and k are respectively 0 or 1; The described first component chiral composition is combined into the chiral composition with certain spiral shell square and distortion power constant, and this composition spiral shell square in its multistable state liquid srystal phase scope varies with temperature rate greater than 0.01 μ m/ degree.
8. a kind of multistable state liquid srystal material according to claim 1 is made LCD, and wherein said second component further comprises high birefringence rate shown at least a general formula X～XII or big dielectric anisotropy compound:
Figure C021007370005C1
In general formula X～XII: R 1-R 3Be 1-15 straight chained alkyl or alkenyl, wherein MU (methylene unit) can be replaced by oxygen atom, or the hydrogen atom on the methylene is replaced by fluorine atom; Z is CO 2,-C 2H 4-or singly-bound; L 1-L 7Independent respectively is H, F or Cl atom, ring A and C are independent respectively to be anti-form-1,4-two cyclohexylidenes, 1,4-phenylene or the phenylene, the pyrimidine-2 that have one or two hydrogen atom to be replaced, 5-two bases, 1 by fluorine atom, 3-dioxan-2, a group in 5-two bases, ring B are respectively 1,4-phenylene or the phenylene, the pyrimidine-2 that have one or two hydrogen atom to be replaced by fluorine atom, 5-two bases, 1,3-dioxan-2,5-two bases; M, n is respectively 0,1, and 2; K is 0 and 1; Y 1And Y 3Be respectively CN, F, NCS, OCF 3, CF 3, OC 2H 5, OCH 3, OC 3H 7, OCHF 2Deng; Y 2Be CN or NCS base.
9. a kind of multistable state liquid srystal material according to claim 1 is made LCD, wherein said second component comprises the compound shown in two kinds of general formula I V, V, VI, VII, the IX at least, every kind of compounds content is the 5-95wt% of second composition weight, in selected scope, the 100wt% that the total amount of two kinds of compounds is, and described second components contents 60-95wt% that is the multistable state liquid srystal material total amount.
10. a kind of multistable state liquid srystal material according to claim 1 is made LCD, wherein said second component comprises the compound shown in three kinds of general formula I V, V, VI, VII, the IX at least, every kind of compounds content is the 5-95wt% of second composition weight, in selected scope, the 100wt% that the total amount of three kinds of compounds is, and described second components contents 60-95wt% that is the multistable state liquid srystal material total amount.
11. a kind of multistable state liquid srystal material according to claim 1 is made LCD, is second component with the compound shown in each general formula in the compound shown in general formula I V, V, VI, VII, the IX; Compounds content shown in the general formula I V is the 3-25wt% of second composition weight, compounds content shown in the general formula V is the 5-40wt% of second composition weight, compounds content shown in the general formula VI is the 5-30wt% of second composition weight, compounds content shown in the general formula VII is the 5-45wt% of second composition weight, and the compounds content shown in the general formula I X is the 5-35wt% of second composition weight.
12. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least three kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of three kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
13. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least four kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of four kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
14. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least five kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of five kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
15. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least six kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of six kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
16. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least seven kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of seven kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
17. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the compound with at least eight kinds of general formulas in the compound shown in general formula I V, V, VI, VII, IX, X, XI, the XII is second component; The compound of eight kinds of general formulas can make up in proportion, but the total amount of second component composition is 100wt%, and described second components contents 60-95wt% that is the liquid-crystal composition total amount.
18. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise the compound shown in 2 kinds of general formulas (IV) in second component of wherein said liquid-crystal composition, or the compound shown in 2 kinds of general formulas (V), or the compound shown in 2 kinds of general formulas (VI), or the compound shown in 2 kinds of general formulas (VII), or the compound shown in 2 kinds of general formulas (IX), or the compound shown in 2 kinds of general formulas (X), or the compound shown in 2 kinds of general formulas (XI), the chemical combination shown in 2 kinds of general formulas (XII).
19. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 3 kinds are selected from the compound shown in general formula I V or V or VI or VII or IX or X or XI or the XI.
20. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 4 kinds are selected from the compound shown in general formula V or VI or VII or IX or X or XI or the XI.
21. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 5 kinds are selected from the compound shown in general formula V or VI or VII or IX or X or XI or the XI.
22. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 6 kinds are selected from the compound shown in general formula V or VI or VII or IX or X or XI or the XI.
23. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 7 kinds are selected from the compound shown in general formula V or VI or VII or IX or X or XI or the XI.
24. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, comprise in second component of wherein said liquid-crystal composition that 8 kinds are selected from the compound shown in general formula V or VI or VII or IX or X or XI or the XI.
25. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein among general formula I V, V, VI, VII, the IX, R 1-R 8Alkyl with 1-12 carbon atom; Ring A-F is respectively separate anti-form-1,4-cyclohexylidene, 1,4-phenylene, pyrimidine-2,5-two bases, 1, the arbitrary group in the 3-dioxan base; L 1-L 5Be respectively H or F; X and Y are respectively F, CN, NCS, CF 3, OCF 3, OCHF 2, C 1-C 7Straight chained alkyl or alkoxy; Z is selected from CO 2, CH 2O ,-CH 2CH 2-, or singly-bound-OCH 2-; M, n, l, q, j, r, k are respectively 0 or 1;
R among general formula X, XI, the XII 1-R 3Be the 1-10 straight chained alkyl; Z is CO 2,-CH 2CH 2-or singly-bound; L 1-L 7Be respectively H or F, ring A and C are respectively anti-form-1,4-two cyclohexylidenes, 1,4-phenylene or the phenylene, the pyrimidine-2 that have one or two hydrogen atom to be replaced by fluorine atom, 5-two bases, 1,3-dioxan-2, a group in 5-two bases, ring B are respectively 1,4-phenylene or the phenylene that has a hydrogen atom to be replaced by fluorine atom; M is 1, and n is respectively 0 or 1; K is preferably 0 and 1; Y 1Be respectively CN, F, C 1-C 5Alkyl, OC 2H 5, OCH 3Or OC 3H 7Y 2Be CN or NCS base; Y 3Be respectively CN, F, NCS or OCHF 2
26. make LCD according to claim 1 or 8 or 9 or 10 described a kind of multistable state liquid srystal materials, wherein the represented compound of 5-7 kind general formula in eight kinds of structures shown in IV, V, VI, VII, IX, X, XI, the XII is combined as second component.
27. one kind prepares the method that the described a kind of multistable state liquid srystal material of claim 1 is made LCD, it is characterized in that the chiral composition of first component in the claim 1 and the composition of second component in the claim 1 are hybridly prepared into the multistable state liquid srystal material with cholesteric phase in proportion, wherein first components contents is the 5-40wt% of multistable state liquid srystal material total amount.
28. one kind prepares the method that the described a kind of multistable state liquid srystal material of claim 27 is made LCD, it is characterized in that the chiral composition of first component in the claim 1 and the composition of second component in the claim 1 are hybridly prepared into the multistable state liquid srystal material with cholesteric phase in proportion, wherein first components contents is the 10-30wt% of multistable state liquid srystal material total amount.
29. one kind prepares the method that the described a kind of multistable state liquid srystal material of claim 28 is made LCD, it is characterized in that the composition of second component in the chiral composition of first component in the claim 1 and the claim 1 is hybridly prepared into the multistable state liquid srystal material with cholesteric phase in proportion, wherein first components contents is the 10-20wt% of multistable state liquid srystal material total amount.
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