Summary of the invention
The technical issues that need to address of the present invention are to provide a kind of positive dielectric liquid crystal composite, especially a kind of liquid-crystal composition containing pyranylation compound, make to there is the features such as the optical anisotropy that rotary viscosity is low, the time of response is fast, nematic phase range is wide, suitable, be applicable to, in active matrix electrooptic element and liquid-crystal display, can be used for manufacturing TFT-LCD.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Containing the liquid-crystal composition of pyranylation compound, comprise the component A being formed by the compound shown in one or more general formula Is, the component B being formed by the compound shown in one or more general formula Is I, the component C being formed by the compound shown in one or more general formula III, the component D being formed by the compound shown in one or more general formula Is V, the component E being formed by the compound shown in one or more general formulas V;
Wherein,
R
11, R
12be respectively 1. following~4. described group wherein any,
①:H、Cl、F、CN、OCN、OCF
3、CF
3、CHF
2、CH
2F、OCHF
2、SCN、NCS、SF
5,
2.: C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15straight alkenyloxy,
3.: 2. in group one or more-CH
2-quilt-CH=CH-,-C ≡ C-,-COO-,-OOC-, sub-cyclobutyl, cyclopentylidene ,-O-or-S-substitute after and not direct connected group of Sauerstoffatom,
4.: 2. or any H of group 3. by F, Cl replace after group;
Ring A
12, ring A
13, ring A
14be respectively singly-bound,
in one;
Z
11, Z
12, Z
13be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-, one in-CF=CF-;
A, b, c, d are respectively 0,1,2,3, and a+b+c+d≤5;
R
21, R
22, R
31, R
32, R
41, R
42, R
51, R
52be respectively F, Cl, CN, C
1~C
7straight chained alkyl, C
1~C
7straight chain alkoxyl group, C
2~C
7straight-chain alkenyl, C
1~C
5straight chain fluoroalkyl;
Ring A
21, ring A
22, ring A
31, ring A
41, ring A
42, ring A
51, ring A
52, ring A
53be respectively singly-bound,
in one;
Z
51be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-in one;
L
21, L
22, L
41be respectively the one in H, F, Cl, CN;
E, f, g, h, i, j are respectively 0,1,2.
Further improvement of the present invention is:
R
11for H, C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15one in straight alkenyloxy,
R
12for H, Cl, F, CN, OCN, OCF
3, CF
3, CHF
2, CH
2f, OCHF
2, SCN, NCS, SF
5, C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15one in straight alkenyloxy,
Z
11, Z
12, Z
13be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-in one.
Further improvement of the present invention is: in liquid-crystal composition, to account for the weight percentage of liquid-crystal composition be 1%~40% to component A, the weight percentage that B component accounts for liquid-crystal composition is 1%~60%, the weight percentage that component C accounts for liquid-crystal composition is 10%~70%, the weight percentage that component D accounts for liquid-crystal composition is 1%~30%, the weight percentage that component E accounts for liquid-crystal composition is 1%~50%, and the weight percentage of said components A, B component, component C, component D, component E is 100%.
Further improvement of the present invention is: in liquid-crystal composition, to account for the weight percentage of liquid-crystal composition be 8%~19% to component A, the weight percentage that B component accounts for liquid-crystal composition is 5%~40%, the weight percentage that component C accounts for liquid-crystal composition is 33%~49%, the weight percentage that component D accounts for liquid-crystal composition is 3%~10%, and the weight percentage that component E accounts for liquid-crystal composition is 5%~30.5%.
Owing to having adopted technique scheme, the obtained technical progress of the present invention is:
The compound of general formula I representative of the present invention, there is the necessary general physical properties of liquid crystal monomer compound, to light, thermally-stabilised, nematic phase range is wider, good with other Compound Phase dissolubilities, especially this compounds has higher optical anisotropy Δ n, larger dielectric anisotropy (Δ ε > 0) and low rotary viscosity γ
1characteristic, can effectively reduce the threshold voltage of mixed liquid crystal, accelerate the time of response simultaneously, improve the low temperature mutual solubility of mixed liquid crystal.
The nematic phase type liquid-crystal composition excellent performance obtaining by the present invention, has low-down overall response time, has lower voltage, high resistivity and voltage retention.By the adjustment to each component concentration, nematic phase type liquid-crystal composition of the present invention can have different threshold voltages and birefringent characteristic, can make client's each individual system used conventionally, is convenient to use under thick at different liquid crystal cells in different driving voltage.And liquid-crystal composition still can show high resistivity after high temperature, this liquid-crystal composition shows excellent have excellent high temperature and UV stable performance.Meanwhile, in embodiment, liquid-crystal composition also shows low viscosity, fast-response time, suitable optical anisotropy and suitable dielectric anisotropy, therefore can have the Electro-Optical Display of active array addressing.
What the present invention relates to is the application of a class pyranyl difluoro methylene oxo bridge ethers monomer in liquid-crystal composition, this type of pyranyl difluoro methylene ether compound is brand-new compound, application in liquid-crystal composition still belongs to the first time, and therefore similar liquid-crystal composition has no any report.Use the liquid crystal material of this class pyranyl difluoro methylene oxygen ether class monomer exploitation excellent performance to have initiative meaning, the liquid-crystal composition of developing has the performance of very outstanding excellence.Concerning high-end TFT indicating meter is used liquid crystal material, be worth great.
Liquid-crystal composition of the present invention; can be for Active Matrix Display; preferably by the matrix addressing of thin film transistor (TFT); be specially adapted to manufacture the active matrix TN-TFT of quick response; IPS-TFT or FFS liquid crystal display device and liquid-crystal display, also belong to protection scope of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated:
Concrete meaning and the test condition of the symbol in embodiment are as follows:
Cp: clearing point, unit ℃;
Δ n: optical anisotropy, Δ n=no-ne, wherein, and the specific refractory power that no is ordinary light, the specific refractory power that ne is extraordinary ray, test condition is, 589nm, 25 ± 0.5 ℃;
Δ ε: dielectric anisotropy, Δ ε=ε
//-ε
⊥, wherein, ε
//for being parallel to the specific inductivity of molecular axis, ε
⊥for the specific inductivity perpendicular to molecular axis, test condition is 25 ± 0.5 ℃; 1KHz; HP4284A; 5.2 the left-handed box of micron TN;
γ
1: rotary viscosity, the mPas of unit, test condition is 25 ± 0.5 ℃.
Containing the liquid-crystal composition of pyranylation compound, comprise the component A being formed by the compound shown in one or more general formula Is, the component B being formed by the compound shown in one or more general formula Is I, the component C being formed by the compound shown in one or more general formula III, the component D being formed by the compound shown in one or more general formula Is V, the component E being formed by the compound shown in one or more general formulas V;
Wherein,
R
11, R
12be respectively 1. following~4. described group wherein any,
①:H、Cl、F、CN、OCN、OCF
3、CF
3、CHF
2、CH
2F、OCHF
2、SCN、NCS、SF
5,
2.: C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15straight alkenyloxy,
3.: 2. in group one or more-CH2-quilt-CH=CH-,-C ≡ C-,-COO-,-OOC-, sub-cyclobutyl, cyclopentylidene ,-O-or-S-substitute after and not direct connected group of Sauerstoffatom,
4.: 2. or any H of group 3. by F, Cl replace after group;
Ring A
12, ring A
13, ring A
14be respectively singly-bound,
in one;
Z
11, Z
12, Z
13be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-,-CF
2cH
2-,-CH
2cF
2-,-C
2f
4-, one in-CF=CF-;
A, b, c, d are respectively 0,1,2,3, and a+b+c+d≤5;
R
21, R
22, R
31, R
32, R
41, R
42, R
51, R
52be respectively F, Cl, CN, C
1~C
7straight chained alkyl, C
1~C
7straight chain alkoxyl group, C
2~C
7straight-chain alkenyl, C
1~C
5straight chain fluoroalkyl;
Ring A
21, ring A
22, ring A
31, ring A
41, ring A
42, ring A
51, ring A
52, ring A
53be respectively singly-bound,
in one;
Z
51be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-in one;
L
21, L
22, L
41be respectively the one in H, F, Cl, CN;
E, f, g, h, i, j are respectively 0,1,2.
Preferably,
R
11for H, C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15one in straight alkenyloxy,
R
12for H, Cl, F, CN, OCN, OCF
3, CF
3, CHF
2, CH
2f, OCHF
2, SCN, NCS, SF
5, C
1~C
15straight chained alkyl, C
1~C
15straight chain alkoxyl group, C
2~C
15straight-chain alkenyl, C
2~C
15one in straight alkenyloxy,
Z
11, Z
12, Z
13be respectively singly-bound ,-CH
2-,-CH
2-CH
2-,-(CH
2)
3-,-(CH
2)
4-,-CH=CH-,-C ≡ C-,-COO-,-OOC-,-CF
2o-,-OCH
2-,-CH
2o-,-OCF
2-in one.
Of the present invention containing in the liquid-crystal composition of pyranylation compound, in liquid-crystal composition, to account for the weight percentage of liquid-crystal composition be 1%~40% to component A, is preferably 8%~19%; The weight percentage that B component accounts for liquid-crystal composition is 1%~60%, is preferably 5%~40%; The weight percentage that component C accounts for liquid-crystal composition is 10%~70%, is preferably 33%~49%; The weight percentage that component D accounts for liquid-crystal composition is 1%~30%, is preferably 3%~10%; The weight percentage that component E accounts for liquid-crystal composition is 1%~50%, is preferably 5%~30.5%; The weight percentage of said components A, B component, component C, component D, component E is 100%.
Of the present invention containing compound shown in the liquid-crystal composition formula of I of pyranylation compound can preferred following formula I-1~formula I-4 shown in one or more in compound, compound shown in general formula I I can preferred following formula II-1~formula II-10 shown in one or more in compound, compound shown in general formula III can preferred following formula III-1~formula III-4 shown in one or more in compound, compound shown in general formula I V can preferred following formula IV-1~formula IV-4 shown in one or more in compound, compound shown in general formula V is specially one or more in compound shown in following formula V-1~formula V-12,
Wherein,
R
11for H or C
1~C
10straight chained alkyl in one,
R
12for F, Cl, OCF
3, CF
3, one in CN, NCS,
(F) be H or F.
It is of the present invention containing further one or more in compound shown in preferred following formula I-1-1~formula I-4-6 of compound shown in the liquid-crystal composition formula of I of pyranylation compound,
Wherein,
R
11for H, CH
3, C
2h
5, C
3h
7, n-C
4h
9, n-C
5h
11, n-C
6h
13in one.
The each composition adopting in following embodiment 1~5, all can synthesize by known method, or obtain by commercial sources.These synthetic technologys are conventional, and the each liquid crystalline cpd obtaining meets electrical type compound standard after tested.
According to the weight percentage of each liquid-crystal composition of following examples 1~5 regulation, prepare liquid-crystal composition.The preparation of described liquid-crystal composition is to carry out according to the ordinary method of this area, as takes heating, ultrasonic wave, and the modes such as suspension according to the rules ratio mixing make.
Embodiment 1
Be mixed with liquid-crystal composition of the present invention by following listed each compound and weight percentage,
Above-mentioned liquid-crystal composition is filled in and between liquid-crystal display two substrates, carries out performance test, and test result is, Cp:87 ℃; Δ n:0.105; Δ ε: 7.2; γ
1: 65mPas;
This liquid-crystal composition has higher clearing point, moderate optical anisotropy, and suitably high dielectric anisotropy, very low rotation viscosity is therefore applicable to the TN-TFT of response fast, IPS-TFT indicating meter very much.
Embodiment 2
Be mixed with liquid-crystal composition of the present invention by following listed each compound and weight percentage,
Above-mentioned liquid-crystal composition is filled in and between liquid-crystal display two substrates, carries out performance test, and test result is, Cp:94 ℃; Δ n:0.125; Δ ε: 7.8; γ
1: 65mPas;
This liquid-crystal composition has higher clearing point, slightly high optical anisotropy, and suitably high dielectric anisotropy, very low rotation viscosity is therefore applicable to the TN-TFT indicating meter of response fast very much.
Embodiment 3
Be mixed with liquid-crystal composition of the present invention by following listed each compound and weight percentage,
Above-mentioned liquid-crystal composition is filled in and between liquid-crystal display two substrates, carries out performance test, and test result is, Cp:87 ℃; Δ n:0.105; Δ ε: 7.2; γ
1: 65mPas;
This liquid-crystal composition has higher clearing point, moderate optical anisotropy, and suitably high dielectric anisotropy, very low rotation viscosity is therefore applicable to the IPS-TFT indicating meter of response fast very much.
Embodiment 4
Be mixed with liquid-crystal composition of the present invention by following listed each compound and weight percentage,
Above-mentioned liquid-crystal composition is filled in and between liquid-crystal display two substrates, carries out performance test, and test result is, Cp:87 ℃; Δ n:0.112; Δ ε: 7.7; γ
1: 65mPas;
This liquid-crystal composition has higher clearing point, higher optical anisotropy, and suitably high dielectric anisotropy, very low rotation viscosity is therefore applicable to the IPS-TFT indicating meter of response fast very much.
Embodiment 5
Be mixed with liquid-crystal composition of the present invention by following listed each compound and weight percentage,
Above-mentioned liquid-crystal composition is filled in and between liquid-crystal display two substrates, carries out performance test, and test result is, Cp:87 ℃; Δ n:0.110; Δ ε: 6.9; γ
1: 63mPas;
This liquid-crystal composition has higher clearing point, moderate optical anisotropy, and suitably high dielectric anisotropy, very low rotation viscosity is therefore applicable to the TN-TFT indicating meter of response fast very much.
Above 5 embodiment, all have good low-temperature stability, and low rotary viscosity, maintains the fast time of response at low-temperature region.Can widen TN-TFT, the use temperature of IPS-TFT or FFS-TFT liquid crystal mode, and there is time of response and wider angular field of view faster, and being highly suitable for TN-TFT, IPS-TFT and FFS-TFT show.
Liquid-crystal composition provided by the present invention contains the difluoro methylene ether compound of pyranyl by use, there is threshold voltage and the effect of time of response of reduction, therefore the present invention develop liquid-crystal composition be the desirable liquid crystal material for the preparation of the TFT liquid-crystal display responding fast.
Although the present invention has only enumerated particular compound and the proportioning consumption (weight percentage) thereof of above-mentioned 5 embodiment, and carry out performance test, but liquid-crystal composition of the present invention can be on the basis of above-described embodiment, utilize the preferred liquid crystalline cpd of the liquid crystalline cpd of general formula I involved in the present invention, II, III, IV representative and general formula I, II, III, IV further expand and revise, by its proportioning consumption is suitably adjusted, all can reach object of the present invention.