Summary of the invention
The object of this invention is to provide a kind of liquid-crystal composition, it possesses suitable optical anisotropy and the characteristic such as dielectric anisotropy, faster response speed and good low temperature storage stability.This liquid-crystal composition can be applicable in AM element, makes this AM element have time of response short, the characteristic such as voltage retention is large, contrast gradient is large, the life-span is long.
One aspect of the present invention provides a kind of liquid-crystal composition, comprises, with described liquid-crystal composition total weight:
One or more of 5-40% are selected from the compound of general formula I
One or more of 30-60% are selected from the compound of general formula II
and
One or more of 5-45% are selected from by general formula III-1, general formula III-2 and the compound that forms thereof
Wherein,
R
1, R
2, R
3, R
4, R
5and R
6identical or different, being selected from by the thiazolinyl that H, carbonatoms are the alkyl of 1-7 or alkoxyl group, carbonatoms is the fluoro-alkyl of 1-7 or fluoroalkyl, carbonatoms is 2-7 or alkene oxygen base or carbonatoms is independently of one another the group that the fluoro thiazolinyl of 2-7 or fluoro alkene oxygen base form;
X
1be selected from by H, F, Cl ,-OCF
3, carbonatoms is alkyl or the alkoxyl group of 1-7, the group of the fluoroalkyl that the fluoro-alkyl that carbonatoms is 1-5, carbonatoms are 1-5, carbonatoms to be the fluoro thiazolinyl of 2-5 or carbonatoms the be fluoro alkene oxygen base composition of 2-5;
with
identical or different, be selected from independently of one another by
with
the group of composition;
L
1, L
2and L
3identical or different, represent H or F independently of one another.
Liquid-crystal composition of the present invention, also comprises:
Account for being selected from by general formulae IV-1, general formulae IV-2 and the compound that forms thereof of described liquid-crystal composition gross weight 1-25%
Wherein,
R
7, R
8and R
9identical or different, be selected from alkyl that carbonatoms is 1-7 independently of one another, group that thiazolinyl that alkoxyl group that carbonatoms is 1-7, carbonatoms are 2-7 or carbonatoms are the alkene oxygen base composition of 2-7;
L
4, L
5, L
6, L
7and L
8identical or different, represent H or F independently of one another.
In some embodiments of the present invention, the compound of preferred described formula I accounts for the 10-35% of described liquid-crystal composition gross weight; The compound of described general formula II accounts for the 35-55% of described liquid-crystal composition gross weight; The compound of described general formula III-1, general formula III-2 and combination composition thereof accounts for the 10-40% of described liquid-crystal composition gross weight; And the compound of described general formulae IV-1, general formulae IV-2 and combination composition thereof accounts for described liquid-crystal composition gross weight 2-20%.
In some embodiments of the present invention, the compound of described formula I is selected from one or more compounds in the group be made up of following compound:
and
Wherein,
Described R
1be selected from the group be made up of the thiazolinyl of carbonatoms to be the alkyl of 1-5 or alkoxyl group and carbonatoms be 2-5 or alkene oxygen base.
In some embodiments of the present invention, the compound of described general formula II is selected from one or more compounds in the group be made up of following compound:
and
Wherein,
Described R
2be selected from the group be made up of the thiazolinyl of carbonatoms to be the alkyl of 1-5 or alkoxyl group and carbonatoms be 2-5 or alkene oxygen base.
In some embodiments of the present invention, the compound of described general formula III-1 is selected from one or more compounds in the group be made up of following compound:
and
Wherein,
Described R
4be selected from the group be made up of the thiazolinyl of carbonatoms to be the alkyl of 1-5 or alkoxyl group and carbonatoms be 2-5 or alkene oxygen base.
Described X
1being selected from by F or carbonatoms is the group that the alkyl of 1-5 or alkoxyl group form.
In some embodiments of the present invention, the compound of described general formula III-2 is selected from one or more compounds in the group be made up of following compound:
and
In some embodiments of the present invention, the compound of described general formulae IV-1 is selected from one or more compounds in the group be made up of following compound:
and
Wherein,
R
7the group that the alkene oxygen base that to be selected from by the thiazolinyl that carbonatoms is the alkyl of 1-5, carbonatoms is the alkoxyl group of 1-5, carbonatoms is 2-5 or carbonatoms be 2-5 forms;
In some embodiments of the present invention, the compound of described general formulae IV-2 is selected from one or more compounds in the group be made up of following compound:
and
Wherein,
R
8and R
9identical or different, be selected from alkyl that carbonatoms is 1-5 independently of one another, group that thiazolinyl that alkoxyl group that carbonatoms is 1-5, carbonatoms are 2-5 or carbonatoms are the alkene oxygen base composition of 2-5;
Another aspect of the present invention provides a kind of liquid crystal display device, and described liquid crystal display device comprises liquid-crystal composition of the present invention.
Another aspect of the invention provides a kind of active matrix liquid crystal display device, and described liquid crystal display device comprises liquid-crystal composition of the present invention.
The present invention by carrying out combination experiment to above-claimed cpd, by with the comparison contrasted, determine the liquid crystal media comprising above-mentioned liquid-crystal composition, have that viscosity is little, low-temperature stability good, characteristic that dielectric anisotropic is large and high to the stability of heat.
In the present invention if no special instructions, described ratio is weight ratio, and all temperature are degree celsius temperature, and the box selected of the test of described response time data is thick is 7 μm.
Embodiment
Below with reference to specific embodiments, the present invention is described.It should be noted that, the following examples are example of the present invention, are only used for the present invention is described, and are not used for limiting the present invention.When not departing from purport of the present invention or scope, other combination and the various improvement in design of the present invention can be carried out.
For ease of expressing, in following embodiment, the coded representation of unit structure listed by table 1 of liquid-crystal composition:
The unit structure code of table 1 liquid crystalline cpd
Compound for following structural formula:
This structural formula as represented by code listed in Table 1, then can be expressed as: nCCGF, and the n in code represents the C atomicity of left end alkyl, and such as n is " 3 ", namely represents that this alkyl is-C
3h
7; C in code represents cyclohexyl.
In following examples test event to write a Chinese character in simplified form code name as follows:
Cp(DEG C): clearing point (to row-isotropic phase transition temperature)
Δ n: optical anisotropy (589nm, 25 DEG C)
Δ ε: dielectric anisotropy (1KHz, 25 DEG C)
γ 1: reverse viscosity (mPa*s, at 20 DEG C)
LTS: low-temperature storage time (at-20 DEG C)
Wherein, refractive anisotrop use Abbe refractometer under sodium lamp (589nm) light source, 25 DEG C test; Measurement box is TN90 type, thick 7 μm of box.
Each composition adopted below in an example, except the compound of formula I, all the other components all can be synthesized by known method, or are obtained by commercial sources.These synthetic technologys are conventional, and each liquid crystalline cpd that obtains meets electrical type compound standard after tested.
Preparation example 1
The synthetic route of chemical formula B represents as follows:
Its concrete technology is as follows:
Wherein, compound B-11 obtains by commercial sources.
(1) synthesis of compd B 2
In 250mL there-necked flask, add 2 successively, 3, 5-tri-fluoro-4-bromo-benzoic acid (B1) 25.5g, 100mL toluene, 1, 3-dimercaptopropane 14.0g, trifluoromethayl sulfonic acid 19.5g, reflux, divide water 3 hours, steam except about 50mL toluene, under nitrogen protection, be cooled to room temperature, 100mL methylene dichloride is added in reaction flask, be cooled to-78 DEG C, 15g triethylamine is dripped in reaction flask, 19g3, 4, the mixture of 5-trifluoromethyl phenol and 50mL methylene dichloride, after dropwising, continue under nitrogen protection, temperature control-78 DEG C stirs after 1 hour, 24g triethylamine compound trihydrofluoride solution is dripped in reaction flask, in reaction flask, 24g bromine is dripped again after 5min, continue temperature control-78 DEG C, stir 1 hour, naturally-30 DEG C are warming up to, reaction solution is poured in the mixture of 8g sodium hydroxide and 300g frozen water, aftertreatment, purify through column chromatography, obtain white solid B216.5g, GC:99.2, yield: 40.5%.
(2) synthesis of compd B 4
In 250mL there-necked flask, add 14.2g successively to bromo-iodobenzene (B3), 9.0g4-n-propyl-2-fluorobenzoic boric acid; 60mL toluene, 30mL ethanol, 30mL water; 11g sodium carbonate, after stirring 5min, under nitrogen protection; add 0.2g4-triphenylphosphine palladium, reflux 5 hours, aftertreatment; purify through column chromatography, obtain off-white color solid B4,13.1g; GC:98.3%, yield: 89.4%.
(3) synthesis of compd B 5
In 250mL there-necked flask, add 13.1g B4,100mL anhydrous tetrahydro furan; under nitrogen protection; be cooled to-78 DEG C, drip the hexane solution (2.4mol/L) of 21mL n-Butyl Lithium, continue temperature control-78 DEG C and stir 1 hour; then in reaction flask, drip the mixture of 12g boric acid three isobutyl ester and 40mL anhydrous tetrahydro furan; continue temperature control-78 DEG C to stir 1 hour, aftertreatment, steam and desolventize to obtain off-white color solid B59.9g; HPLC:95%, yield: 85.8%.
(4) synthesis of compd B
In 250mL there-necked flask, add 5.2g B5 successively, 8.2g B2; 50mL toluene, 25mL ethanol, 25mL water; 4.3g sodium carbonate, after stirring 5min, under nitrogen protection; add 0.1g4-triphenylphosphine palladium, reflux 6 hours, aftertreatment; purify through column chromatography, obtain white solid B, 8.1g; GC:99.8%, yield: 75%.
Profit use the same method can prepare following structural formula Compound D, E, F, G, H:
The liquid crystal property of table 2 compd B, D, E, F, G, H
Compound |
DSC |
Δε |
Δn |
B |
C111.7I |
18 |
0.181 |
C |
C148.6I |
20.2 |
0.17 |
D |
C81.8N118.1I |
19.7 |
0.126 |
E |
C81.7N87.9I |
20 |
0.127 |
F |
C99N113.4I |
22 |
0.18 |
G |
C109.3N144.1I |
17.8 |
0.225 |
Compd B
1h-NMR figure is shown in Fig. 1;
Compound C
1h-NMR figure is shown in Fig. 2;
Compound D
1h-NMR figure is shown in Fig. 3;
Compd E
1h-NMR figure is shown in Fig. 4;
Compound F 17-hydroxy-corticosterone
1h-NMR figure is shown in Fig. 5;
Compound G's
1h-NMR figure is shown in Fig. 6.
According to the proportioning of each liquid-crystal composition of following examples regulation, prepare liquid-crystal composition.The preparation of described liquid-crystal composition carries out according to the ordinary method of this area, and as taked the modes such as heating, ultrasonic wave, suspension, ratio mixing is obtained according to the rules.
Prepare and study the liquid-crystal composition provided in the following example.Show composition and its performance parameter test result of each liquid-crystal composition below.
Be the composition of reference examples liquid-crystal composition, proportioning listed by table 4 and be filled in the test result of carrying out performance test between liquid-crystal display two substrates, so that carry out performance comparison with explanation liquid-crystal composition of the present invention.
Reference examples 1
Be mixed with the liquid-crystal composition of reference examples 1 by each compound listed in table 3 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 3 liquid crystal combination composition formula and test performance thereof
Embodiment 1
Be mixed with the liquid-crystal composition of embodiment 1 by each compound listed in table 4 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 4 liquid crystal combination composition formula and test performance thereof
Embodiment 2
Be mixed with the liquid-crystal composition of embodiment 2 by each compound listed in table 5 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 5 liquid crystal combination composition formula and test performance thereof
Embodiment 3
Be mixed with the liquid-crystal composition of embodiment 3 by each compound listed in table 6 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 6 liquid crystal combination composition formula and test performance thereof
Embodiment 4
Be mixed with the liquid-crystal composition of embodiment 4 by each compound listed in table 7 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 7 liquid crystal combination composition formula and test performance thereof
Embodiment 5
Be mixed with the liquid-crystal composition of embodiment 5 by each compound listed in table 8 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 8 liquid crystal combination composition formula and test performance thereof
Embodiment 6
Be mixed with the liquid-crystal composition of embodiment 6 by each compound listed in table 9 and weight percentage, it is filled between liquid-crystal display two substrates and carries out performance test, and test data is as shown in the table:
Table 9 liquid crystal combination composition formula and test performance thereof
With reference to comparative example 1, from the test data of above embodiment 1,2,3,4,5 and 6, liquid-crystal composition provided by the present invention has less viscosity, larger dielectric anisotropy, suitably high refractive anisotrop and higher clearing point.
Advantage is fast response time, has good display effect and low temperature storage stability, is applicable in AM display device.