CN113717736B - Negative liquid crystal composition with quick response and application thereof - Google Patents
Negative liquid crystal composition with quick response and application thereof Download PDFInfo
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- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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Abstract
The invention relates to a negative liquid crystal composition with quick response and application thereof, belonging to the technical field of liquid crystal materials. The fast response liquid crystal composition material comprises, by mass, 4% -58% of a monomer compound with a structure shown in a general formula I, 1% -55% of a monomer compound with a structure shown in a general formula II, 1% -80% of a monomer compound with a structure shown in a general formula III, and 0% -20% of a monomer compound with a structure shown in a general formula IV. The invention mainly solves the problems of high rotary viscosity, slow response time and the like of the negative liquid crystal material, solves the problem of slow response time of VA, greatly improves the quality of a display device used by VA, and can be used in the field of PSVA and UV 2A.
Description
Technical Field
The invention relates to a negative liquid crystal composition with quick response and application thereof, and belongs to the technical field of liquid crystal materials.
Background
With the rapid development of liquid crystal materials, liquid crystals have penetrated into many fields of modern science, the application range thereof is also expanding, and liquid crystal products such as clocks, flat panels, measuring machines, panels for automobiles, televisions, computer display screens and the like are seen everywhere in life. Liquid crystal display modes include TN, STN, VA, UV2A, PSVA, IPS, FFS, and the like, and liquid crystal materials are classified into positive liquid crystals and negative liquid crystals according to dielectric characteristics. The negative liquid crystal is a liquid crystal material with liquid crystal anisotropic dielectric property, the parallel dielectric constant is less than the vertical dielectric constant, liquid crystal molecules are distributed along the direction vertical to an electric field, and compared with the positive liquid crystal, the twist angular distribution of the liquid crystal material is more uniform, the liquid crystal material shows higher penetration rate, and is about 10 to 15 percent higher than that of the positive liquid crystal molecules.
As the demand for display increases, the demand for high contrast display becomes more important. The VA negative liquid crystal has excellent high contrast. In the prior art, some MVA, PVA and other mode negative liquid crystals gradually appear, and the negative liquid crystals solve the problem of visual angle by utilizing multi-domain.
The above related art has the following drawbacks: the response time of negative liquid crystals in modes such as MVA and PVA is slow, the response speed of a pixel point to an input signal cannot keep up, and a similar residual image or a trail of dragging appears when a picture moving at a high speed is watched, so that the smoothness of the picture cannot be ensured.
Disclosure of Invention
The invention provides a negative liquid crystal composition with quick response, aiming at solving the problems that the negative liquid crystal material has the problems of high rotational viscosity, slow response time and the like for a long time, and the slow response time is always troubled by VA. By improving the problems of high rotary viscosity, slow response time and the like of negative liquid crystal, the liquid crystal composition greatly improves the response time, and meanwhile, the composition can also be applied to the fields of PSVA, UV2A and the like, which has great significance for the high display field.
The liquid crystal composition can be applied to liquid crystal display devices, and solves the problems of high rotary viscosity and slow response time of negative liquid crystal materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a fast-response negative liquid crystal composition material comprises the following components in percentage by mass:
one or more monomer compounds with a structure shown in a general formula I, wherein the mass fraction of the monomer compounds is 4% -58%, and the specific structure of the general formula I is as follows:
in the general formula, R 1 ,R 2 Each independently represents a straight-chain alkyl group having 1 to 5 carbon atoms; a1 Each A2 independently represents cyclohexane or benzene ring;
one or more monomer compounds with a structure shown in a general formula II, wherein the mass fraction of the monomer compounds is 1% -55%, and the specific structure of the general formula II is as follows:
in the general formula, R 3 ,R 4 Each independently of the otherRepresents a linear alkyl group having 2 to 5 carbon atoms; n represents 0 or 1 cyclohexane;
one or more monomer compounds with a structure shown in a general formula III, wherein the mass fraction of the monomer compounds is 1% -80%, and the specific structure of the general formula III is as follows:
in the general formula, R 5 Represents a linear alkyl group having 2 to 5 carbon atoms; r 6 Represents a linear alkyl group or an alkoxy group having 2 to 4 carbon atoms; y is 1 ，Y 2 ，Y 3 Each independently represents a-F or-H group substitution; a3 Each A4 independently represents cyclohexane or a benzene ring;
one or more monomer compounds with a structure shown in a general formula IV, wherein the mass fraction of the monomer compounds is 0% -20%, and the specific structure of the general formula IV is as follows:
in the general formula, R 7 Represents a linear alkyl group having 2 to 5 carbon atoms; r is 8 Represents a linear alkyl group or an alkoxy group having 2 to 6 carbon atoms; a5 represents cyclohexane or a benzene ring, m represents 0 or 1 benzene ring;
the sum of the mass of the monomer compounds with the structures shown in the general formula I, the general formula II, the general formula III and the general formula IV is 100 percent.
Preferably, in the liquid crystal composition material, the compound shown in the general formula I is selected from one or more compounds shown in the general formulas I-1 to I-26:
further preferably, the compound represented by the formula I is one or more selected from the group consisting of liquid crystal compounds represented by the formulae I-5, I-6, I-7, I-8 and I-17.
More preferably, the compound represented by the general formula I is selected from two or more compounds represented by the general formulae I-6, I-8 and I-17.
Preferably, in the liquid crystal composition material, the compound shown in the general formula II comprises one or more of the following compounds shown in the general formulas II-1 to II-18:
further preferably, the compound represented by the formula II is one or more selected from liquid crystal compounds represented by the formulae II-1, II-2, II-5, II-6 and II-7.
More preferably, the compound represented by the general formula II is two or more of the compounds represented by the general formulae II-2, II-5 and II-6.
Preferably, in the liquid crystal composition material, the compound shown in the general formula III is selected from one or more compounds shown in general formulas III-1 to III-27:
further preferably, the compound represented by the formula III is selected from one or more liquid crystal compounds represented by the formulae III-5, III-6, III-9, III-10, III-13, III-20 and III-24.
More preferably, the compound of formula III is selected from one or more compounds of formulae III-5, III-10, III-13, III-20 and III-24.
Preferably, in the liquid crystal composition material, the compound shown in the general formula IV is selected from one or more compounds shown in general formulas IV-1 to IV-20:
further preferably, the compound represented by the general formula IV is selected from one or more liquid crystal compounds represented by general formulas IV-6, IV-7, IV-16 and IV-17.
More preferably, the compound represented by the general formula IV is one or two compounds selected from the general formulas IV-6 and IV-17.
In the quick response liquid crystal composition, the compound shown in the general formula I accounts for 4-58 percent, more preferably 6-50 percent, and still more preferably 9-44 percent by weight; the compound shown in the general formula II is 1-55%, more preferably 2-50%, and still more preferably 2.5-42%; 1 to 80 percent of compound shown in the general formula III, more preferably 2 to 70 percent, and still more preferably 2 to 60 percent; the compound represented by the general formula IV is 0 to 20 percent, more preferably 2 to 16 percent, and still more preferably 4 to 13 percent.
In the liquid crystal composition material, in addition to the monomer compounds, polymerizable compounds accounting for 0.15-0.34% of the total mass of the monomer compounds shown in general formulas I-IV can be added, and the structure is shown in general formula V-A:
further, the fast-response liquid crystal composition material is composed of the following compounds in mass ratio:
10 to 16 percent of compound shown in a general formula I-6,
8 to 12 percent of compound shown in a general formula I-8,
9 to 16 percent of compound shown in a general formula I-17,
6 to 15 percent of compound shown in a general formula II-2,
3 to 10 percent of a compound shown in a general formula II-5,
9 to 18 percent of compound shown in the general formula II-6,
4 to 12 percent of compound shown in a general formula III-5,
4 to 11 percent of compound shown in a general formula III-10,
8 to 17 percent of compound shown in a general formula III-13,
2 to 9 percent of a compound shown in a general formula III-20,
2 to 9 percent of compound shown in a general formula III-24,
2 to 8 percent of compound shown in a general formula IV-6,
3% -8% of a compound shown in a general formula IV-17.
Further preferably, the fast response time liquid crystal composition material is composed of the following compounds in mass ratio:
12 to 15 percent of compound shown in a general formula I-6,
8 to 10 percent of compound shown as a general formula I-8,
9 to 13 percent of compound shown in a general formula II-2,
4 to 6 percent of compound shown in a general formula II-5,
14 to 17 percent of compound shown in a general formula II-6,
5 to 9 percent of compound shown in a general formula III-5,
6 to 11 percent of compound shown in a general formula III-10,
10 to 16 percent of compound shown in a general formula III-13,
4 to 9 percent of compound shown in a general formula III-20,
3 to 8 percent of compound shown in a general formula III-24,
3 to 6 percent of compound shown in the general formula IV-6,
4% -8% of a compound shown in a general formula IV-17.
The negative liquid crystal composition with quick response has lower rotational viscosity and quicker response time, and can be applied to liquid crystal display devices of negative display modes, wherein the negative display modes comprise VA, PSVA, UV2A and the like.
The invention has the advantages that:
the invention mainly solves the problems of high rotary viscosity, slow response time and the like of the negative liquid crystal material. The problem that VA is troubled by the slow response time all the time is solved, the quality of a display device used by the VA is greatly improved, and meanwhile, the display device can also be used in the field of PSVA and UV 2A.
The liquid crystal composition greatly improves the response time, and meanwhile, the composition can also be applied to display modes such as PSVA, UV2A and the like, which is significant for the high display field.
Detailed Description
The abbreviated codes of the test items in the following examples are as follows:
tni: clearing away bright spots;
no: refractive index of ordinary rays (589nm, 25 ℃);
ne: refractive index of extraordinary rays (589nm, 25 ℃);
Δ n: refractive index anisotropy (589nm, 25 ℃);
T on+off : represents the response time measured at 25 ℃ in a4 μm vertical box;
Δ ε: dielectric anisotropy (1KHz, 25 ℃);
wherein, deltaepsilon = epsilon/epsilon ⊥ Wherein ε/' is the dielectric constant parallel to the molecular axis,. Epsilon. Is the dielectric constant perpendicular to the molecular axis, test conditions: 25 ℃ and 1KHz;
k11: a splay elastic constant;
k33: a bending elastic constant;
vth: a threshold voltage;
γ 1: represents the rotational viscosity [ mPas ] measured at 25 ℃ at a box thickness of 20 μm, as measured by Instec;
VHR represents a voltage holding ratio, and the test conditions (1V, 0.5Hz,60 ℃) were measured by Toyo 6254;
ION: indicates the ion concentration.
Example 1:
according to the composition of the liquid crystal composition in Table 1, 14.5% of the I-6 compound, 12.5% of the II-2 compound, 19% of the II-6 compound, 2.5% of the II-5 compound, 7% of the III-20 compound, 3% of the III-5 compound, 14.5% of the I-17 compound, 7% of the III-10 compound, 12% of the I-8 compound, and 8% of the compound of the general formula III-24 in example 1 were weighed and mixed with each other, placed in a hard borosilicate glass bottle, heated under nitrogen protection, and stirred electromagnetically or mechanically until a molten, clear, uniform and transparent solution appeared, and further stirred for 30 minutes, and then the heating was stopped after the materials were thoroughly and uniformly mixed. Degassing under reduced pressure while stirring; the vacuum degree is increased along with the reduction of the temperature, the stirring is stopped until the temperature is cooled to the room temperature, and the vacuum pumping is continued until no bubbles appear.
Filtering the mixed liquid crystal into a clean and dry hard high borosilicate filter flask by using a sand core funnel under the protection of nitrogen; after the filtration, the mixed liquid crystal is transferred to a high borosilicate crystallization dish, and then the crystallization dish is placed in a pressure-resistant vacuum drier, and the pressure is continuously reduced and the degassing is carried out until no micro bubbles appear.
The liquid crystal composition prepared by the method is filled between two substrates of a liquid crystal display to carry out performance test, and the measured physical property parameter results are shown in table 1.
Table 1 composition and test data for liquid crystal composition of example 1
The liquid crystal display device of example 1 has relatively low clearing point and moderate dielectric constant, and particularly has the characteristics of low rotational viscosity, fast response time, high voltage holding ratio, low ion concentration and the like, which is significant for the display devices of VA, PSVA, UV2A and other negative liquid crystals, and the quality of the liquid crystal display device is greatly improved.
In example 1, a PSVA material represented by the symbol PS1 was obtained by adding 0.25% by mass of the V-A polymer based on the total mass of the liquid crystal composition in Table 1. And (3) filling the PS1 liquid crystal into a test box, irradiating the liquid crystal for 120s by using UV light with the illumination intensity of 5mw and the wavelength of 313nm or 365nm under the voltage of 5V, and testing the pretilt angle and the concentration residual condition of the polymer after the exposure is finished.
TABLE 2 Pre-Tilt Angle and Polymer concentration residual test results for PS1 liquid crystals
From the above data, it can be seen that the low residual concentration of the polymer indicates that the polymer has fully reacted and forms a stable pretilt angle, enhancing its anchoring ability.
The PS1 was irradiated under different exposure conditions (light intensity, time, voltage) and the pretilt angle change of the PS1 was tested under different conditions, the test data being shown in tables 3 and 4.
TABLE 3 pretilt angle variation test results of PS1 under different conditions (I)
TABLE 4 pretilt angle variation test results of PS1 under different conditions (II)
The selection of different exposure conditions, such as driving voltage, irradiation time, and light intensity, has a significant effect on the pretilt angle of the material.
Example 2:
the liquid crystal composition prepared according to the method of example 1 was filled between two substrates of a liquid crystal display to perform a performance test with reference to the mixture ratio of the liquid crystal composition in table 5, and the results of the measured physical property parameters are shown in table 5.
Table 5 composition and test data for liquid crystal composition of example 2
In example 2, it was found that the liquid crystal material has a low clearing point and a moderate refractive index and dielectric constant, particularly, has a low rotational viscosity and a fast response time, and greatly improves the fast response of the display device.
In example 2, a PSVA material obtained by adding 0.29% by mass of a V-A polymer to the total amount of the liquid crystal composition was represented by the symbol PS 2. The PS2 was irradiated under different exposure conditions (light intensity, time, voltage) and the pretilt angle change of the PS2 was measured under different conditions, and the test data are shown in tables 6 and 7.
TABLE 6 pretilt angle variation test results of PS2 under different conditions (I)
TABLE 7 pretilt Angle Change test results of PS2 under different conditions (II)
Example 3:
the liquid crystal composition prepared according to the method of example 1 was filled between two substrates of the liquid crystal display to perform the performance test with reference to the mixture ratio of the liquid crystal composition in table 8, and the results of the measured physical property parameters are shown in table 8.
Table 8 composition of liquid crystal composition and test data for example 3
Example 4:
the liquid crystal composition prepared according to the method of example 1 was filled between two substrates of a liquid crystal display to perform a performance test with reference to the mixture ratio of the liquid crystal composition in table 9, and the results of the measured physical property parameters are shown in table 9.
TABLE 9 example 4 liquid crystal composition compositions and test data
Example 5:
the liquid crystal composition prepared according to the method of example 1 was filled between two substrates of a liquid crystal display to perform a performance test with reference to the mixture ratio of the liquid crystal composition in table 10, and the results of the measured physical property parameters are shown in table 10.
TABLE 10 compositions and test data for liquid crystal compositions of example 5
As can be seen from examples 1 to 5, the negative liquid crystal material has a lower rotational viscosity and a faster response time, and has excellent reliability parameters such as a voltage holding ratio and an ion concentration, and a higher voltage holding ratio, a lower ion concentration, and the like, thereby improving the quality of a display device.
The liquid crystal compositions of examples 3 to 5 were added with 0.30% by mass of the V-A polymerizable compound to give polymer materials of PS3, PS4, and PS 5. The test data are shown in tables 11-16, after the test, the pre-tilt angle is changed under different conditions (light intensity, time, voltage).
TABLE 11 pretilt Angle Change test results of PS3 under various conditions (I)
TABLE 12 measurement results of pretilt angle variation of PS3 under different conditions (II)
TABLE 13 pretilt Angle Change test results of PS4 under different conditions (I)
TABLE 14 measurement results of pretilt angle variation of PS4 under different conditions (II)
TABLE 15 pretilt Angle Change test results of PS5 under various conditions (I)
TABLE 16 pretilt Angle Change test results of PS5 under different conditions (II)
From the above data, it can be seen that under different exposure conditions, such as the selection of the driving voltage, the irradiation time, and the light intensity, the pretilt angle of the material is significantly affected, and a stable pretilt angle is formed, so as to enhance the anchoring ability.
The fast-response negative liquid crystal composition has lower rotational viscosity and faster response time, and can be applied to liquid crystal display devices of negative display modes such as VA, PSVA, UV2A and the like.
Claims (8)
1. A negative liquid crystal composition material with fast response, characterized in that: the fast response liquid crystal composition material consists of the following compounds in percentage by mass:
14.5% of a compound of formula I-6:
12% of a compound of formula I-8:
14.5% of a compound of formula I-17:
12.5% of a compound of formula II-2:
2.5% of a compound of formula II-5:
19% of a compound of the formula II-6:
3% of a compound of the formula III-5:
7% of a compound of the formula III-10:
7% of a compound of the formula III-20:
8% of a compound of the formula III-24:
2. a negative liquid crystal composition material with fast response, characterized in that: the fast-response liquid crystal composition material consists of the following compounds in percentage by mass:
14% of a compound of the formula I-6:
9% of a compound of the formula I-8:
14% of a compound of the formula I-17:
12.5% of a compound of formula II-2:
5.5% of a compound of formula II-5:
16% of a compound of formula II-6:
7% of a compound of the formula III-5:
7% of a compound of the formula III-10:
6% of a compound of the formula III-20 is a compound represented by:
5% of a compound of the formula III-24:
4% of a compound of the formula IV-6:
3. a negative liquid crystal composition material with fast response, characterized in that: the fast response liquid crystal composition material consists of the following compounds in percentage by mass:
14% of a compound of the formula I-6:
9% of a compound of the formula I-8:
12% of a compound of formula I-17:
13.5% of a compound of formula II-2:
5.5% of a compound of formula II-5:
15% of a compound of formula II-6:
7% of a compound of the formula III-5:
9% of a compound of the formula III-10:
6% of a compound of the formula III-20:
4% of a compound of the formula III-24:
5% of a compound of the formula IV-6:
4. a negative liquid crystal composition material with fast response, characterized in that: the fast response liquid crystal composition material consists of the following compounds in percentage by mass:
13% of a compound of the formula I-6:
11% of a compound of the formula I-8:
15% of a compound of the formula I-17:
14% of a compound of the formula II-2:
6.5% of a compound of formula II-5:
16% of a compound of the formula II-6:
6% of a compound of the formula III-5:
4% of a compound of the formula
III-13:
6.5% of a compound represented by the general formula III-20:
8% of a compound of the formula III-24:
5. a negative liquid crystal composition material with fast response, characterized in that: the fast response liquid crystal composition material consists of the following compounds in percentage by mass:
13% of a compound of the formula I-6:
12% of a compound of formula I-8:
14.5% of a compound of formula I-17:
14% of a compound of the formula II-2:
3.5% of a compound of formula II-5:
19% of a compound of the formula II-6:
2% of a compound of the formula III-10:
4% of a compound of the formula III-13:
5.5% of a compound of the formula III-20:
7% of a compound of the formula III-24:
5.5% of a compound of formula IV-17:
6. a fast-responding negative working liquid crystal composition material according to any one of claims 1 to 5, wherein: the liquid crystal composition material is also added with a polymerizable compound accounting for 0.15-0.34% of the total mass of the monomer compounds shown in general formulas I-IV, and the structure is shown as a general formula V-A:
7. use of the fast-responding negative liquid crystal composition material according to any one of claims 1 to 5 for the preparation of a liquid crystal display device of negative-type display mode.
8. Use according to claim 7, characterized in that: the liquid crystal display device comprises a VA liquid crystal display device, a PSVA liquid crystal display device and a UV2A liquid crystal display device.
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