CN105331371B - Negative liquid crystal composition and its application - Google Patents
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Abstract
The invention provides a kind of negative liquid crystal composition, the negative liquid crystal composition includes the compound of the compound of at least one formula I, the compound of at least one formula II, the compound of at least one general formula III, and at least one general formulae IV.The negative liquid crystal compound has suitable optical anisotropy and dielectric anisotropy, faster response speed, preferable UV resistance and high temperature reliability.The liquid crystal media that above-mentioned liquid-crystal composition is used as liquid crystal host composition and one or more polymerizable compounds or RM materials is included present invention also offers a kind of.Meanwhile, present invention also offers the liquid crystal display device for including the liquid-crystal composition or liquid crystal media.
Description
Technical Field
The invention relates to a negative liquid crystal composition with high response speed, high UV resistance and high-temperature reliability, and application of the liquid crystal composition in a liquid crystal display element.
Background
Liquid crystal display elements are used in various household electric appliances such as watches and calculators, measuring instruments, automobile panels, word processors, computers, printers, televisions, and the like. Typical examples of the night view display mode include PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), CSH (color super homeotropic), and the like. The device is classified into a PM (passive matrix) type and an AM (active matrix) type according to a driving method of the device. PM is classified into static (static) and multiplex (multiplex) types. AM is classified into a TFT (thin film transistor), an MIM (metal insulator metal), and the like. The types of TFTs are amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to a manufacturing process. Liquid crystal display elements are classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both light sources of natural light and backlight, depending on the type of light source.
Among these display modes, IPS mode, ECB mode, VA mode, CSH mode, and the like are different from TN mode or STN mode which are currently used in general in that the former uses a liquid crystal material having negative dielectric anisotropy. Among these display systems, VA display by AM driving is particularly applied to display elements requiring high speed and wide viewing angle, and among them, liquid crystal elements such as televisions are most expected.
The liquid crystal material used is required to have a low driving voltage, a high response speed, a wide operating temperature range, a large absolute value of negative dielectric anisotropy, a high phase transition temperature, and a low viscosity regardless of the display mode. Among them, in order to realize a good liquid crystal display, it is preferable that the cell thickness of a liquid crystal display element constituting the liquid crystal display and the value of Δ n of a liquid crystal material used be constant (e.jakeman et al, pyhs.lett., 39a.69 (1972)). In addition, the response speed of the liquid crystal display element is inversely proportional to the square of the thickness of the cell used. Therefore, in the production of a liquid crystal display element capable of high-speed response which can be used for displaying moving images and the like, it is necessary to use a liquid crystal composition having a large Δ n value. Various compounds have been developed as liquid crystal monomer components having a large Δ n value, but in general, such a compound having a large Δ n has a highly conjugated molecular structure, but tends to have poor compatibility with other liquid crystal materials, and is difficult to be used as a constituent element of a liquid crystal composition having good electrical characteristics. Further, a liquid crystalline compound used as a component of a liquid crystal composition which requires high insulation (resistivity) such as a thin film transistor liquid crystal display element is required to have high stability.
Although a liquid crystal composition having a large Δ n value is disclosed in the prior art, for example, patent document CN101128566, the prior art still has the performance balance problem that high clearing point, high refractive index anisotropy, appropriate dielectric anisotropy, high response speed, and low driving voltage, which are required in a liquid crystal television, a tablet computer, and the like, cannot be simultaneously satisfied.
The VA mode is normally black similarly to the IPS mode, but is different in that liquid crystal molecules in a liquid crystal layer of a VA mode panel are negative liquid crystals, transparent electrodes are provided on upper and lower substrates, and an electric field perpendicular to the substrates is formed. When not electrified, the long axes of the liquid crystal molecules are vertical to the substrate to form a dark state; when the electric field is applied, the long axes of the liquid crystal molecules fall down in a direction parallel to the substrates. The initial Alignment also requires rubbing of the substrate, which causes contamination and static electricity, and the pretilt angle is difficult to control, and in order to solve the initial Alignment problem of the VA mode, there are various derivative modes, such as Multi-domain Vertical Alignment (MVA), Patterned Vertical Alignment (PVA), Polymer Stabilized Alignment (PSA), and Polymer Stabilized Vertical Alignment (PSVA). Among them, the PSA mode and the PSVA mode are becoming mainstream due to their characteristics of high transmittance, high contrast, and fast response.
A Polymer Stabilized Alignment (PSA) type liquid crystal display device has a Polymer structure formed in a cell in order to control a Pretilt angle (Pretilt angle) of liquid crystal molecules, and is applied as a liquid crystal display element due to its characteristics of fast response and high contrast.
Meanwhile, the PSA principle is being used in various conventional liquid crystal displays, such as known PSA-VA, PSA-OCB, PS-IPS and PS-TN displays. In PSA-VA and PSA-OCB displays, the polymerization is generally carried out with application of an electrode voltage, whereas in PSA-IPS displays the polymerization is carried out with or without application, preferably without application of a voltage. As can be demonstrated in the test cell, the PSA method results in a pre-tilt in the cell. In the case of PSA-OCB displays, therefore, stabilization of the bending structure can be achieved, so that no bias voltage is also possible or can be reduced. In the case of PSA-VA displays, this pretilt has a positive effect on the response time. For PSA-VA displays, standard MVA or PVA pixel and electrode arrangements (Layout) can be used. But additionally, it is also possible, for example, to achieve with only one structured electrode side and without using projections, which considerably simplifies the production and at the same time leads to an excellent contrast while at the same time having excellent light transmission.
PSA-VA displays are described, for example, in JP10-036847A, EP1170626A2, US6861107, US7169449, US20040191428A1, US2000066793A1 and US20060103804A 1. PSA-OCB displays are described, for example, in T.J-Chen et al, Jpn.J.Appl.Phys.45, 2006, 2702-. PS-IPS displays are described, for example, in US6177972 and appl.phys.lett.1999, 75(21), 3264. PS-TN displays are described, for example, in OpticsExpress 2004, 12(7), 1221.
However, it has now been found that the liquid crystal host compositions and RM (reactive mesogen) materials disclosed in the prior art still have some drawbacks when used in PSA displays. Thus, not every arbitrary soluble RM material is suitable for PSA displays, and it is often difficult to find more suitable selection criteria compared to direct PSA tests with pretilt measurements. When it is desired to polymerize by means of UV light and without the addition of a photoinitiator, which may be advantageous for certain applications, the liquid crystal host composition choice becomes smaller.
In addition, the "material system" of the liquid-crystalline composition and the polymerizable components selected should have as good electrical properties as possible, in particular a high "voltage holding ratio" (HR or VHR). High HR after irradiation with UV light is important, especially for application in PSA displays, because UV irradiation is an essential part of the display manufacturing process, although it can also occur as a "normal" load (stress) in the finally made display.
Another problem in the production of PSA displays is the presence and removal of unreacted RM material after the polymerization step for pretilt angle generation. Such unreacted RM materials may negatively affect display performance, for example, by uncontrolled polymerization during its operation in the display.
As a result, prior art PSA displays often exhibit an undesirable "image sticking" effect in which the image produced in the display by addressing a selected pixel remains visible, even when the voltage for that pixel has been switched off or when other pixels have been addressed.
Image sticking may occur, for example, when liquid crystal host compositions having low voltage holding ratios are used, where ambient light or UV components (components) of light emitted by display backlighting may cause unwanted cleavage reactions in the liquid crystal molecules. This may lead to an enrichment of ionic impurities on the electrodes or alignment layers, causing problems with a reduction of the effective voltage applied to the display. This effect is known for conventional displays without polymeric components.
In PSA displays, additional image sticking effects due to the presence of residual unpolymerized RM material may be observed. In such displays, ambient light or the UV component of the light emitted by backlighting causes spontaneous polymerization of the unreacted RM material. In addressed pixels this may change the tilt angle after a few addressing periods, thereby causing a change in transmittance, whereas in unaddressed pixels the tilt angle and transmittance remain unaffected.
It is therefore desirable that the polymerization reaction is as complete as possible when manufacturing the PSA display and that the amount of residual unpolymerized RM material in the PSA display after its manufacture is as low as possible.
For these purposes RM materials and liquid crystal host compositions that are capable of complete and efficient polymerization are desired. In addition, it is desirable to achieve controlled polymerization of any residual amounts of unreacted RM material still present in the display. RM materials and liquid crystal host compositions that can be polymerized faster and more efficiently than the materials known so far are also desired.
It is therefore desirable to have available materials and material combinations, in particular RM materials and liquid crystal host compositions, for use in PS or PSA displays that are suitable for solving the above mentioned problems. In particular, the material should provide one or more of the following improvements:
providing better protection against the adverse effects of UV irradiation for RM photopolymerization;
generally providing improved UV stability;
-reducing the amount of residual unpolymerized RM material in the display;
the ability to produce small tilt angles faster and/or smaller tilt angles than prior art PSA displays and materials;
-reducing image retention in PSA displays.
Therefore, there is a need for a liquid crystal composition that has at least one of the above improvements as a liquid crystal medium consisting of a liquid crystal host composition and an RM material, and that also combines the performance characteristics of higher refractive index anisotropy, suitable dielectric anisotropy, high response speed, low driving voltage, and meets all aspects of the index.
Disclosure of Invention
The invention aims to provide a liquid crystal composition which has the performance characteristics of high response speed, good UV resistance, good high-temperature reliability and the like.
It is another object of the present invention to provide a liquid crystalline medium comprising the above liquid crystalline composition as a liquid crystal host composition and a RM material, which liquid crystalline medium has high voltage holding value after UV exposure and in a high temperature environment.
In particular, it has surprisingly been found that when the liquid crystal host composition of the present invention is used in combination with RM materials, it is able to generate the pretilt angle faster and reduce the UV exposure time and/or UV intensity and/or UV radiation dose, allowing for a more time and cost efficient manufacturing process compared to prior art liquid crystal host compositions. In addition, it allows the residual amount of unreacted RM material to be reduced and the image sticking effect to be suppressed.
It is still another object of the present invention to provide a liquid crystal display device using VA, PSVA, IPS or ECB mode comprising the liquid crystal composition of the present invention.
In order to achieve the above object of the invention, the present invention provides a negative liquid crystal composition comprising:
at least one compound of the general formula I
At least one compound of the general formula II
At least one compound of the formula III
At least one compound of the general formula IV
Wherein,
R1、R2、R3、R4、R5and R6Identical or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkenyloxy group having 2 to 10 carbon atoms;
R7and R8Identical or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms;
Z1、Z2、Z3and Z4Identical or different, each independently of the other, being a single bond, -CH2-CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O、-OCH2-、-COO-，-O-CO-、-C2F4-or-CF ═ CF —;
L1、L2、L3and L4Identical or different, each independently of the others, is F or Cl;
ring (C)And ringIdentical or different, each independently of the otherOr
a represents 0, 1 or 2.
The liquid crystal composition of the invention also comprises:
one or more compounds with the general formula V accounting for 0-30 percent of the weight of the liquid crystal composition
One or more compounds of a general formula VI accounting for 0-15 percent of the weight of the liquid crystal composition
Wherein,
R9and R10The same or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkenyloxy group having 2 to 10 carbon atoms;
R11is alkyl or alkoxy with 1-10 carbon atoms; ring (C)Is thatOr
In some embodiments, preferably, R is1、R2、R3、R4、R5And R6The same or different, each independently of the other, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In some embodiments, preferably, R is7And R8The alkyl or alkoxy groups are the same or different and each independently have 2 to 5 carbon atoms.
In some embodiments, preferably, R is9And R10The same or different, each independently of the other, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In some embodiments, preferably, R is11Is an alkyl group or an alkoxy group having 1 to 5 carbon atoms.
In some embodiments, preferably, Z is1、Z2And Z3Identical or different, each independently of the other, being a single bond, -CH2-CH2-、-CH＝CH-、-CF2O-、-CH2O, -COO-or-CF ═ CF-.
In particular, in some embodiments, Z1、Z2、Z3And Z4Are the same or different and each independently represents a single bond, -CH2-CH2-、-CF2O-、-CH2O or-COO-.
In some embodiments, preferably, the compound of formula i comprises 5 to 15% of the total weight of the liquid crystal composition; the compound of the general formula II accounts for 25-45% of the total weight of the liquid crystal composition; the compound of the general formula III accounts for 10-20% of the total weight of the liquid crystal composition; the compound of the general formula IV accounts for 4-45% of the total weight of the liquid crystal composition; the compound of the general formula V accounts for 0-32% of the total weight of the liquid crystal composition; the compound of the general formula VI accounts for 0-10% of the total weight of the liquid crystal composition.
In particular, in some embodiments, the compound of formula IV is present in an amount of 4 to 36% by weight of the total liquid crystal composition.
In particular, in some embodiments, the compound of formula v comprises 21-27% of the total weight of the liquid crystal composition.
In some embodiments, preferably, the compound of formula i is selected from one or more of the following compounds:
in some embodiments, preferably, the compound of formula ii is selected from one or more of the following compounds:
wherein,
R3and R4The same or different, each independently of the other, represents an alkyl or alkoxy group having 1 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In particular, in some embodiments, the compound of formula II is preferably one or more of the compounds of formulae II-1 to II-12:
wherein,
R3and R4The same or different, each independently of the other, represents an alkyl or alkoxy group having 1 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In some embodiments, preferably, the compound of formula iii is selected from one or more of the following compounds:
wherein,
R5and R6The same or different, each independently of the other, represents an alkyl or alkoxy group having 1 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In particular, in some embodiments, the compound of formula iii is preferably one or more of compounds of formulae iii-1 to iii-5:
wherein,
R5and R6The same or different, each independently of the other, represents an alkyl or alkoxy group having 1 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
In some embodiments, preferably, the compound of formula iv is selected from one or more of the following compounds:
wherein,
R7and R8The same or different, each independently of the other, represents an alkyl or alkoxy group having 1 to 5 carbon atoms.
Another aspect of the present invention provides a liquid crystalline medium comprising a liquid crystalline composition of the present invention, said liquid crystalline medium comprising:
one or more polymerizable compounds or RM materials; and
a negative liquid crystal composition as a liquid crystal host composition.
In some embodiments, preferably, the polymerizable compound or RM material is selected from one or more of the following compounds:
in some embodiments, the liquid crystal composition comprises:
one or more compounds with the general formula I accounting for 5-15 percent of the weight of the liquid crystal composition
One or more compounds with a general formula II accounting for 25-45 percent of the weight of the liquid crystal composition
One or more compounds of a general formula III accounting for 10-20% of the weight of the liquid crystal composition
One or more compounds of the general formula IV accounting for 4-45 percent of the weight of the liquid crystal composition
One or more compounds with the general formula V accounting for 0-30 percent of the weight of the liquid crystal composition
One or more compounds of the general formula IV accounting for 0-15 percent of the weight of the liquid crystal composition
Wherein,
R1、R2、R3、R4、R5and R6The same or different, each independently represent alkyl or alkoxy with 1-10 carbon atoms or alkenyl or alkenyloxy with 2-10 carbon atoms;
R7and R8The alkyl or alkoxy groups may be the same or different and each independently represent an alkyl or alkoxy group having 1 to 10 carbon atoms;
R9and R10The same or different, each independently represent alkyl or alkoxy with 1-10 carbon atoms or alkenyl or alkenyloxy with 2-10 carbon atoms;
R11is an alkyl group or an alkoxy group having 1 to 10 carbon atoms.
Z1、Z2、Z3And Z4Are the same or different and each independently represents a single bond, -CH2-CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O、-OCH2-、-COO-，-O-CO-、-C2F4-or-CF ═ CF —;
L1、L2、L3and L4Identical or different, each independently of the others being represented by F or Cl;
ring (C)And ringIdentical or different, each independently of the otherOr
Ring (C)Is thatOr
a represents 0, 1 or 2.
In another aspect of the invention, there is provided a liquid crystal display device comprising the liquid crystal composition of the invention or the liquid crystal medium.
When the compound represented by the general formula I is used as the component of the liquid crystal composition, the compound can play a role in improving the optical anisotropy of the liquid crystal composition; when the compound represented by the general formula II is used as the component of the liquid crystal composition, the effect of improving the dielectric anisotropy of the liquid crystal composition can be achieved; when the compound represented by the general formula III is used as the component of the liquid crystal composition, the optical anisotropy and the dielectric anisotropy of the liquid crystal composition can be improved, and the upper limit of the nematic phase temperature of the liquid crystal composition can be improved; when the compound represented by the general formula IV is used as the component of the liquid crystal composition, the effect of improving the intersolubility of all compounds in the liquid crystal composition can be achieved; when the compound represented by the general formula V is used as the component of the liquid crystal composition, the effect of reducing the rotational viscosity and response of the liquid crystal composition can be achieved; when the compound represented by the general formula VI is used as a component of the liquid crystal composition of the present invention, the compound can play a role in improving the optical anisotropy of the liquid crystal composition and increasing the upper limit of the nematic phase temperature of the liquid crystal composition.
The compound listed in the general formula I is a preferable compound, when the adding amount is 0, although the object of the invention can be achieved, the display effect is not very good, the response speed is slow, the reliability is poor, and particularly in the application of PSVA liquid crystal, the compound listed in the general formula I can reduce RM residue and improve the display effect; when the compounds listed in the general formulas II to VI are added into the liquid crystal material in proportion, various performances of the liquid crystal material are very stable.
The liquid crystal composition has the characteristics of high response speed, low viscosity, appropriately high optical anisotropy and dielectric anisotropy, better anti-UV performance, high-temperature reliability and the like, and a liquid crystal display device using the liquid crystal composition has the advantages of high response speed, high-temperature resistance, UV resistance and the like, can realize the balance of performances in all aspects, and is suitable for a liquid crystal display of VA, MVA, IPS or ECB mode.
Compared with the prior art, the liquid crystal medium containing the liquid crystal composition and the polymerizable compound or RM material can generate a larger pretilt angle, and the polymerizable compound or RM material has lower residue, so that the problems of poor display and the like in the prior PSVA technology can be improved, and the liquid crystal medium is particularly suitable for a liquid crystal display of PSA or PSVA mode.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
For convenience of expression, in the following examples, the group structure of the liquid crystal composition is represented by the code listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
Compounds of the following formula are exemplified:
the structural formula is represented by the code listed in Table 1, and can be expressed as: nCCGF, wherein n in the code represents the number of C atoms of the left alkyl group, for example, n is 3, namely, the alkyl group is-C3H7(ii) a C in the code represents cyclohexane.
The abbreviated codes of the test items in the following examples are as follows:
cp (. degree. C.) clearing Point (nematic-isotropic phase transition temperature)
Δ n refractive index anisotropy (589nm, 20 ℃ C.)
Delta dielectric anisotropy (1KHz, 25 ℃ C.)
Gamma 1 torsional viscosity (mPas at 20 ℃ C.)
The time required for Ton/ms to go from dark state to bright state
Time for Toff/ms to return from light state to dark state
Ton + Toff/ms response time
VHR (initial) Voltage holding ratio (%, 60 ℃, 5V 6Hz)
VHR (UV) Voltage holding ratio (%, 60 ℃, 5V 6Hz)
VHR (high temperature) Voltage holding ratio (%, 60 ℃, 5V 6Hz)
Wherein, the refractive index anisotropy is obtained by testing an Abbe refractometer under a sodium lamp (589nm) light source at 25 ℃; the dielectric test cell was of the type TN90, the cell thickness being 7 μm.
The components used in the following examples were synthesized by the inventors of the present application in accordance with a known method or by a suitable combination of methods in organic synthetic chemistry, except that the polymerizable compounds of formulae VII-1 to VII-28 were synthesized with reference to CN 101418220A. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds. Methods for introducing a target end group, ring structure and binding group into a starting material are described in publications such as Organic synthesis (John Wiley & Sons, Inc), Organic reaction (Organic reactions, John Wiley & Sons, Inc), Comprehensive Organic synthesis (Pergamon Press), and New Experimental chemical lecture (Takayatsu Co., Ltd.).
Liquid crystal compositions were prepared according to the compounding ratios of the liquid crystal compositions specified in the following examples. The liquid crystal composition is prepared according to the conventional method in the field, such as heating, ultrasonic wave, suspension and the like, and is mixed according to the specified proportion.
Liquid crystal compositions given in the following examples were prepared and studied. The composition of each liquid crystal composition and the results of the performance parameter test thereof are shown below.
The liquid crystal displays used in the following embodiments are all VA-TFT liquid crystal display devices, and have a cell thickness d of 7 μm, and are composed of a polarizer (polarizing plate), an electrode substrate, and the like. The display device is in a normally white mode, i.e. when no voltage difference is applied between the row and column electrodes, a viewer perceives a pixel color that is white. The upper and lower polarizer axes on the substrate are at a 90 degree angle to each other. The space between the two substrates is filled with an optical liquid crystal material.
Tables 2, 3 and 4 show the components and ratios of the liquid crystal composition of the comparative example and the results of the performance test conducted by filling the liquid crystal composition between two substrates of a liquid crystal display, so as to compare the performance with the liquid crystal composition of the present invention.
Comparative example 1
The liquid crystal composition of comparative example 1, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared according to the compounds and weight percentages listed in table 2, and the test data are shown in the following table:
TABLE 2 liquid crystal composition formulations and their test properties
Example 1
The liquid crystal composition of example 1 was prepared according to the compounds and weight percentages listed in table 3, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 3 liquid crystal composition formula and its test performance
Comparative example 2
The liquid crystal composition of comparative example 2, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared according to the compounds and the weight percentages listed in table 4, and the test data are shown in the following table:
TABLE 4 liquid crystal composition formula and its test performance
Example 2
The liquid crystal composition of example 2 was prepared according to the compounds and weight percentages listed in table 5, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 5 liquid crystal composition formulations and their test properties
Comparative example 3
The liquid crystal composition of comparative example 3, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared according to the compounds and weight percentages listed in table 6, and the test data are shown in the following table:
TABLE 6 liquid crystal composition formula and its test performance
Example 3
The liquid crystal composition of example 3 was prepared according to the compounds and weight percentages listed in table 7, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 7 liquid crystal composition formulations and their test properties
Comparative example 4
The liquid crystal composition of comparative example 4, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared according to the compounds and the weight percentages listed in table 8, and the test data are shown in the following table:
TABLE 8 liquid crystal composition formulations and their test properties
Example 4
The liquid crystal composition of example 4 was prepared according to the compounds and weight percentages listed in table 9, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 9 liquid crystal composition formulations and their test properties
Comparative example 5
The liquid crystal composition of comparative example 5, which was filled between two substrates of a liquid crystal display and subjected to a performance test, was prepared according to the compounds and weight percentages listed in table 10, and the test data are shown in the following table:
TABLE 10 liquid crystal composition formulations and their test properties
Example 5
The liquid crystal composition of example 5 was prepared according to the compounds and weight percentages listed in table 11, and filled between two substrates of a liquid crystal display for performance testing, and the test data are shown in the following table:
TABLE 11 liquid crystal composition formulations and their test properties
Application example
0.4% of the polymerizable compound of the formula VII-5 was homogeneously dissolved with 99.6% of the liquid-crystalline compositions of example 5 and comparative example 5, respectively, to give liquid-crystalline media MA1 and MB 1.
MA1 and MB1 were injected into a cell having a gap of 4 μm and a vertical alignment (Homeotropism) by vacuum infusion, and the cell was irradiated with ultraviolet light using a high-pressure mercury ultraviolet lamp while applying a square wave having a frequency of 60Hz and a driving voltage of 16V, so that the irradiation intensity of the cell surface was adjusted to 30mW/cm2And irradiating for 360 seconds to obtain a vertically aligned liquid crystal display element after polymerization of the polymer compound, testing the pretilt angle by using an LCT-5016C liquid crystal photoelectric parameter tester, then decomposing the test cell, and measuring the residual polymer compound in the liquid crystal composition by using High Performance Liquid Chromatography (HPLC). The results are summarized in tables 12 and 13.
TABLE 12 Pre-and post-UV light irradiation pretilt angles
| Composition ratio | UV front pretilt angle (°) | UV back pretilt angle (°) | |
| MA1 | 99.6％A+0.4％RM | 89.6 | 85.2 |
| MB1 | 99.6％B+0.4％RM | 89.4 | 86.4 |
TABLE 13 Polymer residue in liquid Crystal compositions
| UV polymerization time(s) | MA1 Polymer residue (%) | MB1 Polymer residue (%) |
| 0 | 0.40 | 0.40 |
| 120 | 0.36 | 0.38 |
| 180 | 0.28 | 0.33 |
| 240 | 0.19 | 0.25 |
| 300 | 0.11 | 0.16 |
| 360 | 0.05 | 0.13 |
As can be seen from a comparison of tables 12 and 13, the liquid crystal medium of the present invention can generate a larger pretilt angle and the polymerizable compound has a lower residue, which can improve the problems of poor display and the like in the existing PSVA technology.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and equivalent changes and modifications made according to the spirit of the present invention should be covered thereby.
Claims (10)
1. A negative liquid crystal composition, comprising:
at least one compound of the general formula I
At least one compound of the general formula II
At least one compound of the formula III
At least one compound of the general formula IV
Wherein,
R1、R2、R3、R4、R5and R6Identical or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkenyloxy group having 2 to 10 carbon atoms;
R7and R8Identical or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms;
Z1、Z2、Z3and Z4Identical or different, each independently of the other, being a single bond, -CH2-CH2-、-CH＝CH-、-CF2O-、-OCF2-、-CH2O、-OCH2-、-COO-，-O-CO-、-C2F4-or-CF ═ CF —;
L1、L2、L3and L4Identical or different, each independently of the others, is F or Cl;
ring (C)And ringIdentical or different, each independently of the otherOr
a represents 0, 1 or 2;
wherein the compound of the general formula I accounts for 5-15% of the total weight of the liquid crystal composition; the compound of the general formula II accounts for 25-45% of the total weight of the liquid crystal composition; the compound of the general formula III accounts for 10-20% of the total weight of the liquid crystal composition; the compound of the general formula IV accounts for 4-45% of the total weight of the liquid crystal composition.
2. The negative liquid crystal composition according to claim 1, further comprising:
one or more compounds with the general formula V accounting for 0-30 percent of the weight of the liquid crystal composition
One or more compounds of a general formula VI accounting for 0-15 percent of the weight of the liquid crystal composition
Wherein,
R9and R10The same or different, each independently of the others, is an alkyl or alkoxy group having 1 to 10 carbon atoms or an alkenyl or alkenyloxy group having 2 to 10 carbon atoms;
R11is alkyl or alkoxy with 1-10 carbon atoms;
ring (C)Is that
3. The negative liquid crystal composition according to any one of claims 1 and 2,
R1、R2、R3、R4、R5and R6The same or different, each independently of the others, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms;
R7and R8The alkyl or alkoxy groups are the same or different and each independently have 2 to 5 carbon atoms.
R9And R10The same or different, each independently of the others, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms;
R11is alkyl or alkoxy with 1-5 carbon atoms;
Z1、Z2and Z3Identical or different, each independently of the other, being a single bond, -CH2-CH2-、-CH＝CH-、-CF2O-、-CH2O, -COO-or-CF ═ CF-.
4. The negative liquid crystal composition according to claim 3, wherein the compound of formula V is present in an amount of 0 to 32% by weight based on the total weight of the liquid crystal composition; the compound of the general formula VI accounts for 0-10% of the total weight of the liquid crystal composition.
5. The negative liquid crystal composition according to claim 4, wherein the compound of formula II is selected from one or more of the following compounds:
and
wherein,
R3and R4The same or different, each independently of the other, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
6. The negative liquid crystal composition according to claim 4, wherein the compound of formula III is selected from one or more of the following compounds:
and
wherein,
R5and R6The same or different, each independently of the other, is an alkyl or alkoxy group having 2 to 5 carbon atoms or an alkenyl or alkenyloxy group having 2 to 5 carbon atoms.
7. The negative liquid crystal composition according to any one of claims 1 to 6, wherein the negative liquid crystal composition comprises:
compound 2CPWO2 at 8% by weight of the total weight of the negative liquid crystal composition;
compound 3CPWO2 at 9% by weight of the total negative liquid crystal composition;
compound 3C1OWO2 at 5% by weight of the total negative liquid crystal composition;
compound 2CC1OWO2 at 11% of the total weight of the negative liquid crystal composition;
compound 3CC1OWO2 at 11% of the total weight of the negative liquid crystal composition;
compound 3IWP2 at 5% by weight of the total negative liquid crystal composition;
compound 3CPO2 at 4% by weight of the total negative liquid crystal composition;
compound 5CPO2 at 5% of the total weight of the negative liquid crystal composition;
3% by weight of the total negative liquid crystal composition of compound 3CCP 1;
compound 5PP1 at 12% by weight of the total weight of the negative liquid crystal composition; and
27% by weight of compound 3CCV based on the total weight of the negative liquid crystal composition,
or the negative liquid crystal composition further comprises:
compound 3CWO2 in an amount of 20% by weight based on the total weight of the negative liquid crystal composition;
5CWO2, 5% by weight of the negative liquid crystal composition;
compound 3CPWO2 at 6% by weight of the total negative liquid crystal composition;
compound 3CPWO3 at 7% by weight of the total weight of the negative liquid crystal composition;
compound 4CCWO2 at 11% by weight of the total negative liquid crystal composition;
compound 3CCWO3 at 6% by weight of the total negative liquid crystal composition;
compound 3IWP2 at 12% by weight of the total negative liquid crystal composition;
compound VCCP1 at 8% by weight of the total weight of the negative liquid crystal composition;
compound 3CCV at 21% by weight of the total negative liquid crystal composition; and
compound 5CC3 at 4% by weight of the total weight of the negative liquid crystal composition,
or the negative liquid crystal composition further comprises:
compound 3CC2WO2 at 7% by weight of the total negative liquid crystal composition;
compound 3CC2WO4 at 8% by weight of the total negative liquid crystal composition;
compound 3CPWO2 at 7% by weight of the total weight of the negative liquid crystal composition;
compound 3CPWO4 at 8% by weight of the total weight of the negative liquid crystal composition;
compound 3C2WO2 at 5% by weight of the total weight of the negative liquid crystal composition;
compound 3C2WO4 at 10% by weight of the total weight of the negative liquid crystal composition;
compound 4IWP3 at 10% by weight of the total negative liquid crystal composition;
compound 5CC3 in an amount of 10% by weight of the total negative liquid crystal composition;
compound 4CC3 in an amount of 15% by weight of the total negative liquid crystal composition;
compound 3CCO1 in an amount of 5% by weight based on the total weight of the negative liquid crystal composition;
compound 5CCO1 in an amount of 5% by weight based on the total weight of the negative liquid crystal composition; and
compound 3CCP1 at 10% of the total weight of the negative liquid crystal composition,
or the negative liquid crystal composition further comprises:
compound 3CPO2 at 4% by weight of the total negative liquid crystal composition;
compound 2CPWO2 at 6% by weight of the total negative liquid crystal composition;
compound 3CPWO2 at 10% by weight of the total weight of the negative liquid crystal composition;
compound 3C1OWO2 at 10% by weight of the total negative liquid crystal composition;
compound 2CC1OWO2 at 7% by weight of the total negative liquid crystal composition;
compound 3CC1OWO2 at 15% of the total weight of the negative liquid crystal composition;
compound 2IWP5 at 8% by weight of the total negative liquid crystal composition;
compound 5CC2 in an amount of 10% by weight of the total negative liquid crystal composition;
compound 4CC3, at 13% by total weight of the negative liquid crystal composition;
compound 3PP2 at 8% by weight of the total negative liquid crystal composition; and
compound 5PP1 in an amount of 9% by weight based on the total weight of the negative liquid crystal composition,
or the negative liquid crystal composition further comprises:
compound 3CWO2 in an amount of 15% by weight based on the total weight of the negative liquid crystal composition;
compound 5CWO4 in an amount of 8% by weight based on the total weight of the negative liquid crystal composition;
compound 3CCWO3 at 9% by weight of the total negative liquid crystal composition;
compound 4CCWO2 at 6% by weight of the total negative liquid crystal composition;
compound 2CPWO2 at 4% by weight of the total weight of the negative liquid crystal composition;
compound 3CPWO2 at 10% by weight of the total weight of the negative liquid crystal composition;
compound 3IWP2 at 5% by weight of the total negative liquid crystal composition;
compound 3CCW1 at 7% by weight of the total negative liquid crystal composition;
compound 4CC3 at 9% by weight of the total negative liquid crystal composition;
compound 5CC2, at 5% by total weight of the negative liquid crystal composition;
compound 3CC2 at 11% of the total weight of the negative liquid crystal composition;
compound 3CCO1 in an amount of 5% by weight based on the total weight of the negative liquid crystal composition; and
compound 3CC1 at 6% by total weight of the negative liquid crystal composition.
8. A liquid crystal medium, comprising:
one or more reactive mesogenic materials; and
a liquid crystal host composition comprising the liquid crystal composition of any one of claims 1-7.
9. Liquid-crystalline medium according to claim 8, characterized in that the reactive mesogenic material is selected from one or more of the following compounds:
and
10. a liquid crystal display device comprising a liquid crystal composition according to any of claims 1 to 7 or a liquid crystal medium according to any of claims 8 to 9.
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| JPH09104867A (en) * | 1995-10-12 | 1997-04-22 | Canon Inc | Liquid crystal composition, liquid crystal element and liquid crystal device using the same element |
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| CN102690167B (en) * | 2012-06-14 | 2014-10-22 | 江苏和成显示科技股份有限公司 | Liquid crystal compound containing saturated indene rings and composition thereof |
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| CN102898272B (en) * | 2012-10-13 | 2015-10-07 | 江苏和成显示科技股份有限公司 | Containing six hydrogen indenes class novel liquid crystals and composition thereof and application in a liquid crystal display |
| CN102911673B (en) * | 2012-10-13 | 2014-07-30 | 江苏和成显示科技股份有限公司 | Liquid crystal composite and electro-optical display device comprising same |
| CN103351275B (en) * | 2013-07-01 | 2015-06-10 | 江苏和成显示科技股份有限公司 | Liquid crystal compound including polyfluoroindan, composition thereof and application |
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