CN108929704B - Liquid crystal composition and photoelectric element - Google Patents

Liquid crystal composition and photoelectric element Download PDF

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CN108929704B
CN108929704B CN201810707530.8A CN201810707530A CN108929704B CN 108929704 B CN108929704 B CN 108929704B CN 201810707530 A CN201810707530 A CN 201810707530A CN 108929704 B CN108929704 B CN 108929704B
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liquid crystal
cycloalkyl
alkenyl
carbon atoms
alkenyloxy
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CN108929704A (en
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邓登
别国军
杜渭松
高嫒嫒
张广平
陆涛
闫璐
许培培
刘俞彤
郭计化
张伟杰
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Xi'an Caijing Opto Electrical Science & Technology Co ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—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
    • 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 discloses a liquid crystal composition and a photoelectric element, wherein the composition comprises a first component and a second component, and the weight percentages are as follows: the first component is 17-36.5 percent, the second component is 63.5-83 percent, and the sum of the weight percentages of the components is 100 percent. The liquid crystal composition provided by the invention has the advantages of low viscosity, high delta, proper optical anisotropy, low threshold voltage, high VHR, good reliability and thermal stability and excellent low-temperature reliability, and solves the dual requirements of the current novel display mode and the low-temperature reliability. The liquid crystal composition can keep stable at the low temperature of below 40 ℃, is used for TN-TFT (twisted nematic phase), IPS (in-plane switching), FFS (fringe field switching), PSA (polymer stabilization) mode liquid crystal display devices and reinforced liquid crystal display devices, and greatly widens the application of liquid crystal display under the conditions of engineering, outdoors, high altitude, high latitude and severe working conditions.

Description

Liquid crystal composition and photoelectric element
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a liquid crystal composition and a photoelectric element.
Background
As is well known in the art, a single liquid crystal compound cannot satisfy all requirements, and therefore, a liquid crystal material for flat panel display is usually prepared by mixing 5 to 20 liquid crystal compounds with different characteristics in a certain ratio, wherein each compound contributes differently to a liquid crystal formulation, for example, the liquid crystal material has a liquid crystal compound component with a relatively high polarity and a non-polar liquid crystal compound component; the liquid crystal display has liquid crystal components with high clearing points and liquid crystal components with low clearing points and small viscosity, and can make up for deficiencies of each other after being mixed to form a formula, so that the best display performance can be obtained and the liquid crystal display can be used as a commercial liquid crystal display terminal. However, among the various flat panel displays, the liquid crystal display has the worst low temperature operation characteristics, which greatly hinders the application of the active matrix liquid crystal display (AMD-LCD) having better photoelectric properties at low temperatures. The properties of the liquid crystal mixture material have contradictory relations, and adjusting one parameter easily causes the change of the other parameter, so how to balance the parameter values is very critical to achieve uniform properties or outstanding properties. When the nematic phase temperature is increased, Vth and Vsat can be sacrificed, and the response time is slowed, for example, in a liquid crystal material with the temperature of 100 ℃ of TNI, the temperature of-40 ℃ of TCN, the Vth is more than 2.1v, and the Vsat is more than 3.1v, which is calculated according to the viscosity, the response time is more than 30ms, and is not suitable for the prior art requirements. On the other hand, when Vth and Vsat are increased, the driving voltage of the device is increased, power consumption is increased, standby time of some mobile devices such as mobile phones, PDAs and notebook computers is seriously affected, charging frequency is increased, battery service time is shortened, and environmental protection and energy conservation are not facilitated. And the response time is too slow, the display effect is influenced, and high-definition images cannot be realized. Therefore, under the condition of meeting the requirements of the performance of the current liquid crystal display, more creative technical breakthroughs are needed for preparing the liquid crystal material.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a liquid crystal composition and a photoelectric element, and overcomes the defects of narrow use temperature range and poor low-temperature working performance of the existing liquid crystal material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a liquid crystal composition, which comprises a first component and a second component; wherein the first component is one or more of the compounds shown in the following general formula I, general formula II and/or general formula III:
Figure BDA0001715818290000021
wherein R is1、R3、R5And R6The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
R2and R4The same or different, each independently represents-H, -F, -Cl, -CN, -NCS, -CF3 or-OCF 3, or a linear or branched alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy group can be substituted by F;
X1～X2the same or different, each independently represents-H, -F, -Cl, -CN, -NCS, -CF3 or-OCF 3;
z represents a single bond, -CH2CH2-, trans-CH ═ CH-, -CH2O-, CH2S-, or,
Figure BDA0001715818290000022
Figure BDA0001715818290000023
Or one or more of H in said groups may be taken by FGeneration;
ring (C)
Figure BDA0001715818290000024
Identical or different, each independently of the other
Figure BDA0001715818290000025
Figure BDA0001715818290000031
The second component is one or more of the compounds according to the following general formula IV and/or general formula V:
Figure BDA0001715818290000032
wherein R is20～R23The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
Figure BDA0001715818290000033
identical or different, each independently of the other
Figure BDA0001715818290000034
Optionally, in weight percent: the first component is 17-36.5 percent, the second component is 63.5-83 percent, and the sum of the weight percentages of the components is 100 percent.
Alternatively, the compound of formula i is selected from one or more of the following compounds:
Figure BDA0001715818290000041
wherein R is7And R8The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X7～X14the same or different, each independently represents-H, -F, -Cl.
The introduction of the polyfluoro-substituted benzene causes the viscosity of the compound to be reduced and the response time to be shortened due to the action of fluorine atoms. Meanwhile, the ethylene bridge bond has a flexible carbon-carbon single bond which can rotate freely, so that the essential linear structure of the liquid crystal molecules can be maintained, meanwhile, the molecules have a certain flexible region degree, the rigidity of the molecules is weakened, the compatibility with other liquid crystals can be improved, and the viscosity of the compound can be reduced. The liquid crystal molecules with the introduced-CF 2O-bridge bond solve the contradiction between the low threshold value and the fast response speed of the liquid crystal, so that the liquid crystal with low viscosity can be obtained under the condition of the same delta. The preferable polyfluorobenzene compound containing ethylene bridge bonds further improves the compatibility of the liquid crystal composition, expands the lowest eutectic point to a low-temperature region, and can well meet other display performances.
Further, in the present invention, it is preferred that the general formula I mainly comprises the following compounds but is not limited to these compounds:
Figure BDA0001715818290000042
Figure BDA0001715818290000051
Figure BDA0001715818290000061
r is as defined above36～R44The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a linear or branched alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F.
Alternatively, the compound of formula ii is selected from one or more of the following compounds:
Figure BDA0001715818290000071
wherein R is9～R11The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
the compound containing the 3, 4-difluorothiophenol structure has the characteristic of wide liquid crystal phase range, but has higher viscosity, and saturated cyclohexane is used for replacing unsaturated benzene rings in the liquid crystal compound, so that the conjugation degree of molecules is reduced, the polarity of the molecules is weakened, the compatibility of the liquid crystal compound with other liquid crystal compounds is improved, and the viscosity of the liquid crystal compound is reduced. The preferred thioester compound in the invention not only widens the application temperature range of the liquid crystal composition, but also can well meet other display performances. The liquid crystal compound is further improved by introducing an ethylene bridge bond into the liquid crystal compound, wherein the ethylene bridge bond has a flexible carbon-carbon single bond capable of freely rotating, so that the essential linear structure of liquid crystal molecules can be maintained, meanwhile, the molecules have a certain flexible region degree, the rigidity of the molecules is weakened, the compatibility with other liquid crystals can be improved, and the viscosity of the compound can be reduced. The preferable ethylene bridge bond-containing compound in the invention further improves the compatibility of the liquid crystal composition, expands the lowest eutectic point to a low-temperature region, and can well meet other display performances.
Further, in the present invention, it is preferable that the general formula II mainly comprises the following compounds but not limited to these compounds:
Figure BDA0001715818290000081
Figure BDA0001715818290000091
the R is45～R56The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a linear or branched alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F.
Optionally, the compound of formula iii is selected from one or more of the following compounds:
Figure BDA0001715818290000092
wherein R is12～R19The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
with the increase of the number of six-membered rings in the liquid crystal molecular skeleton, such as three rings, four rings and the like, the clearing point of the liquid crystal material can be obviously improved, but with the increase of the number of rings, the viscosity also increases sharply. For example, japanese patent publication JP5865251 reports ester liquid crystals of the following structural formula:
Figure BDA0001715818290000101
the liquid crystal compound has the characteristics of wide liquid crystal phase region and high clearing point (>300 ℃). The compatibility with other liquid crystal compounds is poor, and crystallization is easily caused when the liquid crystal compound is added into a formula. For example, in CN100348693 and CN100386406, the above mentioned compounds also have the disadvantage of high viscosity, the present invention can overcome the disadvantages of such compounds, and provide a liquid crystal compound having both high clearing point and low viscosity, and in order to achieve the above object, the present invention inserts flexible ethylene bridge bonds between the benzene ring of the main chain of the liquid crystal compound and cyclohexane, respectively, to make the molecule flexible, reduce the viscosity of the compound, and improve the compatibility with other liquid crystals. The preferable tetracyclic ester compound containing ethylene bridge bonds improves the compatibility of the liquid crystal composition, expands the lowest eutectic point to a low-temperature region, and can well meet other display performances.
Optionally, the compound of formula iv is selected from one or more of the following compounds:
Figure BDA0001715818290000102
wherein R is24～R27The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X23and X24The same or different, each independently represents-H, -F, -Cl.
Optionally, the compound of formula v is selected from one or more of the following compounds:
Figure BDA0001715818290000103
Figure BDA0001715818290000111
wherein R is28～R35The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X25and X32The same or different, each independently represents-H, -F, -Cl.
Further, in the present invention, it is preferable that the general formula iv mainly contains the following compounds but not limited to these compounds:
Figure BDA0001715818290000112
Figure BDA0001715818290000121
the R is57～R63The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a linear or branched alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F.
Further, in the present invention, it is preferable that formula V comprises mainly but not limited to the following compounds:
Figure BDA0001715818290000122
Figure BDA0001715818290000131
the above-mentionedR64～R81The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a linear or branched alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F.
Optionally, the liquid crystal composition can also be added with one or more of a stabilizer, an antioxidant, an anti-ultraviolet agent, a chiral agent with optical activity and a polymerizable compound; the chemical elements in each of the compounds include their corresponding isotopes.
In the present invention, it is also provided that one or more stabilizers, antioxidants or anti-ultraviolet agents may be added in consideration of chemical and physical effects of moisture and air on the liquid crystal composition and the liquid crystal cell during the manufacturing process and the use process of the liquid crystal display device, and also the effects of radiation in, for example, heat, infrared rays, visible light and ultraviolet regions, and direct current and alternating current electric fields.
This not only relates to the usual life cycle of the displays, but also to a separate step in the preparation of the displays, which in some cases are subjected to extreme loads compared to usual operation. Thus, for example, the methods usually used in the bonding of the preparation frames lead to very high thermal loads of the displays already containing the liquid crystals. In order to make the liquid crystals as resistant as possible to such strong thermal loads without damage, it is accordingly advantageous to add one or more thermal stabilizers to the liquid crystal formulation. During the subsequent daily operation of the display, loads due to the light of the backlight and to ambient light (typically daylight), and temperature loads from the environment, may exist as various disadvantages. Thus, the present invention also provides, as a corollary, the option of adding one or more stabilizers, antioxidants or anti-uv agents.
The stabilizer, antioxidant or anti-ultraviolet agent is additionally added to the liquid crystal composition in an amount of 0.001-5% by weight of the total weight of the liquid crystal composition, preferably, but not limiting the invention, from the following compounds:
Figure BDA0001715818290000132
Figure BDA0001715818290000141
the stabilizers, antioxidants or anti-ultraviolet agents listed above can be purchased in the market, or the references are easy to prepare, the stabilizers, antioxidants or anti-ultraviolet agents themselves are also a mature chemical industrial system, and the stabilizers, antioxidants or anti-ultraviolet agents known by those skilled in the art can be selected according to different needs and added into the liquid crystal composition provided by the invention additionally to achieve the purpose of improving the reliability of the liquid crystal composition and the liquid crystal element.
In the present invention, in some use cases, the liquid crystal composition needs to provide a certain twisting force to match the optical design of the liquid crystal element, and as well known to those skilled in the art, the design purpose can be achieved by adding a chiral agent, and therefore, the present invention necessarily also provides an option of adding one or more chiral agents.
The chiral agent is additionally added to the liquid crystal composition in an amount of 0.001-5% of the total mass of the liquid crystal composition, preferably, but not limiting the invention, and is derived from the following compounds:
Figure BDA0001715818290000151
the chiral agents listed can be purchased in the market, or the references are easy to prepare, and the chiral agents known to those skilled in the art can be selected according to different needs and additionally added into the liquid crystal composition provided by the invention to achieve the purpose of being suitable for the optical design of the liquid crystal element.
In the present invention, in some use cases, the liquid crystal composition needs to provide a stable orientation of the polymer to match the optical design of the liquid crystal cell, which is well known to those skilled in the art, and the design purpose can be achieved by adding a polymerizable compound, and therefore, the present invention necessarily also provides an option to add one or more polymerizable compounds.
The polymerizable compound is additionally added to the liquid crystal composition in an amount of 0.001 to 5% by weight based on the total weight of the liquid crystal composition, preferably, but not limiting to the invention, from the following compounds:
Figure BDA0001715818290000161
Figure BDA0001715818290000171
the listed polymers can be purchased in the market, or the references are easy to prepare, and chiral agents known to those skilled in the art can be selected according to different needs and additionally added into the liquid crystal composition provided by the invention to achieve the purpose of being suitable for the optical design of the liquid crystal element.
The invention also provides a photoelectric element which is prepared by adopting the liquid crystal composition and is a photoelectric component, a photoelectric component or a display.
Optionally, the display comprises an active matrix addressing device.
Compared with the prior art, the invention has the beneficial technical effects that:
(I) the liquid crystal composition of the present invention has an extremely low TcnThe low temperature storage temperature (T) is reducedst) And low temperature operating temperature (T)op) Lower viscosity, appropriate optical anisotropy, dielectric anisotropy, lower threshold voltage, higher VHR, good reliability and thermal stability, and can be used in positive TN-TFT (twisted nematic phase), IPS (in-plane switching), FFS (fringe field switching), and PSA (polymer stabilized) mode liquid crystals. It has now been found that such liquid crystal compositions can achieve lower viscosity, higher delta, suitable optical anisotropy, lower threshold voltage, higher VHR, good reliability and thermal stability, excellent low temperature reliability without materials from the prior artThe defects of the display panel and the display panel solve the dual requirements of the current novel display mode and low-temperature reliability.
The liquid crystal composition provided by the invention can keep stability at low temperature of below-40 ℃, is used for TN-TFT (twisted nematic phase), IPS (in-plane switching), FFS (fringe field switching), PSA (polymer stabilization) mode liquid crystal display devices and reinforced liquid crystal display devices, and greatly widens the application of liquid crystal display under the conditions of engineering, outdoor, high altitude, high latitude and severe working conditions.
The invention also provides an electro-optical element comprising the liquid crystal composition, in particular an active matrix addressed display, especially for use in a reinforced liquid crystal display. The liquid crystal composition and the photoelectric element comprising the same have excellent low-temperature reliability.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present embodiment, the monomer liquid crystal component is labeled as follows:
Figure BDA0001715818290000181
Figure BDA0001715818290000191
take the following structure as an example:
Figure BDA0001715818290000192
the structure is represented by the codes in the table above, and can be represented as: v3 CEBSUF.
Take the following structure as an example:
Figure BDA0001715818290000193
the structure is represented by the codes in the table above, and can be represented as: nCEBZGECm.
The liquid crystal characteristic value test in the invention adopts the Japanese electronic mechanical industry (Standard of Electric Industries Association of Japan) EIAJ. ED-2521A which is popular in the industry, and is briefly described as follows:
the optical anisotropy test adopts Abbe refractometer, polarizing plate is added on ocular lens, constant temperature of 25 deg.C is maintained, main prism is vertically oriented, 589nm light source is adopted, when the polarized light is consistent with orientation direction, n is measured∥Measurement of rotating polarizing plate n⊥，Δn＝n∥-n⊥And taking the average value of three parallel measurements as the optical anisotropy value of the mixed liquid crystal.
Threshold voltage and saturation voltage adopt 4um liquid crystal empty box, after the liquid crystal composition is perfused, a driving power supply is added, the voltage is stepped from 0v to 4.5v by 0.01v, and the corresponding voltage of the light transmittance at 10% and 90% is recorded, namely Vth and Vsat voltage.
And VHR, testing the liquid crystal box by adopting the threshold voltage and saturation voltage, externally adding 5v of voltage for charging, testing the voltage of the liquid crystal box after 16.67ms, and determining the ratio of the voltage to the initial voltage as VHR.
Pitch, HTP value was measured in a phase microscope after perfusion of the liquid crystal composition using a wedge liquid crystal cell.
Rotational viscosity, namely testing the threshold voltage and the saturation voltage to finish a liquid crystal box, an INSTEC rotational viscosity testing module, and a 5V voltage to obtain gamma1。
And (4) ultraviolet aging, namely placing the liquid crystal box after the VHR value is tested in an ultraviolet aging box, and testing the VHR value after the irradiation of 5000mj is finished.
And (3) low-temperature reliability investigation:
and (3) low-temperature storage: the initial NTSC was obtained by pouring the liquid crystal composition into a liquid crystal empty cell (the china tube company CLAD015GA01), placing the liquid crystal composition in a test frame, and measuring RGB values using a colorimeter according to the CIE1976 standard. Then, the tested liquid crystal box is placed at a low-temperature storage temperature (T)st) A low-temperature incubator at minus 40 ℃, taking out after 500 hours, and testing NT of the incubatorAnd SC, comparing the change before and after, and judging as unqualified if three or more bright and dark points or areas appear on the screen or the NTSC change exceeds more than 10%.
Low-temperature operation: the liquid crystal composition was poured into a liquid crystal empty cell (CLAD 015GA01, China tubes Inc.), placed in a test frame, and RGB values were measured using a colorimeter to obtain an initial NTSC. Then, the tested liquid crystal box is placed at a low-temperature storage temperature (T)st) A cryostat at-30 ℃, the color of the test frame is switched in the order of red-green-blue every 10 seconds, and the test frame is taken out after 240 hours, tested for NTSC according to the CIE1976 standard, and compared with the change before and after comparison. If three or more bright and dark points or areas appear on the screen, or the NTSC change exceeds more than 10 percent, or the whole or partial area of the screen can not be normally displayed by naked eyes in the low-temperature working process, the screen is judged to be unqualified.
In the following examples, the compounds of the general formulae I, II and III according to the invention are used and are supplied by the company SiAn color Crystal opto-electronic technology.
In the following examples, other components used are commercially available, readily available, or synthesized by the inventors of the present application according to a known method. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds.
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 prepared according to the specified mass percentage of each liquid crystal composition.
The liquid crystal compositions given in the following examples were prepared and studied according to the following examples, and the compositions of the respective liquid crystal compositions and the results of the performance parameter tests thereof are given below, and the low temperature reliability was tested.
Example 1:
Figure BDA0001715818290000211
example 2:
Figure BDA0001715818290000212
example 3:
Figure BDA0001715818290000221
example 4:
Figure BDA0001715818290000222
example 5:
Figure BDA0001715818290000231
example 6:
Figure BDA0001715818290000232
example 7:
Figure BDA0001715818290000233
Figure BDA0001715818290000241
comparative example 1:
Figure BDA0001715818290000242
comparative example 2:
Figure BDA0001715818290000243
Figure BDA0001715818290000251
and (3) low-temperature reliability investigation:
TABLE 1 Low temperature reliability parameters for example 1 and comparative example 1
Figure BDA0001715818290000252
In table 1, the composition of comparative example 1 completely failed after low temperature storage, and in some weapons or equipment instruments, there is a fatal risk in the face of chilly weather, and compared with the liquid crystal composition of example 1, 2BUQUF, 3 cczaf and 3CBZBC3 are replaced by 2LEBQUOT, 3CECSUF and 3CEBZBC3 which are structurally similar, but have good compatibility and lower viscosity, so that the compatibility of each monomer component of the liquid crystal composition is greatly improved, and the lowest eutectic point is reduced, therefore, the low temperature operation of example 1 is normal, the low temperature condition of-40 ℃ can be endured, and the rotational viscosity is reduced by 17%, which is beneficial for improving the display performance, completely adapts to the severe environment condition, and achieves the purpose of the invention.
TABLE 2 Low temperature reliability parameters for example 2 and comparative example 2
Figure BDA0001715818290000253
In table 2, the liquid crystal composition of example 2 has a partial failure after low temperature storage, and has a fatal risk in some weapons or equipment instruments facing cold weather, compared with the liquid crystal composition of example 2, 5BUQUF, 3CCQUF, 5 cczaf, 3CCBUF and 5CCBUF are replaced by 5LEUQUOT, 3 lecout, 5CEBSUF, 5 CEBZCC 5 and 3CEBZCC3 which have good compatibility and low viscosity, so that the compatibility of each monomer component of the liquid crystal composition is greatly improved, and the lowest eutectic point is reduced, therefore, the liquid crystal composition of example 2 can normally work at low temperature, can resist the low temperature condition of-40 ℃, has 21.5 percent reduced rotary viscosity, is beneficial to improving display performance, and completely adapts to severe environmental conditions, and achieves the aim of the invention.
TABLE 3 Low temperature reliability parameters for examples 2 to 7
Figure BDA0001715818290000261
Example 8:
when conditions for using the twisted nematic liquid crystal composition are required, 0.14% R2011 is added to MLC-003 to test the pitch HTP value of 58 um.
Example 9:
when conditions for using the twisted nematic liquid crystal composition are required, 0.14% R2011 is added to MLC-004, and the pitch HTP value is tested to be 53 um.
Example 10:
when conditions for using the twisted nematic liquid crystal composition are required, 0.2% S811 is added to MLC-005 and the pitch HTP value is measured to be 49 um.
Example 11:
when conditions for using the twisted nematic liquid crystal composition are required, 0.18% CM-44 is added to MLC-006 and the pitch HTP value is measured to be 69 um.
Example 12:
when the twisted nematic liquid crystal composition is required to be used, 100 PPM-resistant oxidant BHT is added into MLC-005, and after ultraviolet aging, the VHR value is tested without change before and after the test.
Example 13:
when the twisted nematic liquid crystal composition is required to be used, 100PPM antioxidant BHT is added into MLC-006, and after ultraviolet aging, the VHR value is tested without change before and after the aging.
Example 14:
when the liquid crystal composition and the stability of the liquid crystal cell were additionally improved, 100PPM of BHT as an antioxidant was added to the liquid crystal composition of example 9, and after uv aging, the VHR value was measured without any change before and after.
Example 15:
when the stability of the liquid crystal composition and the liquid crystal element needs to be additionally improved, 100PPM antioxidant is added into MLC-006:
Figure BDA0001715818290000271
after UV aging, the VHR value was measured and decreased by 0.02%.
Example 16:
when it is necessary to additionally improve the stability of the liquid crystal composition and the liquid crystal cell, the following examples9 liquid crystal composition with addition of 100PPM resistant oxidizing agent:
Figure BDA0001715818290000272
after ultraviolet aging, the VHR value is tested and is unchanged.
Example 17:
when it is desired to prepare a PSA liquid crystal composition and a liquid crystal cell, 0.3% of a polymerizable compound is added to example 6
Figure BDA0001715818290000273
Example 18:
when it is desired to prepare a PSA liquid crystal composition and a liquid crystal cell, 0.3% of a polymerizable compound is added to the liquid crystal composition of example 12
Figure BDA0001715818290000281
Example 19:
when it is desired to prepare a PSA liquid crystal composition and a liquid crystal cell, 0.3% of a polymerizable compound is added to the liquid crystal composition of example 6
Figure BDA0001715818290000282
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (4)

1. A liquid crystal composition comprising a first component and a second component; wherein the first component is a compound according to formula I, formula II and formula III:
the compound of the general formula I is selected from one or more of the following compounds:
Figure FDA0002534016050000011
wherein R is7And R8The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X7～X14the same or different, each independently represent-H, -F, -Cl;
the compound of the general formula II is selected from one or more of the following compounds:
Figure FDA0002534016050000012
Figure FDA0002534016050000021
wherein R is9～R11The alkyl, the alkoxy, the alkenyl, the alkenyloxy, the cycloalkyl or the cycloalkoxy are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy with 1-10 carbon atoms, or an alkenyl or alkenyloxy with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy with 3-6 carbon atoms, wherein one of the alkyl, the alkoxy, the alkenyl, the alkenyloxy, the cycloalkyl or the cycloalkoxy isOr more H may be substituted by F;
X15～X22the same or different, each independently represent-H, -F, -Cl;
the compound of the general formula III is selected from one or more of the following compounds:
Figure FDA0002534016050000022
wherein R is12～R19The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
the second component is a compound corresponding to formula IV and formula V:
the compound of the general formula IV is selected from one or more of the following compounds:
Figure FDA0002534016050000023
Figure FDA0002534016050000031
wherein R is24～R27The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X23and X24The same or different, each independently represent-H, -F, -Cl;
the compound of the general formula V is selected from one or more of the following compounds:
Figure FDA0002534016050000032
wherein R is28～R35The alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups are the same or different, and each independently represents-H or-F, or a straight chain or branched chain alkyl or alkoxy group with 1-10 carbon atoms, or an alkenyl or alkenyloxy group with 2-10 carbon atoms, or a cycloalkyl or cycloalkoxy group with 3-6 carbon atoms, wherein one or more H in the alkyl, alkoxy, alkenyl, alkenyloxy, cycloalkyl or cycloalkoxy groups can be substituted by F;
X25and X32The same or different, each independently represent-H, -F, -Cl;
the weight percentage is as follows: the first component is 17-36.5 percent, the second component is 63.5-83 percent, and the sum of the weight percentages of the components is 100 percent.
2. The liquid crystal composition of claim 1, wherein the liquid crystal composition further comprises one or more of a stabilizer, an antioxidant, an anti-ultraviolet agent, a chiral agent having an optical activity, and a polymerizable compound; the chemical elements in each of the compounds include their corresponding isotopes.
3. An electro-optical element prepared from the liquid crystal composition according to any one of claims 1 to 2, wherein the electro-optical element is an electro-optical module, an electro-optical device, or a display.
4. The optoelectronic element of claim 3, wherein the display comprises an active matrix addressing device.
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