Polymerizable liquid crystal composition and liquid crystal display device
Technical Field
The present invention relates to a liquid crystal composition and applications thereof, and more particularly, to a polymerizable liquid crystal composition containing a polymerizable compound and a liquid crystal display containing the polymerizable liquid crystal composition.
Background
In recent years, liquid crystal displays have replaced the conventional cathode ray tube displays, become mainstream products in the information display field, and are widely used in various displays such as instruments, computers, televisions, and the like. Liquid crystal display elements can be classified into various modes such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane switching (IPS) mode, and a Vertical Alignment (VA) mode, depending on the liquid crystal display mode.
TFT-L CD is an active matrix Display formed by introducing a Thin Film Transistor switch on the basis of twisted nematic liquid Crystal Display, overcomes the characteristics of cross interference, less information amount, slow writing speed and the like in passive matrix Display, greatly improves the Display quality, and is rapidly developed.
The advantages of the TFT-L CD can be summarized as that (1) the use characteristics are good, low-voltage application and low driving voltage are achieved, the flat panel display is flat and light, a large amount of raw materials and use space are saved, the display quality is good from the simplest single-color character graph to video displays of various specifications and models with high resolution, high color fidelity, high brightness, high contrast and high response speed, the display modes comprise a direct-view type display mode, a projection type display mode, a perspective type display mode, a reflection type display mode and the like, (2) the environment-friendly characteristic is good, the TFT-L CD is free of radiation and flicker, the health of users is not damaged, particularly the TFT-L CD electronic books appear, human beings are brought into a paperless office and paperless printing era, the revolution of human learning, transmission and civilization modes is initiated, (3) the application range is wide, the TFT-L CD can be normally used in a range of-20 ℃ to 50 ℃, the TFT-L CD can be used as a low-temperature operating temperature, the TFT-L CD can be used as a mobile terminal, and the TFT-365 can be used as a high-integration display screen, and the integrated television display technology is easy to be replaced by a new television (3).
The liquid crystal material used for the display needs to meet the following performances of (1) good chemical, physical and thermal stability, stability to electric fields and electromagnetic radiation, (2) low viscosity (gamma 1), (3) proper dielectric anisotropy delta, (4) proper optical anisotropy delta n, and (5) good compatibility with other liquid crystal compounds, and has higher requirements than common liquid crystal materials when being used as the liquid crystal material for TFT-L CD.
However, due to the limitations of liquid crystal materials, TFT-L CD still has many defects such as slow response speed, high voltage, poor ultraviolet resistance, and so on.
Disclosure of Invention
The invention aims to provide a polymerizable liquid crystal composition which has proper optical anisotropy, proper dielectric anisotropy, a wider nematic phase temperature range, a higher clearing point, a faster response speed and good UV stability, can be suitable for a liquid crystal display, and can meet the requirements of the liquid crystal display on fast response and good display under UV conditions.
The technical scheme adopted by the invention is as follows:
provided is a polymerizable liquid crystal composition comprising:
one or more compounds selected from the group consisting of formula I-1, formula I-2, and combinations thereof
One or more compounds selected from the group consisting of formula II-1, formula II-2, formula II-3, formula II-4, and combinations thereof
one or more compounds selected from the group consisting of compounds of formula III
Wherein the content of the first and second substances,
R1and R2The same or different, each independently represents an alkyl group having 2 to 5 carbon atoms;
R3represents H or an alkyl group having 1 to 5 carbon atoms;
R4、R5、R6and R7The same or different, each independently represents an alkyl group having 1 to 5 carbon atoms;
L1、L2、L3、L4、L5、L6And X, which are identical or different, each independently represent H or F;
y represents F, -OCF2CF=CF2or-O (CF)2)kF, wherein k represents 2, 3 or 4;
Z1and Z2The same or different, each independently represents a single bond or a straight-chain alkyl group having 1 to 5 carbon atoms;
l, m and n are the same or different and each independently represents 0 or 1.
In some embodiments of the present invention, the substrate is,
to represent
In some embodiments, L1Represents H.
In some embodiments, L2Represents H.
In some embodiments, L4Represents F.
In some embodiments, L5Represents F.
In some embodiments, Y represents F or-OCF2CF=CF2。
In the embodiment of the present invention, it is preferable that Z is1And Z2The same or different, each independently represents a single bond or an alkyl group having 1 to 3 carbon atoms.
In some embodiments, Z1Represents a single bond.
In the embodiment of the present invention, it is preferable that the compound selected from the group consisting of the general formula I-1, the general formula I-2, the general formula I-3 and a combination thereof accounts for 10 to 80% of the total weight of the polymerizable liquid crystal composition; a compound selected from the group consisting of formula II-1, formula II-2, formula II-3, formula II-4, and combinations thereof, in an amount of 15 to 85% by weight of the total polymerizable liquid crystal composition; and the compound of the general formula III accounts for 0.1-5% of the total weight of the polymerizable liquid crystal composition.
In some embodiments, the compound of formula I-1 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of formula I-1 is selected from the group consisting of:
in some embodiments, the compound of formula I-2 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of formula I-2 is selected from the group consisting of:
in some embodiments, the compound of formula I-3 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of formula I-3 is selected from the group consisting of:
in some embodiments, the compound of formula II-1 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of the formula II-1 is selected from the group consisting of:
in some embodiments, the compound of formula ii-2 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of the formula II-2 is selected from the group consisting of:
in some embodiments, the compound of formula ii-3 is selected from the group consisting of:
as a particularly preferred embodiment, the compound of the general formula II-3 is selected from the group consisting of:
in some embodiments, the compound of formula ii-4 is selected from the group consisting of:
in some embodiments, the compound of formula iii is selected from the group consisting of:
as a particularly preferred embodiment, the compound of formula iii is selected from the group consisting of:
in an embodiment of the present invention, the polymerizable liquid crystal composition further comprises:
wherein the content of the first and second substances,
R8and R9The same or different, each independently represents an alkyl group having 1 to 5 carbon atoms; or an alkenyl group having 2 to 5 carbon atoms.
In some embodiments, R8Represents an alkyl group having 1 to 5 carbon atoms.
In some embodiments, R9Represents an alkenyl group having 2 to 5 carbon atoms.
In some embodiments, the compound of formula iv is selected from the group consisting of:
in an embodiment of the present invention, it is preferable that the compound of formula IV is 15 to 40% by weight based on the total weight of the polymerizable liquid crystal composition.
As a particularly preferred embodiment, the compound of formula iv is selected from the group consisting of:
in an embodiment of the present invention, it is preferable that the compound of the group consisting of the general formula I-1, the general formula I-2, the general formula I-3 and a combination thereof accounts for 10 to 50% of the total weight of the polymerizable liquid crystal composition; the compounds of the group consisting of formula II-1, formula II-2, formula II-3, formula II-4 and combinations thereof account for 15-65% of the total weight of the polymerizable liquid crystal composition; the compound of the general formula III accounts for 0.1-2% of the total weight of the polymerizable liquid crystal composition; the compound of the general formula IV accounts for 19-40% of the total weight of the polymerizable liquid crystal composition.
In an embodiment of the present invention, the liquid crystal composition further comprises:
one or more compounds selected from the group consisting of compounds of formula V
Wherein the content of the first and second substances,
R10represents an alkyl group having 1 to 5 carbon atoms.
In some embodiments, the compound of formula v is selected from the group consisting of:
in an embodiment of the present invention, the polymerizable liquid crystal composition further comprises:
one or more compounds selected from the group consisting of compounds of formula VI
Wherein the content of the first and second substances,
R11represents an alkyl group having 1 to 5 carbon atoms;
R12represents F or an alkyl group having 1 to 5 carbon atoms;
L7represents H or F;
p represents 0, 1 or 2.
In some embodiments, p represents 0 or 2.
In some embodiments, the compound of formula vi is selected from the group consisting of:
more preferably, the compounds of the group consisting of formula I-1, formula I-2, formula I-3 and combinations thereof account for 14-35% of the total weight of the polymerizable liquid crystal composition; the compounds of the group consisting of formula II-1, formula II-2, formula II-3, formula II-4 and combinations thereof account for 18-60% of the total weight of the polymerizable liquid crystal composition; the compound of the general formula III accounts for 0.2 to 1 percent of the total weight of the polymerizable liquid crystal composition; the compound of the general formula IV accounts for 19 to 35 percent of the total weight of the polymerizable liquid crystal composition; the compound of the general formula V accounts for 0-15% of the total weight of the polymerizable liquid crystal composition; and the compound of the general formula VI accounts for 0-8% of the total weight of the polymerizable liquid crystal composition.
As a particularly preferred embodiment, the compounds of the group consisting of formula I-1, formula I-2, formula I-3 and combinations thereof account for 14 to 29% of the total weight of the polymerizable liquid crystal composition; the compounds of the group consisting of formula II-1, formula II-2, formula II-3, formula II-4 and combinations thereof account for 19-59% of the total weight of the polymerizable liquid crystal composition; the compound of the general formula III accounts for 0.3 to 0.5 percent of the total weight of the polymerizable liquid crystal composition; the compound of the general formula IV accounts for 19 to 32 percent of the total weight of the polymerizable liquid crystal composition; the compound of the general formula V accounts for 0-12% of the total weight of the polymerizable liquid crystal composition; and the compound of the general formula VI accounts for 0-7% of the total weight of the polymerizable liquid crystal composition.
The invention also provides a liquid crystal display device which comprises the polymerizable liquid crystal composition provided by the invention.
Compared with the prior art, the technical scheme adopted by the invention has the following technical progress:
the polymerizable liquid crystal composition provided by the invention has proper optical anisotropy, proper dielectric anisotropy, wider nematic phase temperature range, higher clearing point, faster response speed and good UV stability, can be suitable for a liquid crystal display, can meet the requirements of fast response of the liquid crystal display and good display under the UV condition, and makes obvious technical progress.
In the present invention, unless otherwise specified, the proportions are weight ratios, all temperatures are in degrees centigrade, and the thickness of the box selected for the response time data test is 7 μm.
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: v (1) EPPE (1) V, wherein V (1) E in the code represents methyl propionyl acid methyl ester; p in the code represents 1, 4-phenylene.
The abbreviated codes of the test items in the following examples are as follows:
cp (. degree. C.): clearing points (nematic-isotropic phase transition temperature)
Δ n: refractive index anisotropy (589nm, 25 ℃ C.)
Δ: dielectric anisotropy (1KHz, 25 ℃ C.)
γ 1: rotational viscosity (mPas at 20 ℃ C.)
VHR (initial): voltage holding ratio (%)
VHR (UV,6000 mJ): voltage holding ratio after UV light irradiation (%)
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.
Δ | - ⊥, where | is the dielectric constant parallel to the molecular axis, ⊥ is the dielectric constant perpendicular to the molecular axis, test conditions 25 ℃, 1KHz, test cell type TN90, cell thickness 7 μm.
VHR (initial) was measured using a TOYO6254 type liquid crystal physical property evaluation system; the test temperature is 60 ℃, the test voltage is 5V, and the test time is 166.7 ms; VHR (UV,6000mJ) was obtained by testing the liquid crystal after irradiation of 6000mJ UV light using a TOYO6254 type liquid crystal physical property evaluation system; the test temperature was 60 ℃, the test voltage was 5V, and the test time was 166.7 ms.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthesis techniques are conventional, and the resulting liquid crystal compounds were tested to meet the standards for electronic compounds.
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.
Comparative example 1
Liquid crystal composition L C-1 shown below was formulated with specific test data as shown in the following table:
TABLE 2 liquid crystal composition formulations and their test properties
A polymerizable liquid crystal composition L CM-1 was prepared by adding 0.5% of a compound represented by the following formula III-1 to 99.5% of the above liquid crystal composition L C-1, and the physical properties of L CM-1 were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.11 percent;
VHR(UV 6000mJ):97.90%。
comparative example 2
Liquid crystal composition L C-2 shown below was formulated with specific test data as shown in the following table:
TABLE 3 liquid crystal composition formula and its test performance
To 99.6% of the above-mentioned liquid crystal composition L C-2, 0.2% of a compound represented by the following formula III-2 and 0.2% of a compound represented by the following formula III-4 were added, respectively, to prepare a polymerizable liquid crystal composition L CM-2, and the physical property values and the addition period of the resultant L CM-2 were almost unchanged.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.13 percent;
VHR(UV 6000mJ):97.26%。
comparative example 3
Liquid crystal composition L C-3 shown below was formulated with specific test data as shown in the following table:
TABLE 4 liquid crystal composition formula and its test performance
A polymerizable liquid crystal composition L CM-3 was prepared by adding 0.3% of a compound represented by the following formula III-5 to 99.7% of the above liquid crystal composition L C-3, and the physical properties of L CM-3 obtained were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.99 percent;
VHR(UV 6000mJ):97.54%。
example 1
The liquid crystal composition L C-4 of example 1 was prepared according to the following compounds and weight percentages listed in Table 5, and filled between two substrates of a liquid crystal display for performance testing, the test data are shown in the following table:
TABLE 5 liquid crystal composition formulations and their test properties
A polymerizable liquid crystal composition L CM-4 was prepared by adding 0.5% of a compound represented by the following formula III-1 to 99.5% of the above liquid crystal composition L C-4, and the physical properties of L CM-4 were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.38 percent;
VHR(UV 6000mJ):98.66%。
example 2
To 99.6% of the above liquid crystal composition L C-4, 0.2% of a compound represented by the following formula III-2 and 0.2% of a compound represented by the following formula III-4 were added to prepare a polymerizable liquid crystal composition L CM-5, and the physical property values and addition period of the resultant L CM-5 were almost unchanged.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.41 percent;
VHR(UV 6000mJ):98.53%。
example 3
To 99.7% of the above liquid crystal composition L C-4 was added 0.3% of a compound represented by the following formula III-5 to prepare a polymerizable liquid crystal composition L CM-6, and the physical property values of L CM-6 obtained and before the addition were hardly changed.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.4 percent;
VHR(UV 6000mJ):98.82%。
example 4
The liquid crystal composition L C-5 of example 4 was prepared according to the following compounds and weight percentages listed in Table 6, and filled between two substrates of a liquid crystal display for performance testing, the test data are shown in the following table:
TABLE 6 liquid crystal composition formula and its test performance
A polymerizable liquid crystal composition L CM-7 was prepared by adding 0.5% of a compound represented by the following formula III-1 to 99.5% of the above liquid crystal composition L C-5, and the physical properties of L CM-7 were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.23 percent;
VHR(UV 6000mJ):98.81%。
example 5
To 99.6% of the above liquid crystal composition L C-5, 0.2% of a compound represented by the following formula III-2 and 0.2% of a compound represented by the following formula III-4 were added to prepare a polymerizable liquid crystal composition L CM-8, and the physical property values and addition period of the resultant L CM-8 were almost unchanged.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.42 percent;
VHR(UV 6000mJ):98.64%。
example 6
To 99.7% of the above liquid crystal composition L C-5 was added 0.3% of a compound represented by the following formula III-5 to prepare a polymerizable liquid crystal composition L CM-9, and the physical property values of L CM-9 obtained were almost unchanged from before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.34 percent;
VHR(UV 6000mJ):98.22%。
example 7
The liquid crystal composition L C-6 of example 7 was prepared according to the following compounds and weight percentages listed in Table 7, and filled between two substrates of a liquid crystal display for performance testing, the test data are shown in the following table:
TABLE 7 liquid crystal composition formulations and their test properties
A polymerizable liquid crystal composition L CM-10 was prepared by adding 0.5% of a compound represented by the following formula III-1 to 99.5% of the above liquid crystal composition L C-6, and the physical properties of L CM-10 were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.15 percent;
VHR(UV 6000mJ):98.58%。
example 8
To 99.6% of the above liquid crystal composition L C-6, 0.2% of a compound represented by the following formula III-2 and 0.2% of a compound represented by the following formula III-4 were added to prepare a polymerizable liquid crystal composition L CM-11, and the physical property values and addition period of the resultant L CM-11 were almost unchanged.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.52 percent;
VHR(UV 6000mJ):98.37%。
example 9
To 99.7% of the above liquid crystal composition L C-6 was added 0.3% of a compound represented by the following formula III-5 to prepare a polymerizable liquid crystal composition L CM-12, and the physical property values of L CM-12 obtained and before the addition were hardly changed.
The VHR of the polymerizable liquid crystal composition was tested as follows:
VHR (initial): 96.55 percent;
VHR(UV 6000mJ):98.65%。
example 10
The liquid crystal composition L C-7 of example 8 was prepared according to the following compounds and weight percentages listed in Table 8, and filled between two substrates of a liquid crystal display for performance testing, the test data are shown in the following table:
TABLE 8 liquid crystal composition formulations and their test properties
A polymerizable liquid crystal composition L CM-13 was prepared by adding 0.5% of a compound represented by the following formula III-1 to 99.5% of the above liquid crystal composition L C-7, and the physical properties of L CM-13 were almost unchanged from those before the addition.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.26 percent;
VHR(UV 6000mJ):98.49%。
example 11
To 99.6% of the above liquid crystal composition L C-7, 0.2% of a compound represented by the following formula III-2 and 0.2% of a compound represented by the following formula III-4 were added to prepare a polymerizable liquid crystal composition L CM-14, and the physical property values and addition period of the resultant L CM-14 were almost unchanged.
The VHR values of the polymeric liquid crystal compositions were tested as follows:
VHR (initial): 96.71 percent;
VHR(UV 6000mJ):98.58%。
example 12
To 99.7% of the above liquid crystal composition L C-7 was added 0.3% of a compound represented by the following formula III-5 to prepare a polymerizable liquid crystal composition L CM-15, and the physical property values of L CM-15 obtained were almost unchanged from before the addition.
The VHR of the polymerizable liquid crystal composition was tested as follows:
VHR (initial): 96.33 percent;
VHR(UV 6000mJ):98.79%。
as can be seen from the above comparative examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, the polymerizable liquid crystal composition provided by the present invention has suitable optical anisotropy, suitable dielectric anisotropy, wide nematic phase temperature range, high clearing point, fast response speed and good UV stability, and is applicable to liquid crystal displays. Compared with comparative examples 1, 2 and 3, when the optical anisotropy value, the dielectric anisotropy value and the clearing point are close, the polymerizable liquid crystal composition provided by the invention has shorter response time and better UV stability, can meet the requirements of fast response of a liquid crystal display and good display under the UV condition, and achieves obvious technical progress.
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.