Patent Grant
10655062
The present invention belongs to the technical field of liquid crystal materials, and particularly relates to a highly vertical dielectric liquid crystal composition and a liquid crystal display device containing such a liquid crystal.
At present, the expansion of application range of liquid crystal compounds is becoming larger and larger, and the liquid crystal compounds can be used in various types of displays, electro-optical devices, sensors, etc. There are a great variety of liquid crystal compounds used in the above-mentioned display field, wherein nematic liquid crystals are used most extensively. Nematic liquid crystals have been used in passive TN and STN matrix displays and systems having a TFT active matrix.
With regard to the application field of thin film transistor techniques (TFT-LCD), although the market in recent years has become very huge, and the techniques also have become gradually mature, requirements of display techniques are increasing continuously, especially in terms of achieving a quick response, reducing the drive voltage for reducing power consumption, etc. Liquid crystal materials, as one of the important optoelectronic materials for liquid crystal displays, play an important role in improving the performance of a liquid crystal display.
Liquid crystal materials need to have good chemical and thermal stabilities and stabilities to electric fields and electromagnetic radiations. Moreover, as liquid crystal materials used for thin film transistor techniques (TFT-LCD), they not only need to have the stabilities as mentioned above, but also should have properties, such as a broader nematic phase temperature range, an appropriate birefringence anisotropy, a very high electrical resistivity, a good ultraviolet resistant property, a high charge retention rate, a low vapor pressure, etc.
For dynamic picture display applications, the elimination of display picture ghosting and trailing requires liquid crystals to have a very quick response speed, and therefore the liquid crystals are required to have a lower rotary viscosity γ1. Moreover, for portable devices, in order to reduce the device energy consumption, it is desirable for the drive voltage of the liquid crystals to be as low as possible; and for displays for uses such as televisions, the requirements for the drive voltage of the liquid crystals are not as low as necessary.
The viscosity, in particular rotary viscosity γ1, of a liquid crystal compound directly affects the response time after the liquid crystal is energized, and both the rise time (ton) and fall time (toff) are proportional to the rotary viscosity γ1 of the liquid crystal. Moreover, since the rise time (ton) is related to a liquid crystal cell and the drive voltage, it can be adjusted by means of increasing the drive voltage and reducing the thickness of the liquid crystal cell; while the fall time (toff) is irrelevant to the drive voltage, but is mainly related to the elastic constant of the liquid crystal and the thickness of the liquid crystal cell, and thinning of cell thickness can result in a decrease in fall time (toff). Moreover, in different display modes, the movement manners of liquid crystal molecules are different, and the three modes TN, IPS and VA are inversely proportional to the mean elastic constant K, twist elastic constant and bend elastic constant, respectively.
According to the continuum theory of liquid crystal, a variety of different liquid crystals deformed under the action of an external force (an electric field, a magnetic field) can “rebound” back to the original shapes by intermolecular interactions; likewise, liquid crystals also form a “viscosity” due to the intermolecular force. Small changes of liquid crystal molecules may result in obvious changes in the conventional parameter performance of the liquid crystal, wherein for some of these changes, there is a certain rule, while for some changes, it is difficult to find a rule, which may also have obvious effects on the intermolecular interaction of the liquid crystal, these effects are very subtle, and to date, no perfect theoretical explanation has been formed yet.
The viscosity of a liquid crystal is related to the molecular structure of the liquid crystal, and studying the relationship between the viscosity of a liquid crystal system formed from different liquid crystal molecules and the molecular structures of the liquid crystals is one of important tasks of liquid crystal formulation engineers.
The reason why a liquid crystal display panel has a high energy consumption is that only about 5% of backlight can transmit through a display device and then be captured by human eyes, while most of the light is “wasted”. If a liquid crystal having a high light transmittance can be developed, then the backlight intensity can be reduced, thereby achieving the purpose of saving energy consumption and extending the service time of a device.
The technical problem to be solved by the present invention is to provide a liquid crystal composition having a good stability against light and heat, a lower viscosity, a wider refractive index that may be achieved by adjusting the monomer ratio, and a higher clearing point (a very wide service temperature range), and in particular, the liquid crystal composition has a higher light transmittance, thus allowing a display device to have a higher brightness or an energy saving effect.
In order to solve the above-mentioned technical problems, the present invention provides a liquid crystal composition comprising one or more compounds represented by formula I, one or more compounds represented by formula II and one or more compounds represented by formula III:
wherein
wherein R1, R2, R3, R5 and R6 each independently represent an alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10 or an alkenoxy group having a carbon atom number of 3-8, and any one or more non-connected CH2 in the groups represented by R1 and R3 may be substituted with cyclopentyl, cyclobutyl, cyclopropyl or —O—;
R4 represents F, CF3, OCF3, OCHF2 or OCH2F;
each independently represent one or more of
and any fluorobenzene;
each independently represent one or two of benzene or fluorobenzene;
represents one or more of
or any fluorobenzene;
m, p and w each independently represent 1, 2 or 3; and
n and q each independently represent 0 or 1.
The one or more compounds represented by formula I are preferably one or more of compounds represented by formulas I1 to I14; the one or more compounds represented by formula II are preferably one or more of compounds represented by formulas II1 to II14; and the one or more compounds represented by formula III are preferably one or more of compounds represented by formulas III1 to III5:
wherein R11 and R31 each independently represents an alkyl group having a carbon atom number of 1-6;
R21 each independently represents an alkyl group having a carbon atom number of 1-5; and
R51 and R61 each independently represent an alkyl group having a carbon atom number of 1-6, an alkoxy group having a carbon atom number of 1-6, an alkenyl group having a carbon atom number of 2-6 or an alkenoxy group having a carbon atom number of 3-6.
In the liquid crystal composition of the present invention, the total content in mass percentage of the one or more compounds represented by formula I is preferably 1-40%, the total content in mass percentage of the one or more compounds represented by formula II is preferably 1-40%, and the total content in mass percentage of the one or more compounds represented by formula III is preferably 1-80%.
The compounds represented by formula I also have a larger dielectric anisotropy in the liquid crystal molecule major axis parallel direction and vertical direction, with the difference (Δε) between the major axis parallel direction dielectric anisotropy and vertical direction dielectric anisotropy being smaller. The compounds represented by formula II also have a larger dielectric anisotropy in the liquid crystal molecule major axis parallel direction and vertical direction, with the difference (Δε) between the major axis parallel direction dielectric anisotropy and vertical direction dielectric anisotropy being greater. The two when used in combination have an effect of significantly improving the vertical direction dielectric anisotropy of the mixed liquid crystal without causing the Δε of the mixed liquid crystal to decrease. Therefore, the addition amount cannot be limited by Δε, so that a larger amount of addition can be achieved, thereby significantly improving the light transmittance of the liquid crystal mixture. The compounds of formula III have a low rotary viscosity, and further have a higher clearing point (CP), and when they are used in combination with compounds represented by formulas I and II, the liquid crystal mixture has a very low rotary viscosity and a fast response speed.
The liquid crystal composition provided by the present invention may further comprise one or more compounds represented by formula IV:
wherein R7 represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or an fluoro-substituted alkenoxy group having a carbon atom number of 3-8; and any one or more CH2 in the groups represented by R7 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl;
each independently represent:
one or more of
r represents 0, 1, 2 or 3;
Z1 and Z2 each independently represent a single bond, —CF2O—, —CH2CH2— or —CH2O—; and
Y2 represents F, a fluoro-substituted alkyl group having a carbon atom number of 1-5, a fluoro-substituted alkoxy group having a carbon atom number of 1-5, a fluoro-substituted alkenyl group having a carbon atom number of 2-5 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8.
The one or more compounds represented by formula IV are preferably compounds of formulas IV0 to IV25
wherein X1 and X2 each independently represent H or F;
R7 each independently represents an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or two CH2 in the groups represented by R7 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl;
the (F)s each independently represent H or F.
The compounds represented by the formula IV have a larger dielectric anisotropy (Δε), so the addition of an appropriate amount thereof is advantageous to improve the dielectric anisotropy (Δε) of the mixed liquid crystal while reducing the drive voltage of the liquid crystal. They are suitable for use in positive TN, IPS and FFS modes, or may also be suitable for use in PSA-positive TN, IPS and FFS modes.
The addition amount of the compounds represented by the formula IV is preferably between 0% and 60%, further preferably 5-30%.
The liquid crystal composition may further comprise one or more compounds represented by formula V
wherein R8 and R9 each independently represent an alkyl group having a carbon atom number of 1-10, fluorine, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more CH2 in the groups represented by R8 and R9 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl;
Z3 and Z4 each independently represent a single bond, —CH2CH2— or —CH2O—;
each independently represent one or more of
m represents 1, 2 or 3; and
n represents 0 or 1.
The one or more compounds represented by formula V are preferably one or more compounds of V1 to V11:
wherein R8 and R9 each independently represent an alkyl group having a carbon atom number of 1-10, fluorine, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more CH2 in the groups represented by R8 and R9 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl.
The liquid crystal composition further comprises one or more compounds represented by formula VI
wherein R10 and R11 each independently represent an alkyl group having a carbon atom number of 1-10, a fluoro-substituted alkyl group having a carbon atom number of 1-10, an alkoxy group having a carbon atom number of 1-10, a fluoro-substituted alkoxy group having a carbon atom number of 1-10, an alkenyl group having a carbon atom number of 2-10, a fluoro-substituted alkenyl group having a carbon atom number of 2-10, an alkenoxy group having a carbon atom number of 3-8 or a fluoro-substituted alkenoxy group having a carbon atom number of 3-8, and any one or more CH2 in the groups represented by R10 and R11 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl; and
W represents —O—, —S— or —CH2O—.
The liquid crystal composition may further comprise one or more compounds represented by formula VII
wherein R12 represents an alkyl group having a carbon atom number of 1-5 or an alkenyl group having a carbon atom number of 2-5;
R13 represents an F atom, an alkyl group having a carbon atom number of 1-5, an alkoxy group having a carbon atom number of 1-5 or an alkenyl group having a carbon atom number of 2-5, and any one or more CH2 in the groups represented by R12 and R13 may be substituted with cyclopentyl, cyclobutyl or cyclopropyl;
n represents 0 or 1; and
the (F)s each independently represent H or F.
The present invention relates to a liquid crystal display element or liquid crystal display comprising the above-mentioned liquid crystal composition, wherein the liquid crystal display element or liquid crystal display is an active matrix display element or display or a passive matrix display element or display.
The display element or display may be of a TN, ECB, VA, IPS, FFS, PS-TN, PS-VA, PS-IPS, PS-FFS, PA-VA, PA-IPS, PA-FFS, PI-less VA, PI-less IPS, or PI-less-FFS LCD mode.
The present invention is further described as below in combination with particular embodiments, but the present invention is not limited to the following embodiments. The methods are all conventional methods, unless otherwise specified. The raw materials, unless otherwise specified, are commercially available.
The reaction process is generally monitored through TLC (Note to client: insert what TLC stands for), and the post-treatments after the reaction is completed are generally water washing, extracting, combining organic phases and then drying, evaporating and removing the solvent under a reduced pressure, recrystallization and column chromatographic separation; and a person skilled in the art would be able to achieve the present invention according to the following description.
In this description, the percentages are mass percentages, the temperatures are in degree Celsius (° C.), and the specific meanings of other symbols and the test conditions are as follows:
Cp represents the clearing point (° C.) of the liquid crystal measured by a DSC quantitative method;
Δn represents the optical anisotropy, no is the refractive index of an ordinary light, ne is the refractive index of an extraordinary light, the test condition is 25±2° C. and 589 nm, and an abbe refractometer is used for the test;
Δε represents the dielectric anisotropy, Δε=ε//−ε⊥, wherein ε// is a dielectric constant parallel to a molecular axis, and ε⊥ is a dielectric constant perpendicular to the molecular axis, the test condition is 25±0.5° C., a 20 micron parallel cell is used, and INSTEC: ALCT-IR1 is used for the test;
γ1 represents a rotary viscosity (mPa·s), the test condition is 25±0.5° C., a 20 micron parallel cell is used, and INSTEC: ALCT-IR1 is used for the test; and
Tr (%) represents a transmittance, Tr (%)=100%*bright state (Vop) luminance/light source luminance, the test device is DMS501, the test condition is 25±0.5° C., the test cell is a 3.3 micron IPS test cell, both the electrode spacing and the electrode width are 10 microns, and the included angle between the frictional direction and the electrode is 10°; therefore, there is a positive correlation between ε⊥ and Tr, so in the evaluation of the transmittance, εL can be used as an evaluation index for indication.
In the examples of the present invention application, liquid crystal monomer structures are represented by codes, wherein the code representation of cyclic structures, end groups and linking groups of the liquid crystals are shown in tables (I) and (II) below
For example:
After filling test cells with the liquid crystal compositions for testing, the following results are obtained: the transmittance of Comparative Example 1 is 5.4%, the transmittance of Comparative Example 2 is 5.3%, and the transmittance of Example 1 is 6% which is increased by 11% and 13%, respectively, as compared with those of Comparative Examples 1 and 2.
The liquid crystal composition of the present invention has a good stability against light and heat, a lower viscosity, a wider refractive index that may be achieved by adjustment, and a higher clearing point (a very wide service temperature range), and in particular, the liquid crystal composition has a higher light transmittance, thus allowing a display device to have a higher brightness or an energy saving effect.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017 1 0917336 | Sep 2017 | CN | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20090141215 | Bremer | Jun 2009 | A1 |
| Number | Date | Country |
|---|---|---|
| 105131971 | Dec 2015 | CN |
| Number | Date | Country | |
|---|---|---|---|
| 20190100696 A1 | Apr 2019 | US |
