CN105419816A - Liquid crystal medium and liquid crystal display including same - Google Patents
Liquid crystal medium and liquid crystal display including same Download PDFInfo
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- CN105419816A CN105419816A CN201510885925.3A CN201510885925A CN105419816A CN 105419816 A CN105419816 A CN 105419816A CN 201510885925 A CN201510885925 A CN 201510885925A CN 105419816 A CN105419816 A CN 105419816A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 112
- 150000001875 compounds Chemical class 0.000 claims abstract description 111
- 230000000694 effects Effects 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 75
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Chemical group 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000000654 additive Substances 0.000 description 20
- 230000006750 UV protection Effects 0.000 description 15
- 239000000178 monomer Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-O CC(C)(C1)[NH2+]C(C)(C)CC1O Chemical compound CC(C)(C1)[NH2+]C(C)(C)CC1O VDVUCLWJZJHFAV-UHFFFAOYSA-O 0.000 description 1
- PCCXPPXVNZAZLU-UHFFFAOYSA-N CC(C)(C1CCCC1)C(OC1CC(C)(C)NCC1)=O Chemical compound CC(C)(C1CCCC1)C(OC1CC(C)(C)NCC1)=O PCCXPPXVNZAZLU-UHFFFAOYSA-N 0.000 description 1
- VQZVJHINQPYDPY-UHFFFAOYSA-N CC(C)CCC(CCC(C)(C)NN)O Chemical compound CC(C)CCC(CCC(C)(C)NN)O VQZVJHINQPYDPY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- -1 R-R Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
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Abstract
The invention discloses a liquid crystal medium. The liquid crystal medium is a compound containing the following components, wherein a first component must contains one or more compounds represented in the general formula I1 and further contains one or more contain compounds represented in the general formulae (I2-I5) or not; a second component contains one or more liquid crystal compounds represented in the general formula II, and the dielectric anisotropy of the liquid crystal compounds are negative; a third compound contains one or more liquid crystal compounds, the dielectric anisotropy of the liquid crystal compounds are negative, and the absolute values of the liquid crystal compounds are more than 3. A liquid crystal composition disclosed by the invention has the characteristics of negative dielectricity, low rotary viscosity, high response speed and particularly good ultraviolet stability, is applicable to the manufacturing of the liquid crystal medium with negative dielectric anisotropy for displays addressed through active matrixes and particularly liquid crystal displays based on a VA effect or an ECB effect.
Description
Technical Field
The present invention relates to compounds for use in liquid-crystalline media and to liquid-crystalline displays comprising said liquid-crystalline media, in particular displays addressed by active matrix, in particular liquid-crystalline media of negative dielectric anisotropy for liquid-crystalline displays based on the VA or ECB effect.
Background
The TFT-LCD has been widely used in industrial fields and home consumer fields to almost completely replace the conventional CRT display market. 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.
Most of the current liquid crystal display devices are Twisted Nematic (TN) mode, but they have the disadvantages of low contrast and narrow viewing angle, while the display of Vertical Alignment (VA) mode has been widely used due to its advantages of wide viewing angle, high contrast and no rubbing alignment, and becomes a common display mode of TFT-LCD for large-sized TV, and in addition, the contrast of VA mode display has less dependence on the birefringence of liquid crystal, the thickness of liquid crystal layer and the wavelength of incident light, and thus VA mode becomes a liquid crystal display technology with great prospect.
For liquid crystal materials used for active matrix addressing display devices based on the VA effect, it is required to have (r) a low driving voltage: the liquid crystal material has proper negative dielectric anisotropy; quick response: the liquid crystal material has proper optical anisotropy; high reliability: high charge retention rate, high specific resistance value, excellent high-temperature stability, strict requirements on the stability of UV light or irradiation by conventional backlight illumination and the like. However, when the basic characteristics (low driving voltage, fast response) required by our liquid crystal material are achieved, the reliability problem is exposed, especially the stability of UV light is deteriorated. This is mainly because some groups in the molecular structure of the compound with negative dielectric anisotropy are easy to combine with inorganic ions, so that the ion content becomes large; the compound with negative dielectric anisotropy usually needs a large amount of catalytic coupling reaction in the synthesis process, and is easy to have the reasons of trace metal catalyst residue and the like. Therefore, it is a troublesome problem to solve the reliability of such liquid crystal media, in other words, we have demanded to invent or propose one or more compounds for improving the stability of the liquid crystal media to solve the reliability problem of the liquid crystal media.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a liquid crystal medium with optical anisotropy within the range of 0.080-0.150, proper high negative dielectric anisotropy and quick response time, and the liquid crystal medium overcomes the defects of unstable high-temperature resistance, unstable UV light resistance and the like in the conventional liquid crystal medium.
In order to solve the technical problem of reliability, the technical scheme adopted by the invention is as follows:
a liquid-crystalline medium comprising compounds of the following components, where the first component must contain one or more compounds of the general formula I1, the first component also contains one or more or no compounds of the general formulae I2 to I5, the second component contains one or more liquid-crystalline compounds of the general formula II with negative dielectric anisotropy, and the third component contains one or more liquid-crystalline compounds with negative dielectric anisotropy and an absolute value of more than 3;
wherein,
R1、R2、R3one selected from linear alkyl groups with 1-20 carbon atoms;
R1、R2preferably one of linear alkyl groups with 1-10 carbon atoms; particularly preferably one of linear alkyl groups with 2-7 carbon atoms;
R4one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R5one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
L1、L2respectively represents one of H, halogen, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkoxy with 1-7 carbon atoms at any substituted position of a benzene ring; preferably, one of H, halogen and linear alkyl with 1-7 carbon atoms is selected at any substituted position of a benzene ring; particularly preferably H, F, methyl, wherein the benzene ring is optionally substituted;
a is selected from any integer of 1-16, preferably an integer of 1-10, and particularly preferably 2, 4, 6, 8, 10;
b. c and e are selected from any integer of 1-5;
d. f is selected from 0, 1, 2, preferably 0 or 1;
is selected fromOr (2) to (d).
The technical scheme of the invention is further improved as follows: the third component at least comprises two liquid crystal compounds shown in a general formula III, and also comprises or does not comprise a liquid crystal compound shown in a general formula IV,
wherein,
R7、R9one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
R6、R8one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
Z1、Z2each independently selected from the group consisting of a single bond, -O-, -CH2CH2-, -COO-or-CH2One of O-is preferably selected from the group consisting of a single bond, -CH2One of O < - >;
x, Y is selected from-CH2One of-O-, and X and Y are not the same group;
g represents 1 or 2;
h represents 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
Is selected fromWhen g is 2,which may be the same or different, when g ═ 1,to represent
Is selected from Or (2) to (d).
The technical scheme of the invention is further improved as follows: the compound shown in the general formula I1 is one or more of compounds shown in formulas I1-1 to I1-4,
the compound shown in the general formula I2 is specifically one or more compounds shown in general formulas I2-1 to I2-9,
wherein,
when b is 1, c is 1, F-and CH3-each independently represents a position which may be at any position on the phenyl ring; when b is more than 1 and less than or equal to 5 and c is more than 1 and less than or equal to 5, F-and CH3Each independently represents any number of positions on the phenyl ring.
The compound shown in the general formula I3 is one or more of compounds shown in formulas I3-1 to I3-11,
the compound shown in the general formula I5 is specifically one or more compounds shown in formulas I5-1 to I5-5,
the compound shown in the general formula II is one or more compounds shown in formulas II-1 to II-8,
the compound shown in the general formula III is one or more compounds shown in formulas III 1 to III 7,
wherein,
R6one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R7one selected from linear alkyl groups having 1 to 7 carbon atoms and linear alkoxy groups having 1 to 7 carbon atoms.
Preferably, the compound shown in the general formula III is one or more of compounds shown in formulas III 1-1 to III 7-10,
the compound shown in the general formula IV is one or more of compounds shown in formulas IV-1 to IV-18,
wherein,
R8one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R9one selected from linear alkyl groups having 1 to 7 carbon atoms and linear alkoxy groups having 1 to 7 carbon atoms.
The technical scheme of the invention is further improved as follows: the liquid-crystalline medium also comprises a fourth component composed of at least two dielectric neutral compounds of the general formula V and/or VI,
wherein,
R10、R12one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
R11、R13one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
r is any integer from 1 to 4;
s is selected from 0, 1;
to represent And when r is more than or equal to 2,may be the same or different.
The compound shown in the general formula V is one or more compounds shown in formulas V-1 to V-9,
the compound shown in the general formula VI is specifically one or more compounds shown in formulas VI-1 to VI-25,
the technical scheme of the invention is further improved as follows: the liquid-crystalline medium also comprises a fifth component consisting of one or more compounds of the general formula VII,
wherein,
R14one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R15one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
L3、L4are respectively selected from one of H and halogen.
The compound shown in the general formula VII is specifically one or more compounds shown in formulas VII-1 to VII-10,
the technical scheme of the invention is further improved as follows: the concentration of the first component in the liquid crystal medium is 10-1000 ppm. Preferably 10 to 600ppm, particularly preferably 10 to 400 ppm. The composition of the first component is preferably: it is necessary to include one or more compounds of the formula I1 and also one or more compounds of the formula I2 and/or of the formula I3.
The technical scheme of the invention is further improved as follows: the liquid crystal medium comprises 1-30 wt% of a second component, 10-70 wt% of a liquid crystal compound shown in a general formula III in a third component, 0-20 wt% of a liquid crystal compound shown in a general formula IV in a third component, 12-50 wt% of a dielectric neutral compound shown in a general formula V in a fourth component, 2-50 wt% of a dielectric neutral compound shown in a general formula VI in a fourth component, and 0-25 wt% of a fifth component.
Preferably, the liquid crystal medium comprises 5-25 wt% of a second component, 20-50 wt% of a liquid crystal compound shown in a general formula III in a third component, 0-15 wt% of a liquid crystal compound shown in a general formula IV in a third component, 15-40 wt% of a dielectric neutral compound shown in a general formula V in a fourth component, 5-40 wt% of a dielectric neutral compound shown in a general formula VI in a fourth component, and 0-20 wt% of a fifth component.
The technical scheme of the invention is further improved as follows: the optical anisotropy of the liquid crystal medium is within the range of 0.080-0.150.
The invention also discloses a liquid crystal display containing the liquid crystal medium, and the liquid crystal display contains the liquid crystal medium.
The technical scheme of the invention is further improved as follows: the display is based on the VA or ECB effect and comprises active matrix addressing devices.
Due to the adoption of the technical scheme, the technical progress of the invention is as follows:
the invention discloses a liquid crystal medium with negative dielectric anisotropy, which has the optical anisotropy within the range of 0.080-0.150, appropriately high negative dielectric anisotropy and relatively fast response time, has good reliability performances such as high temperature resistance, UV light resistance and the like, is very suitable for a liquid crystal display element based on VA or ECB effect, and is particularly suitable for an active matrix display element.
According to the invention, one or more compounds shown in a general formula I1 are added into a liquid crystal medium with negative dielectric anisotropy, and one or more compounds shown in general formulas I2-I5 can be added in a matching way, so that the liquid crystal medium is fully stable in high temperature resistance, UV light resistance and other conditions.
The compounds shown in general formulas I1-I5 provided by the invention are optimally combined and matched or used independently to improve the stability problem of a liquid crystal medium to UV light and heat. The action mechanism of the compound shown in the general formula I1 in the material is roughly as follows due to the specific structure: (1) the secondary amine group of the tetramethyl piperidine is oxidized by peroxides such as hydroperoxide generated by material photo-aging and thermo-oxidative aging, and is converted into nitroxide radical NO; (2) the generated nitroxide radical NO is oxidized to capture destructive active groups generated by high polymer materials, such as radicals R, RO, ROO and the like; also converting it into a relatively stable compound (e.g., R-R, R-O-R, R-O-O-R); (3) in the process, the nitroxide radical NO is regenerated and continues to react with other radicals in the material. The aging speed of the material by light and heat is greatly delayed by the circulation. The compounds of the general formulae I3 and I5, which contain phenolic groups, have the main effect of interrupting the propagation of the active chain by reaction of the oxidizing radicals R, ROO generated by oxidation in the material.
The compounds shown in the general formulas II, III and IV have negative dielectric anisotropy and absolute values larger than 3, wherein the general formulas II and III generally have larger negative dielectric anisotropy, lower viscosity and good intersolubility so as to improve the response speed of liquid crystal; the general formula IV has very large negative dielectric anisotropy to meet the requirement of the device on low driving voltage, and also has the properties of appropriately large optical anisotropy and appropriately high Tni to meet the requirement of the current device on large refractive index and high brightness of liquid crystal materials.
The compounds shown in the general formula V, the general formula VI and the general formula VII are provided, wherein the general formula V has extremely low viscosity so that the liquid crystal material has qualitative change on response speed; the addition of the general formula VI is required for improving the performance parameters of the liquid crystal system and solving the problem of low-temperature intersolubility; the general formula VII has great optical anisotropy and can meet the requirement of liquid crystal materials with the refractive index of more than 0.110.
According to the invention, the reliability of the liquid crystal medium is improved by selecting the compounds, properly adjusting the weight percentage of the compounds and adding the compounds with the general formulas I1 to I5, so that the liquid crystal medium can obtain stable characteristics of different dielectric anisotropy, clearing points, birefringence and the like, and can be conveniently used under different liquid crystal box thicknesses and different driving voltages.
The invention uses one or more compounds with general formulas I1-I5 and one or more compounds with negative dielectric anisotropy and absolute value larger than 3, achieves the performance parameters required by a display by optimizing combination and proportioning and adopting other liquid crystal compounds with characteristics, even more than ten liquid crystal compounds, and has the characteristics of proper negative dielectric anisotropy, faster response speed, larger optical anisotropy, excellent UV resistance, high temperature resistance and the like, thereby developing a novel liquid crystal material for VA mode display with excellent performance.
The invention also discloses the application of the liquid crystal medium in an active matrix display element and an active matrix display based on VA or ECB effect.
Detailed Description
The invention discloses a liquid crystal medium, which comprises compounds of the following components, wherein the first component necessarily comprises one or more compounds shown as a general formula I1, the first component also comprises one or more compounds or does not comprise compounds shown as general formulas I2-I5, the second component comprises one or more liquid crystal compounds shown as a general formula II and with negative dielectric anisotropy, and the third component comprises one or more liquid crystal compounds with negative dielectric anisotropy and an absolute value larger than 3;
wherein,
R1、R2、R3one selected from linear alkyl groups with 1-20 carbon atoms;
R4one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R5one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
L1、L2respectively represents one of H, halogen, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkoxy with 1-7 carbon atoms at any substituted position of a benzene ring;
a is any integer from 1 to 16;
b. c and e are selected from any integer of 1-5;
d. f is selected from 0, 1 and 2;
is selected fromOr (2) to (d).
The third component of the invention at least comprises two liquid crystal compounds shown in a general formula III, and also comprises or does not comprise a liquid crystal compound shown in a general formula IV,
wherein,
R7、R9one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
R6、R8one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
Z1、Z2each independently selected from the group consisting of a single bond, -O-, -CH2CH2-, -COO-or-CH2One of O < - >;
x, Y is selected from-CH2One of-O-, and X and Y are not the same group;
g represents 1 or 2;
h represents 0, 1 or 2.
Is selected fromWhen g is 2,which may be the same or different, when g ═ 1,to represent
Is selected from Or (2) to (d).
The liquid-crystalline medium according to the invention also comprises a fourth component of at least two dielectric neutral compounds of the formula V and/or VI,
wherein,
R10、R12one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
R11、R13one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
r is any integer from 1 to 4;
s is selected from 0, 1;
to represent And when r is more than or equal to 2,may be the same or different.
The liquid-crystalline medium according to the invention also comprises a fifth component which is composed of one or more compounds of the formula VII,
wherein,
R14one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R15one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
L3、L4are respectively selected from one of H and halogen.
For the purposes of the present invention and in the examples described below, the structures of the mixed-crystal compounds are described by means of acronyms. Among these abbreviations, the chemical formulae are abbreviated as follows by using the following tables a to C. The codes used for the ring elements of the core structure of the compounds are shown in table a, the linking groups are shown in table B, and the coding meanings for the left or right end groups are given in table C. Exemplary structures of some of the compounds and their respective abbreviations are listed in table D.
Table a:
table B:
E-CH2CH2-O-O-
ME：-CH2O-Z-COO-
table C:
left terminal group and right terminal group
Wherein n and m each represent an integer.
In the following table, exemplary structures are given along with their respective abbreviations. These exemplary structures are shown to demonstrate the meaning of the principles of the abbreviations, which represent only some of the compounds preferably used. (n, m and l each independently represents an integer of 1 to 7)
The present invention will be described in further detail with reference to the following examples:
the parts referred to in the following examples are all weight percentages, the temperature unit is, and the specific meanings and test conditions of other symbols are as follows:
S-N represents the crystalline to nematic melting point (. degree. C.) of the liquid crystal;
cd represents the clearing point (. degree. C.) of the liquid crystal, and the test instrument: a Mettler-Toledo-FPSystems micro thermal analyzer;
γ 1 is rotational viscosity (mPa · s) and the test conditions are: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
K11is a torsional elastic constant, K33For the splay spring constant, the test conditions were: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
△ denotes dielectric anisotropy, △ ═∥-⊥Wherein∥is the dielectric constant parallel to the molecular axis,⊥for the dielectric constant perpendicular to the molecular axis, test conditions: at 25 ℃, INSTEC, ALCT-IR1 and 18 micron vertical box;
Δ n represents optical anisotropy, △ n ═ no-neWherein n isoRefractive index of ordinary light, neFor the refractive index of extraordinary rays, test conditions: 589nm, 25 + -0.2 deg.C;
VHR represents the voltage holding ratio, test conditions: 20 plus or minus 0.2 ℃ and 60 Hz;
the UV light energy is 8000mJ, and the test conditions are as follows: 365nm, 60mw/cm2Carrying out irradiation;
heat represents high temperature aging, test conditions: 100 ℃ for 1 hour.
The following examples 1 to 4 were prepared by weighing the liquid crystal compounds in the respective proportions to prepare liquid crystal media. In order to fully verify the effects of various additives, a plurality of different liquid crystal media are prepared, a large number of reliability experiments in the aspects of additive content, additive types, different collocation combinations and the like are carried out, various experimental data are provided, and generally, the less additive is added, the more obvious the quality improvement is, the better the quality improvement is. The various liquid crystal monomers used may be synthesized by known methods or may be obtained commercially.
The equipment and the equipment used for preparing the liquid crystal medium are as follows:
(1) electronic precision balance (precision 0.1mg)
(2) Stainless steel beaker: for weighing liquid crystals
(3) Spoon: for adding monomers
(4) A magnetic rotor: for stirring
(5) Temperature-controlled electromagnetic stirrer
The preparation method of the liquid crystal medium comprises the following steps:
(1) orderly placing the monomers;
(2) placing the stainless steel beaker on a balance, and putting the monomer into the stainless steel beaker by using a small spoon;
(3) sequentially adding monomer liquid crystal according to the required weight;
(4) placing the stainless steel beaker added with the materials on a magnetic stirring instrument for heating and melting;
(5) and after most of the mixture in the stainless steel beaker is melted, adding a magnetic rotor into the stainless steel beaker, uniformly stirring the liquid crystal mixture, and cooling to room temperature to obtain the liquid crystal medium.
And filling the obtained liquid crystal medium between two substrates of the liquid crystal display for performance test. The monomer structure, the amount (weight percentage) of the specific compound and the performance parameter test results of the obtained liquid crystal medium are all listed in the table.
Example 1
The liquid-crystalline medium of this example was prepared in accordance with the component ratios of the liquid-crystalline medium in Table 1.
TABLE 1 component ratios and performance parameters of the liquid-crystalline media of example 1
Table 2 example 1 reliability data after addition of different amounts/different kinds of additives
From the above table, it can be seen that the use of the additives I1-4 and I2-1 alone in a negative liquid crystal material is very significant for improving the UV resistance of the liquid crystal material, and the additives I1-4 are more excellent in the UV resistance than the additives I2-1, while the UV resistance and high temperature resistance of the liquid crystal material are excellent when the combination of I1-4 + I3-2 is used.
Example 2
The liquid-crystalline medium of this example was prepared in accordance with the component ratios of the liquid-crystalline medium in Table 3.
TABLE 3 component ratios and performance parameters for the liquid crystal composition of example 2
Table 4 example 2 reliability data after addition of different amounts/different kinds of additives
From the above table, it can be seen that the use of the additives I1-4 and I2-1 alone in a negative liquid crystal material is very significant for improving the UV resistance of the liquid crystal material, and the additives I1-4 are improved most prominently in the UV resistance than the additives I2-1, while when the combination of I1-4 + I3-2 is used, the liquid crystal material is excellent in the UV resistance and high temperature resistance, and the addition of I1-4 is 30ppm, and the addition of I3-2 is 300ppm, which is excellent for improving the reliability.
Example 3
The liquid-crystalline medium of this example was prepared in accordance with the component ratios of the liquid-crystalline medium in Table 5.
TABLE 5 component ratios and performance parameters for the liquid crystal composition of example 3
Table 6 example 3 reliability data after addition of different amounts/different kinds of additives
From the above table, it can be seen that the use of the additives I1-4 and I2-1 alone in a negative liquid crystal material is very significant for improving the UV resistance of the liquid crystal material, and the additives I1-4 are improved most prominently in the UV resistance than the additives I2-1, while when the combination of I1-4 + I3-2 is used, the liquid crystal material is excellent in the UV resistance and high temperature resistance, and the addition of I1-4 is 30ppm, and the addition of I3-2 is 300ppm, which is excellent for improving the reliability.
Example 4
The liquid-crystalline medium of this example was prepared in accordance with the component ratios of the liquid-crystalline medium in Table 7.
TABLE 7 component ratios and performance parameters for the liquid crystal composition of example 4
Table 8 example 4 reliability data after addition of different amounts/different kinds of additives
From the above table, it can be seen that the use of additives I1-4 and I2-1 alone in a negative liquid crystal medium is very significant for improving the UV resistance of the liquid crystal material, and that the additives I1-4 are the most improved in UV resistance than I2-1, while when the combination of I1-4 + I3-2 is used, the liquid crystal material is excellent in UV resistance and high temperature resistance, and the addition of I1-4 at 30ppm and the addition of I3-2 at 300ppm is excellent for improving the reliability.
From the performance parameters of the liquid crystal media shown in examples 1 to 4, it can be seen that the liquid crystal compounds i 1 to i 5 of the present invention are added to the above examples, and although the uv resistance and the high temperature resistance are improved slightly, the uv resistance is improved most remarkably when i 1 to i 4 are added, and the added liquid crystal media have good chemical and thermal stability, and are very suitable for active matrix display elements, such as active matrix displays of ECB, FFS, IPS, or MVA effects.
Although the invention only lists the specific compounds and the proportioning amounts (weight percentage content) of the 4 embodiments, and performs performance tests, especially tests of VHR data of the liquid crystal medium after additives are added, the liquid crystal compounds represented by the general formulas I1-I5 and the preferable liquid crystal compounds of the general formulas II, III, IV, V, VI and VII related to the invention are further expanded and modified, and the aim of the invention can be achieved by properly adjusting the proportioning amounts.
Claims (10)
1. A liquid crystal medium, characterized by: the liquid crystal medium comprises compounds of the following components, wherein the first component necessarily comprises one or more compounds shown in a general formula I1, the first component also comprises one or more compounds shown in a general formula I2-a general formula I5 or does not comprise the compounds, the second component comprises one or more liquid crystal compounds shown in a general formula II and with negative dielectric anisotropy, and the third component comprises one or more liquid crystal compounds with negative dielectric anisotropy and an absolute value larger than 3;
wherein,
R1、R2、R3one selected from linear alkyl groups with 1-20 carbon atoms;
R4one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R5one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
L1、L2respectively represents one of H, halogen, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkoxy with 1-7 carbon atoms at any substituted position of a benzene ring;
a is any integer from 1 to 16;
b. c and e are selected from any integer of 1-5;
d. f is selected from 0, 1 and 2;
is selected fromOr (2) to (d).
2. The liquid-crystalline medium according to claim 1, wherein the third component comprises at least two liquid-crystalline compounds of the formula III, optionally with a liquid-crystalline compound of the formula IV,
wherein,
R7、R9selected from linear alkyl group with 1-7 carbon atoms and carbon atoms1 to 7 of linear alkoxy groups;
R6、R8one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms, straight-chain alkoxy with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
Z1、Z2each independently selected from the group consisting of a single bond, -O-, -CH2CH2-, -COO-or-CH2One of O < - >;
x, Y is selected from-CH2One of-O-, and X and Y are not the same group;
g represents 1 or 2;
h represents 0, 1 or 2;
is selected fromWhen g is 2,which may be the same or different, when g ═ 1,to representOr
Is selected from Or (2) to (d).
3. The liquid-crystalline medium according to claim 1, characterized in that the compound of the formula I1 is in particular one or more compounds of the formulae I1-1 to I1-4,
the compound shown in the general formula I2 is specifically one or more compounds shown in general formulas I2-1 to I2-9,
wherein,
when b is 1, c is 1, F-and CH3-each independently represents a position which may be at any position on the phenyl ring; when b is more than 1 and less than or equal to 5 and c is more than 1 and less than or equal to 5, F-and CH3-each independently represents a number of positions on the phenyl ring which may be any number of positions;
the compound shown in the general formula I3 is one or more of compounds shown in formulas I3-1 to I3-11,
the compound shown in the general formula I5 is one or more of compounds shown in formulas I5-1-I5-5,
4. the liquid-crystalline medium according to claim 1, further comprising a fourth component of at least two dielectric neutral compounds of the formula V and/or VI,
wherein,
R10、R12one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
R11、R13one selected from linear alkyl with 1-7 carbon atoms and linear alkoxy with 1-7 carbon atoms;
r is any integer from 1 to 4;
s is selected from 0, 1;
to represent And when r is more than or equal to 2,may be the same or different.
5. A liquid-crystalline medium according to claim 4, further comprising a fifth component which is composed of one or more compounds of the formula VII,
wherein,
R14one of cyclopropyl, cyclobutyl, cyclopentyl, straight-chain alkyl with 1-7 carbon atoms and straight-chain alkenyl with 2-7 carbon atoms;
R15one selected from linear alkyl with 1-7 carbon atoms and linear alkenyl with 2-7 carbon atoms;
L3、L4are respectively selected from one of H and halogen.
6. The liquid-crystalline medium according to claim 1, wherein the concentration of the first component in the liquid-crystalline medium is 10 to 1000 ppm.
7. The liquid crystal medium of claim 5, wherein the liquid crystal medium comprises 1-30 wt% of the second component, 10-70 wt% of the liquid crystal compound of formula III, 0-20 wt% of the liquid crystal compound of formula IV, 12-50 wt% of the dielectric neutral compound of formula V, 2-50 wt% of the dielectric neutral compound of formula VI, and 0-25 wt% of the fifth component.
8. Liquid-crystalline medium according to any one of claims 1 to 7, characterized in that: the optical anisotropy of the liquid crystal medium is within the range of 0.080-0.150.
9. Liquid crystal display, characterized in that it comprises a liquid-crystalline medium according to any one of claims 1 to 7.
10. The display according to claim 9, wherein the display is based on the VA or ECB effect and comprises active matrix addressing devices.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107400521A (en) * | 2016-05-19 | 2017-11-28 | 默克专利股份有限公司 | Liquid crystal media |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482577A (en) * | 2009-09-08 | 2012-05-30 | 默克专利股份有限公司 | Liquid-crystal display |
| CN103180409A (en) * | 2010-10-20 | 2013-06-26 | 默克专利股份有限公司 | Switch element comprising liquid-crystalline medium |
| WO2014208320A1 (en) * | 2013-06-26 | 2014-12-31 | Jnc株式会社 | Liquid crystal composition, and liquid crystal display element |
| WO2014208318A1 (en) * | 2013-06-26 | 2014-12-31 | Jnc株式会社 | Liquid crystal composition, and liquid crystal display element |
| CN104371744A (en) * | 2013-08-02 | 2015-02-25 | 默克专利股份有限公司 | Liquid crystal medium |
| CN104513666A (en) * | 2014-10-10 | 2015-04-15 | 石家庄诚志永华显示材料有限公司 | Liquid crystal medium and application |
| CN104593001A (en) * | 2015-02-15 | 2015-05-06 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition and application thereof |
| WO2015079797A1 (en) * | 2013-11-29 | 2015-06-04 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
-
2015
- 2015-12-07 CN CN201510885925.3A patent/CN105419816A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482577A (en) * | 2009-09-08 | 2012-05-30 | 默克专利股份有限公司 | Liquid-crystal display |
| CN103180409A (en) * | 2010-10-20 | 2013-06-26 | 默克专利股份有限公司 | Switch element comprising liquid-crystalline medium |
| WO2014208320A1 (en) * | 2013-06-26 | 2014-12-31 | Jnc株式会社 | Liquid crystal composition, and liquid crystal display element |
| WO2014208318A1 (en) * | 2013-06-26 | 2014-12-31 | Jnc株式会社 | Liquid crystal composition, and liquid crystal display element |
| CN104371744A (en) * | 2013-08-02 | 2015-02-25 | 默克专利股份有限公司 | Liquid crystal medium |
| WO2015079797A1 (en) * | 2013-11-29 | 2015-06-04 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| CN104513666A (en) * | 2014-10-10 | 2015-04-15 | 石家庄诚志永华显示材料有限公司 | Liquid crystal medium and application |
| CN104593001A (en) * | 2015-02-15 | 2015-05-06 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170131260A (en) * | 2016-05-19 | 2017-11-29 | 메르크 파텐트 게엠베하 | Liquid-crystal medium |
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| CN107400521A (en) * | 2016-05-19 | 2017-11-28 | 默克专利股份有限公司 | Liquid crystal media |
| JP7065571B2 (en) | 2016-05-19 | 2022-05-12 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Liquid crystal medium |
| KR102353427B1 (en) * | 2016-05-19 | 2022-01-20 | 메르크 파텐트 게엠베하 | Liquid-crystal medium |
| CN108003893B (en) * | 2016-11-02 | 2021-08-03 | 石家庄诚志永华显示材料有限公司 | High vertical dielectric liquid crystal compound, liquid crystal composition and liquid crystal display device |
| CN108003893A (en) * | 2016-11-02 | 2018-05-08 | 石家庄诚志永华显示材料有限公司 | A kind of high vertical dielectric liquid-crystal compounds, liquid-crystal composition, liquid crystal display device |
| CN107794055A (en) * | 2017-11-06 | 2018-03-13 | 晶美晟光电材料（南京）有限公司 | A kind of negative type liquid crystal mixture and its application |
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| CN109837097A (en) * | 2019-03-29 | 2019-06-04 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition, liquid crystal display element, liquid crystal display |
| US20210095209A1 (en) * | 2019-09-30 | 2021-04-01 | Jiangsu Hecheng Display Technology Co., Ltd. | Liquid crystal composition and photoelectric display device thereof |
| WO2021127952A1 (en) * | 2019-12-24 | 2021-07-01 | 北京八亿时空液晶科技股份有限公司 | Low-viscosity, fast-response liquid crystal composition and application in liquid crystal display |
| CN117004409A (en) * | 2023-07-31 | 2023-11-07 | 河北化工医药职业技术学院 | Liquid crystal additive, preparation method thereof, liquid crystal composition, display element and display |
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