CN104152154B - A kind of TFT nematic phase liquid crystal composition and its preparation method and application - Google Patents
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 62
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- 238000002360 preparation method Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000004988 Nematic liquid crystal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 6
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 230000004044 response Effects 0.000 abstract description 9
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Abstract
The invention discloses a kind of TFT nematic phase liquid crystal composition and its preparation method and application, described liquid-crystal composition comprises component one and component two.Wherein, described component one is selected from least one in compound shown in formula I; Described component two is at least one in formula II compound or the mixture that is made up of at least one in compound described at least one in formula II compound and formula III to formula V.Liquid-crystal composition provided by the invention has wide temperature range, electric charge conservation rate is high, fast response time, driving voltage is low, rotary viscosity is low, the features such as the high and energy consumption of resistivity is low, can reach and maintain higher electric charge conservation rate at high-temperature area, in the effect of low-temperature region maintenance fast response time, the field such as Materials science and display can be widely used in, have broad application prospects and using value.
Description
Technical Field
The invention belongs to the field of liquid crystal materials and liquid crystal display, and particularly relates to a nematic phase liquid crystal composition for a TFT (thin film transistor), and a preparation method and application thereof.
Background
The 'twelve five' national strategic emerging industry development program ranks a novel flat panel display project as one of major projects, and requires development of key technology and new process development of a thin film transistor liquid crystal display (TFT-LCD) display panel and implementation of industrialization projects of key matching materials such as a glass substrate and core production equipment. The liquid crystal display is accelerating the update and development of the flat panel display industry as an important component of the flat panel display. Liquid crystal displays have also replaced conventional cathode ray tube display technology in the market and are becoming the mainstream products of flat panel displays.
Liquid crystal display technologies are classified into various modes such as Twisted Nematic (TN), Super Twisted Nematic (STN), in-plane switching (IPS), and vertical mode (VA) according to display principles.
In recent years, with the development of Thin Film Transistor (TFT) technology, a new liquid crystal display system, a TFT array-driven liquid crystal display, has been rapidly developed and has become the leader of the liquid crystal display and the entire flat panel display field. As a new generation of mainstream display, TFT-LCD has wide application in the fields of TV, computer, tablet computer, mobile phone, large screen, etc. Its main advantage is:
1. the service property is good: the low-voltage application, low driving voltage and improved safety and reliability of solidification use; the board is flat, light and thin, and a large amount of raw materials and use space are saved; the power consumption is low, the power consumption is about one tenth of that of a CRT display, and the reflective TFT-LCD is even about one hundredth of the CRT, so that a great deal of energy is saved.
2. The environmental protection characteristic is good: no radiation, no flicker, and no harm to the health of the user.
3. The application range is wide, the TFT-LCD can be normally used within the temperature range from minus 20 ℃ to plus 50 ℃, and the low-temperature working temperature of the TFT-LCD subjected to temperature reinforcement can reach minus 80 ℃. The display screen can be used as a mobile terminal display, a desktop terminal display and a large-screen projection television, and is a full-size video display terminal with excellent performance.
4. The manufacturing technology has high automation degree and good large-scale industrial production characteristics.
The TFT-LCD is easy to integrate and update, is a perfect combination of large-scale semiconductor integrated circuit technology and light source technology, and has great continuous development potential. There are amorphous, polycrystalline and monocrystalline silicon TFT-LCDs, and there will be TFTs of other materials in the future, both glass and plastic substrates.
Based on the advantages of the above displays, higher demands are made on the quality of liquid crystal materials used for liquid crystal displays. The liquid crystal material for TFT-LCD is different from the traditional liquid crystal material, and besides the requirements of good physical and chemical stability and wide working temperature range, the liquid crystal material also needs to have the following characteristics:
1. the viscosity is low, and the viscosity at 20 ℃ is less than 35mPa & s so as to meet the requirement of quick response.
2. High voltage holding ratio (v.h.r), which means that the liquid crystal material must have a high resistivity, generally requires at least more than 1012 Ω · cm.
3. Lower threshold voltage (V)th) So as to achieve the purposes of low-voltage driving and power consumption reduction.
4. Optical anisotropy (Δ n) matched to TFT-LCD to eliminate rainbow effect and obtain large contrast and wide-angle visual field. The value of Δ n should be in the range of 0.07-0.11, preferably about 0.08-0.1.
Liquid crystal materials with cyano-terminated groups widely used in TN and STN liquid crystal display industries, such as biphenyl and phenylcyclohexane liquid crystals containing cyano groups, have high delta and good electro-optical properties, but research shows that ionic impurities are easily introduced into compounds containing the cyano-terminated groups, and the voltage holding ratio is low; the viscosity is still higher compared with fluorine-containing liquid crystal with the same molecular structure, and the application of the compound in TFT-LCD is limited by the adverse factors. The ester liquid crystal has the characteristics of simple synthesis method and various varieties, and has wider phase change interval, but the higher viscosity thereof causes the dosage of the ester liquid crystal in a TFT-LCD formula to be greatly reduced. Therefore, the development of liquid crystal materials satisfying the above requirements has become a major issue in research on liquid crystal chemistry.
Disclosure of Invention
The invention aims to provide a nematic liquid crystal composition for a TFT, which has the characteristics of wide temperature range, high charge retention rate, high response speed, low driving voltage, low rotational viscosity, high resistivity, low energy consumption and the like, and can achieve the effects of maintaining high charge retention rate in a high-temperature region and maintaining high response speed in a low-temperature region.
In order to achieve the purpose, the invention adopts the technical scheme that:
a liquid crystal composition provided by a nematic liquid crystal composition for a TFT comprises a component I and a component II, wherein the component I is at least one selected from compounds shown in a formula I;
the second component is at least one of the compounds in the formula II, or a mixture consisting of at least one of the compounds in the formula II and at least one of the compounds in the formulae III to V.
Wherein,
formula I is:
formula II is:
the formula III is:
the formula IV is:
the formula V is:
in the formulae I to V, R1-R7Are selected from any one of alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms and alkenyloxy group having 3 to 8 carbon atoms.
A1Is trans-1, 4-cyclohexylene or 1, 4-phenylene.
A2、A3、A4And A5Are selected from any one of the following groups a and b:
the group a is any one of the following groups: trans 1, 4-cyclohexylene group and 1-CH in trans 1, 4-cyclohexylene group2Or 2 non-adjacent-CH2A group substituted with an oxygen atom or a sulfur atom; the group b is any one of the following groups: 1, 4-phenylene and 1, 4-phenylene, wherein 1 or 2-CH is substituted by a nitrogen atom.
X1-X10Are all selected from any one of hydrogen atoms, halogen atoms and trifluoromethyl and trifluoromethoxy.
n is an integer from 1 to 3.
The bridge Y being C2H4And CF2And O is any one of the above.
Of course, the liquid crystal composition provided by the invention can also consist of the component I and the component II.
In the liquid crystal composition, the compound shown in the formula I is a compound shown in formulas Ia to Ie: formula Ia
Formula Ib
Formula Ic
Formula Id
Formula Ie
In the formulae Ia to Ie, R1And R2The definitions of (a) are the same as the previous definitions. The compound shown in the formula II is a compound shown in formulas IIa-IIf:
formula IIa
Formula IIb
Formula IIc
Formula IId
Formula IIe
Formula IIf
In the formulae IIa to IIf, R3The definitions of (a) are the same as the previous definitions.
The compound shown in the formula III is a compound shown in formulas IIIa and IIIb:
formula IIIa
Formula IIIb
In the formulae IIIa and IIIb, R4And R5The definitions of (a) are the same as the previous definitions. The compound shown in the formula IV is a compound shown in formulas IVa-IVd:
formula IVa
Formula IVb
Formula IVc
Formula IVd
Formula IVe
In the formulae IVa to IVd, R6The definitions of (a) are the same as the previous definitions.
In the liquid crystal composition provided by the invention, the mass ratio of the component I to the component II is 36-46: 54-64.
Preferably, in the second component, the compound represented by the formula II accounts for 48-97% of the second component by mass, the compound represented by the formula III accounts for 3-6% of the second component by mass, the compound represented by the formula IV accounts for 0-42.5% of the second component by mass, and the compound represented by the formula V accounts for 0-6% of the second component by mass.
The preparation method of the liquid crystal composition provided by the invention comprises the following steps: and mixing the first component and the second component, heating, stirring and uniformly mixing to obtain the liquid crystal composition.
The invention also provides application of the nematic phase liquid crystal composition for the TFT in preparing a liquid crystal display element or a liquid crystal display.
The nematic liquid crystal composition for the TFT has the characteristics of wide temperature range, high charge retention rate, high response speed, low driving voltage, low rotational viscosity, high resistivity, low energy consumption and the like, can maintain higher charge retention rate in a high-temperature region and maintain high response speed in a low-temperature region, can be widely applied to the fields of material science, display and the like, has wide application prospect and application value, and can be applied to TFT-LCD display devices.
Detailed Description
In order to better explain the technical content of the invention, specific examples are specifically illustrated below in combination with the attached table. The method is a conventional method unless otherwise specified.
In the invention, the percentages are all mass percentages, the temperatures are all centigrade temperatures, and the symbols represent the following meanings:
s → N represents a transition temperature between a crystal and a nematic liquid crystal; ClearingPoint is the transition temperature between the liquid crystal phase and the isotropic phase, namely the clearing point temperature; n iseIs an extraordinary refractive index; n isoIs the ordinary refractive index; Δ n is a birefringence coefficient;∥liquid crystal long axis dielectric coefficient;⊥is the liquid crystal minor axis permittivity; Δ is the dielectric anisotropy constant; v10Is the liquid crystal threshold voltage; v90Is the liquid crystal saturation voltage. The refractive index test temperature involved in the invention is 25 ℃, and the corresponding wavelength is 589 nm. The dielectric constant test conditions involved are: 1KHz,25 ℃. The viscosity test temperature referred to is 25 ℃.
Example 1:
according to the structural formula compounds given in the table 1 and the corresponding mass percentages thereof, the compounds are uniformly mixed according to the method to obtain the liquid crystal composition of the invention.
Table 1: the structural formula and the type of the compound of each component in the example 1 and the percentage of the compound accounting for the mass of the liquid crystal composition
The liquid crystal composition was tested for its relevant properties including phase transition temperature, viscosity, refractive index, dielectric constant, and driving voltage according to a common method, and the results are shown in table 2:
table 2: example 1 results of Property test of liquid Crystal composition
| Item | Results |
| S→N(℃) | -41.0 |
| Clearing Point(℃) | 98.0 |
| Viscosity(mm2s-1,25℃) | 15.0 |
| Δn(589nm,25℃) | 0.10 |
| ne(589nm,25℃) | 1.57 |
| no(589nm,25℃) | 1.47 |
| ε∥(1KHz,25℃) | 9.6 |
| ε⊥(1KHz,25℃) | 3.0 |
| Δε(1KHz,25℃) | 6.6 |
| V10,25(V) | 1.9 |
| V90,25(V) | 2.8 |
The symbols have the same meanings as above, wherein the birefringence index Deltan ═ ne-no(ii) a Dielectric anisotropy constant Δ ═∥-⊥。
Example 2:
according to the structural formula compounds given in the table 3 and the corresponding mass percentages thereof, the compounds are uniformly mixed according to the method to obtain the liquid crystal composition of the invention.
Table 3: in example 2, the structural formula and type of each component compound and the percentage of the compound in the liquid crystal composition by weight
The liquid crystal composition was tested for its relevant properties including phase transition temperature, viscosity, refractive index, dielectric constant, and driving voltage according to a common method, and the results are shown in Table 4:
table 4: example 2 results of Property test of liquid Crystal composition
| Item | Results |
| S→N(℃) | -38.0 |
| Clearing Point(℃) | 96.0 |
| Viscosity(mm2s-1,25℃) | 15.5 |
| Δn(589nm,25℃) | 0.10 |
| ne(589nm,25℃) | 1.54 |
| no(589nm,25℃) | 1.44 |
| ε∥(1KHz,25℃) | 9.2 |
| ε⊥(1KHz,25℃) | 2.9 |
| Δε(1KHz,25℃) | 6.3 |
| V10,25(V) | 2.1 |
| V90,25(V) | 3.0 |
The symbols have the same meanings as above, wherein the birefringence index Deltan ═ ne-no(ii) a Dielectric anisotropy constant Δ ═∥-⊥。
Example 3:
according to the structural formula compounds given in the table 5 and the corresponding mass percentages thereof, the compounds were mixed uniformly according to the method described above to obtain the liquid crystal composition of the present invention.
Table 5: in example 3, the structural formula and type of each component compound and the percentage of the compound in the liquid crystal mixture by weight
The liquid crystal composition is tested according to the common method for relevant properties, including phase transition temperature, viscosity, refractive index, dielectric coefficient, driving voltage and the like, and the measured results are as follows:
table 6: example 3 Property test results of liquid Crystal composition
| Item | Results |
| S→N(℃) | -38.0 |
| Clearing Point(℃) | 96.0 |
| Viscosity(mm2s-1,25℃) | 14.7 |
| Δn(589nm,25℃) | 0.09 |
| ne(589nm,25℃) | 1.53 |
| no(589nm,25℃) | 1.44 |
| ε∥(1KHz,25℃) | 9.4 |
| ε⊥(1KHz,25℃) | 3.0 |
| Δε(1KHz,25℃) | 6.4 |
| V10,25(V) | 2.1 |
| V90,25(V) | 3.0 |
The symbols have the same meanings as above, wherein the birefringence index Deltan ═ ne-no(ii) a Dielectric anisotropy constant Δ ═∥-⊥。
Example 4:
according to the structural formula compounds given in Table 7 and the corresponding mass percentages thereof, the liquid crystal compositions of the present invention were obtained by mixing the compounds uniformly according to the methods described above.
Table 7: in example 4, the structural formula and type of each component compound and the percentage of the compound in the liquid crystal mixture by weight
The liquid crystal composition is tested according to the common method for relevant properties, including phase transition temperature, viscosity, refractive index, dielectric coefficient, driving voltage and the like, and the measured results are as follows:
table 8: example 4 Property test results of liquid Crystal composition
| Item | Results |
| S→N(℃) | -40.0 |
| Clearing Point(℃) | 97.0 |
| Viscosity(mm2s-1,25℃) | 14.8 |
| Δn(589nm,25℃) | 0.11 |
| ne(589nm,25℃) | 1.55 |
| no(589nm,25℃) | 1.44 |
| ε∥(1KHz,25℃) | 9.3 |
| ε⊥(1KHz,25℃) | 2.8 |
| Δε(1KHz,25℃) | 6.5 |
| V10,25(V) | 1.9 |
| V90,25(V) | 2.9 |
The symbols have the same meanings as above, wherein the birefringence index Deltan ═ ne-no(ii) a Dielectric anisotropy constant Δ ═∥-⊥。
The embodiments show that the nematic liquid crystal composition for the TFT provided by the invention has the characteristics of wide temperature range, high charge retention rate, fast response speed, low driving voltage, low rotational viscosity, high resistivity, low energy consumption and the like, can maintain a high charge retention rate in a high temperature region, can maintain a fast response speed in a low temperature region, can be widely applied to the fields of material science, display and the like, and has wide application prospects and application values.
Claims (8)
1. A nematic liquid crystal composition for a TFT (thin film transistor) is characterized by comprising a first component and a second component, wherein the first component is at least one selected from compounds shown in a formula I;
the second component is a mixture consisting of at least one compound shown in a formula II and at least one compound shown in a formula III to a formula V;
wherein,
the formula I is as follows:
the formula II is:
the formula III is:
the formula IV is:
formula V is:
in the formulae I to V, R1-R7Are selected from any one of alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms and alkenyloxy with 3-8 carbon atoms;
A1is trans-1, 4-cyclohexylene or 1, 4-phenylene;
A2、A3、A4and A5Are selected from any one of the following groups a and b:
the group a is any one of the following groups: trans 1, 4-cyclohexylene group and 1-CH in trans 1, 4-cyclohexylene group2Or 2 non-adjacent-CH2A group substituted with an oxygen atom or a sulfur atom;
the group b is any one of the following groups: 1, 4-phenylene and 1, 4-phenylene in which 1 or 2-CH is substituted by nitrogen atom;
X1-X10are all selected from any one of hydrogen atoms, halogen atoms and trifluoromethyl and trifluoromethoxy;
n is an integer from 1 to 3;
the bridge Y being C2H4And CF2Any one of O;
in the second component, the compound shown in the formula II accounts for 48-97% of the second component by mass, the compound shown in the formula III accounts for 3-6% of the second component by mass, the compound shown in the formula IV accounts for 0-42.5% of the second component by mass, and the compound shown in the formula V accounts for 0-6% of the second component by mass.
2. The nematic liquid crystal composition for a TFT according to claim 1, wherein the compound represented by the formula I is a compound represented by the formulae Ia to ie:
3. the nematic liquid crystal composition for TFTs according to claim 1, characterized in that the compound represented by the formula II is a compound represented by the formulae IIa to IIf:
4. the nematic liquid crystal composition for a TFT according to claim 1, wherein the compound represented by the formula III is a compound represented by the formulae IIIa to IIIb:
5. the nematic liquid crystal composition for a TFT according to claim 1, wherein the compound represented by the formula IV is a compound represented by the formulae IVa to IVd:
6. the nematic liquid crystal composition for TFTs according to claim 1, characterized in that the mass ratio of component one to component two is 36-46: 54-66.
7. The method for preparing a nematic liquid crystal composition for TFTs described in any one of claims 1 to 6, which comprises the steps of: and mixing the first component and the second component, heating, stirring and uniformly mixing to obtain the nematic phase liquid crystal composition for the TFT.
8. Use of the nematic liquid crystal composition for TFTs according to any one of claims 1 to 6 for producing liquid crystal display elements or liquid crystal displays.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544893A (en) * | 2009-05-07 | 2009-09-30 | 石家庄永生华清液晶有限公司 | Liquid crystal composition and liquid crystal display element |
| CN101831307A (en) * | 2010-03-10 | 2010-09-15 | 北京八亿时空液晶材料科技有限公司 | Liquid crystal composition for TFT (Thin-Film Transistor) display |
| CN102226090A (en) * | 2011-04-19 | 2011-10-26 | 西安瑞联近代电子材料有限责任公司 | Liquid crystal composition |
| CN102304364A (en) * | 2011-05-23 | 2012-01-04 | 西安彩晶光电科技股份有限公司 | Wide nematic phase mixed liquid crystal material with low threshold value |
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| KR20050006629A (en) * | 2003-07-09 | 2005-01-17 | 삼성전자주식회사 | Nematic liquid crystal composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544893A (en) * | 2009-05-07 | 2009-09-30 | 石家庄永生华清液晶有限公司 | Liquid crystal composition and liquid crystal display element |
| CN101831307A (en) * | 2010-03-10 | 2010-09-15 | 北京八亿时空液晶材料科技有限公司 | Liquid crystal composition for TFT (Thin-Film Transistor) display |
| CN102226090A (en) * | 2011-04-19 | 2011-10-26 | 西安瑞联近代电子材料有限责任公司 | Liquid crystal composition |
| CN102304364A (en) * | 2011-05-23 | 2012-01-04 | 西安彩晶光电科技股份有限公司 | Wide nematic phase mixed liquid crystal material with low threshold value |
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