CN103897708B - A kind of positive dielectric anisotropy liquid crystal composition - Google Patents
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Abstract
The invention discloses a kind of positive dielectric anisotropy liquid crystal composition, described liquid-crystal composition comprises the liquid-crystal compounds shown in general formula III of the liquid-crystal compounds shown in formula II, 1%～50% of liquid-crystal compounds, 1%～70% shown in the formula I that weight/mass percentage composition is 1%～80%.The positive dielectric anisotropy that said composition is bigger, less optical anisotropy, the highest clearing point, good low-temperature stability and relatively low rotary viscosity, be particularly well-suited to manufacture IPS mode LCD and FFS mode liquid crystal display.
Description
Technical field
The present invention relates to a kind of liquid-crystal composition, refer in particular to one and can be used for manufacturing IPS mode liquid crystal and show
Device or the positive dielectric anisotropy liquid crystal composition of FFS mode liquid crystal display.
Background technology
Thin Film Transistor-LCD (TFT-LCD), is 21 century the most rising Display Technique
One of, all it is widely used in the field such as notebook computer, LCD TV.TFT-LCD is at twisted-nematic
The Active Matrix LCD At introducing thin film transistor switch on the basis of liquid crystal display (TN-LCD) and formed, gram
Take the shortcomings such as cross interference during passive matrix shows, quantity of information is few, writing speed is slow, substantially improved aobvious
Show quality, therefore obtain fast development.
The disadvantage of TFT-LCD is viewing angle problem, little including visual angle anisotropy and angular field of view.When making
User is when the direction leaving display floater normal is observed, and the contrast of liquid crystal display will be decreased obviously, depending on
It also occur that gray scale and the phenomenon of colour reversal when angle is big.Along with the increase of TFT-LCD product size, especially
Being the TFT-LCD extensive application in TV field, viewing angle problem becomes the most serious.Therefore, have and extensively regard
Plane conversion (In-Plane Swiching, IPS) the display pattern of wild angle feature is arisen at the historic moment.IPS shows mould
Formula has outstanding angle of visibility characteristic, dynamic definition and color rendition effect, is mainly used in scientific and technological content
The fields such as higher space flight, medical treatment, design.
IPS display pattern is that the pair of electrodes controlling liquid crystal molecule deflection is all installed on the same substrate, utilizes
The transverse electric field being applied between this pair of electrodes, to control the state of liquid crystal molecule, makes liquid crystal molecule parallel
Rotate in the plane of substrate, produce twist distortion.Hang down mutually in the polarizer of this pattern and the direction of analyzer
Directly, the direction of director is identical with polarizer direction.When no voltage is applied, liquid crystal molecule does not rotates, liquid
Crystal display is dark-state, demonstrates the black that comparison is pure；After applying voltage, liquid crystal molecule rotates, light
When by the liquid crystal layer of distortion modulated, electric field is different, and the transmitance of light is different.
Hyundai company develops fringe field switching (Fringe Field on the basis of IPS pattern
Switching, FFS) display pattern, by same plane between pixel electrode produce fringe field, make electrode
Between and electrode directly over aligned liquid-crystal molecule can (being parallel to substrate) in-plane produce rotate turn
Change, thus while increasing visual angle, improve the light transmission efficiency of liquid crystal layer.FFS mode by IPS pattern not
Transparent metal electrode changes transparent ITO electrode into increase light transmittance, positive and negative electrode is passed through insulating barrier simultaneously
Separating heavy stack arrangement, is greatly reduced electrode width and spacing.When applying voltage, at electric field action bottom electrode
Between and electrode on liquid crystal molecule all in the face being parallel to panel rotate, it is ensured that light is all worn in all directions
Cross the short axle of liquid crystal molecule, do not have directional dependence to expand visual angle.FFS technology is before realizing wide viewing angle
Put, be simultaneously achieved the good characteristics such as high light transmission efficiency, high-contrast, high brightness, low aberration.
Liquid crystal material is as one of important photoelectron material of liquid crystal display, to the property improving liquid crystal display
Can play an important role.As display liquid crystal material must be requested that have wider nematic temperature range,
Higher stability, applicable rotary viscosity and the quick response to electric field.But up to the present,
Also do not find any single liquid-crystal compounds can reach above-mentioned performance requirement, it is necessary to by plurality of liquid crystals
Compound is combined into liquid-crystal composition, can meet the performance requirement of liquid crystal display material.
Owing to IPS display pattern, FFS display pattern show the displaying principle of pattern, liquid crystal cell with conventional TN
Structure is the most different, so, the requirement to liquid crystal material is also different from TN display mode liquid crystal material.In order to reach
To good display effect, the liquid crystal material for IPS display pattern and FFS display pattern must be fulfilled for
Lower requirement:
(1) high stability: include ultraviolet light stability, heat stability and chemical stability；
(2) optical anisotropy of appropriateness: less Δ n can obtain wider visual angle；
(3) low viscosity: viscosity is the lowest, response time is the least, and response speed is the fastest；
(4) bigger dielectric anisotropy: Δ ε is the biggest for dielectric anisotropy, and the threshold voltage of liquid crystal is the least,
But the ion in liquid crystal material the most easily separates out, become free ion and cause resistivity to reduce；
(5) wide temperature range: preferably storage temperature range is-40 DEG C～100 DEG C, typically has special applications
Such as car-mounted display, this temperature may widen-40 DEG C～110 DEG C.
Show and FFS mode shows to realize IPS pattern, and obtain stable, there is broad view
Liquid-crystal composition, needs the systematicness of active force and the Liquid Crystal Molecules Alignment designing between liquid crystal molecule, therefore,
The liquid crystal material continually developing new excellent performance has great importance.
Summary of the invention
The technical issues that need to address of the present invention be to provide one can be used for manufacture IPS mode LCD or
FFS mode liquid crystal display, that rotary viscosity is low, the quick positive dielectric anisotropic liquid crystals combination responded
Thing.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of positive dielectric anisotropy liquid crystal composition, comprises the liquid-crystal compounds shown in formula I, formula II
Liquid-crystal compounds shown in shown liquid-crystal compounds and general formula III；
Wherein,
R1、R2、R3、R4Be respectively H atom, carbon number be 1～10 alkyl, carbon number be 1～10
Arbitrary group in the alkoxyl of individual carbon atom or alkenyl that carbon number is 2～10；
Ring A1, ring A2, ring A3, ring A4, ring A7It is singly-bound, trans 1,4-cyclohexylidene or any respectively
Trans 1,4-cyclohexylidene, 1,4-phenylene or arbitrarily-H that-H is replaced by-F are by the 1,4-phenylene of-F replacement
In arbitrary group；
Ring A5, ring A6It is following arbitrary group 1.～in the most described group respectively:
The most non-conterminous-CH in the most trans 1,4-cyclohexylidene or trans 1,4-cyclohexylidene2-by-O-or-S-
The group formed after replacement；
2. the group formed after the most non-conterminous-CH-is replaced by-N-in 1,4-phenylene or 1,4-phenylene；
3. the most described group that arbitrarily-H is replaced by-F；
4. 1,4-cyclohexadienylidene, 1,4-bis-cyclooctylene, piperidines-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-
Diyl or 1,2,3,4-tetra-hydrogen-based naphthalene-2,6-diyl；
B is the arbitrary group in following groups:
Z1It is singly-bound ,-CH2CH2-、-COO-、-CF2O-、-CH2Any of which of O-；
X1、X2、X3、X4、X5、X6、X7、X8、X9Be respectively-H ,-Cl ,-F ,-CN ,-OCN,
-OCF3、-CF3、-CHF2、-CH2F、-OCHF2,-SCN ,-NCS or-SF5In arbitrary group；
A, b, c, d, e, f, g are any integer in 0,1 or 2 respectively.
Described liquid-crystal composition comprise the liquid-crystal compounds shown in the formula I that weight/mass percentage composition is 1%～80%,
The liquid-crystal compounds shown in formula II of 1%～70% and the liquid-crystal compounds shown in general formula III of 1%～50%.Its
In, the weight/mass percentage composition of liquid-crystal compounds shown in general formula III is preferably 5%～40%；Most preferably
10%～30%.
Described liquid-crystal composition is also added with the stabilizer of 0.01%～the 0.5% of liquid-crystal composition quality sum.
The performance of described liquid-crystal composition meets at least one in following (a)～(d) condition,
(a) optical anisotropy Δ n scope: 0.08～0.13；
(b) dielectric anisotropy Δ ε scope: 6～12；
(c) clearing point c.p. >=95 DEG C；
(d) rotary viscosity γ1≤110mpa·s。
Owing to have employed technique scheme, the technological progress acquired by the present invention is:
The invention discloses a kind of positive dielectric anisotropy liquid crystal composition, said composition excellent performance, have
Bigger positive dielectric anisotropy, less optical anisotropy, the highest clearing point, good low temperature
Stability and relatively low rotary viscosity, it is possible to maintain high electric charge conservation rate at high-temperature area, tie up at low-temperature region
Hold response speed faster, it is possible to significantly widen IPS display pattern or the use temperature of FFS display pattern,
And can guarantee that response time and wider angular field of view faster, it is very suitable for IPS display pattern or FFS shows
Show pattern, be particularly suitable for the vehicle-mounted IPS liquid crystal display of low voltage drive and vehicle-mounted FFS liquid crystal
Show device, there is wide market prospect and using value.
By to the adjustment of each constituent mass percentage composition in liquid-crystal composition, liquid-crystal composition can obtain
Different dielectric anisotropy, optical anisotropy, clearing point and rotary viscosities, it is simple at different liquid crystal cells
Using under thickness and different driving voltage, the scope of application is the widest.
Shown in formula I containing benzofurans liquid-crystal compounds, not only have necessary to liquid crystal material one
As physical property, and to light, thermally-stabilised, there is wider nematic temperature range, with other compounds
Intermiscibility is good, the low rotary viscosity γ that especially this compounds has1With big dielectric anisotropy (△ ε > 0)
Characteristic, the threshold voltage of liquid-crystal composition can be effectively reduced, accelerate response time simultaneously, improve mixed
Close the low temperature intersolubility of liquid crystal, and then the obvious performance optimizing liquid-crystal composition, be highly suitable for low-voltage
The liquid crystal monomer of IPS-TFT or FFS-TFT drive, quickly responded.
Difluoro methylene ether compound shown in general formula III, has bigger nematic temperature range, bigger
Dielectric anisotropy and relatively low rotary viscosity；Its add effectively improve the dielectric of liquid-crystal composition respectively to
The opposite sex and response speed.
Liquid-crystal compounds shown in formula II and general formula III includes fluorine atom, has low viscosity, moderate Jie
The characteristics such as electrical anisotropy, high resistivity, high electric charge conservation rate, are TFT liquid crystal display liquid crystal materials
Main component.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further details:
Number involved in following embodiment is weight/mass percentage composition, and temperature unit is DEG C, other symbols
Concrete meaning and test condition as follows:
S-N represents that the crystalline state of liquid crystal is to nematic fusing point (DEG C)；
C.p. the clearing point (DEG C) of liquid crystal is represented, method of testing: DSC quantitative method；
Δ n represents optical anisotropy, △ n=no-ne, wherein, noFor the refractive index of ordinary light, neSeek for non-
The refractive index of ordinary light, test condition: 589nm, 25 ± 2 DEG C, test instrunment: Abbe refractometer；
△ ε represents dielectric anisotropy, △ ε=ε∥-ε⊥, wherein, ε∥For being parallel to the dielectric constant of molecular axis,
ε⊥For being perpendicular to the dielectric constant of molecular axis, test condition: 25 ± 0.5 DEG C, 20 microns of parallel boxes, tester
Device: INSTEC:ALCT-IR1；
γ1Expression rotary viscosity (mPa s), test condition: 25 ± 0.5 DEG C, 20 microns of parallel boxes, test instrunment:
INSTEC:ALCT-IR1。
A kind of positive dielectric anisotropy liquid crystal composition, comprises the liquid-crystal compounds shown in formula I, formula II
Liquid-crystal compounds shown in shown liquid-crystal compounds and general formula III；
Wherein,
R1、R2、R3、R4Be respectively H atom, carbon number be 1～10 alkyl, carbon number be 1～10
Arbitrary group in the alkoxyl of individual carbon atom or alkenyl that carbon number is 2～10；
Ring A1, ring A2, ring A3, ring A4, ring A7It is singly-bound, trans 1,4-cyclohexylidene or any respectively
Trans 1,4-cyclohexylidene, 1,4-phenylene or arbitrarily-H that-H is replaced by-F are by the 1,4-phenylene of-F replacement
In arbitrary group；
Ring A5, ring A6It is following arbitrary group 1.～in the most described group respectively:
The most non-conterminous-CH in the most trans 1,4-cyclohexylidene or trans 1,4-cyclohexylidene2-by-O-or-S-
The group formed after replacement；
2. the group formed after the most non-conterminous-CH-is replaced by-N-in 1,4-phenylene or 1,4-phenylene；
3. the most described group that arbitrarily-H is replaced by-F；
4. 1,4-cyclohexadienylidene, 1,4-bis-cyclooctylene, piperidines-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-
Diyl or 1,2,3,4-tetra-hydrogen-based naphthalene-2,6-diyl；
B is the arbitrary group in following groups:
Z1It is singly-bound ,-CH2CH2-、-COO-、-CF2O-、-CH2Any of which of O-；
X1、X2、X3、X4、X5、X6、X7、X8、X9Be respectively-H ,-Cl ,-F ,-CN ,-OCN,
-OCF3、-CF3、-CHF2、-CH2F、-OCHF2,-SCN ,-NCS or-SF5In arbitrary group；
A, b, c, d, e, f, g are any integer in 0,1 or 2 respectively.
Described liquid-crystal composition comprise the liquid-crystal compounds shown in the formula I that weight/mass percentage composition is 1%～80%,
The liquid-crystal compounds shown in formula II of 1%～70% and the liquid-crystal compounds shown in general formula III of 1%～50%；Its
In, the weight/mass percentage composition of liquid-crystal compounds shown in general formula III preferably 5%～40%, most preferably 10%～30%.
Described liquid-crystal composition preferably comprises the liquid-crystalization shown in the formula I that weight/mass percentage composition is 28%～60%
The liquid-crystalization shown in general formula III of the liquid-crystal compounds shown in formula II, 20%～33% of compound, 17%～39%
Compound.
Can also add stabilizer in described liquid-crystal composition, the addition of stabilizer is liquid-crystal composition quality
The 0.01%～0.5% of sum.Described stabilizer is in phenol antioxidant and/or benzotriazole ultraviolet absorber
Any one or a few.
The performance of described liquid-crystal composition meets at least one in following (a)～(d) condition,
(a) optical anisotropy Δ n scope: 0.08～0.13；
(b) dielectric anisotropy Δ ε scope: 6～12；
(c) clearing point c.p. >=95 DEG C；
(d) rotary viscosity γ1≤110mpa·s。
Liquid-crystal compounds shown in liquid-crystal compounds shown in described formula I preferably I-a～I-h:
Liquid-crystal compounds shown in described formula II preferably is selected from the liquid-crystal compounds shown in II-a～II-i:
Liquid-crystal compounds shown in described general formula III preferably is selected from the liquid-crystal compounds shown in III-a～III-h:
Wherein ,-(F) is-H or-F；
Liquid-crystal compounds shown in described general formula III is most preferably from following compounds:
Example 1 below～10 weighs formula I, the liquid-crystal compounds shown in II, III, system the most in proportion
For obtaining liquid-crystal composition.The various liquid crystal monomers used all can be synthesized by known method, or
By being either commercially available.The preparation method of liquid-crystal composition takes conventional method, the most at high temperature will be each
The liquid crystal monomer dissolving planting component mixes in a solvent, solvent is evaporated off the most at reduced pressure conditions, obtains
Liquid-crystal composition；Or take the methods such as heating, ultrasound wave, suspension to be mixed in proportion by liquid crystal monomer prepared.
The liquid-crystal composition of gained is filled between liquid crystal display two substrates and carries out performance test.Particular compound
Monomer structure, consumption (weight/mass percentage composition), gained the performance parameter test result of liquid-crystal composition equal
It is listed in table.The corresponding embodiment 1～10 of table 1～10.
The component proportion of the liquid-crystal composition of table 1 embodiment 1 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 2 embodiment 2 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 3 embodiment 3 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 4 embodiment 4 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 5 embodiment 5 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 7 embodiment 7 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 8 embodiment 8 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 9 embodiment 9 and performance parameter thereof
The component proportion of the liquid-crystal composition of table 10 embodiment 10 and performance parameter thereof
From the performance parameter of the liquid-crystal composition shown in embodiment 1～10, the positive dielectric of the present invention is respectively to different
Property liquid-crystal composition has bigger positive dielectric anisotropy, less optical anisotropy, the highest clear
Bright spot, good low-temperature stability and relatively low rotary viscosity, it is possible to maintain high electric charge to keep at high-temperature area
Rate, maintains response speed faster at low-temperature region, is very suitable for IPS display pattern or FFS shows pattern.
The use of liquid-crystal composition of the present invention, it is possible to significantly widen IPS display pattern or FFS shows making of pattern
By temperature, and can guarantee that response time and wider angular field of view faster, be particularly suitable for low voltage drive
Vehicle-mounted IPS and vehicle-mounted FFS show, have broad application prospects and using value.
Although the present invention only lists particular compound and the proportioning consumption (quality thereof of above-mentioned 10 embodiments
Percentage composition), and carried out performance test, but the liquid-crystal composition of the present invention can be at above-described embodiment
On the basis of, utilize formula I involved in the present invention, the liquid-crystal compounds representated by II, III, Yi Jitong
Formula I, the most preferred liquid-crystal compounds preferred, general formula III of II, III are expanded further and revise,
And add stabilizer on this basis, by the liquid-crystal compounds representated by mutual-through type I, II, III and stable
The consumption of agent suitably adjusts, to all reaching the purpose of the present invention.
Claims (6)
1. a positive dielectric anisotropy liquid crystal composition, it is characterised in that: described liquid-crystal composition comprises matter
Amount percentage composition be 28%～60% the liquid-crystal compounds shown in formula I, weight/mass percentage composition be 17%～39%
The liquid-crystal compounds shown in formula II and general formula III-f that weight/mass percentage composition is 20%～33%～III-h shown in
Liquid-crystal compounds in one or more；
Wherein,
R1、R2、R3、R4Be respectively H atom, carbon number be 1～10 alkyl, carbon number be 1～10
Arbitrary group in the alkoxyl of individual carbon atom or alkenyl that carbon number is 2～10；
Ring A1, ring A2, ring A3, ring A4It is that singly-bound, trans 1,4-cyclohexylidene or arbitrarily-H are by-F respectively
Arbitrary in the 1,4-phenylene that substituted trans 1,4-cyclohexylidene, 1,4-phenylene or arbitrarily-H are replaced by-F
Group；
Ring A5, ring A6It is following arbitrary group 1.～in the most described group respectively:
The most non-conterminous-CH in the most trans 1,4-cyclohexylidene or trans 1,4-cyclohexylidene2-by-O-or-S-
The group formed after replacement；
2. the group formed after the most non-conterminous-CH-is replaced by-N-in 1,4-phenylene or 1,4-phenylene；
3. the most described group that arbitrarily-H is replaced by-F；
4. 1,4-cyclohexadienylidene, 1,4-bis-cyclooctylene, piperidines-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-
Diyl or 1,2,3,4-tetra-hydrogen-based naphthalene-2,6-diyl；
Z1It is singly-bound ,-CH2CH2-、-COO-、-CF2O-、-CH2Any of which of O-；
X1、X2、X3、X4It is-H ,-Cl ,-F ,-CN ,-OCN ,-OCF respectively3、-CF3、-CHF2、
-CH2F、-OCHF2,-SCN ,-NCS or-SF5In arbitrary group；
A, b, c, d, e are any integer in 0,1 or 2 respectively；
-(F) is-H or-F.
The positive dielectric anisotropy liquid crystal composition of one the most according to claim 1, it is characterised in that:
Liquid-crystal compounds shown in described general formula III-f～III-h is the one or several in compound shown in III-f-1～III-h-4
Kind:
The positive dielectric anisotropy liquid crystal composition of one the most according to claim 1, it is characterised in that:
Liquid-crystal compounds shown in described formula I is one or more in compound shown in I-a～I-h:
The positive dielectric anisotropy liquid crystal composition of one the most according to claim 1, it is characterised in that:
Liquid-crystal compounds shown in described formula II is one or more in compound shown in II-a～II-i:
The positive dielectric anisotropy liquid crystal composition of one the most according to claim 1, it is characterised in that:
Described liquid-crystal composition is also added with the stabilizer of 0.01%～the 0.5% of liquid-crystal composition quality sum.
6., according to a kind of positive dielectric anisotropy liquid crystal composition described in any one of Claims 1 to 5, it is special
Levy and be: the performance of described liquid-crystal composition meets at least one in following (a)～(d) condition,
(a) optical anisotropy Δ n scope: 0.08～0.13；
(b) dielectric anisotropy Δ ε scope: 6～12；
(c) clearing point c.p. >=95 DEG C；
(d) rotary viscosity γ1≤110mpa·s。
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| CN105295951B (en) * | 2014-12-12 | 2018-04-24 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal compounds and liquid crystal compound containing cyclopropyl |
| CN108291148B (en) * | 2015-12-09 | 2022-03-01 | 默克专利股份有限公司 | Naphthalene compounds for liquid crystal mixtures |
| CN109796990B (en) * | 2017-11-16 | 2022-09-09 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing lateral trifluoromethyl, liquid crystal mixture and display device thereof |
| CN107903915A (en) * | 2017-12-07 | 2018-04-13 | 西安近代化学研究所 | A kind of negative liquid crystal compound with benzofuran ring and combinations thereof |
| CN114106850B (en) * | 2021-12-17 | 2022-11-18 | 重庆汉朗精工科技有限公司 | Positive liquid crystal composition and application thereof in liquid crystal display device |
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| CN103205263A (en) * | 2013-03-13 | 2013-07-17 | 江苏和成显示科技股份有限公司 | Liquid crystal composition and liquid crystal display device |
| CN103242856A (en) * | 2013-04-11 | 2013-08-14 | 江苏和成显示科技股份有限公司 | Liquid crystal composition and liquid crystal display device |
| CN103242862A (en) * | 2013-05-30 | 2013-08-14 | 江苏和成显示科技股份有限公司 | Liquid crystal composition with low-temperature storage stability and liquid crystal display device |
| CN103305232A (en) * | 2013-06-14 | 2013-09-18 | 石家庄诚志永华显示材料有限公司 | Nematic phase liquid crystal composition |
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