CN110484281A - A kind of negative liquid crystal composition and its application - Google Patents
A kind of negative liquid crystal composition and its application Download PDFInfo
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- CN110484281A CN110484281A CN201910699434.8A CN201910699434A CN110484281A CN 110484281 A CN110484281 A CN 110484281A CN 201910699434 A CN201910699434 A CN 201910699434A CN 110484281 A CN110484281 A CN 110484281A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13712—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering the liquid crystal having negative dielectric anisotropy
Abstract
The present invention relates to liquid crystal material technical fields, more particularly to a kind of negative liquid crystal composition and its application, include polymerizable compound and nematic phase liquid crystal composition in the composition, the polymerizable compound is the one or two of polymerizable compound representated by general formula IA and IB:
Description
Technical field
The invention belongs to liquid crystal material technical fields, and in particular to comprising one or more polymerizable compounds and have negative
Mixture composed by the liquid-crystal composition of dielectric anisotropy, and it is related to it in the application of field of liquid crystal display.
Background technique
Liquid crystal is widely used in display field at present, and display is that electric signal (data information) is changed into visually
The process of light (visual information) completes the equipment i.e. man-machine interface (Man-Machine Interface, MMI) of display.Liquid crystal
Show and experienced very long road for development with the discovery of liquid crystal.Austria botanist Friedrich Reinitzer in 1888
Have found the first liquid crystal material benzoic acid cholesterol (cholesteryl benzoate).Manguin is invented within 1917
Rubbing, to make single domain liquid crystal and research optical anisotropy.E.Bose in 1909 establishes moving (Swarm)
It says, and (1918) are supported in the experiment for obtaining L.S.Ormstein and F.Zernike et al., are discussed as uniting by De Gennes
Meter property rises and falls.G.W.Oseen and H.Zocher obtains F.C.Frank perfect (1958 in foundation continuum theory in 1933
Year).M.Born (1916) and K.Lichtennecker (nineteen twenty-six) has found and has studied the dielectric anisotropy of liquid crystal.
1932, nematic phase was divided into positive and negative property two major classes accordingly by W.Kast.Nineteen twenty-seven, V.Freedericksz and V.Zolinao hair
Existing nematic liquid crystal is under electric field or magnetic fields, and deformation occurs and there are voltage threshold (Freederichsz transformations).This
The production for being found to be liquid crystal display provides foundation.
Continuous improvement with people to display weight demands, contrast problem become the display index being concerned, VA
Display pattern has very excellent contrast performance, but there are apparent viewing angle problem and response time problems, to understand
Certainly viewing angle problem, the display technologies such as MVA, PVA, CPA propose that the essence of these technologies is to solve viewing angle problem using multidomain,
And achieve good effect.But is appointed due to difficulty increased in technique and response time problem and so annoying display row
Industry, until PSVA (polymer stabilizing vertical orientation) technology proposes, which realizes multidomain and pre-tilt angle control using polymer
Make the liquid crystal display to realize fast-response and wide viewing angle.For PSVA liquid crystal display, the stability of pre-tilt angle becomes shadow
Ring liquid crystal display image retention, the most important index of display effect.
Liquid-crystal composition provided by the present invention is intended to the pre-tilt angle stability of PSVA liquid crystal display, improves liquid crystal display
Image retention.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of negative liquid crystal composition, wraps in the composition
Polymerizable compound and nematic phase liquid crystal composition are included, the polymerizable compound is polymerizableization representated by general formula IA and IB
Close the one or two of object:
The nematic phase liquid crystal composition includes:
Compound representated by one or more general formula II of 5~25 parts by weight:
Wherein R1、R2It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；
Compound representated by one or more general formula IIIs of 35~55 parts by weight:
Wherein R3、R4It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；A1、A2It is independently represented each other
Trans- Isosorbide-5-Nitrae-cyclohexyl or Isosorbide-5-Nitrae-phenylene；
Compound representated by one or more general formula IV of 20~35 parts by weight:
Wherein, R5、R6It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；N represents 0 or 1；
Compound representated by one or more general formula V of 3~15 parts by weight::
Wherein, R7、R8It is independently represented each other C1~C12Straight chained alkyl, A3It is independently represented each other trans- Isosorbide-5-Nitrae-hexamethylene
Base or Isosorbide-5-Nitrae-phenylene；
The described of 0.1~0.5% mass percent is added in the nematic phase liquid crystal composition of every 100 parts by weight to gather
Polymerisable compounds, the polymerizable compound of preferably 0.2~0.45% mass percent, more preferable 0.25~0.40% mass hundred
Divide the polymerizable compound of ratio；The polymerizable compound of particularly preferred 0.25~0.30% mass percent.
Preferably, compound representated by general formula II provided by the present invention is the chemical combination for containing 2,3- difluorobenzene structure
Object, the structure have negative dielectric anisotropy.
Specifically, compound described in the general formula II is one of Formula II A1~Formula II A8 or a variety of:
Preferably, the nematic liquid crystal compound include parts by weight be 8~23 selected from Formula II A1, IIA2, IIA3,
One of IIA6 or a variety of；
It is highly preferred that it is 10~20 parts in Formula II A1, IIA2 that the nematic phase liquid crystal composition, which includes parts by weight,
One or two kinds of compounds.
Compound representated by general formula III provided by the present invention is two ring neutral compounds, which has
Low rotary viscosity and excellent intersolubility.
Specifically, the compounds of formula III is selected from one of formula III A~formula III C or a variety of:
Wherein, R3It is independently represented each other C1~C7Straight chained alkyl, R4It is independently represented each other C1~C7Straight chained alkyl
Or unbranched alkoxy.
Preferably, compound representated by general formula III at least contains a kind of formula III A and at least contains a kind of formula III C institute
The compound of representative.
Preferably, compound representated by the general formula III is selected from one of formula III A1~formula III C4 or a variety of:
Preferably, the nematic liquid crystal compound includes chemical combination representated by general formula III of the parts by weight for 40~53 parts
Object；It is highly preferred that nematic phase liquid crystal composition provided by the present invention includes representated by general formula III of the parts by weight for 43~50 parts
Compound.
Preferably, compound representated by general formula III be selected from IIIA3, IIIA5, IIIA8, IIIA9, IIIB2,
One of IIIB6, IIIC2, IIIC4 or a variety of；
Preferably, compound representated by general formula III be selected from formula III A3, IIIA8, IIIA9, IIIB2, IIIB6,
One of IIIC2, IIIC4 or a variety of.
It is further preferred that in the nematic phase liquid crystal composition comprising parts by weight be 24~30 parts selected from IIIA3,
One of IIIA8, IIIA9 or multiple compounds are 4~6 parts selected from one of IIIB2 or IIIB6 comprising parts by weight
Or two kinds of compounds, parts by weight are 15~18 selected from one or both of IIIC2 or IIIC4 compound.
The compound of formula III A3 and IIIA8 that more preferable parts by weight are 24~28 parts, 4~6 parts of parts by weight of formula III B6
Compound, parts by weight be 15~18 parts be selected from one or both of IIIC2 or IIIC4 compound.
Compounds of formula IV provided by the present invention is the negative dielectric anisotropic compound containing methoxyl group bridged bond, should
Class compound has big negative dielectric anisotropic.
Specifically, compound representated by general formula IV is selected from one or more representated by IVA~IVB:
Wherein, R5、R6It is independently represented each other C1~C7Straight chained alkyl or unbranched alkoxy；
Preferably, compound representated by general formula IV at least contains a kind of formula IV A and at least containing representated by a kind of IVB
Compound；
It is further preferred that compound representated by general formula IV is selected from one of formula IV A1~IVB4 or a variety of:
Preferably, compound representated by general formula IV be selected from IVA2, IVA5, IVA6, IVA7, IVA8, IVB1, IVB2,
One of IVB4 or a variety of, it is highly preferred that compound representated by general formula IV be selected from IVA2, IVA5, IVA6, IVB1, IVB2,
One of IVB4 or a variety of；It is particularly preferred that compound at least one representated by general formula IV is selected from IVA2, IVA5 or IVA6
The compound for being included, at least one is selected from one of IVB1, IVB2 or IVB4 or a variety of.
Most preferably, chemical combination representated by general formula IV of the nematic phase liquid crystal composition comprising 25~35 parts of parts by weight
Object, it is highly preferred that the compound for the formula IV A6 that liquid-crystal composition provided by the present invention is 9~12 parts comprising parts by weight, includes
The compound of IVB1 and IVB2 that parts by weight are 17~22 parts.
Preferably, compound representated by general formula V is selected from one of Formula V A~Formula V B or a variety of:
Wherein, R7、R8It is independently represented each other C1~C7Straight chained alkyl；
Preferably, compound representated by general formula V is selected from one of Formula V A1~Formula V B16 or a variety of:
It is highly preferred that compound representated by general formula V is selected from VA1, VA2, VA6, VA10, VB1, VB2, VB4, VB6, VB8
One of or it is a variety of, particularly preferably, the nematic phase liquid crystal composition include parts by weight be 5~11 parts selected from Formula V A2,
One of VA10, VB1, VB2, VB4, VB6 or a variety of；Most preferably, representated by the Formula V A2 for being 5~8 parts comprising parts by weight
Compound.
Polymerizable compound provided by the present invention preferably passes through photopolymerization reaction, by suitable initiator in UV illumination
It penetrates down and polymerize.
Compound representated by general formula II provided by the present invention is that 2,3- difluoro benzene-like compounds have biggish negative Jie
Electrical anisotropy generates low threshold voltage according to liquid-crystal composition provided by the present invention；
Compound representated by general formula III provided by the present invention is two ring structure compounds, such compound has low
The rotary viscosity of liquid-crystal composition can be effectively reduced in rotary viscosity and excellent intersolubility, promote the response time.
Compound representated by general formula IV provided by the present invention is the change containing methoxyl group bridged bond and 2,3- difluorobenzene
Object is closed, which has big negative dielectric anisotropic, reduce the driving voltage of liquid-crystal composition；
Compound representated by general formula V provided by the present invention is tricyclic neutral compound, such compound has big
Elastic constant and high clearing point.
Preferably, composition of the present invention further includes one or more stabilizers such as flowering structure:
Wherein, R11It is independently represented each other C1~C7Straight chained alkyl, A3It is independently represented each other trans- Isosorbide-5-Nitrae-cyclohexyl,
1,3- dioxane -2,5- diyl.
Preferably, provided by VIIA-1 or VIIC-1 of the liquid-crystal composition provided by the present invention comprising 0~0.04%
Stabilizer, it is highly preferred that VIIA-1 or VIIC-1 that liquid-crystal composition provided by the present invention includes 0.005~0.04% are mentioned
The stabilizer of confession；It is particularly preferred that the VIIA-1 that liquid-crystal composition provided by the present invention includes 0.005~0.04% is provided
Stabilizer.
Liquid-crystal composition provided by the present invention has extraordinary stability, and is capable of providing VA mode LCD
Middle stable setting pre-tilt angle, is obviously shortened the response time compared with the VA mode display for also having technology, especially grey
The rank response time.
Preferably, stabilizer representated by general formula VI is selected from one of flowering structure or a variety of:
It is highly preferred that the stabilizer for including in liquid-crystal composition provided by the present invention is selected from VIA-1 and VIC-1 institute's generation
The compound of table:
Preferably, liquid-crystal composition provided by the present invention is included as 0~0.04% weight of nematic phase liquid crystal composition
Stabilizer provided by the VIIA-1 or VIIC-1 of percentage is measured, it is highly preferred that liquid-crystal composition provided by the present invention includes
Stabilizer provided by VIIA-1 or VIIC-1 for 0.005~0.04% weight fraction of nematic phase liquid crystal composition；It is special
Not preferably, liquid-crystal composition provided by the present invention is included as 0.005~0.04% weight of nematic phase liquid crystal composition
Stabilizer provided by the VIIA-1 of percentage.
As a preferred option, it is made of following compound:
Nematic phase liquid crystal composition:
Ingredients weight parts
And the polymerizable compound IB comprising nematic phase liquid crystal composition weight percent 0.265%:
And the heat-stable compound VIIA-1 comprising nematic phase liquid crystal composition weight percent 0.037%:
Or
Nematic phase liquid crystal composition:
Ingredients weight parts
And the polymerizable compound IA comprising nematic phase liquid crystal composition weight percent 0.29%:
And the heat-stable compound VIIA-1 comprising nematic phase liquid crystal composition weight percent 0.005%:
The preparation method of liquid-crystal composition of the present invention can be used conventional method and change two or more without specifically limited
It closes object mixing to be produced, such as the method preparation by mixing different component at high temperature and being soluble in one another, wherein by liquid crystal group
It closes object to dissolve in solvent in the solvent used for the compound and mix, then distills out the solvent under reduced pressure；Or it is of the present invention
Liquid-crystal composition can be prepared conventionally, such as wherein the lesser component of content will be dissolved in content at a higher temperature
In biggish main component, or each affiliated component dissolved in organic solvent, such as acetone, chloroform or methanol, it then will be molten
It is obtained after liquid mixing removal solvent.
The unit of parts by weight of the present invention is the standard units commonly used in the art such as g kg.
It is another object of the present invention to protect application of any one of the above liquid-crystal composition in PSVA mode display.
Liquid-crystal composition of the present invention has low ion concentration, can be obvious using energy in PSVA mode display
Improve liquid crystal display display effect.
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Unless otherwise indicated, percentage is weight percentage in the present invention；Temperature unit is degree Celsius；△ n represents optics
Anisotropy (25 DEG C)；△ ε represents dielectric anisotropy (25 DEG C, 1000Hz)；γ 1 represents rotary viscosity (mPa.s, 25 DEG C)；
Cp represents the clearing point (DEG C) of liquid-crystal composition；K11、K22、K33Respectively represent splay, distortion and bend elastic constant (pN, 25
DEG C), V10The threshold voltage (V, 25 DEG C, 64Hz) of liquid crystal display is represented, T is represented response time (ms, 25 DEG C), pre-tilt angle (°,
25 DEG C) represent the angle of liquid crystal molecule and glass substrate.
In following embodiment, unit structure code shown in table 1 is indicated in liquid-crystal compounds.
Table 1: the group structure code of liquid-crystal compounds
By taking following compound structure as an example:
It indicates are as follows: 3CPWO2
It indicates are as follows: 2PWP3
It indicates are as follows: 5CC1OWO2
In following embodiment, the preparation of liquid-crystal composition is all made of heat of solution method, comprising the following steps: is pressed with balance
Weight percent weighs liquid-crystal compounds, wherein weighing addition sequence without particular requirement, heating stirring makes at 60~100 DEG C
Each component melts uniformly, using filter, revolving, finally encapsulates up to target sample.
In following embodiment, the performance parameter of the weight percent of each component when liquid-crystal composition is shown in liquid-crystal composition
Following table.The each compound being related to is known compound, commercially available to obtain or by Bayi Space liquid crystal high-tech stock
Part company provides.
Embodiment 1
Nematic phase liquid crystal composition N1 is formulated as follows:
| Classification | Compound code | Parts by weight | Performance parameter | Parameter value |
| II | 2CPWO2 | 4 | Cp | 76 |
| II | 3CPWO2 | 10.5 | △n | 0.100 |
| III | 5PP1 | 15 | △ε | -3.3 |
| III | 3CC2 | 18.5 | K11 | 14.8 |
| III | 3CC4 | 6 | K33 | 15.4 |
| III | 3CPO2 | 4 | γ1 | 99.0 |
| IV | 3C1OWO2 | 12 | ||
| IV | 2CC1OWO2 | 7 | ||
| IV | 3CC1OWO2 | 15 | ||
| V | 3CCP1 | 8 |
It is added on the basis of nematic liquid crystal N1 polymerizable representated by the IA that mass percent is N1 total amount 0.29%
Compound and 0.005% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P1 after mixing；
It is added on the basis of nematic liquid crystal N1 polymerizable representated by the IB that mass percent is N1 total amount 0.265%
Compound and 0.037% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P2 after mixing；
It is added on the basis of nematic liquid crystal N1 polymerizable representated by the IA that mass percent is N1 total amount 0.28%
Compound obtains PSVA liquid-crystal composition P3 after mixing；
It is added on the basis of nematic liquid crystal N1 polymerizable representated by the IA that mass percent is N1 total amount 0.30%
Compound and 0.012% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P4 after mixing；
It is added on the basis of nematic liquid crystal N1 polymerizable representated by the IB that mass percent is N1 total amount 0.30%
Compound and 0.04% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P5 after mixing；
P1, P2, P3, P4, P5 are packed into standard VA testing cassete, then test test pre-tilt angle is applying 20V voltage
Lower utilization intensity is irradiated 90s for the UV light of 5.5mw/cm2 (313nm) and promotes polymerizable compound representated by general formula I poly-
It closes, orientation is carried out to liquid crystal using the film formed after polymerization, pre-tilt angle after last test UV irradiation:
| P1 | P2 | P3 | P4 | P5 | |
| Before irradiation (°) | 89.7 | 89.7 | 89.7 | 89.7 | 89.7 |
| After irradiation (°) | 88.0 | 87.8 | 87.9 | 88.0 | 87.4 |
After polymerization, stable pre-tilt angle is formed；
Then above-mentioned liquid crystal test box is irradiated 100min using the UV light of 6mw/cm2 (365nm), promoted remaining
Polymerizable compound is polymerize, and after the completion of irradiation, tests the residual content of polymerizable compound, test result is as follows table:
| P1 | P2 | P3 | P4 | P5 | |
| Polymerizable compound residual content | 58ppm | 30ppm | 44ppm | 87ppm | 55ppm |
Remaining polymerisable monomer is seldom after the completion of polymerization, has using liquid crystal display made of the composition good
Image retention performance improves the display effect of liquid crystal display.
The response time of testing cassete made by P1, P2, P3, P4, P5, VHR after the completion of testing nematic phase N1 and irradiating
(voltage retention) and ION (ion concentration), the phase, test result is as follows:
| Test item | N1 | P1 | P2 | P3 | P4 | P5 |
| T (25 DEG C, ms) | 33.5 | 13.1 | 13.0 | 13.2 | 13.2 | 12.8 |
| VHR (1V, 0.5Hz, 60 DEG C, %) | 89.37 | 92.56 | 93.08 | 92.83 | 92.05 | 92.67 |
| ION (3V, 0.1Hz, 60 DEG C, pC/cm3) | 131.31 | 43.73 | 31.35 | 38.37 | 48.35 | 40.45 |
Relative to nematic liquid crystal, when there is response faster after PSVA liquid-crystal composition polymerization provided by the present invention
Between, higher voltage retention and lower ion concentration.
Embodiment 2
Nematic phase liquid crystal composition N2 is formulated as follows:
| Classification | Compound code | Parts by weight | Performance parameter | Parameter value |
| II | 2CPWO2 | 6 | Cp | 76 |
| II | 3CPWO2 | 10.5 | △n | 0.104 |
| III | 3PP1 | 15 | △ε | -3.3 |
| III | 3CPO2 | 4 | K11 | 15.2 |
| III | 3CC2 | 18.5 | K33 | 15.6 |
| III | 3CC4 | 6 | γ1 | 95 |
| IV | 3C1OWO2 | 11 | ||
| IV | 2CC1OWO2 | 6 | ||
| IV | 3CC1OWO2 | 15 | ||
| V | 3CCP1 | 8 |
It is added on the basis of nematic liquid crystal N2 polymerizable representated by the IA that mass percent is N2 total amount 0.29%
Compound and 0.005% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P6 after mixing；
It is added on the basis of nematic liquid crystal N2 polymerizable representated by the IB that mass percent is N2 total amount 0.27%
Compound and 0.04% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P7 after mixing；
P6, P7 are packed into the VA testing cassete of standard, pre-tilt angle is tested, intensity is then utilized in the case where applying 20V voltage
For 5.5mw/cm2 (313nm) UV light be irradiated 90s promote polymerizable compound representated by general formula I polymerize, utilize polymerization
The film formed afterwards carries out orientation to liquid crystal, pre-tilt angle after last test UV irradiation:
| P6 | P7 | |
| Before irradiation | 89.7 | 89.7 |
| After irradiation | 87.8 | 87.7 |
After polymerization, stable pre-tilt angle is formed；
Then above-mentioned liquid crystal test box is irradiated 100min using the UV light of 6mw/cm2 (365nm), promoted remaining
General formula I is polymerize, and after the completion of irradiation, tests the participation content of general formula I, test result is as follows table:
| P6 | P7 | |
| Polymerizable compound residual content | 48ppm | 34ppm |
Remaining polymerisable monomer is seldom after the completion of polymerization, has using liquid crystal display made of the composition good
Image retention performance improves the display effect of liquid crystal display.
(voltage is kept by the response time of testing cassete made by P6, P7, VHR after the completion of testing nematic phase N2 and irradiating
Rate) and ION (ion concentration), the phase, test result is as follows:
| Test item | N1 | P1 | P2 |
| T (25 DEG C, ms) | 32.5 | 12.1 | 12.0 |
| VHR (1V, 0.5Hz, 60 DEG C, %) | 89.44 | 92.65 | 93.17 |
| ION (3V, 0.1Hz, 60 DEG C, pC/cm3) | 128.27 | 41.47 | 28.34 |
Relative to nematic liquid crystal, when there is response faster after PSVA liquid-crystal composition polymerization provided by the present invention
Between, higher voltage retention and lower ion concentration.
Embodiment 3
Nematic phase liquid crystal composition N3 is formulated as follows:
Nematic phase liquid crystal composition N4 is formulated as follows:
| Classification | Compound code | Parts by weight | Performance parameter | Parameter value |
| II | 3CPWO2 | 10.5 | Cp | 75 |
| III | 5PP1 | 13 | △n | 0.098 |
| III | 3PP1 | 5 | △ε | -2.8 |
| III | 3CC2 | 18.5 | K11 | 14.4 |
| III | 3CC4 | 9 | K33 | 15.6 |
| III | 3CPO2 | 4 | γ1 | 87 |
| IV | 3C1OWO2 | 10 | ||
| IV | 2CC1OWO2 | 7 | ||
| IV | 3CC1OWO2 | 15 | ||
| V | 3CCP1 | 8 |
Nematic phase liquid crystal composition N5 is formulated as follows:
| Classification | Compound code | Parts by weight | Performance parameter | Parameter value |
| II | 2CPWO2 | 10 | Cp | 75 |
| II | 3CPWO2 | 10 | △n | 0.104 |
| III | 5PP1 | 15 | △ε | -3.3 |
| III | 3CC2 | 19 | K11 | 14.9 |
| III | 3CC4 | 6 | K33 | 15.2 |
| III | 3CPO2 | 4 | γ1 | 104 |
| IV | 3C1OWO2 | 12 | ||
| IV | 2CC1OWO2 | 4 | ||
| IV | 3CC1OWO2 | 15 | ||
| V | 3CCP1 | 5 |
Nematic phase liquid crystal composition N6 is formulated as follows:
| Classification | Compound code | Parts by weight | Performance parameter | Parameter value |
| II | 2CPWO2 | 10 | Cp | 77 |
| II | 3CPWO2 | 10 | △n | 0.101 |
| III | 5PP1 | 15 | △ε | -2.8 |
| III | 3CC2 | 19 | K11 | 14.9 |
| III | 3CC4 | 6 | K33 | 15.4 |
| III | 3CPO2 | 4 | γ1 | 96 |
| III | 3CC5 | 5 | ||
| IV | 3C1OWO2 | 9 | ||
| IV | 2CC1OWO2 | 4 | ||
| IV | 3CC1OWO2 | 13 | ||
| V | 3CCP1 | 5 |
It is added on the basis of nematic liquid crystal N3 polymerizable representated by the IA that mass percent is N3 total amount 0.30%
Compound and 0.012% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P8 after mixing；
It is added on the basis of nematic liquid crystal N4 polymerizable representated by the IB that mass percent is N4 total amount 0.25%
Compound and 0.017% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P9 after mixing；
It is added on the basis of nematic liquid crystal N5 polymerizable representated by the IB that mass percent is N5 total amount 0.28%
Compound and 0.03% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P10 after mixing；
It is added on the basis of nematic liquid crystal N6 polymerizable representated by the IB that mass percent is N6 total amount 0.40%
Compound and 0.03% VIIA-1 representated by stabilizer, obtain PSVA liquid-crystal composition P11 after mixing；
P8, P9, P10, P11 are packed into the VA testing cassete of standard, pre-tilt angle is tested, then in the case where applying 20V voltage
Being irradiated 90s using the UV light that intensity is 5.5mw/cm2 (313nm) promotes polymerizable compound representated by general formula I to polymerize,
Orientation is carried out to liquid crystal using the film formed after polymerization, pre-tilt angle after last test UV irradiation:
| P8 | P9 | P10 | P11 | |
| Before irradiation | 89.7 | 89.7 | 89.7 | 89.7 |
| After irradiation | 87.6 | 88.2 | 87.5 | 86.8 |
After polymerization, stable pre-tilt angle is formed；
Then above-mentioned liquid crystal test box is irradiated 100min using the UV light of 6mw/cm2 (365nm), promoted remaining
General formula I is polymerize, and after the completion of irradiation, tests the participation content of general formula I, test result is as follows table:
| P8 | P9 | P10 | P11 | |
| Polymerizable compound residual content | 85ppm | 24ppm | 35ppm | 95ppm |
Remaining polymerisable monomer is seldom after the completion of polymerization, has using liquid crystal display made of the composition good
Image retention performance improves the display effect of liquid crystal display.
The response of testing cassete made by P8, P9, P10, P11 after the completion of testing nematic phase N3, N3, N5, N6 and irradiating
Time, VHR (voltage retention) and ION (ion concentration), the phase, test result is as follows:
| Test item | N3 | P8 | N4 | P9 | N5 | P10 | N6 | P11 |
| T (25 DEG C, ms) | 30.3 | 10.4 | 29.6 | 9.7 | 35.3 | 12.6 | 30.8 | 10.6 |
| VHR (1V, 0.5Hz, 60 DEG C, %) | 90.35 | 93.45 | 90.41 | 94.31 | 89.11 | 92.51 | 90.44 | 92.31 |
| ION (3V, 0.1Hz, 60 DEG C, pC/cm3) | 97.36 | 35.47 | 99.83 | 24.55 | 133.43 | 47.48 | 96.54 | 55.48 |
Relative to nematic liquid crystal, when there is response faster after PSVA liquid-crystal composition polymerization provided by the present invention
Between, higher voltage retention and lower ion concentration.
Compared with corresponding nematic liquid crystal, the response time adds the liquid-crystal compounds with polymerizable compound after polymerisation
Fastly, VHR is increased.ION is reduced, and the response time and image retention and flashing for improvement liquid crystal display are highly effective.
As seen from the above embodiment, the liquid-crystal composition provided by the present invention comprising polymerizable compound polymerize in UV
Afterwards, there is a biggish pre-tilt angle, the response time of liquid crystal display is substantially improved, while polymerization process will exist in liquid crystal
Ion be wrapped in polymeric membrane, reduce the ion in liquid crystal display, promote the quality of liquid crystal display, improve liquid crystal display
The image retention performance of device.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of negative liquid crystal composition, which is characterized in that include polymerizable compound and nematic liquid crystal in the composition
Composition, the polymerizable compound are the one or two of polymerizable compound representated by general formula IA and IB:
The nematic phase liquid crystal composition includes:
Compound representated by one or more general formula II of 5~25 parts by weight:
Wherein R1、R2It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；
Compound representated by one or more general formula IIIs of 35~55 parts by weight:
Wherein R3、R4It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；A1、A2It is independently represented each other trans-
Isosorbide-5-Nitrae-cyclohexyl or Isosorbide-5-Nitrae-phenylene；
Compound representated by one or more general formula IV of 20~35 parts by weight:
Wherein, R5、R6It is independently represented each other C1~C12Straight chained alkyl, unbranched alkoxy；N represents 0 or 1；
Compound representated by one or more general formula V of 3~15 parts by weight:
Wherein, R7、R8It is independently represented each other C1~C12Straight chained alkyl, A3Be independently represented each other trans- Isosorbide-5-Nitrae-cyclohexyl or
Isosorbide-5-Nitrae-phenylene；
Polymerizableization of 0.1~0.5% mass percent is added in the nematic phase liquid crystal composition of every 100 parts by weight
Close object, the polymerizable compound of preferably 0.2~0.45% mass percent, more preferable 0.25~0.40% mass percent
The polymerizable compound；The polymerizable compound of particularly preferred 0.25~0.30% mass percent.
2. composition according to claim 1, which is characterized in that compound described in the general formula II is Formula II A1~formula
One of IIA8 or a variety of:
Preferably, it is 8~23 in Formula II A1, IIA2, IIA3, IIA6 that the nematic liquid crystal compound, which includes parts by weight,
It is one or more；
It is highly preferred that the nematic phase liquid crystal composition includes one in Formula II A1, IIA2 that parts by weight are 10~20 parts
Kind or two kinds of compound.
3. compound according to claim 1 or 2, which is characterized in that the compounds of formula III be selected from formula III A~
One of formula III C or a variety of:
Wherein, R3It is independently represented each other C1~C7Straight chained alkyl, R4It is independently represented each other C1~C7Straight chained alkyl or straight
Chain alkoxy；
Preferably, compound representated by general formula III at least contains a kind of formula III A and at least containing representated by a kind of formula III C
Compound.
4. compound according to claim 3, which is characterized in that compound representated by the general formula III is selected from formula
One of IIIA1~formula III C4 or a variety of:
Preferably, the nematic liquid crystal compound includes compound representated by general formula III of the parts by weight for 40~53 parts；More
Preferably, nematic phase liquid crystal composition provided by the present invention includes change representated by general formula III of the parts by weight for 43~50 parts
Close object.
5. compound according to claim 4, which is characterized in that compound representated by general formula III be selected from IIIA3,
One of IIIA5, IIIA8, IIIA9, IIIB2, IIIB6, IIIC2, IIIC4 or a variety of；
Preferably, compound representated by general formula III be selected from formula III A3, IIIA8, IIIA9, IIIB2, IIIB6, IIIC2,
One of IIIC4 or a variety of；
It is further preferred that in the nematic phase liquid crystal composition comprising parts by weight be 24~30 parts selected from IIIA3, IIIA8,
One of IIIA9 or multiple compounds are 4~6 parts selected from one or both of IIIB2 or IIIB6 comprising parts by weight
Compound, parts by weight are 15~18 selected from one or both of IIIC2 or IIIC4 compound；
The compound of formula III A3 and IIIA8 that more preferable parts by weight are 24~28 parts, the change of 4~6 parts of parts by weight of formula III B6
Object is closed, parts by weight are 15~18 parts selected from one or both of IIIC2 or IIIC4 compound.
6. described in any item liquid-crystal compositions according to claim 1~5, which is characterized in that compound representated by general formula IV
It is one or more representated by IVA~IVB:
Wherein, R5、R6It is independently represented each other C1~C7Straight chained alkyl or unbranched alkoxy；
Preferably, compound representated by general formula IV at least contains a kind of formula IV A and at least containing change representated by a kind of IVB
Close object；
It is further preferred that compound representated by general formula IV is selected from one of formula IV A1~IVB4 or a variety of:
Preferably, compound representated by general formula IV is in IVA2, IVA5, IVA6, IVA7, IVA8, IVB1, IVB2, IVB4
It is one or more, it is highly preferred that compound representated by general formula IV is in IVA2, IVA5, IVA6, IVB1, IVB2, IVB4
It is one or more；It is particularly preferred that compound at least one representated by general formula IV is included selected from IVA2, IVA5 or IVA6
Compound, at least one is selected from one of IVB1, IVB2 or IVB4 or a variety of；
Most preferably, compound representated by general formula IV of the nematic phase liquid crystal composition comprising 25~35 parts of parts by weight, more
Preferably, liquid-crystal composition provided by the present invention includes the compound for the formula IV A6 that parts by weight are 9~12 parts, includes parts by weight
For the compound of 17~22 parts of IVB1 and IVB2.
7. described in any item liquid-crystal compositions according to claim 1~6, which is characterized in that the choosing of compound representated by general formula V
From one of Formula V A~Formula V B or a variety of:
Wherein, R7、R8It is independently represented each other C1~C7Straight chained alkyl；
Preferably, compound representated by general formula V is selected from one of Formula V A1~Formula V B16 or a variety of:
It is highly preferred that compound representated by general formula V is in VA1, VA2, VA6, VA10, VB1, VB2, VB4, VB6, VB8
It is one or more, particularly preferably, the nematic phase liquid crystal composition include parts by weight be 5~11 parts selected from Formula V A2,
One of VA10, VB1, VB2, VB4, VB6 or a variety of；Most preferably, representated by the Formula V A2 for being 5~8 parts comprising parts by weight
Compound.
8. described in any item liquid-crystal compositions according to claim 1~7, which is characterized in that further include one or more as follows
The stabilizer of structure:
Wherein, R11It is independently represented each other C1~C7Straight chained alkyl, A3It is independently represented each other trans- Isosorbide-5-Nitrae-cyclohexyl, 1,3-
Dioxane -2,5- diyl；
Preferably, stabilizer representated by general formula VI is selected from one of flowering structure or a variety of:
It is highly preferred that the stabilizer for including in liquid-crystal composition provided by the present invention is selected from representated by VIA-1 and VIC-1
Compound:
Preferably, liquid-crystal composition provided by the present invention is included as 0~0.04% weight hundred of nematic phase liquid crystal composition
Stabilizer provided by the VIIA-1 or VIIC-1 of score, it is highly preferred that liquid-crystal composition provided by the present invention is included as institute
State stabilizer provided by the VIIA-1 or VIIC-1 of 0.005~0.04% weight fraction of nematic phase liquid crystal composition；It is especially excellent
Selection of land, liquid-crystal composition provided by the present invention are included as 0.005~0.04% weight percent of nematic phase liquid crystal composition
Stabilizer provided by several VIIA-1.
9. described in any item liquid-crystal compositions according to claim 1~8, which is characterized in that by the compound of following parts by weight
Composition:
Nematic phase liquid crystal composition:
And the polymerizable compound IB comprising nematic phase liquid crystal composition weight percent 0.265%:
And the heat-stable compound VIIA-1 comprising nematic phase liquid crystal composition weight percent 0.037%:
Or
Nematic phase liquid crystal composition:
And the polymerizable compound IA comprising nematic phase liquid crystal composition weight percent 0.29%:
And the heat-stable compound VIIA-1 comprising nematic phase liquid crystal composition weight percent 0.005%:
10. application of the liquid-crystal composition according to any one of claims 1 to 9 in PSVA mode display.
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