CN105294664B - Compound and preparation method, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal cell - Google Patents
Compound and preparation method, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal cell Download PDFInfo
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- CN105294664B CN105294664B CN201510766087.8A CN201510766087A CN105294664B CN 105294664 B CN105294664 B CN 105294664B CN 201510766087 A CN201510766087 A CN 201510766087A CN 105294664 B CN105294664 B CN 105294664B
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
The invention discloses a kind of compound and preparation method thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal cells.Compound disclosed by the invention is shown in formula I：Wherein, R1、R2、R3And R4It is each independently selected from H, CH3、‑CH2CH3And CH2CH2CH3.The preparation method of compound disclosed by the invention includes：Amidation step, step of hydrogenation and epoxidation step.The invention also discloses the aligning agent for liquid crystal including the compounds of this invention and liquid crystal orientation film and the liquid crystal cell containing liquid crystal orientation film of the present invention made of aligning agent for liquid crystal of the present invention.
Description
Technical field
The present invention relates to field of liquid crystal display more particularly to compound and preparation method thereof, aligning agent for liquid crystal, liquid crystal alignings
Film and liquid crystal cell.
Background technology
Liquid crystal orientation film is by being made after glass baseplate surface coats aligning agent for liquid crystal hot setting, is to form liquid crystal
The important component of box.As people are higher and higher to display picture quality requirement, to the characteristic and packet of liquid crystal orientation film
The characteristic requirements of liquid crystal cell containing liquid crystal orientation film are more and more stringenter.
When being prepared liquid crystal orientation film with existing aligning agent for liquid crystal and being prepared the liquid crystal cell comprising liquid crystal orientation film,
Cannot meet simultaneously makes liquid crystal orientation film have good wearability and coating and make the liquid crystal made of liquid crystal orientation film
Box has the characteristics that good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
It is therefore desirable to provide a kind of aligning agent for liquid crystal can meet above-mentioned characteristic simultaneously.
Invention content
The present invention provides a kind of compound and preparation method thereof, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal cells.With this
The compound of invention is added to as additive in aligning agent for liquid crystal, and solve satisfaction cannot be taken in the prior art with liquid crystal simultaneously
Liquid crystal orientation film is prepared with good wearability and coating to agent and makes the liquid crystal cell made of liquid crystal orientation film
The problem of with good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
According to an aspect of the invention, there is provided a kind of compound, the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
Optionally, compound according to the present invention, the compound is as shown in Formulas I -1：
Optionally, the preparation method of compound according to the present invention, this method include：
Amidation step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formula V；
Epoxidation step：Compound shown in Formula V and epichlorohydrin reaction are converted into compound shown in Formulas I；
Wherein, the R in Formula II, formula IV and compound shown in Formula V1、R2、R3And R4It is each independently selected from-H ,-CH3、-
CH2CH3With-CH2CH2CH3。
Optionally, preparation in accordance with the present invention, compound shown in Formula II are by compound shown in Formula IV and sulfurous
Acyl chloride reaction is transformed,
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
Optionally, preparation in accordance with the present invention, in the amidation step：
Compound shown in compound shown in Formula II and formula III is placed under alkaline condition and is reacted, is converted into formula IV shownization
Close object.
Optionally, preparation in accordance with the present invention, in the step of hydrogenation：Compound shown in formula IV is in palladium carbon conduct
Hydro-conversion is compound shown in Formula V under conditions of catalyst.
Optionally, preparation in accordance with the present invention, in the epoxidation step, compound shown in Formula V and epoxy chlorine
Propane reacts under alkaline condition is converted into compound shown in Formulas I.
According to another aspect of the present invention, a kind of aligning agent for liquid crystal is provided, which includes：Polyamides propylhomoserin
And/or compound described in polyimide solution and claims 1 or 2；Wherein, the compound is as additive, and accounts for
The solution by percentage to the quality 0.25~0.5%.
According to another aspect of the present invention, a kind of liquid crystal orientation film is provided, the liquid crystal orientation film is by according to the present invention
Hot setting is made on the glass substrate for aligning agent for liquid crystal coating.
According to another aspect of the present invention, a kind of liquid crystal cell is provided, which takes including liquid crystal according to the present invention
To film.
Beneficial effects of the present invention are as follows：
The compound of the present invention contains glycidol group, triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural,
Additive can be used as to be added in aligning agent for liquid crystal, improve property of the performance of aligning agent for liquid crystal so as to improve liquid crystal orientation film
Energy can also improve the performance of liquid crystal cell.
It is mixed the compound of the present invention as at least one of additive and polyamides propylhomoserin and/or polyimides polymer
Aligning agent for liquid crystal is prepared in conjunction, which is applied on substrate, liquid crystal orientation film is made after hot setting,
Middle polyamides propylhomoserin is converted into polyimides through high-temperature heating, due to containing glycidyl in the compounds of this invention, in preparation solution
The adhesion property between aligning agent for liquid crystal and substrate can be increased during brilliant alignment films, so as to improve the wearability of liquid crystal orientation film and
Coating；Since the compound contains triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, contain the liquid crystal aligning
The liquid crystal cell of film has good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
Specific embodiment
Specific embodiment is only the description of the invention, without forming the limitation to the content of present invention, below in conjunction with
Specific embodiment is further described and describes to the present invention.
According to an aspect of the present invention, a kind of compound is provided, the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
Compound shown in Formulas I contains glycidyl, triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, can
To be added in aligning agent for liquid crystal as additive, improve the performance of aligning agent for liquid crystal, so as to improve the coating of liquid crystal orientation film
Property and wearability, while improve the liquid crystal cell containing the liquid crystal film liquid crystal aligning, improve voltage retention and reduce charge
Residual rate.
It is mixed with to obtain liquid crystal aligning using compound shown in Formulas I as additive and polyamides propylhomoserin and/or polyimides
The aligning agent for liquid crystal is applied on substrate and liquid crystal orientation film is made after hot setting by agent, and wherein polyamides propylhomoserin adds through high temperature
Thermal transition is polyimides, due to containing glycidol group in the compounds of this invention, can be increased when preparing liquid crystal orientation film
Add the adhesion property between aligning agent for liquid crystal and substrate, so as to improve the wearability of liquid crystal orientation film and coating, due to the change
It closes object and contains triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, the liquid crystal cell containing the liquid crystal orientation film has
Good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
A kind of embodiment according to the present invention, the compound is as shown in Formulas I -1：
According to another aspect of the present invention, a kind of preparation method of compound is provided, this method includes：
Amidation step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formula V；
Epoxidation step：Compound shown in Formula V and epichlorohydrin reaction are converted into compound shown in Formulas I；
Wherein, the R in Formula II, formula IV and compound shown in Formula V1、R2、R3And R4It is each independently selected from-H ,-CH3、-
CH2CH3With-CH2CH2CH3。
A kind of embodiment of method produced according to the present invention, compound shown in Formula II be by compound shown in Formula IV with
Thionyl chloride reaction is transformed,
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
A kind of embodiment of method produced according to the present invention, in amidation step：
Compound shown in compound shown in Formula II and formula III is placed under alkaline condition and is reacted, is converted into formula IV shownization
Close object.
A kind of embodiment of method produced according to the present invention, in step of hydrogenation：Compound shown in formula IV is made in palladium carbon
It is compound shown in Formula V for hydro-conversion under conditions of catalyst.
A kind of embodiment of preparation in accordance with the present invention, in epoxidation step, compound shown in Formula V and epoxy
Chloropropane reacts under alkaline condition is converted into compound shown in Formulas I.
In order to illustrate the synthetic method of compound shown in Formulas I, a kind of synthesis of particular compound is selected to be carried out as example
Explanation.
The structural formula of the particular compound of synthesis is as shown in Formulas I -1：
First, compound 4- (4 '-nitrobenzophenone) chlorobenzoyl chloride shown in Formula II -1 is synthesized, reaction equation is as follows：
Specifically reaction condition is：12.15g (50mmol) 4- (4 '-nitrobenzophenone) benzoic acid is placed in 250mL flasks,
80mL SOCl are added in flask2With 5 drop catalytic amounts DMF, make above-mentioned solution 80 DEG C reflux, with TLC monitoring react into
Degree, is waited after the completion of reacting, and reaction solution is rotated and removes solution, and it is molten that 50mL dichloromethane is added in the substance after removing solution
Solution carries out revolving removal solvent and with solvent by remaining SOCl again2It takes mixture out of, obtains 12.5g solid products, receive
Rate is 95.7%.
Then, amidation step is carried out, reaction equation is as follows：
By compound 3,5- diaminostilbenes, 2,4- triazoles, 3.64g shown in 1.49g (15mmol, 1eq) formula III -1
(36mmol, 2.4eq) triethylamine is dissolved in 50mL dichloromethane, and 50mL is slowly added dropwise at 0 DEG C (shown in the 11-1 of formula containing 9.39g
Compound 4- (4 '-nitrobenzophenone) chlorobenzoyl chloride) dichloromethane solution.After being added dropwise to complete, reaction solution reacts at room temperature
For 24 hours, then reaction solution is washed with 200mL pure water, after organic phase is washed twice with saturated sodium carbonate solution after layering
It is dried with anhydrous magnesium sulfate, organic phase is rotated to obtain crude product, crude product is recrystallized to give chemical combination shown in 6.52g formula IVs -1
Object, yield 80%.
The compound being recrystallized to give is subjected to nuclear-magnetism identification, the data of identification are as follows：
1H-NMR (400MHz, CDCl3), δ (ppm)：13.1 (1H, s), 9.10 (2H, s), 8.30 (4H, d), 8.05 (4H,
D), 7.95 (4H, d), 7.83 (4H, d)；
The compound being recrystallized to give as can be seen from the above data is compound shown in formula IV -1.
Step of hydrogenation is carried out later, and reaction equation is as follows：
Compound shown in 5.49g (10mmol, 1eq) formula IV -1 is dissolved in 100mL absolute ethyl alcohols and DMF in the mixed solvents,
Add in 1.5g Pd/C, by mixture under hydrogen atmosphere compressive reaction 6h.After reaction, Filtration of catalyst, by filtrate
It rotates, compound shown in 3.72g Formula V -1, yield 76% is obtained after recrystallization.
Nuclear-magnetism identification is carried out to obtained compound, the parsing data of nuclear magnetic spectrogram are as follows：
1H-NMR (400MHz, CDCl3), δ (ppm)：13.5 (1H, s), 9.15 (2H, s), 8.05 (4H, t), 7.82 (4H,
T), 7.40 (4H, t), 6.48 (4H, t), 3.79 (4H, s).
The compound according to the compound that above-mentioned data can be seen that for Formula V -1.
Epoxidation step is finally carried out, specific synthesis equation is as follows：
Compound shown in 3g (6.12mmol, 1eq) Formula V -1 and 6.76g (48.96mmol, 8eq) potassium carbonate are dissolved in
In 50ml DMSO, above-mentioned mixed liquor is placed in ice bath, and 4.53g (48.96mmol, 8eq) epoxychloropropane is slowly added dropwise,
After being added dropwise to complete, reaction solution reacts for 24 hours at room temperature, rotary evaporation, and the crude product of gained is dissolved with 50mL toluene, adds in 50mL
Pure water three times, with anhydrous magnesium sulfate dried by organic phase, and revolving removes solvent, and products therefrom obtains after purification by silicagel column
Compound 2.02g shown in Formulas I, yield 46%.
Gained compound is subjected to nuclear-magnetism identification, nuclear magnetic spectrogram parsing data are as follows：
1H-NMR (400MHz, CDCl3), δ (ppm)：11.5 (1H, s), 9.18 (2H, s), 8.03 (4H, t), 7.81 (4H,
T), 7.40 (4H, t), 6.92 (4H, t), 3.55 (4H, m), 2.96 (8H, m), 3.35 (8H, m).
The compound according to the compound that above-mentioned data can be seen that for Formulas I -1.
According to another aspect of the present invention, a kind of aligning agent for liquid crystal is provided, which includes：Polyamides propylhomoserin
And/or compound described in polyimide solution and claims 1 or 2；Wherein, the compound is as additive, and accounts for
The solution by percentage to the quality 0.25~0.5%.
It is molten that aligning agent for liquid crystal according to the present invention is that the compound as shown in polyamides propylhomoserin and/or polyimides with Formulas I is dissolved in
It is made in agent (preferably N-Methyl pyrrolidone and/or butyl cellosolve).
And polyamides propylhomoserin therein generally selects diamine compounds and anhydride compound to react and be transformed.Wherein,
The preferably following compounds of diamine compounds：
Wherein, the preferably following compounds of anhydride compound:
Wherein, formula VII is a kind of table of polyamic acid being prepared by above-mentioned diamine compounds and anhydride compound
Existing form:
The polyamides propylhomoserin dehydration closed-loop of the form of expression described in formula VII can be converted into the polyimides shown in formula VIII：
Below in conjunction with the specific synthesis example of polyamides propylhomoserin and polyimides, the present invention will be described.
Synthesis example 1
By compound 1.84g shown in compound 8.64g (80mmol, 0.8eq) shown in diamine compound B-1, B-3
Compound 5.22g (15mmol, 0.15eq) shown in (10mmol, 0.1eq) and B-4 is dissolved in the (letter of 200mL N-Methyl pyrrolidones
Claim NMP) in solvent, with the air in nitrogen displacement container, the acid of compound shown in A-1 is slowly added into above-mentioned mixed solution
The polyamic acid solution for for 24 hours, obtaining that mass concentration is 15% is stirred in acid anhydride 19.6g (100mmol, 1eq), entire reaction at room temperature
(PAA-1)。
Synthesis example 2
Compound 6.48g (60mmol, 0.6eq), B-2 shown in diamine compound B-1 are added in the three-necked flask of 500ml
Shown compound 2.48g (25mmol, 0.25eq), compound 3.68g shown in B-3 (20mmol, 0.2eq) and 180mL NMP are molten
Agent, magnetic agitation dissolves at room temperature, and replaces the air in flask with nitrogen.A-1 institutes are slowly added into above-mentioned mixed solution
Show the acid anhydrides 2.18g (10mmol, 0.1eq) of compound shown in the acid anhydrides 17.64g (90mmol, 0.9eq) and A-2 of compound, it is whole
The polyamic acid solution (PAA-2) for for 24 hours, obtaining that mass concentration is 15% is stirred in a reaction at room temperature.
Synthesis example 3
Polyamic acid (PAA-2) prepared by synthesis example 2 is diluted to the polyamide that mass concentration is 8% using nmp solvent
Acid solution.The 150g polyamic acid solutions are weighed, 7.8g acetic anhydride and 6.1g pyridines is added in, 3h is reacted at 80 DEG C, by solution
It is poured into excessive methanol and precipitates, be dried under reduced pressure after washing 3 times to sediment with methanol, obtain polyimide powder, be labeled as
SPI-1。
In the following, utilize compound, N- methyl shown in the polyamides propylhomoserin or polyimides, Formulas I -1 synthesized in above-mentioned synthesis example
Pyrrolidones and butyl cellosolve illustrate the preparation of aligning agent for liquid crystal.
When aligning agent for liquid crystal is prepared, the required raw material added in is calculated according to the following equation, wherein,
The N-Methyl pyrrolidone of required addition is B grams：
B=F*C-85%*A
The butyl cellosolve of required addition is C grams：
Or
Compound shown in the Formulas I -1 of required addition is D grams：
Wherein, A represents to add in the quality (gram) of polyamic acid, in embodiments of the present invention, the quality of polyamic acid solution
The 98%-100% for accounting for polyamides propylhomoserin and/or polyimide solution gross mass by percentage to the quality；H represents to add in polyamides Asia
The quality (gram) of amine, in embodiments of the present invention, the quality of polyimide solution by percentage to the quality account for polyamides propylhomoserin and/
Or the 0%-2% of polyimide solution gross mass；E represents the solid content of aligning agent for liquid crystal, and in embodiments of the present invention, liquid crystal takes
It is 6% to the solid content E of agent；Compound shown in G expressions I-1 accounts for polyamic acid and/or the total matter of polyimides as additive
The mass percent of amount, G is 0.25%~0.5% in embodiments of the present invention；F represents N- methyl in the aligning agent for liquid crystal prepared
The mass ratio of pyrrolidones and butyl cellosolve, in embodiments of the present invention F be set as 2.5：1.In following embodiments and comparative example
In other parameters can be obtained according to above-mentioned formula.
Wherein, the type and content of component of polymer and additive in the aligning agent for liquid crystal prepared in embodiment and comparative example
As shown in table 1.
Table 1
Embodiment 1
Polyamic acid solution (PAA-1) 50g obtained in synthesis example 1 is weighed, adds in 45.1g NMP, 35g butyl cellosolves
Compound shown in (abbreviation BC), 0.326g Formulas I -1, at room temperature magnetic agitation obtain aligning agent for liquid crystal 1.
Embodiment 2
Weigh polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add in 49.0g NMP, 36.6g BC,
Compound shown in 0.682g Formulas I -1, magnetic agitation, obtains aligning agent for liquid crystal 2 at room temperature.
Embodiment 3
Polyamic acid solution (PAA-2) 50g obtained in synthesis example 2 is weighed, adds in 45.1g NMP, 35g BC, 0.326g
Compound shown in Formulas I -1, magnetic agitation, obtains aligning agent for liquid crystal 3 at room temperature.
Embodiment 4
Weigh polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add in 49.0g NMP, 36.6g BC,
Compound shown in 0.682g Formulas I -1, magnetic agitation, obtains aligning agent for liquid crystal 4 at room temperature.
Embodiment 5
Weigh polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add in 45.7g NMP, 35.3g BC,
Compound shown in 0.3947g Formulas I -1, magnetic agitation, obtains aligning agent for liquid crystal 5 at room temperature.
Embodiment 6
Weigh polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add in 47.5g NMP, 36.0g BC,
Compound shown in 0.5357g Formulas I -1, magnetic agitation, obtains aligning agent for liquid crystal 6 at room temperature.
Embodiment 7
Polyamic acid solution (PAA-1) 48g obtained in synthesis example 1 is weighed, it is sub- to add in the polyamides obtained in 2g synthesis examples 3
Amine powder (SPI-1), 64.1g NMP, 41.9g BC, compound shown in 0.40g Formulas I -1, magnetic agitation, obtains liquid crystal at room temperature
Alignment agent 7.
Embodiment 8
Polyamic acid solution (PAA-1) 48g obtained in synthesis example 1 is weighed, it is sub- to add in the polyamides obtained in 2g synthesis examples 3
Amine powder (SPI-1), 71.46g NMP, 44.9g BC, compound shown in 0.836g Formulas I -1, magnetic agitation, obtains liquid at room temperature
Brilliant alignment agent 8.
And it is prepared for not adding in the aligning agent for liquid crystal of the compounds of this invention shown in Formulas I -1 as comparative example.
Comparative example 1
Polyamic acid solution (PAA-1) 50g obtained in synthesis example 1 is weighed, adds in 41.4g NMP, 33.6g BC, room temperature
Lower magnetic agitation, obtains aligning agent for liquid crystal 9.
Comparative example 2
Polyamic acid solution (PAA-2) 50g obtained in synthesis example 2 is weighed, adds in 41.4g NMP, 33.6g BC, room temperature
Lower magnetic agitation, obtains aligning agent for liquid crystal 10.
Comparative example 3
Polyamic acid solution (PAA-1) 48g obtained in synthesis example 1 is weighed, it is sub- to add in the polyamides obtained in 2g synthesis examples 3
Amine powder (SPI-1), 62.2g NMP, 41.2g BC, magnetic agitation, obtains aligning agent for liquid crystal 11 at room temperature.
And the aligning agent for liquid crystal for being prepared for adding compound D-1 as additive and preparing is as comparative example.
Comparative example 4
Weigh polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add in 49.0g NMP, 36.6g BC,
0.682g compound D-1, magnetic agitation, obtains aligning agent for liquid crystal 12 at room temperature.
Comparative example 5
Weigh polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add in 49.0g NMP, 36.6g BC,
0.682g compound D-1, magnetic agitation, obtains aligning agent for liquid crystal 13 at room temperature.
Comparative example 6
Polyamic acid solution (PAA-1) 48g obtained in synthesis example 1 is weighed, it is sub- to add in the polyamides obtained in 2g synthesis examples 3
Amine powder (SPI-1), 71.46g NMP, 44.9g BC, 0.836g compound D-1, magnetic agitation, obtains liquid crystal aligning at room temperature
Agent 14.
Wherein compound D-1 is shown below：
Wherein, compound shown in formula D-1 is the additive being frequently added in prepared by the aligning agent for liquid crystal of the prior art, but
It is to add in compound shown in D-1, although can make liquid crystal orientation film that there is good coating and wearability, by the liquid crystal aligning
The liquid crystal cell that film preparation obtains does not have good orientation and residual charge is higher；Therefore as additive, with incite somebody to action this
Compound shown in invention compound Chinese style I-1 is compared as a comparison case as the aligning agent for liquid crystal of additive.
According to another aspect of the present invention, a kind of liquid crystal orientation film is provided, the liquid crystal orientation film is by according to the present invention
Hot setting is made on the glass substrate for aligning agent for liquid crystal coating.
According to another aspect of the present invention, a kind of liquid crystal cell is provided, which takes including liquid crystal according to the present invention
To film.
By embodiment 1-8, aligning agent for liquid crystal spin coating prepared by comparative example 1-6 forms liquid crystal orientation film on the glass substrate
Afterwards, the coating of liquid crystal orientation film and wearability are evaluated.It will be made after two pieces of substrate fittings with liquid crystal orientation film
Liquid crystal cell carries out the evaluation of orientation characteristic, voltage retention, residual charge respectively.
The specific preparation of liquid crystal cell：
Aligning agent for liquid crystal is spun on the ito glass substrate surface after over cleaning, the preliminary drying 55s on 85 DEG C of hot plate,
With after curing 30min in 230 DEG C of drying boxes, the film that thickness is about 100nm is formed on ito glass substrate surface.Using rubbing
Aligning device is wiped with fixed friction condition (substrate speed of service 30mm/sec, roller intrusion 0.4mm, friction velocity
It 1000rpm) rubs to the film, obtains the ito glass substrate with liquid crystal aligning ability.2 blocks of above-mentioned band liquid crystal is taken to take
To the substrate of agent, after 6 μm of spacer is placed on one piece of glass substrate wherein, according to preset program in substrate table
Face is coated with sealant, then fits on another piece of substrate and is made in a manner that alignment layer surface is antiparallel relative to frictional direction
Empty liquid crystal cell.Liquid crystal (MAT-09-1284, Merck KGaA corporation) is injected into the liquid crystal cell, horizontal stroke is made in injection hole sealing
Electric Field Mode (FFS or IPS) type liquid crystal cell.
The evaluation method of aligning agent for liquid crystal：
The evaluation of coating
Aligning agent for liquid crystal is spun on glass substrate, by 85 DEG C, after 55s preliminary dryings and 230 DEG C/30min curings,
Glass baseplate surface forms the film that thickness is about 100nm.Substrate with liquid crystal orientation film is placed under microscope, amplification 20
Its surface state is observed again.If there is no crawling, then it is assumed that coating is good；If pin hole or coating are observed in surface
When irregular, then it is assumed that coating is bad.
The evaluation of wearability
Aligning agent for liquid crystal is spun on glass substrate, by 85 DEG C, after 55s preliminary dryings and 230 DEG C/30min curings,
Glass baseplate surface forms the film that thickness is about 100nm.Using friction orientation equipment, to carrying polyimides, (polyamides propylhomoserin is molten
Liquid is converted into polyimides under conditions of hot setting) glass substrate of film rubs, and friction condition is：Substrate is run
Speed 30mm/sec, roller intrusion 0.4mm, friction velocity 1000rpm.Glass substrate after friction matching is placed in microscope
Lower its surface state of observation.If surface is without clast and scar, then it is assumed that rub resistance is good；Conversely, it wears no resistance.
The evaluation of liquid crystal aligning
The liquid crystal cell of above-mentioned making is observed using petrographic microscope, it will be almost without the liquid crystal cell for finding that light penetrates
It is considered as liquid crystal aligning " excellent ", find minute quantity light transmission is considered as " good ", there is being considered as " bad " for a large amount of light transmissions.
The evaluation of voltage retention (VHR)
Using the voltage retention of the above-mentioned liquid crystal cell of liquid crystal evaluation of physical property system measurement, apply 4V electricity at 25 DEG C to liquid crystal cell
Pressure measures the voltage retention after 16.67ms.
The evaluation of residual charge (RDC)
Using the RDC of the above-mentioned liquid crystal cell of liquid crystal evaluation of physical property system measurement, 10V voltages are applied to liquid crystal cell at 25 DEG C
Discharge 1min after 30min, measures the residual voltage value (mV) after 30min.
The evaluation of the orientation, voltage retention, residual charge of coating and wearability, liquid crystal cell to liquid crystal orientation film
The results are shown in Table 2.
Table 2
The liquid crystal that can be seen that Examples 1 to 8 aligning agent for liquid crystal preparation provided by the present invention by the result of table 2 takes
There is good coating and wearability to film；There is the liquid crystal cell containing liquid crystal orientation film of the present invention good liquid crystal to take simultaneously
Tropism, high voltage holding ratio and low-residual charge；And be not added with any additive Comparative Examples 1 and 2 and 3 coatings it is bad and resistance to
Mill property is poor, and residual charge is high；4,5 and 6 liquid crystal alignings of additive comparative example for being added to compound shown in formula D-1 are bad,
Voltage retention is low, residual charge is high.Therefore, it is added to the liquid crystal aligning that the aligning agent for liquid crystal of the compounds of this invention is prepared
Film has good wearability and coating, and the liquid crystal cell containing the liquid crystal orientation film has good liquid crystal aligning simultaneously
Property, high voltage holding ratio and low charge residue rate.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of compound, which is characterized in that the compound is shown in formula I：
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
2. compound as described in claim 1, which is characterized in that the compound is as shown in Formulas I -1：
3. a kind of preparation method of compound as claimed in claim 1 or 2, which is characterized in that this method includes：
Amidation step：Compound shown in Formula II is reacted with compound shown in formula III, is converted into compound shown in formula IV；
Step of hydrogenation：- NO in compound shown in formula IV2It is reduced to-NH2Afterwards, it is converted into compound shown in Formula V；
Epoxidation step：Compound shown in Formula V and epichlorohydrin reaction are converted into compound shown in Formulas I；
Wherein, the R in Formula II, formula IV and compound shown in Formula V1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3
With-CH2CH2CH3。
4. preparation method as claimed in claim 3, which is characterized in that compound shown in Formula II is by compound shown in Formula IV
It reacts and is transformed with thionyl chloride,
Wherein, R1、R2、R3And R4It is each independently selected from-H ,-CH3、-CH2CH3With-CH2CH2CH3。
5. preparation method as claimed in claim 3, which is characterized in that in the amidation step：
Compound shown in compound shown in Formula II and formula III is placed under alkaline condition and is reacted, is converted into compound shown in formula IV.
6. preparation method as claimed in claim 3, which is characterized in that in the step of hydrogenation：Compound exists shown in formula IV
Palladium carbon is compound shown in Formula V as hydro-conversion under conditions of catalyst.
7. preparation method as claimed in claim 3, which is characterized in that in the epoxidation step, compound shown in Formula V with
Epoxychloropropane reacts under alkaline condition is converted into compound shown in Formulas I.
8. a kind of aligning agent for liquid crystal, which is characterized in that the aligning agent for liquid crystal includes：Polyamides propylhomoserin and/or polyimide solution,
And compound described in claims 1 or 2；Wherein, the compound is as additive, and accounts for the solution with quality percentage
Than the 0.25~0.5% of meter.
9. a kind of liquid crystal orientation film, which is characterized in that the liquid crystal orientation film is coated in by aligning agent for liquid crystal according to any one of claims 8
Hot setting is made on glass substrate.
10. a kind of liquid crystal cell, which is characterized in that the liquid crystal cell includes liquid crystal orientation film as claimed in claim 9.
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