CN105294664A - Compound and preparation method thereof, liquid crystal aligning agent, liquid crystal aligning membrane and liquid crystal cell - Google Patents
Compound and preparation method thereof, liquid crystal aligning agent, liquid crystal aligning membrane and liquid crystal cell Download PDFInfo
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- 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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- 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
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- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- 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 compound and a preparation method thereof, a liquid crystal aligning agent, a liquid crystal aligning membrane and a liquid crystal cell. The compound disclosed by the invention is shown as a formula I, wherein, R1, R2, R3 and R4 are respectively and independently selected from -H, -CH3, -CH2CH3 and -CH2CH2CH3. The preparation method of the compound comprises the following steps: amidation, hydrogenation and epoxidation. The invention also discloses the liquid crystal aligning agent and the liquid crystal aligning membrane, and the liquid crystal cell containing the liquid crystal aligning membrane.
Description
Technical field
The present invention relates to field of liquid crystal display, particularly relate to compound and preparation method thereof, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal cell.
Background technology
Liquid crystal orientation film is by making after glass baseplate surface coating liquid crystal aligning agent hot setting, is the important component part forming liquid crystal cell.Along with people are more and more higher to display frame quality requirements, more and more stricter to the characteristic requirements of the characteristic of liquid crystal orientation film and the liquid crystal cell that comprises liquid crystal orientation film.
Liquid crystal orientation film is being prepared with existing liquid crystal aligning agent, and preparation is when comprising the liquid crystal cell of liquid crystal orientation film, can not meet makes liquid crystal orientation film have good wear resistance and coating simultaneously, and makes the liquid crystal cell be made up of liquid crystal orientation film have the feature of good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
Therefore can meet above-mentioned characteristic desirable to provide a kind of liquid crystal aligning agent simultaneously.
Summary of the invention
The invention provides a kind of compound and preparation method thereof, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal cell.Be added in liquid crystal aligning agent with compound of the present invention as additive, to solve in prior art and can not prepare liquid crystal orientation film there is good wear resistance and coating by satisfied liquid crystal aligning agent simultaneously, and make the liquid crystal cell be made up of liquid crystal orientation film have the problem of good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
According to an aspect of the present invention, provide a kind of compound, this compound is such as formula shown in I:
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
Alternatively, according to compound of the present invention, this compound is such as formula shown in I-1:
Alternatively, according to the preparation method of compound of the present invention, the method comprises:
Amidation step: compound shown in compound and formula III shown in formula II reacts, and is converted into compound shown in formula IV;
The step of hydrogenation :-NO in compound shown in formula IV
2be reduced to-NH
2after, be converted into compound shown in formula V;
Epoxidation step: compound shown in formula V and epichlorohydrin reaction, is converted into compound shown in formula I;
Wherein, the R in compound shown in formula II, formula IV and formula V
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
Alternatively, preparation in accordance with the present invention, compound shown in formula II is that compound shown in through type VI and thionyl chloride are reacted and be transformed,
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
Alternatively, preparation in accordance with the present invention, in described amidation step:
React under compound shown in compound and formula III shown in formula II is placed in alkaline condition, be converted into compound shown in formula IV.
Alternatively, preparation in accordance with the present invention, in described step of hydrogenation: the hydrocracking under palladium carbon is as the condition of catalyzer of compound shown in formula IV is compound shown in formula V.
Alternatively, preparation in accordance with the present invention, in described epoxidation step, compound shown in formula V and epoxy chloropropane react in the basic conditions and are converted into compound shown in formula I.
According to a further aspect in the invention, provide a kind of liquid crystal aligning agent, this liquid crystal aligning agent comprises: polyamides propylhomoserin and/or polyimide solution, and compound described in claim 1 or 2; Wherein, described compound as additive, and account for described solution by percentage to the quality 0.25 ~ 0.5%.
According to a further aspect in the invention, provide a kind of liquid crystal orientation film, this liquid crystal orientation film applies hot setting on the glass substrate by liquid crystal aligning agent according to the present invention and makes.
According to a further aspect in the invention, provide a kind of liquid crystal cell, this liquid crystal cell comprises according to liquid crystal orientation film of the present invention.
Beneficial effect of the present invention is as follows:
Compound of the present invention contains Racemic glycidol group, triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, can be added in liquid crystal aligning agent as additive, improve the performance of liquid crystal aligning agent thus improve the performance of liquid crystal orientation film, also can improve the performance of liquid crystal cell.
Compound of the present invention is prepared liquid crystal aligning agent as at least one mixed with polymers in additive and polyamides propylhomoserin and/or polyimide, this liquid crystal aligning agent is applied on substrate after hot setting, makes liquid crystal orientation film, wherein polyamides propylhomoserin is converted into polyimide through heat, owing to containing glycidyl in the compounds of this invention, the adhesion property between liquid crystal aligning agent and substrate can be increased when preparing liquid crystal orientation film, thus improve wear resistance and the coating of liquid crystal orientation film; Because this compound contains triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, the liquid crystal cell containing this liquid crystal orientation film has good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
Embodiment
Embodiment is only explanation of the present invention, and does not form the restriction to content of the present invention, to be further described and to describe below in conjunction with concrete embodiment to the present invention.
According to an aspect of the present invention, provide a kind of compound, this compound is such as formula shown in I:
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
Compound shown in formula I contains glycidyl, triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, can be added in liquid crystal aligning agent as additive, improve the performance of liquid crystal aligning agent, thus improve coating and the wear resistance of liquid crystal orientation film, improve the liquid crystal aligning of the liquid crystal cell containing this liquid crystal film simultaneously, improve voltage retention and reduce charge residue rate.
Compound shown in formula I is mixed with as additive and polyamides propylhomoserin and/or polyimide and obtains liquid crystal aligning agent, this liquid crystal aligning agent is applied on substrate after hot setting, makes liquid crystal orientation film, wherein polyamides propylhomoserin is converted into polyimide through heat, owing to containing Racemic glycidol group in the compounds of this invention, the adhesion property between liquid crystal aligning agent and substrate can be increased when preparing liquid crystal orientation film, thus improve wear resistance and the coating of liquid crystal orientation film, because this compound contains triazole aromatic heterocycle structure, tertiary amine structure and biphenyl structural, liquid crystal cell containing this liquid crystal orientation film has good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
According to one embodiment of the present invention, this compound is such as formula shown in I-1:
According to a further aspect in the invention, provide a kind of preparation method of compound, the method comprises:
Amidation step: compound shown in compound and formula III shown in formula II reacts, and is converted into compound shown in formula IV;
The step of hydrogenation :-NO in compound shown in formula IV
2be reduced to-NH
2after, be converted into compound shown in formula V;
Epoxidation step: compound shown in formula V and epichlorohydrin reaction, is converted into compound shown in formula I;
Wherein, the R in compound shown in formula II, formula IV and formula V
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
A kind of embodiment of method produced according to the present invention, compound shown in formula II is that compound shown in through type VI and thionyl chloride are reacted and be transformed,
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
A kind of embodiment of method produced according to the present invention, in amidation step:
React under compound shown in compound and formula III shown in formula II is placed in alkaline condition, be converted into compound shown in formula IV.
A kind of embodiment of method produced according to the present invention, in step of hydrogenation: the hydrocracking under palladium carbon is as the condition of catalyzer of compound shown in formula IV is compound shown in formula V.
A kind of embodiment of preparation in accordance with the present invention, in epoxidation step, compound shown in formula V and epoxy chloropropane react in the basic conditions and are converted into compound shown in formula I.
In order to the synthetic method of compound shown in formula I, a kind of synthesis of particular compound is selected exemplarily to be described.
The structural formula of the particular compound of synthesis is such as formula shown in I-1:
First, compound 4-shown in synthesis type II-1 (4 '-nitrophenyl) Benzoyl chloride, reaction equation is as follows:
Concrete reaction conditions is: 12.15g (50mmol) 4-(4 '-nitrophenyl) phenylformic acid is placed in 250mL flask, in flask, adds 80mLSOCl
2with the DMF of 5 catalytic amounts, make above-mentioned solution 80 DEG C of backflows, monitor extent of reaction with TLC, after question response completes, reaction solution is revolved steam removing solution, removing solution after material in add 50mL methylene dichloride dissolve, again carry out revolving boil off desolventize and with solvent by remaining SOCl
2take mixture out of, obtain 12.5g solid phase prod, yield is 95.7%.
Then, carry out amidation step, reaction equation is as follows:
By 1.49g (15mmol, 1eq) compound 3 shown in formula III-1,5-diaminostilbene, 2,4-triazole, 3.64g (36mmol, 2.4eq) triethylamine is dissolved in 50mL methylene dichloride, slowly drips the dichloromethane solution of 50mL (containing compound 4-shown in 9.39g formula 11-1 (4 '-nitrophenyl) Benzoyl chloride) at 0 DEG C.After being added dropwise to complete, reaction solution reacts 24h under room temperature, with 200mL pure water, reaction solution is washed subsequently, after layering, organic phase saturated sodium carbonate solution is washed twice rear anhydrous magnesium sulfate drying, organic phase is revolved steaming and obtain thick product, thick product recrystallization is obtained compound shown in 6.52g formula IV-1, and productive rate is 80%.
The compound obtained by recrystallization carries out nuclear-magnetism qualification, and the data of qualification are as follows:
1H-NMR(400MHz，CDCl
3)，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 that recrystallization obtains as can be seen from the above data is compound shown in formula IV-1.
Carry out step of hydrogenation afterwards, reaction equation is as follows:
Compound shown in 5.49g (10mmol, 1eq) formula IV-1 is dissolved in 100mL dehydrated alcohol and DMF mixed solvent, adds 1.5gPd/C, by mixture compressive reaction 6h under hydrogen atmosphere.After reaction terminates, Filtration of catalyst, revolves steaming by filtrate, obtains compound shown in 3.72g formula V-1 after recrystallization, and productive rate is 76%.
Carried out nuclear-magnetism qualification to the compound obtained, the resolution data of nuclear magnetic spectrogram is 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)。
Can find out according to above-mentioned data, the described compound obtained is compound shown in formula V-1.
Finally carry out epoxidation step, concrete synthesis equation is as follows:
By 3g (6.12mmol, 1eq) compound shown in formula V-1 and 6.76g (48.96mmol, 8eq) salt of wormwood is dissolved in 50mlDMSO, above-mentioned mixed solution is placed in ice bath, and slowly drip 4.53g (48.96mmol, 8eq) epoxy chloropropane, after being added dropwise to complete, reaction solution reacts 24h under room temperature, rotary evaporation, the crude product of gained dissolves with 50mL toluene, add 50mL pure water three times, organic phase anhydrous magnesium sulfate drying, revolve and steam except desolventizing, products therefrom obtains the 2.02g of compound shown in formula I after silica column purification, productive rate is 46%.
Gained compound is carried out nuclear-magnetism qualification, and nuclear magnetic spectrogram resolution data is as follows:
1H-NMR(400MHz，CDCl
3)，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)。
Can find out according to above-mentioned data, the compound obtained is compound shown in formula I-1.
According to a further aspect in the invention, provide a kind of liquid crystal aligning agent, this liquid crystal aligning agent comprises: polyamides propylhomoserin and/or polyimide solution, and compound described in claim 1 or 2; Wherein, described compound as additive, and account for described solution by percentage to the quality 0.25 ~ 0.5%.
Liquid crystal aligning agent according to the present invention is dissolved in solvent (preferred N-Methyl pyrrolidone and/or ethylene glycol butyl ether) by compound shown in polyamides propylhomoserin and/or polyimide and formula I making.
And polyamides propylhomoserin wherein generally selects diamine compounds and the reaction of anhydrides compound to be transformed.Wherein, the preferred following compound of diamine compounds:
Wherein, the preferred following compound of anhydrides compound:
Wherein, formula VII is a kind of manifestation of the polyamic acid prepared by above-mentioned diamine compounds and anhydrides compound:
The polyamides propylhomoserin dehydration closed-loop of manifestation described in formula VII can be converted into the polyimide shown in formula VIII:
Below in conjunction with the concrete synthesis example of polyamides propylhomoserin and polyimide, the present invention will be described.
Synthesis example 1
By (the 80mmol of compound 8.64g shown in diamine compound B-1,0.8eq), the 1.84g of compound shown in B-3 (10mmol, 0.1eq) with compound 5.22g (15mmol shown in B-4,0.15eq) be dissolved in 200mLN-methyl-2-pyrrolidone (being called for short NMP) solvent, with the air in nitrogen replacement container, acid anhydrides 19.6g (the 100mmol of compound shown in A-1 is slowly added in above-mentioned mixing solutions, 1eq), wholely react on stirred at ambient temperature 24h, obtain the polyamic acid solution (PAA-1) that mass concentration is 15%.
Synthesis example 2
Compound 6.48g (60mmol shown in diamine compound B-1 is added in the there-necked flask of 500ml, 0.6eq), the 2.48g of compound shown in B-2 (25mmol, 0.25eq), the 3.68g of compound shown in B-3 (20mmol, 0.2eq) and 180mLNMP solvent, room temperature lower magnetic force stirring and dissolving, and with the air in nitrogen replacement flask.Acid anhydrides 17.64g (the 90mmol of compound shown in A-1 is slowly added in above-mentioned mixing solutions, 0.9eq) and the acid anhydrides 2.18g (10mmol of compound shown in A-2,0.1eq), wholely react on stirred at ambient temperature 24h, obtain the polyamic acid solution (PAA-2) that mass concentration is 15%.
Synthesis example 3
Polyamic acid (PAA-2) prepared by synthesis example 2 use nmp solvent to be diluted to polyamic acid solution that mass concentration is 8%.Take this polyamic acid solution of 150g, add 7.8g acetic anhydride and 6.1g pyridine, at 80 DEG C, react 3h, precipitate in methyl alcohol excessive for solution impouring, drying under reduced pressure after washing 3 times with methyl alcohol to throw out, obtains polyimide powder, is labeled as SPI-1.
Below, compound, N-Methyl pyrrolidone and the ethylene glycol butyl ether preparation to liquid crystal aligning agent shown in the polyamides propylhomoserin synthesized in above-mentioned synthesis example or polyimide, formula I-1 is utilized to be described.
When liquid crystal aligning agent is prepared, the raw material added needed for calculating according to the following equation, wherein,
Needed for the N-Methyl pyrrolidone that adds be B gram:
B＝F*C-85％*A
Needed for the ethylene glycol butyl ether that adds be C gram:
Or
Needed for compound shown in the formula I-1 that adds be D gram:
Wherein, A represents the quality (gram) adding polyamic acid, in embodiments of the present invention, and the quality 98%-100% accounting for polyamides propylhomoserin and/or polyimide solution total mass by percentage to the quality of polyamic acid solution; H represents the quality (gram) adding polyimide, in embodiments of the present invention, and the quality 0%-2% accounting for polyamides propylhomoserin and/or polyimide solution total mass by percentage to the quality of polyimide solution; E represents the solid content of liquid crystal aligning agent, and in embodiments of the present invention, the solid content E of liquid crystal aligning agent is 6%; Shown in G expression I-1, compound accounts for the mass percent of polyamic acid and/or polyimide total mass as additive, and G is 0.25% ~ 0.5% in embodiments of the present invention; F represents the mass ratio of N-Methyl pyrrolidone and ethylene glycol butyl ether in the liquid crystal aligning agent of preparation, and F is set to 2.5:1 in embodiments of the present invention.Other parameter in following embodiment and comparative example can be obtained according to above-mentioned formula.
Wherein, in the liquid crystal aligning agent prepared in embodiment and comparative example the kind of component of polymer and additive and content as shown in table 1.
Table 1
Embodiment 1
Take polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add compound shown in 45.1gNMP, 35g ethylene glycol butyl ether (being called for short BC), 0.326g formula I-1, room temperature lower magnetic force stirs and obtains liquid crystal aligning agent 1.
Embodiment 2
Take polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add compound shown in 49.0gNMP, 36.6gBC, 0.682g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 2.
Embodiment 3
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add compound shown in 45.1gNMP, 35gBC, 0.326g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 3.
Embodiment 4
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add compound shown in 49.0gNMP, 36.6gBC, 0.682g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 4.
Embodiment 5
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add compound shown in 45.7gNMP, 35.3gBC, 0.3947g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 5.
Embodiment 6
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add compound shown in 47.5gNMP, 36.0gBC, 0.5357g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 6.
Embodiment 7
Take polyamic acid solution (PAA-1) 48g obtained in synthesis example 1, add compound shown in the polyimide powder (SPI-1) of acquisition in 2g synthesis example 3,64.1gNMP, 41.9gBC, 0.40g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 7.
Embodiment 8
Take polyamic acid solution (PAA-1) 48g obtained in synthesis example 1, add compound shown in the polyimide powder (SPI-1) of acquisition in 2g synthesis example 3,71.46gNMP, 44.9gBC, 0.836g formula I-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 8.
And prepared do not add the compounds of this invention shown in formula I-1 liquid crystal aligning agent as comparative example.
Comparative example 1
Take polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add 41.4gNMP, 33.6gBC, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 9.
Comparative example 2
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add 41.4gNMP, 33.6gBC, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 10.
Comparative example 3
Take polyamic acid solution (PAA-1) 48g obtained in synthesis example 1, add the polyimide powder (SPI-1) of acquisition in 2g synthesis example 3,62.2gNMP, 41.2gBC, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 11.
And prepared and add liquid crystal aligning agent that Compound D-1 prepared as additive as comparative example.
Comparative example 4
Take polyamic acid solution (PAA-1) 50g obtained in synthesis example 1, add 49.0gNMP, 36.6gBC, 0.682g Compound D-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 12.
Comparative example 5
Take polyamic acid solution (PAA-2) 50g obtained in synthesis example 2, add 49.0gNMP, 36.6gBC, 0.682g Compound D-1, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 13.
Comparative example 6
Take polyamic acid solution (PAA-1) 48g obtained in synthesis example 1, add the polyimide powder (SPI-1), 71.46gNMP, 44.9gBC, 0.836g Compound D-1 that obtain in 2g synthesis example 3, room temperature lower magnetic force stirs, and obtains liquid crystal aligning agent 14.
Wherein Compound D-1 is shown below:
Wherein, compound shown in formula D-1 is the additive often added in the liquid crystal aligning agent preparation of prior art, but add compound shown in D-1, although liquid crystal orientation film can be made to have good coating and wear resistance, the liquid crystal cell prepared by this liquid crystal orientation film does not have good orientation and residual charge is higher; Therefore it can be used as additive, compare as a comparison case as the liquid crystal aligning agent of additive with using compound shown in the compounds of this invention Chinese style I-1.
According to a further aspect in the invention, provide a kind of liquid crystal orientation film, this liquid crystal orientation film applies hot setting on the glass substrate by liquid crystal aligning agent according to the present invention and makes.
According to a further aspect in the invention, provide a kind of liquid crystal cell, this liquid crystal cell comprises according to liquid crystal orientation film of the present invention.
By embodiment 1-8, after liquid crystal aligning agent spin coating prepared by comparative example 1-6 forms liquid crystal orientation film on the glass substrate, the coating of liquid crystal orientation film and wear resistance are evaluated.Make liquid crystal cell by two pieces with after the baseplate-laminating of liquid crystal orientation film, carry out the evaluation of orientation characteristic, voltage retention, residual charge respectively.
The concrete preparation of liquid crystal cell:
Liquid crystal aligning agent is spun on the ito glass substrate surface after cleaning, on the hot plate of 85 DEG C, preliminary drying 55s, solidifies 30min subsequently in 230 DEG C of loft drier, forms the film that thickness is about 100nm on ito glass substrate surface.Adopt friction orientation device to rub to this film with fixing friction condition (substrate travelling speed 30mm/sec, running roller intrusion 0.4mm, friction velocity 1000rpm), obtain the ito glass substrate with liquid crystal aligning ability.Get the substrate of 2 pieces of above-mentioned band liquid crystal aligning agent, after one piece of glass substrate wherein being placed the spacer of 6 μm, be coated with sealed plastic box according to the program preset at substrate surface, fit on another block substrate relative to the antiparallel mode of frictional direction with alignment layer surface subsequently and make sky liquid crystal cell.In this liquid crystal cell, inject liquid crystal (MAT-09-1284, Merck KGaA Inc.), lateral electric field type (FFS or IPS) type liquid crystal cell is made in filling orifice sealing.
The evaluation method of liquid crystal aligning agent:
The evaluation of coating
Liquid crystal aligning agent is spun on glass substrate, through 85 DEG C, after 55s preliminary drying and 230 DEG C/30min solidify, is about the film of 100nm at glass baseplate surface formation thickness.Under substrate with liquid crystal orientation film is placed in microscope, magnify 20 observes its condition of surface.If when there is no crawling, then think that coating is good; If surface observation is to pin hole or when being coated with irregular, then think that coating is bad.
The evaluation of wear resistance
Liquid crystal aligning agent is spun on glass substrate, through 85 DEG C, after 55s preliminary drying and 230 DEG C/30min solidify, is about the film of 100nm at glass baseplate surface formation thickness.Friction orientation equipment is adopted to rub to the glass substrate with polyimide (polyamine acid solution is converted into polyimide under the condition of hot setting) film, friction condition is: substrate travelling speed 30mm/sec, running roller intrusion 0.4mm, friction velocity 1000rpm.Glass substrate after friction matching is placed in its condition of surface of basis of microscopic observation.If surface without chip and scar, then thinks that rub resistance is good; Otherwise, wear no resistance.
The evaluation of liquid crystal aligning
Use polarizing microscope to observe to the liquid crystal cell of above-mentioned making, almost will not find that the liquid crystal cell of light transmission is considered as liquid crystal aligning " excellent ", find being considered as " well " of minute quantity light transmission, have being considered as " bad " of a large amount of light transmission.
The evaluation of voltage retention (VHR)
Adopt the voltage retention of the above-mentioned liquid crystal cell of liquid crystal evaluation of physical property systems measurement, at 25 DEG C, 4V voltage is applied to liquid crystal cell, measure the voltage retention after 16.67ms.
The evaluation of residual charge (RDC)
Adopt the RDC of the above-mentioned liquid crystal cell of liquid crystal evaluation of physical property systems measurement, discharge after applying 10V voltage 30min to liquid crystal cell at 25 DEG C 1min, measures the retained voltage value (mV) after 30min.
As shown in table 2 to the evaluation result of the orientation of the coating of liquid crystal orientation film and wear resistance, liquid crystal cell, voltage retention, residual charge.
Table 2
Can be found out by the result of table 2, the liquid crystal orientation film that embodiment 1 ~ 8 is prepared by liquid crystal aligning agent provided by the invention has good coating and wear resistance; Liquid crystal cell simultaneously containing liquid crystal orientation film of the present invention has good liquid crystal aligning, high voltage holding ratio and low residue electric charge; The comparative example 1,2 and 3 not adding any additive then coating is bad and wear no resistance, and residual charge is high; Additive comparative example 4,5 and 6 liquid crystal alignings that with the addition of compound shown in formula D-1 are bad, and voltage retention is low, residual charge is high.Therefore, the liquid crystal orientation film that the liquid crystal aligning agent that with the addition of the compounds of this invention prepares has good wear resistance and coating, and the liquid crystal cell simultaneously containing this liquid crystal orientation film has good liquid crystal aligning, high voltage holding ratio and low charge residue rate.
Obviously, those skilled in the art can carry out various change and modification to the present invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a compound, is characterized in that, this compound is such as formula shown in I:
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
2. compound as claimed in claim 1, it is characterized in that, this compound is such as formula shown in I-1:
3. a preparation method for compound as claimed in claim 1 or 2, it is characterized in that, the method comprises:
Amidation step: compound shown in compound and formula III shown in formula II reacts, and is converted into compound shown in formula IV;
The step of hydrogenation :-NO in compound shown in formula IV
2be reduced to-NH
2after, be converted into compound shown in formula V;
Epoxidation step: compound shown in formula V and epichlorohydrin reaction, is converted into compound shown in formula I;
Wherein, the R in compound shown in formula II, formula IV and formula V
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
4. preparation method as claimed in claim 3, is characterized in that, compound shown in formula II is that compound shown in through type VI and thionyl chloride are reacted and be transformed,
Wherein, R
1, R
2, R
3and R
4be selected from-H ,-CH independently of one another
3,-CH
2cH
3with-CH
2cH
2cH
3.
5. preparation method as claimed in claim 3, is characterized in that, in described amidation step:
React under compound shown in compound and formula III shown in formula II is placed in alkaline condition, be converted into compound shown in formula IV.
6. preparation method as claimed in claim 3, is characterized in that, in described step of hydrogenation: the hydrocracking under palladium carbon is as the condition of catalyzer of compound shown in formula IV is compound shown in formula V.
7. preparation method as claimed in claim 3, it is characterized in that, in described epoxidation step, compound shown in formula V and epoxy chloropropane react in the basic conditions and are converted into compound shown in formula I.
8. a liquid crystal aligning agent, is characterized in that, this liquid crystal aligning agent comprises: polyamides propylhomoserin and/or polyimide solution, and compound described in claim 1 or 2; Wherein, described compound as additive, and account for described solution by percentage to the quality 0.25 ~ 0.5%.
9. a liquid crystal orientation film, is characterized in that, this liquid crystal orientation film applies hot setting on the glass substrate by liquid crystal aligning agent according to claim 8 and makes.
10. a liquid crystal cell, is characterized in that, this liquid crystal cell comprises liquid crystal orientation film as claimed in claim 9.
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