CN109970975A - A kind of high voltage holding ratio type polyimides and its preparation method and application - Google Patents
A kind of high voltage holding ratio type polyimides and its preparation method and application Download PDFInfo
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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
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Abstract
The invention discloses a kind of high voltage holding ratio type polyimides and its preparation method and application, and the structural formula of the polyimides is shown in formula I, are to be prepared by alicyclic dianhydride compound and aromatic diamine compound for raw material.The polyimide material not only has good heat-resistant stability, and there are excellent optical transparence, excellent photoelectric properties, high voltage holding ratio (VHR) and relatively low pre-dumping corner characteristics, solves the problems such as PI aligning film material VHR is relatively low in the prior art, can be used as aligning agent for liquid crystal or liquid crystal orientation film and be applied to in-plane switching LCD(IPS-LCD), fringe field switching LCD(FFS-LCD) etc. advanced liquid crystal display device manufacturing field, have a extensive future.
Description
Technical field
The present invention relates to a kind of polyimides, and in particular to it is poly- to further relate to this for a kind of high voltage holding ratio type polyimides
The application of imido preparation method and aligning agent for liquid crystal and liquid crystal orientation film in liquid crystal display device, belongs to functional polyamides
Imines material technical field.
Background technique
Liquid crystal orientation film is a kind of functional material in liquid crystal display device (LCD) manufacture, and effect is induction liquid crystal
(LC) orientation of molecule, to generate uniform response to applied voltage.The various arrangement modes of liquid crystal molecule, such as 90 ° of distortions,
Arrange or be arranged vertically in 180 ° of -270 ° of supertwists, plane etc., different display modes can be all generated, to generate various liquid
Crystal panel, including twisted nematic liquid crystal display (TN-LCD), Supertwist liquid crystal display (STN-LCD), thin film transistor (TFT)
Drive liquid crystal display (TFT-LCD) etc..The LCD of various modes generally depends on LCD panel to the performance requirement of alignment films
Display pattern.Some common general character require to include high-purity (low ion concentration), good film forming ability, good with LC molecule
Good compatibility, to the good alignment capability of LC molecule and good processing performance, it is as good in having during friction orientation technique
Good rub resistance characteristic has good lightsensitivity etc. in light orientation technical process, and full color thin film transistor (TFT) drives LCD
(TFT-LCD), such as plane internal switch LCD (IPS-LCD) and fringe field switching LCD (FFS-LCD) also needs alignment films to have
Solidification temperature is low, voltage retention (VHR) high characteristic.Polyimides (PI) is proved to be most to have with its excellent comprehensive performance
The TFT-LCD aligning film material of future.In recent decades, PI alignment films have been applied successfully to TN-LCD and STN-LCD device
In the production of part.
However, in order to be applied in full color TFT-LCD, it is necessary to the molecular structure of well-designed PI alignment films, with
Meet crucial, sometimes even conflicting performance requirement.Chemically from the perspective of structure, PI alignment films are generally included
Two types: two class of organic soluble PI (SPI) of polyamic acid (PAA) type and pre- imidization.PAA type alignment films are due to pole
Property-COOH and-CONH- key presence, have the characteristics that polarity is higher, therefore usually have that resistivity is low, voltage retention
(VHR) feature low, residual DC voltage (RDC) is low.On the contrary, SPI type alignment films usually have resistivity height, VHR high, RDC
High feature.VHR and RDC is the important photoelectric parameter of TFT-LCD device, and VHR is mainly close with the contrast of device and flashing
Correlation, and RDC is mainly closely related with the image retention of device.In practical application, it is high performance to develop to generally use mixed method
PI alignment films.In the manufacture of TFT-LCD panel, compound work is carried out between PAA and SPI or PAA with different resistivity
Process is frequently used to exploitation high-performance PI aligning film material, and the aligning film material of this hydridization type often can provide good
Photoelectric characteristic.In the prior art, the research of PAA type alignment films is comparatively abundant, but the type of SPI is extremely limited, this is very
The development of PI liquid crystal orientation film is limited in big degree.
CN102408399 reports a kind of alkyl and replaces 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic alicyclic ring two
Anhydride monomer and its SPI aligning agent for liquid crystal of preparation；CN102898407 reports a kind of fluorine and replaces 3,4- dicarboxyl -1,2,3,4-
Tetrahydro -1- naphthalene succinic alicyclic dianhydride monomer and its SPI aligning agent for liquid crystal of preparation；CN101611031 reports a kind of tertiary fourth
Base replaces the SPI aligning agent for liquid crystal of 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic alicyclic dianhydride monomer and its preparation.
Above-mentioned aligning agent for liquid crystal shows good photoelectric properties.But since this kind of tetrahydro naphthyl dianhydride monomer still contains part
Aromatic rings, therefore the VHR of the SPI aligning agent for liquid crystal prepared need to be improved.Patent CN108864014 reports one kind and is based on 3,
4- dicarboxyl -1,2,3,4,5,6,7,8- decahydro -1- naphthalene succinic alicyclic dianhydride and 4,4'- diaminodiphenyl ether (ODA) or
The soluble polyimide of 4,4'- diamino-diphenylamine (NDA) monomer and its in integrated circuit, optical-fibre communications and solar cell
In application, but verified, VHR is low when which contains ehter bond (- O-) or amido (- NH-), is not used as liquid crystal aligning
Membrane material.(2005,37 (2): Polymer Journal 126) is reported based on 5- (2,5- dioxotetrahydro furans document
Base) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride (DOCDA) monomer organic soluble polyimides, but DOCDA molecule knot
Its hot property is greatly lowered in double bond in structure, is unable to satisfy the application demand of liquid crystal orientation film.
Summary of the invention
The object of the present invention is to provide a kind of polyimides, which does not contain ehter bond, voltage retention height, pre-dumping
Angle is suitable, light transmittance is high, glass transition temperature is high, stability is good, can be used for liquid crystal display device field.
It is a further object of the present invention to provide the preparation methods of the polyimides, and this method is with 5- (2,5- dioxotetrahydros
Furyl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride (H-DOCDA) be raw material, reacted with aromatic diamine compound
To polyimides, process flow is simple, easy to implement, is convenient for industrialized production.
Aligning agent for liquid crystal or liquid crystal it is a further object of the present invention to provide the polyimides as liquid crystal display device take
Effective component application to film, the polyimides voltage retention is high, can be compound with SPI type polyimides, to improve liquid crystal
The performance of display device.
To achieve the goals above, the present invention is using technical solution in detail below:
A kind of polyimides, with structural formula shown in following formula I:
Further, in Formulas I, R1=-CaH2a+1, a is the integer of 0-10；R3=-CbH2b+1, b is the integer of 0-10；R4
=-CdH2d+1, d is the integer of 0-10；R1, R3, R4 may be the same or different.
Further, in Formulas I, R2For any one in following radicals, R5=-CeH2e+1, e is the integer of 0-10:
Further, in Formulas I, n is the integer of 1-100, it is preferred that n is the integer of 30-60.
Further, R1 is preferably H, methyl or ethyl, and R2 is preferably R3 is preferably H, methyl or ethyl,
R4 is preferably H, methyl or ethyl.When selecting these preferred substituents, the performance of resulting polyimides is more preferably.
In addition, the present invention also provides a kind of mixture of polyimides, which is two or more, on
State the mixture of the polyimides of structural formula shown in Formulas I.Each substituent group is defined as above in Formulas I.
Further, polyimides of the present invention is high voltage holding ratio type polyimides, and high voltage holding ratio is meant
Voltage retention is 99% or more.
Further, the present invention also provides the preparation sides of polyimides shown in above-mentioned Formulas I or polyimide mixture
Method, method includes the following steps: using alicyclic dianhydride compound and aromatic diamine compound as raw material, in aprotic, polar
Property solvent in carry out polymerization reaction, obtain polyamic acid solution, be added into polyamic acid (PAA) solution acetic anhydride and pyridine into
The reaction of row chemical imidization, obtains polyimides.When aromatic diamine compound selects two or more, can obtain
To polyimide mixture.
Further, the alicyclic dianhydride compound is 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- hexamethylene
Base -1,2- dicarboxylic anhydride (H-DOCDA) or its substituent, structural formula are as follows:Wherein R1
It defines identical as the definition in formula I above.5- (the 2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic acids
Acid anhydride (H-DOCDA) or its substituent can be by 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexene -1,2- dicarboxyls
Acid anhydrides (DOCDA) or its corresponding substituent double-bond hydrogenation obtain.
Preferably, the alicyclic dianhydride compound is 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- hexamethylene
Base -1,2- dicarboxylic anhydride (H-DOCDA), 5- methyl-(2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexyl -1,2- two
Carboxylic acid anhydrides (H-MDOCDA), 5- ethyl-(2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride
(H-MDOCDA) etc., more preferably 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride (H-
DOCDA)。
Further, the structural formula of the aromatic diamine compound are as follows:Wherein the definition of R2, R3 and R4 are identical as the definition in formula I above.It is preferred that
, the aromatic diamine compound is 4,4'- diaminodiphenylmethane (MDA), 3,3', 5,5'- tetramethyl -4,4'- diaminos
Base diphenyl-methane (TMMDA), 3,3', 5,5'- tetraethyl -4,4'- diaminodiphenylmethane (TEMDA), dimethyl -5 3,3'-,
Bis- (4- amino -3,5- 3,5-dimethylphenyl) methane of 5'- diethyl -4,4'- diaminodiphenylmethane (DMDEDA), 1,1-
(PDMDA), bis- [2- (4- the aminophenyl) -2- propyl] benzene (BISP) of 1,4- and 1,3- bis- [2- (4- aminophenyl) -2- propyl]
At least one of benzene (BISM), preferably 4,4'- diaminodiphenylmethane (MDA).
Further, in above-mentioned preparation method, the alicyclic dianhydride compound monomer and aromatic diamine compound
Molar ratio is 1.00:(0.95~1.00), preferably 1.00:(0.99~1.00).
Further, in above-mentioned preparation method, the molar ratio of the alicyclic dianhydride compound monomer and acetic anhydride is
1.00:(2.00~10.00), preferably 1.00:3.00-5.00.
Further, in above-mentioned preparation method, the molar ratio of the alicyclic dianhydride compound monomer and pyridine is 1.00:
(2.00~8.00), preferably 1.00:3.00-4.00.
Further, in above-mentioned preparation method, the polar aprotic solvent be selected from N-Methyl pyrrolidone (NMP),
Metacresol, N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) and γ-Ding Nei
At least one of ester, preferably gamma-butyrolacton or N-Methyl pyrrolidone (NMP).The dosage of polar aprotic solvent is pressed
It being adjusted according to actual demand, those skilled in the art are easily achieved, in the specific embodiment of the invention, polar aprotic
The dosage of solvent makes the total content 10- of raw material (aromatic diamine compound and alicyclic dianhydride compound) in the reaction system
30wt%, preferably 15~25wt%.
Further, in above-mentioned preparation method, aromatic diamine compound polymerize with alicyclic dianhydride compound anti-
The temperature answered is 0-35 DEG C, preferably 15-25 DEG C.Party reaction time be 10~30 hours, preferably 20~25 hours, more
Preferably 24 hours.
Further, in above-mentioned preparation method, when carrying out chemical imidization reaction, reaction temperature is 0-35 DEG C, preferably
It is 15-25 DEG C, the reaction time is 10~30 hours, preferably 20~25 hours, more preferably 24 hours.
It further, further include being carried out to the reaction solution after reaction after chemical imidization reaction in above-mentioned preparation method
The step of post-processing obtains polyimides, last handling process are as follows: the reaction solution after reaction is added in ethyl alcohol and reels off raw silk from cocoons, obtains
Gained white stringy solids ethanol washing is obtained final polyimides by white stringy solids.
The polyimides of the above-mentioned structure shown in formula I of the present invention has organic soluble, not ether-containing key, and voltage retention is high, light transmission
Rate is high, and thermal stability is good, and therefore, the polyimides of above-mentioned structure shown in formula I can be used in liquid crystal display device, can specifically make
For the aligning agent for liquid crystal of liquid crystal display device or the effective component of liquid crystal orientation film.Liquid crystal orientation film containing polyimides has
The features such as voltage retention height, excellent transparency, pre-tilt angle are suitable for, stability is good, can be applied to in-plane switching LCD (IPS-
LCD), in the contour performance liquid crystal display device of fringe field switching type LCD (FFS-LCD).
Further, the present invention also provides a kind of aligning agent for liquid crystal or liquid crystal orientation film, the aligning agent for liquid crystal or liquid crystal
The ingredient of alignment films includes the polyimides of structure shown in formula I or the mixture of polyimides.The liquid crystal orientation film is to take liquid crystal
It is applied to agent and to be formed on substrate.
Further, the present invention also provides a kind of liquid crystal display device, which includes mentioned component packet
Include the polyimides of structure shown in formula I or the liquid crystal orientation film of polyimide mixture.Liquid crystal display device can be in-plane switching
LCD (IPS-LCD), the contour performance liquid crystal display device of fringe field switching type LCD (FFS-LCD).
The present invention provides the polyimides or polyimide mixture of a kind of formula (I) structure, by alicyclic two
Acid anhydride compound and aromatic diamine compound are prepared for raw material.The polyimide material not only has good heat-resisting steady
It is qualitative, and there is excellent optical transparence, excellent photoelectric properties, high voltage holding ratio (VHR) and relatively low
Pre-dumping corner characteristics solve the problems such as PI aligning film material VHR is relatively low in the prior art, can be used as aligning agent for liquid crystal or liquid
Brilliant alignment films are applied to the advanced liquid crystal display device such as in-plane switching LCD (IPS-LCD), fringe field switching LCD (FFS-LCD)
Manufacturing field has a extensive future.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the Kapton of embodiment and comparative example preparation.
Fig. 2 is the TGA spectrogram of the Kapton of embodiment and comparative example preparation.
Fig. 3 is the DSC spectrogram of the Kapton of embodiment and comparative example preparation.
Fig. 4 is the UV-Vis spectrogram of the Kapton of embodiment and comparative example preparation.
Fig. 5 is the volume resistivity data of the Kapton of embodiment and comparative example preparation.
Fig. 6 is voltage retention (VHR) spectrogram of the Kapton of embodiment and comparative example preparation.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The material can be bought unless otherwise instructed from public commercial source.
The molecular weight of polyimides obtained by following embodiments measures (Japanese Shimadzu Corporation, GPC system) according to GPC method
And obtain, gained molecular weight is number-average molecular weight (Mn)。
The performance parameter of polyimides obtained by following embodiments is tested using following methods:
Amination rate test: using FTIR spectrum (German Brooker, Tensor-27) respectively test 230 DEG C with
300 DEG C of PI film sample, contrast sample is in imide ring carbonyl asymmetric stretching vibration (1780cm-1) absorption peak intensity,
With phenyl ring in 1500cm-1The absorption peak at place calculates amination rate as reference.
Glass transition temperature (Tg) evaluation method: calorimetric differential scanning method (DSC).The Kapton of preparation is existed
Test in calorimetric differential scanning instrument (TA company, the U.S., Q100 series), heating rate: 10 DEG C/min.
Thermal decomposition temperature (T5%) evaluation method: by the Kapton of preparation thermogravimetric analyzer (TA company, the U.S.,
Q50 series) in test, heating rate: 10 DEG C/min.
Light transmittance test method: by the Kapton of preparation in ultraviolet-visible spectrophotometer (Hitachi, Japan, U-
3900) it is tested when 25 DEG C of room temperature on.
Volume resistivity test method: by the Kapton of preparation according to ASTM D- on high pressure, high resistant tester
257-91 standard is tested when 25 DEG C of room temperature.
In following embodiments, in terms of liquid crystal cell performance test, the voltage retention (VHR) and pre-tilt angle (TPA) of liquid crystal cell
Pass through 6254 system testing of Toyo Model.The liquid crystal cell box of VHR test is away from being 5~6 μm.The rectangular wave that VHR applies when testing
Voltage is+5V, pulse width: 60us, frame period: 16.67ms, test temperature: 25 DEG C.The calculating of VHR is according to area ratio.TPA
It is to be measured by crystal rotation method.
Polyimides (the R as shown in H-DOCDA and MDA preparation formula I of embodiment 11、R3、R4It is-H, R2For-CH2-)
In a 500mL there-necked flask equipped with nitrogen inlet, 19.826g (0.1mol) 4,4 '-diamino hexichol is added
Methane (MDA) and 109.4g gamma-butyrolacton, are stirred at room temperature after making it completely dissolved, and 26.625g (0.1mol) H-DOCDA is added,
And 30g gamma-butyrolacton is added, solid content is adjusted to 25% (weight percent).After being stirred at room temperature for 24 hours, 51.0g is added
(0.5mol) acetic anhydride and 31.6g (0.4mol) pyridine continue stirring for 24 hours.Gained colorless viscous solution is fallen in 1000mL second
In alcohol, white stringy solids are obtained.Collect solid, and with ethanol washing three times after, in vacuum drying oven 120 DEG C drying to get
Polyimides (PI) resin.
The PI hard resin of the above-mentioned preparation of 3.0g is weighed, NMP and ethylene glycol monobutyl ether (BC) mixed solvent 47g is added
(NMP:37.6g；BC:9.4g), after solid is completely dissolved, filtered by 0.25um Teflon filtration film, admittedly contained
Amount is the PI solution of 6% (weight percent).On a glass by the coating of PI solution, it is painted with laggard line program heating, process is:
In 80 DEG C of heat preservation 2h, 150 DEG C of heat preservation 1h are then risen to, then rise to 200 DEG C of heat preservation 1h, then rise to 230 DEG C of heat preservation 1h.Program
It is cooled to room temperature, glass plate is impregnated in water, removing obtains Kapton after heating.
Using the Kapton as sample, each performance of polyimides is tested, as a result as follows:
Number-average molecular weight (Mn): 18853g/mol；
Infrared spectroscopy is as shown in Figure 1；
TGA spectrogram is as shown in Fig. 2, it can be seen from the figure that its 5% thermal weight loss temperature (T5%) are as follows: 402 DEG C.
DSC spectrogram is as shown in figure 3, it can be seen from the figure that its glass transition temperature (Tg) are as follows: 267 DEG C.
UV-Vis spectrogram is as shown in figure 4, it can be seen from the figure that light transmittance (T at its 400nm wavelength400) are as follows:
98.7%.
Its volume resistivity is 4.9 × 1015Ω cm, as shown in Figure 5.
In conjunction with raw material, molecular weight and infrared spectrogram it was determined that the structural formula of polyimides is as follows, R1、R3、R4It is
Hydrogen, R2For-CH2, n=44:
The assembling process of liquid crystal cell is as follows: cleaning the oxidation being placed in clip with supersonic cleaning machine supersonic cleaning machine first
Each 10 minutes of indium tin (ITO) substrate two sides.Then obtained ito substrate is wiped with acetone, is dried.PI hard resin is made into
Alignment solution, then on an ito substrate by solution coating, in rotary coating on spin coater, (5s is from static to 1000rpm, dimension
Hold 5s；10s accelerates to 5000rpm, stops after spin coating 20s).Then the ito substrate for being coated with alignment solution is placed in thermal station
90 DEG C of preheating 90s are finally putting into small oven in 230 DEG C of heating 30min, obtain the PI alignment films that film thickness is about 100nm.It will
PI alignment films carry out friction treatment with semi-automatic rubbing machine, then the ito substrate of friction are placed on dispenser again, under vacuum
The coating for carrying out epoxy frame adhesive, then in 90 DEG C of preheating 90s in thermal station.Finally, by frictional direction it is antiparallel be coated with PI
Two pieces of ito substrates of alignment films are assembled into sandwich structure face-to-face, place 120 DEG C of heating 10min in an oven, make sealant
Solidification.The ito substrate of obtained sandwich structure is cut into step-like capsule along sealant with glass cutting machine, is used later
Syringe pours into liquid crystal in sealant, is sealed using UV glue, places 120 DEG C of heating 10min in an oven, makes sealing compound
Solidification, obtains liquid crystal cell.Using the liquid crystal cell as sample, its voltage retention (VHR) and pre-tilt angle (TPA) are tested, obtained pre-
Inclination angle (TPA) is 2.54 °, and voltage retention (VHR) is that 99.84%, VHR spectrogram is as shown in Figure 6.
Polyimides (the R as shown in H-DOCDA and BISP preparation formula I of embodiment 21、R3、R4It is-H；R2For)
In a 500mL there-necked flask equipped with nitrogen inlet, bis- [2- (the 4- amino of 34.449g (0.1mol) Isosorbide-5-Nitrae-are added
Phenyl) -2- propyl] benzene (BISP) and 153.2g gamma-butyrolacton, it is stirred at room temperature and makes it completely dissolved, 26.625g is then added
(0.1mol) H-DOCDA, and gamma-butyrolacton is added, solid content is adjusted to 25% (weight percent).It is stirred at room temperature for 24 hours
Afterwards, 51.0g (0.5mol) acetic anhydride and 31.6g (0.4mol) pyridine is added, continues stirring for 24 hours.By gained colorless viscous solution
In 1000mL ethyl alcohol, white stringy solids are obtained.Collect solid, and with ethanol washing three times after, 120 in vacuum drying oven
DEG C drying, as PI resin.
3.0g PI hard resin obtained above is weighed, NMP and ethylene glycol monobutyl ether (BC) mixed solvent 47g is added
(NMP:37.6g；BC:9.4g), after solid is completely dissolved, filtered by 0.25um Teflon filtration film, admittedly contained
Amount is the PI solution of 6% (weight percent).On a glass by the coating of PI solution, it is painted with laggard line program heating, process is:
In 80 DEG C of heat preservation 2h, 150 DEG C of heat preservation 1h are then risen to, then rise to 200 DEG C of heat preservation 1h, then rise to 230 DEG C of heat preservation 1h.Program
It is cooled to room temperature, glass plate is impregnated in water, removing obtains Kapton after heating.
Using the Kapton as sample, each performance of polyimides is tested, as a result as follows:
Number-average molecular weight (Mn): 18391g/mol；
Infrared spectroscopy is as shown in Figure 1；
TGA spectrogram is as shown in Fig. 2, it can be seen from the figure that its 5% thermal weight loss temperature (T5%) are as follows: 466 DEG C；
DSC spectrogram is as shown in figure 3, it can be seen from the figure that its glass transition temperature (Tg) are as follows: 244 DEG C；
UV-Vis spectrogram is as shown in figure 4, it can be seen from the figure that light transmittance (T at its 400nm wavelength400) are as follows:
97.1%；
Its volume resistivity are as follows: 3.6 × 1015Ω cm, as shown in Figure 5.
In conjunction with raw material, molecular weight and infrared spectrogram it was determined that the structural formula of polyimides is as follows, R1、R3、R4It is
Hydrogen, R2ForN=32:
Liquid crystal cell is assembled according to the method for embodiment 1, the pre-tilt angle of gained liquid crystal cell is 2.73 °, VHR=99.64%,
VHR spectrogram is as shown in Figure 6.
Polyimides (the R as shown in H-DOCDA and BISM preparation formula I of embodiment 31、R3、R4It is-H；R2For)
In a 500mL there-necked flask equipped with nitrogen inlet, bis- [2- (the 4- amino of 34.449g (0.1mol) 1,3- are added
Phenyl) -2- propyl] benzene (BISM) and 153.2g gamma-butyrolacton.It is stirred at room temperature after making it completely dissolved, 26.625g is added
(0.1mol) H-DOCDA, and gamma-butyrolacton is added, solid content is adjusted to 25% (weight percent).It is stirred at room temperature for 24 hours
Afterwards, 51.0g (0.5mol) acetic anhydride and 31.6g (0.4mol) pyridine is added, continues stirring for 24 hours.By gained colorless viscous solution
In 1000mL ethyl alcohol, white stringy solids are obtained.Collect solid, and with ethanol washing three times after, 120 in vacuum drying oven
DEG C drying, as PI resin.
The PI hard resin of the above-mentioned preparation of 3.0g is weighed, NMP and ethylene glycol monobutyl ether (BC) mixed solvent 47g is added
(NMP:37.6g；BC:9.4g), after solid is completely dissolved, solid content is obtained by filtration by 0.25um Teflon filtration film
For the PI solution of 6% (weight percent).On a glass by the coating of PI solution, it is painted with laggard line program heating, process is:
Then 80 DEG C of heat preservation 2h rise to 150 DEG C of heat preservation 1h, then rise to 200 DEG C of heat preservation 1h, then rise to 230 DEG C of heat preservation 1h.Program adds
It is cooled to room temperature, glass plate is impregnated in water, removing obtains Kapton after heat.
Using the Kapton as sample, each performance of polyimides is tested, as a result as follows:
Number-average molecular weight (Mn): 17241g/mol；
Infrared spectroscopy is as shown in Figure 1；
TGA spectrogram is as shown in Fig. 2, it can be seen from the figure that its 5% thermal weight loss temperature (T5%) are as follows: 388 DEG C；
DSC spectrogram is as shown in figure 3, it can be seen from the figure that its glass transition temperature (Tg) are as follows: 199 DEG C；
UV-Vis spectrogram is as shown in figure 4, it can be seen from the figure that light transmittance (T at its 400nm wavelength400) are as follows:
98.0%；
Its volume resistivity are as follows: 2.3 × 1015Ω cm, as shown in Figure 5.
In conjunction with raw material, molecular weight and infrared spectrogram it was determined that the structural formula of polyimides is as follows, R1、R3、R4It is
Hydrogen, R2ForN=30:
Liquid crystal cell is assembled according to the method for embodiment 1, the pre-tilt angle of gained liquid crystal cell is 2.92 °, VHR=99.68%,
VHR spectrogram is as shown in Figure 6.
Comparative example 1 prepares polyimides by H-DOCDA and 4,4 '-diamino-diphenylamine (NDA)
In a 500mL there-necked flask equipped with nitrogen inlet, 19.925g (0.1mol) NDA and 109.7g N- first is added
Base pyrrolidones (NMP), is stirred at room temperature after making it completely dissolved, and 26.625g (0.1mol) H-DOCDA is added, and 30g is added
Solid content is adjusted to 25% (weight percent) by NMP.After being stirred at room temperature for 24 hours, be added 51.0g (0.5mol) acetic anhydride and
31.6g (0.4mol) pyridine continues stirring for 24 hours.Gained colorless viscous solution is fallen in 1000mL ethyl alcohol, white filiform is obtained
Solid.Collect solid, and with ethanol washing three times after, in vacuum drying oven 120 DEG C drying to get PI resin.
Kapton is prepared according to the method for embodiment 1, and each performance of polyimides is tested using it as sample,
As a result as follows:
Number-average molecular weight (Mn): 12884g/mol；
Infrared spectroscopy is as shown in Figure 1；
TGA spectrogram is as shown in Fig. 2, it can be seen from the figure that its 5% thermal weight loss temperature (T5%): 343 DEG C；
DSC spectrogram is as shown in figure 3, it can be seen from the figure that its glass transition temperature (Tg): 283 DEG C；
UV-Vis spectrogram is as shown in figure 4, it can be seen from the figure that light transmittance (T at its 400nm wavelength400): 93.1%；
Volume resistivity: 6.6 × 1014Ω cm, as shown in Figure 5；
The structural formula of polyimides is as follows, R1、R3、R4It is hydrogen, R2For-NH-, n=30:
Liquid crystal cell is assembled according to the method for embodiment 1, the pre-tilt angle of gained liquid crystal cell is 2.56 °, VHR=96.58%,
VHR spectrogram is as shown in Figure 6.
Comparative example 2 prepares polyimides by H-DOCDA and 4,4 '-diaminodiphenyl ether (ODA)
In a 500mL there-necked flask equipped with nitrogen inlet, 20.024g (0.1mol) ODA and 110.0g N- first is added
Base pyrrolidones (NMP), is stirred at room temperature after making it completely dissolved, and 26.625g (0.1mol) H-DOCDA is added, and 30g is added
Solid content is adjusted to 25% (weight percent) by NMP.After being stirred at room temperature for 24 hours, be added 51.0g (0.5mol) acetic anhydride and
31.6g (0.4mol) pyridine continues stirring for 24 hours.Gained colorless viscous solution is fallen in 1000mL ethyl alcohol, white filiform is obtained
Solid.Collect solid, and with ethanol washing three times after, in vacuum drying oven 120 DEG C drying to get PI resin.
Kapton is prepared according to the method for embodiment 1, and each performance of polyimides is tested using it as sample,
As a result as follows:
5% thermal weight loss temperature (T5%): 421 DEG C；
Glass transition temperature (Tg): 288 DEG C；
Light transmittance (T at 400nm wavelength400): 95.2%；
Volume resistivity: 1.6 × 1015Ω·cm；
The structural formula of polyimides is as follows, R1、R3、R4It is hydrogen, R2For-O-, n=32:
Liquid crystal cell is assembled according to the method for embodiment 1, and the pre-tilt angle of gained liquid crystal cell is 2.23 °, VHR=97.32%.
Comparative example 3 prepares polyimides by DOCDA and 4,4 '-diaminodiphenylmethane (MDA)
In a 500mL there-necked flask equipped with nitrogen inlet, 0.1mol MDA and 110.0g N- crassitude is added
Ketone (NMP).It is stirred at room temperature after making it completely dissolved, 0.1mol DOCDA is added, and NMP is added, solid content is adjusted to 25%
(weight percent).After being stirred at room temperature for 24 hours, 51.0g (0.5mol) acetic anhydride and 31.6g (0.4mol) pyridine is added, after
Continuous stirring is for 24 hours.Gained colorless viscous solution is fallen in 1000mL ethyl alcohol, white stringy solids are obtained.Solid is collected, and uses second
After alcohol washing three times, 120 DEG C of drying are in vacuum drying oven to get PI resin.
Kapton is prepared according to the method for embodiment 1, and each performance of polyimides is tested using it as sample,
As a result as follows:
5% thermal weight loss temperature (T5%): 396 DEG C；
Glass transition temperature (Tg): 271 DEG C；
Light transmittance (T at 400nm wavelength400): 88.3%；
Volume resistivity: 2.1 × 1015Ω·cm；
The structural formula of polyimides is as follows:
Liquid crystal cell is assembled according to the method for embodiment 1, and the pre-tilt angle of gained liquid crystal cell is 2.66 °, VHR=97.13%.
The partial properties of above-described embodiment and the polyimides of comparative example are summarized, as shown in table 1 below:
The performance of table 1, Kapton
1 data of table are compared as can be seen that the obtained polyimides of the embodiment of the present invention has high VHR, high
Resistivity and high light transmittance characteristics are above the containing containing ether type and comparative example 3 containing amine type, comparative example 2 of comparative example 1
Double bond type polyimides.In addition, soluble polyimide film of the present invention has suitable glass transition temperature (Tg: 198-
267 DEG C), therefore higher amination rate is maintained under TFT-LCD preparation process temperature (230 DEG C), be conducive to liquid crystal molecule
The stability of orientation.And the Kapton T prepared in comparative exampleg270 DEG C are above, therefore in TFT-LCD preparation process
Higher amination rate can not be obtained at temperature (230 DEG C), is unfavorable for the stability of subsequent liquid crystal molecular orientation.Finally, being based on
The PI film of H-DOCDA dianhydride monomer all has suitable pre-tilt angle, can be applied to the IPS-LCD and FFS-LCD of wide viewing angle
In equal devices.
Claims (10)
1. a kind of polyimides, it is characterized in that: being the single substance with structural formula shown in following formula I, or for following formula I
Shown in structural formula single substance mixture:
In formula I above, R1=-CaH2a+1, a is the integer of 0-10；R3=-CbH2b+1, b is the integer of 0-10；R4=-CdH2d+1, d is
The integer of 0-10；
R2For any one in following radicals, R5=-CeH2e+1, e is the integer of 0-10:
。
2. polyimides according to claim 1, it is characterized in that: n is the integer of 1-100 in Formulas I, it is preferred that n is
The integer of 30-60；R1 is preferably H, methyl or ethyl；R2 is preferably、Or；R3 is preferably H, methyl or ethyl；R4 is H, methyl or ethyl.
3. a kind of preparation method of polyimides described in claim 1, it is characterized in that the following steps are included: by aromatic diamine
Compound and alicyclic dianhydride compound carry out polymerization reaction in polar aprotic solvent, obtain polyamic acid solution, to
Acetic anhydride is added in polyamic acid solution and pyridine carries out chemical imidization reaction, obtains polyimides；The aromatic series two
The structural formula of amine compounds are as follows:, the knot of the alicyclic dianhydride compound
Structure formula are as follows:, the same Formulas I of the definition of R1, R2, R3, R4.
4. preparation method according to claim 3, it is characterized in that: the alicyclic dianhydride compound is selected from 5- (2,5- bis-
Oxo-tetrahydrofuran base) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride, 5- methyl-(2,5- dioxotetrahydrofuryl) -3-
Methyl -3- cyclohexyl -1,2- dicarboxylic anhydride or cyclohexyl -1 5- ethyl-(2,5- dioxotetrahydrofuryl) -3- methyl -3-,
2- dicarboxylic anhydride, preferably 5- (2,5- dioxotetrahydrofuryl) -3- methyl -3- cyclohexyl -1,2- dicarboxylic anhydride；The virtue
Fragrant race's diamine compound be selected from 4,4'- diaminodiphenylmethane, 3,3', 5,5'- tetramethyl -4,4'- diaminodiphenylmethane, 3,
3', 5,5'- tetraethyl -4,4'- diaminodiphenylmethane, 3,3'- dimethyl -5,5'- diethyl -4,4'- diamino hexichol first
Bis- (4- amino -3,5- 3,5-dimethylphenyl) methane of alkane, 1,1-, bis- [2- (4- the aminophenyl) -2- propyl] benzene of 1,4- and 1,3- are bis-
At least one of [2- (4- aminophenyl) -2- propyl] benzene, preferably 4,4'- diaminodiphenylmethane.
5. preparation method according to claim 3 or 4, it is characterized in that: alicyclic dianhydride compound and aromatic diamine
The molar ratio for closing object is 1.00:0.95 ~ 1.00, preferably 1.00:0.99 ~ 1.00；Alicyclic dianhydride compound and acetic anhydride
Molar ratio is 1.00:2.00 ~ 10.00, preferably 1.00:3.00-5.00；The molar ratio of alicyclic dianhydride compound and pyridine
For 1.00:2.00 ~ 8.00, preferably 1.00:3.00-4.00.
6. preparation method according to claim 3 or 4, it is characterized in that: the polar aprotic solvent is selected fromNMethyl
Pyrrolidones, metacresol,N,NDimethylformamide,N,NIn dimethyl acetamide, dimethyl sulfoxide and gamma-butyrolacton extremely
Few one kind；The dosage of polar aprotic solvent makes the total content of aromatic diamine compound and alicyclic dianhydride compound
10-30wt%, preferably 15 ~ 25wt%.
7. preparation method according to claim 3, it is characterized in that: aromatic diamine compound and alicyclic dianhydride compound
Carry out polymerization reaction temperature be 0-35 DEG C (preferably 15-25 DEG C), the time be 10 ~ 30 hours (preferably 20 ~ 25 hours, more
Preferably 24 hours)；When carrying out chemical imidization reaction, reaction temperature is 0-35 DEG C (preferably 15-25 DEG C), the reaction time
It is 10 ~ 30 hours (preferably 20 ~ 25 hours, more preferably 24 hours).
8. application of the polyimides of any of claims 1 or 2 in liquid crystal display device, it is characterized in that: polyimides conduct
The aligning agent for liquid crystal of liquid crystal display device or the effective component of liquid crystal orientation film；The liquid crystal display device is in-plane switching
LCD or fringe field switching type LCD.
9. a kind of aligning agent for liquid crystal or liquid crystal orientation film, it is characterized in that: ingredient includes polyimides of any of claims 1 or 2；
Preferably, the liquid crystal orientation film is formed by the way that aligning agent for liquid crystal to be applied on substrate.
10. a kind of liquid crystal display device, it is characterized in that: including liquid crystal orientation film as claimed in claim 9.
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| CN111978540A (en) * | 2020-09-01 | 2020-11-24 | 中国科学技术大学 | Copolymer for high-temperature dielectric energy storage, nanocomposite and preparation method thereof |
| CN114058384A (en) * | 2021-11-26 | 2022-02-18 | 深圳市道尔顿电子材料有限公司 | Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box |
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| CN101452154A (en) * | 2007-12-07 | 2009-06-10 | 第一毛织株式会社 | Liquid crystal photo-alignment agent and liquid crystal photo-alignment film and liquid crystal display |
| CN101747906A (en) * | 2008-12-02 | 2010-06-23 | 第一毛织株式会社 | Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display including same |
| CN105778929A (en) * | 2016-04-27 | 2016-07-20 | 深圳市道尔顿电子材料有限公司 | Liquid crystal orientation agent, diamine compound and polyamide acid |
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| CN101452154A (en) * | 2007-12-07 | 2009-06-10 | 第一毛织株式会社 | Liquid crystal photo-alignment agent and liquid crystal photo-alignment film and liquid crystal display |
| CN101747906A (en) * | 2008-12-02 | 2010-06-23 | 第一毛织株式会社 | Liquid crystal alignment agent, and liquid crystal alignment film and liquid crystal display including same |
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| CN114058384A (en) * | 2021-11-26 | 2022-02-18 | 深圳市道尔顿电子材料有限公司 | Polyimide photo-alignment agent solution and preparation method thereof, photo-alignment film and liquid crystal box |
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