CN109422876A - Solution, Kapton and its application of polyamic acid - Google Patents
Solution, Kapton and its application of polyamic acid Download PDFInfo
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- CN109422876A CN109422876A CN201810262578.2A CN201810262578A CN109422876A CN 109422876 A CN109422876 A CN 109422876A CN 201810262578 A CN201810262578 A CN 201810262578A CN 109422876 A CN109422876 A CN 109422876A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses the solution of the polyamic acid as heat-proof polyimide presoma, and the Kapton and display base plate that are produced from it.The polyamic acid polymerize to obtain via polymerized monomer；The viscosity of the solution of the polyamic acid is 3000-15000 centipoise, and solid content is 10%-30% weight percent.The solution of the polyamic acid has lower viscosity and higher solid content, film forming easy to process, and its institute is through film, it is dry, Kapton obtained has good heat resistance after high-temperature heat treatment, mechanical performance and dimensional stability are suitable as the baseplate material of flexible display.
Description
Technical field
The present invention relates to the solution of polyamic acid, more particularly it relates to as heat-proof polyimide presoma
The solution of polyamic acid.
Background technique
Flexible display has light, thin, non-friable feature, and mode of appearance diversification, has unlimited product design can
Energy.Compared with liquid crystal display (LCD), Organic Light Emitting Diode (OLED) display device structure is simple, and it is flexible aobvious to be more suitable for production
Show device.OLED display is about 12.5 hundred million dollars in market scale in 2010, it is contemplated that the year two thousand twenty that ecology location 16,000,000,000 is beautiful
Member.OLED has high-luminous-efficiency, and high contrast, in mobile phone, digital camera, navigator, commercial mark etc. can get wide
General application.To adapt to low energy consumption, quick response, high-resolution requirement is accelerated aobvious to Active Matrix OLED (AMOLED)
Show the development of device, and then promotes it in the application in mobile phone and other fields.These characteristics depend greatly on it
The processing temperature of electronic component.Thin film transistor (TFT) (TFT) array deposition of AMOLED is on underlay substrate, depositing temperature pair
The characteristic electron of TFT influences very big.When glass is substrate material, it can bear high depositing temperature (being greater than 500 DEG C), produce
The raw TFT with good characteristic.But glass itself is thicker heavier, and frangible, these all limit display product design and
Diversity.Mobile phone manufacturer is to light-weight, and size is thin, and non-friable display has very high cry.Polymer substrate
Baseplate material makes it possible flexible display.
For high molecular material since specific gravity is small, flexibility is good, non-friable, can be easily made film, most holds promise as ideal
Baseplate material, in flexible electronic device production.Flexible base board material compared with the glass substrate of rigidity, in electronic device
Apparent advantage that there are many material, for example, it is frivolous, it is not easy to fall damage etc..
Usable polymers solution is cast into thin polymer film on the glass substrate on site.In this polymer film/glass base
After all functional layers are made on plate, glass substrate is peeled off, the Flexible Displays using thin polymer film as substrate are obtained
Device.Polymer film thickness in the process is generally 10 to 50 microns, must endure as the very high temperature in TFT production
Degree, so the thermal stability of thin polymer film is extremely crucial to the production of flexible OLED.Before being separated with glass substrate, polymerization
Object film must keep good dimensional stability and have good be bonded with glass.
For top light emitting OLED device, the light transmission of flexible polymer substrate material is not wanted in visible-range
It asks, but allows for bearing the rigor condition in device fabrication processes.Some key requests include: 1) polymer solution in glass
There is good levelability on glass substrate, the film of formation is good with substrate bonding, surfacing；2) there is high Heat-resistant stable
Property, since the small molecule that thermal decomposition generates causes the pollution to device, product yield is influenced to avoid in high temperature working processes；
3) good mechanical performance, such as very high tensile strength and higher elongation at break, keep the device of manufacture thinner, more softly；
4) there is good dimensional stability, and there is thermal expansion coefficient (CTE) similar with glass substrate or semiconductor material, to prevent
Only leads to the bending of substrate since thermal expansion coefficient mismatches, falls off and interfacial stress.
Aromatic polyimide is famous with its excellent thermal mechanical performance, it is considered to be the substrate material of production flexibility OLED
The best candidate material of material.In classical preparation process, aromatic dianhydride and aromatic diamines are anti-in an aprotic dipolar solvents
It answers, forms soluble presoma polyamic acid, pour film with it, then the production of Kapton is completed in high temperature imidization.
In a variety of polyimides kinds, with biphenyl dianhydride BPDA, equal benzene dianhydride PMDA and p-phenylenediamine pPDA are raw material
Polymer have excellent mechanical property and extremely low CTE.These performances should and linear macromolecule structure firm with its it is related.
Its full aromatic structure also makes it have higher thermal decomposition temperature.
Polyamic acid based on BPDA/PMDA/pPDA typically exhibits very big solution viscosity, this gives its film manufacturing process
Bring difficulty.Usual production line is difficult to film system of the processing solution viscosity greater than the Polymer Solution of the viscosity of 15000 centipoises
Make.Though existing method can be such that solution viscosity is controlled by reducing molecular weight, it is generally understood that, low molecular weight will be led
The reduced performance of film product is caused, especially to mechanical performance, thermal stability, thermal expansion coefficient has larger impact, it is difficult to reach
High-mechanical property, thermal stability, the rigors of low thermal coefficient of expansion；In addition, high molecular weight BPDA/PMDA/pPDA's is poly-
The solution of amic acid can reduce solution viscosity by way of reducing solid content, but this will lead to removed in film-forming process it is molten
Dosage is substantially increased, and film forming efficiency declines, and further results in film forming cost increase, the increase of pollution and energy consumption.Therefore, one
Kind has high solids content and low viscosity, and it corresponds to film mechanical performance, thermal stability, the excellent polyamides of thermal expansion coefficient
The solution of amino acid is that market lacks and craving.
Exceed ours it is anticipated that discovery is using the polyimides based on BPDA/PMDA/pPDA, Ke Yitong under study for action
One or more of modes are crossed to control the preparation of polymer, the solution of the polyamic acid of low viscosity while high solids content is made.Base
In the solution of the polyamic acid of the low apparent viscosity of this high concentration, it can still obtain that there are good mechanical properties and very low thermal expansion system
The Kapton of number (CTE).Meanwhile Kapton still has good heat resistance, shows high heat point
Solve temperature.
Summary of the invention
First aspect present invention is related to a kind of solution of polyamic acid as heat-proof polyimide presoma, via poly-
It closes monomer polymerization to obtain, the polymerized monomer includes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,2,4,5- equal benzene four
Formic acid dianhydride (PMDA), p-phenylenediamine (pPDA), and at least one third dianhydride and/or the second diamines；The polyamic acid
Solution viscosity be 3000-15000 centipoise, solid content be 10%-30% weight percent.
In some embodiments of the present invention, the third dianhydride is selected from by 3,3 ', 4,4 '-diphenyl ether dianhydrides
(ODPA), 4,4 '-(hexafluoroisopropylidenyl) double phthalic anhydrides (6FDA), 3,3 ', 4,4 '-diphenylsulfone acid's dianhydrides
(DSDA), the double phthalic anhydrides (BisADA) of 4,4 '-(4,4 '-isopropylidene, two phenoxy groups), 3,3 ', 4,4 '-benzophenone four
The group of acid dianhydride (BTDA) and combinations thereof composition.
In some embodiments of the present invention, second diamines is selected from by m-phenylene diamine (MPD) (mPDA), 4,4 '-diamino
Diphenyl ether (ODA), 3,4 '-diaminodiphenyl ethers (3,4 '-ODA), 4,4 '-diaminodiphenylsulfones (DDS), 3,3 '-diamino two
Phenylate (3,3 '-DDS), 2,2 '-dimethyl -4,4 '-benzidines (OTOL), 4,4 '-diaminodiphenylmethane (MDA), 4,
4 '-diaminobenzophenones, 4,4 '-diamino hexichol -2,2- hexafluoropropane, 9,9- be bis--and (4- aminophenyl) fluorenes, 9,9- be bis- -
(fluoro- 4 aminophenyl of 3-) fluorenes, 2,2 '-two (trifluoromethyl) -4,4 '-benzidines (PFMB), double-(2- trifluoromethyl -4-
Amino-benzene oxygen) biphenyl and combinations thereof composition group.
In some embodiments of the present invention, the molal quantity of the third dianhydride accounts for the percentage of dianhydride monomer total mole number
Than being not more than 20%.
In some embodiments of the present invention, the molal quantity of second diamines accounts for the percentage of diamine monomer total mole number
Than being not more than 20%.
The second aspect of the present invention is related to a kind of solution of polyamic acid as heat-proof polyimide presoma, described poly-
Amic acid polymerize to obtain via polymerized monomer, the polymerized monomer include 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,
2,4,5- pyromellitic acid anhydrides (PMDA), p-phenylenediamine (pPDA), and at least one aromatic anhydride or at least one fragrance
Amine, the viscosity of the solution of the polyamic acid are 3000-15000 centipoise, and solid content is 10%-30% weight percent.
In some embodiments of the present invention, the molal quantity of the aromatic anhydride accounts for the percentage of anhydride monomers total mole number
Than being not more than 10%.
In some embodiments of the present invention, the aromatic anhydride is selected from by phthalic anhydride, 2,3- neighbour's naphthalene diacid
The group of acid anhydride and combinations thereof composition.
In some embodiments of the present invention, the molal quantity of the aromatic amine accounts for the percentage of amine monomers total mole number not
Greater than 20%.
In some embodiments of the present invention, the aromatic amine is selected from and is made of aniline, 2- amino naphthalenes and combinations thereof
Group.
The third aspect of the present invention is related to a kind of solution of polyamic acid as heat-proof polyimide presoma, described poly-
Amic acid polymerize to obtain via polymerized monomer, the polymerized monomer include 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,
2,4,5- pyromellitic acid anhydrides (PMDA) and p-phenylenediamine (pPDA)；The viscosity of the solution of the polyamic acid is 3000-
5000 centipoises, solid content are 10%-30% weight percent, which is characterized in that the solution of the polyamic acid is by described poly-
It closes monomer the solid of the original solution after polymerization reaction or the polyamic acid occurs and be dissolved in solvent solution obtained and heavy
Shallow lake agent is mixed and is obtained.
In some embodiments of the present invention, the precipitating reagent selects Free water, isopropanol, methanol, ethyl alcohol, acetone,
The group of MIBK and combinations thereof composition.
The fourth aspect of the present invention is related to a kind of solution by the polyamic acid through film, dry, after high-temperature heat treatment
Kapton obtained.
The invention further relates to a kind of display base plates prepared by the Kapton.
In some embodiments of the present invention, the molal quantity of BPDA accounts for the 30% to 70% of dianhydride monomer total mole number.
In some embodiments of the present invention, the polymerized monomer occur the original solution after polymerization reaction directly as
The solution of the polyamic acid.
In some embodiments of the present invention, the solution of the polyamic acid is dissolved in by the solid of the polyamic acid
It is made in solvent.
In some embodiments of the present invention, the solvent is selected from by n,N-Dimethylformamide (DMF), N, N- diformazan
Yl acetamide (DMAc), N- methyl arsenic pyrrolidone (NMP), N- ethyl arsenic pyrrolidone (NEP), dimethyl sulfoxide (DMSO), pregnancy
The group of base phosphamide (HMPA) and combinations thereof composition.
In some embodiments of the present invention, there is monofunctional monomer can use such as phthalic anhydride or aniline
Do the end-capping reagent of macromolecular end group.
Statement according to the present invention, the solid content of the solution of polyamic acid according to weight ratio between 10% to 30%, more
Good is between 15% to 20%.
Statement according to the present invention, polymerization temperature is between 0 DEG C to 80 DEG C, preferably between 0 DEG C to 60 DEG C.
Statement according to the present invention, the solution apparent viscosity of polyamic acid is between 3000 to 15000 centipoises.
Statement according to the present invention, thermal decomposition temperature of the Kapton in nitrogen are greater than 500 DEG C, drawing at room temperature
Modulus is stretched greater than 8GPa, and tensile strength is greater than 300MPa, and tension fracture elongation rate is greater than 10%；Thermal expansion coefficient room temperature extremely
It is less than 10ppm/ DEG C between 400 DEG C.
The viscosity of the solution for the polyamic acid polymerizeing via polymerized monomer is 3000-15000 centipoise, and solid content is
10%-30% weight percent.The solution of the polyamic acid has lower viscosity and higher solid content, easy to process
Film forming, and its institute is through film, dry, Kapton obtained has good heat resistance after high-temperature heat treatment, mechanical
Performance and dimensional stability are suitable as the baseplate material of flexible display.The film of the solution preparation of the polyamic acid
Excellent heat resistance and dimensional stability are shown in a wide high temperature range.It is beyond expectation, from BPDA/PMDA/
PPDA polyamic acid sets out, by method of viscosity control described in this patent, even the polyamides based on low viscosity high solids content
The solution of amino acid, gained Kapton still show good thermal mechanical performance.Which provides one kind by large arch dam
The solution preparation for measuring the polyamic acid of low viscosity uses the practical plan of Kapton.This polyamides with excellent characteristics
Imines film can be used as baseplate material, to make flexible OLED devices.
Specific embodiment
Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention
Example, be only used to illustrate the present invention, and be not limited to the present invention.Without departing from the spirit or scope of the invention,
It can carry out other combinations and the various improvement in present inventive concept.
Heat-proof polyimide presoma is the original solution or polyamic acid solution occurred after polymerization reaction by polymerized monomer
It is mixed in a certain proportion and impregnates under stiring with precipitating reagent, precipitating reagent and impurity is removed by filtration, will obtain after drying
The solid of polyamic acid be dissolved in solvent in certain proportion, viscosity and the suitable polyamic acid of solid content can be obtained
Solution, as the presoma for preparing Kapton.
Unless otherwise indicated, the viscosity in the present invention is volume viscosity.
Unless otherwise indicated, the solid content in the present invention refers both to polyamic acid.
The method of Kapton: the solution of polyamic acid is made by polymerized monomer by condensation polymerization first.This
The solution of polyamic acid casting film on a underlay substrate then heats imidization, completes film preparation.By carefully preferred
Monomer used, the glass transition temperature of gained film, the available optimization of the performances such as CTE and thermal decomposition temperature.
Representational dianhydride is exemplified below in the present invention:
Pyromellitic dianhydride (PMDA)；
Biphenyl dianhydride (BPDA)；
Monoether dianhydride (ODPA)；
Hexafluorodianhydride (6FDA) (6FDA)；
Diphenyl sulfone dianhydride (DSDA)；
Two ether dianhydride of bisphenol-A (BisADA)；
Benzophenone dianhydride (BTDA) etc..
Representative aromatic diamines are exemplified below in the present invention:
P-phenylenediamine (PPDA),
M-phenylene diamine (MPD) (MPDA),
4,4 '-diaminodiphenyl ethers (ODA),
3,4 '-diaminodiphenyl ethers (3,4 ' ODA),
4,4'-diaminodiphenyl sulfone (DDS),
3,3 '-diaminodiphenyl ethers (3,3 '-DDS),
2,2 '-dimethyl -4,4 '-benzidines (OTOL)
4,4 '-diaminodiphenylmethane (MDA),
4,4 '-diaminobenzophenones,
4,4 '-diamino hexichol -2,2- hexafluoropropane,
9,9- bis--(4- aminophenyl) fluorenes,
9,9- bis--(fluoro- 4 aminophenyl of 3-) fluorenes,
2,2 '-two (trifluoromethyl) -4,4 '-benzidines (PFMB),
Double-(2- trifluoromethyl-4-aminophenoxyl) biphenyl etc..
In a polymerization process using normal charging sequence, aromatic diamines or monoamine are initially dissolved in solvent, then
Aromatic dianhydride is added or single acid anhydride starting polymerization hair is answered.With the formation of polyamic acid, solution viscosity constantly increases.
It can be used as the end-capping reagent of macromolecular end group such as phthalic anhydride or aniline with monofunctional monomer.
Solution viscosity test: using Brookfield DV-I type viscosimeter in 30 DEG C of measurement solution viscosities.
Filming performance test: sample solution is poured on the glass substrate, and hot-air dries and removes residual solvent, then high
(400-500 DEG C) of temperature heating obtains Kapton.Protrusion is evaluated whether there is by observation, inhomogenous, crackle and powdered
Phenomena such as.The film for not observing defect is evaluated as excellent, it is bad to observe that defective film is evaluated as.
Heat stability testing: film heat stability is measured by thermogravimetric analyzer (TGA) model TA-Q50, sample with 20 DEG C/
Minute rate be heated to 650 DEG C from room temperature in nitrogen atmosphere, 500 DEG C of thermal decomposition temperature the above are excellent, 500 DEG C the following are
It is bad.
Dimensional stability test: film dimensions variation with temperature is surveyed by thermomechanical analyzer (TMA) model TA-Q400
Out.Sample is heated in nitrogen atmosphere from 0 DEG C to 500 DEG C with 10 DEG C/min of rate.In room temperature between 400 DEG C, CTE <
10ppm/ DEG C to be excellent, CTE > 10ppm/ DEG C is bad.
Measuring mechanical property: the mechanical performance of film is measured by 5969 series of INSTRON tensilometer Instron.10 microns
Film sample to 20 micron thickness is stretched in room temperature with 10 millimeters of rates of extension per minute, and initial length is 25.4 millis
Rice.Stretch modulus > 8GPa, tensile strength > 300MPa, elongation > 10% 3 it is qualified be it is excellent, three Xiang Zhongyou mono- are not
Up to standard is bad.
Comparative example 1
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 87.43 grams of NMP,
30.00 mMs of BPDA, 30.00 mMs of PMDA and 60.00 mM of pPDA.It is reacted at room temperature, then in nitrogen
The air-flow lower reaction time 5 hours.Obtained reaction solution apparent viscosity is greater than 400000 centipoises (viscosity measurement way limit), Gu
Content is 20.0%.Since solution viscosity is excessive, it is difficult to form smooth film, not meet the requirement of high-solid-content and low-viscosity.
Smooth film is formed due to being difficult to, is unable to characterize the physical parameter of film.
Comparative example 2
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 72.35 grams of NMP,
24.75 mMs of BPDA, 24.75 mMs of PMDA and 50.00 mM of pPDA.Then under nitrogen flowing, reacted at 60 DEG C
At a temperature of reacted, the reaction time 5 hours.Obtained 80000 centipoise of reaction solution apparent viscosity, solid content are
20.0%.Since solution viscosity is excessive, it is difficult to form smooth film, not meet the requirement of high-solid-content and low-viscosity.Due to difficulty
To form smooth film, it is unable to characterize the physical parameter of film.
Embodiment 1
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 71.76 grams of NMP,
19.80 mMs of BPDA, 29.70 mMs of PMDA, 47.50 mMs of pPDA and 2.50 mM of ODA.Then in nitrogen stream
Under, it is reacted at room temperature, the reaction time 5 hours.
Obtained reaction solution apparent viscosity is 8000 centipoises, solid content 20.0%.Compared to comparative example 1-2, glue
Degree is apparently substantially reduced, and is the solution of the polyamic acid of the low apparent viscosity of high solids content.For this solution, in solid content height
While, viscosity is suitable, is easy to form a film, and the thermal stability for measuring Kapton as made from it is excellent, dimensional stability
To be excellent, mechanical performance is excellent.
Embodiment 2
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 70.94 grams of NMP,
19.80 mMs of BPDA, 29.70 mMs of PMDA, 49.75 mMs of pPDA and 0.25 mM of ODA.Then in nitrogen stream
Under, it is reacted at room temperature, the reaction time 5 hours.
Obtained reaction solution apparent viscosity is 13000 centipoises, solid content 20.0%.Compared to comparative example 1-2, glue
Degree is apparently substantially reduced, and is the solution of the polyamic acid of the low apparent viscosity of high solids content.Solution solid content is high, and viscosity size is closed
It is suitable, be easy to form a film, measure the thermal stability of its corresponding Kapton be it is excellent, dimensional stability be it is excellent, mechanical performance is
It is excellent.
Embodiment 3
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 73.10 grams of NMP,
24.25 mMs of BPDA, 24.25 mMs of PMDA, 50 mMs of pPDA and 3.00 mM of phthalic anhydrides.Then exist
It under nitrogen stream, is reacted at room temperature, the reaction time 5 hours.
Obtained reaction solution apparent viscosity is 7000 centipoises, solid content 20.0%.For this solution, viscosity is closed
It is suitable, be easy to form a film, measure the thermal stability of its corresponding Kapton be it is excellent, dimensional stability be it is excellent, mechanical performance is
It is excellent.
Embodiment 4
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 77.33 grams of NMP,
25.00 mMs of BPDA, 25.00 mMs of PMDA, 48.50 mMs of pPDA and 3.00 mM of aniline.Then in nitrogen
It flows down, is reacted at room temperature, the reaction time 5 hours.
Obtained reaction solution apparent viscosity is 5100 centipoises, solid content 20.0%.For this solution, in Gao Gu
Viscosity is suitable under content, is easy to form a film, measure its corresponding Kapton thermal stability be it is excellent, dimensional stability is
Excellent, mechanical performance is excellent.
Embodiment 5
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 87.43 grams of NMP,
30.00 mMs of BPDA, 30.00 mMs of PMDA and 60.00 mM of pPDA.Then under nitrogen flowing, reacted at 60 DEG C
At a temperature of reacted, the reaction time 2 hours.
Obtained above-mentioned reaction solution is precipitated in water with 1: 10 ratio under high velocity agitation, and is repeatedly soaked with pure water
Bubble, filtering discard water phase and impurity, and final products are impregnated through isopropanol, as far as possible removing impurity.Isopropanol is discarded after filtering simultaneously
It is dry, solid sample is dissolved in NMP, obtaining solid content is 20.0%, and apparent viscosity is the Polymer Solution of 5000 centipoises.
High for this solution solid content, viscosity is suitable, is easy to form a film, and the thermal stability for measuring its corresponding Kapton is
It is excellent, dimensional stability be it is excellent, mechanical performance be it is excellent.
Embodiment 6
Equipped with blender, stirring blade in the flask of nitrogen protection and condensing unit, puts into 73.35 grams of NMP,
25.00 mMs of BPDA, 22.00 mMs of PMDA, 2.50 mMs of ODPA and 50.00 mM of pPDA.Then in nitrogen
It flows down, is reacted under 60 DEG C of reaction temperatures, the reaction time 2 hours.
Obtained reaction solution apparent viscosity is 14000 centipoises, solid content 20.0%.For this solution, in height
Viscosity is suitable under solid content, is easy to form a film, measure its corresponding Kapton thermal stability be it is excellent, dimensional stability is
Excellent, mechanical performance is excellent.
Referring to comparative example 1-2, the solution tool of polyamic acid provided by the present invention can be seen that from above embodiments 1-6
There are lower viscosity and higher solid content, film forming easy to process, and its institute is dried through film, is made after high-temperature heat treatment
Kapton have good heat resistance, mechanical performance and dimensional stability, be suitable as flexible display
Baseplate material.The film of the solution preparation of the polyamic acid shows excellent heat-resisting in a wide high temperature range
Property, dimensional stability and mechanical performance.
The technical concepts and features of embodiment of above only to illustrate the invention, its object is to allow be familiar with technique
People understands the content of present invention and is implemented, and it is not intended to limit the scope of the present invention, and all spirit according to the present invention is real
The equivalent change or modification that matter is done, should be covered by the scope of protection of the present invention.
Claims (26)
1. a kind of solution of the polyamic acid as heat-proof polyimide presoma, the polyamic acid polymerize via polymerized monomer
It obtains, the polymerized monomer includes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,2,4,5- pyromellitic acid anhydride
(PMDA), p-phenylenediamine (pPDA), and at least one third dianhydride and/or the second diamines；The solution of the polyamic acid
Viscosity is 3000-15000 centipoise, and solid content is 10%-30% weight percent.
2. the solution of polyamic acid as described in claim 1, wherein the third dianhydride is selected from by 3,3 ', 4,4 '-diphenyl ether
Dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidenyl) double phthalic anhydrides (6FDA), 3,3 ', 4,4 '-diphenylsulfone acid's dianhydrides
(DSDA), the double phthalic anhydrides (BisADA) of 4,4 '-(4,4 '-isopropylidene, two phenoxy groups), 3,3 ', 4,4 '-benzophenone four
The group of acid dianhydride (BTDA) and combinations thereof composition.
3. the solution of polyamic acid as described in claim 1, wherein second diamines is selected from by m-phenylene diamine (MPD) (mPDA), 4,
4 '-diaminodiphenyl ethers (ODA), 3,4 '-diaminodiphenyl ethers (3,4 '-ODA), 4,4 '-diaminodiphenylsulfones (DDS), 3,3 '-
Diaminodiphenyl ether (3,3 '-DDS), 2,2 '-dimethyl -4,4 '-benzidines (OTOL), 4,4 '-diaminodiphenylmethane
(MDA), 4,4 '-diaminobenzophenones, 4,4 '-diamino hexichol -2,2- hexafluoropropane, 9,9- be bis--(4- aminophenyl) fluorenes,
9,9- bis--(fluoro- 4 aminophenyl of 3-) fluorenes, 2,2 '-two (trifluoromethyl) -4,4 '-benzidines (PFMB), double-(2- trifluoro
Methyl -4- amino-benzene oxygen) biphenyl and combinations thereof composition group.
4. the solution of polyamic acid as claimed in claim 2, wherein the molal quantity of the third dianhydride accounts for dianhydride monomer and always rubs
The percentage of your number is not more than 20%.
5. the solution of polyamic acid as claimed in claim 3, wherein the molal quantity of second diamines accounts for diamine monomer and always rubs
The percentage of your number is not more than 20%.
6. the solution of polyamic acid according to any one of claims 1 to 5, which is characterized in that the molal quantity of BPDA accounts for dianhydride
The 30% to 70% of total moles monomer.
7. the solution of polyamic acid as described in claim 1, which is characterized in that after polymerization reaction occurs for the polymerized monomer
Solution of the original solution directly as the polyamic acid.
8. the solution of polyamic acid as described in claim 1, which is characterized in that the solution of the polyamic acid is by the polyamides
The solid of amino acid is dissolved in solvent and is made.
9. the solution of polyamic acid as claimed in claim 8, which is characterized in that the solvent is selected from by N, N- dimethyl formyl
Amine (DMF), n,N-dimethylacetamide (DMAc), N- methyl arsenic pyrrolidone (NMP), N- ethyl arsenic pyrrolidone (NEP), dimethyl
Sulfoxide (DMSO), the group of hexamethyl phosphoramide (HMPA) and combinations thereof composition.
10. a kind of solution of the polyamic acid as heat-proof polyimide presoma, the polyamic acid is poly- via polymerized monomer
Conjunction obtains, and the polymerized monomer includes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,2,4,5- pyromellitic acid anhydride
(PMDA), p-phenylenediamine (pPDA), and at least one aromatic anhydride or at least one aromatic amine, the solution of the polyamic acid
Viscosity be 3000-15000 centipoise, solid content be 10%-30% weight percent.
11. the solution of polyamic acid as claimed in claim 10, wherein to account for anhydride monomers total for the molal quantity of the aromatic anhydride
The percentage of molal quantity is not more than 10%.
12. the solution of polyamic acid as claimed in claim 11, wherein the aromatic anhydride is selected from by phthalic anhydride, 2,
The group of 3- neighbour's naphthalene dicarboxylic anhydride and combinations thereof composition.
13. the solution of polyamic acid as claimed in claim 10, wherein the molal quantity of the aromatic amine accounts for amine monomers total moles
Several percentage is not more than 20%.
14. the solution of polyamic acid as claimed in claim 13, the aromatic amine is selected from by aniline, 2- amino naphthalenes and combinations thereof
The group of composition.
15. the solution of the polyamic acid as described in any one of claim 10-14, which is characterized in that the molal quantity of BPDA accounts for
The 30% to 70% of anhydride monomers total mole number.
16. the solution of polyamic acid as claimed in claim 10, which is characterized in that after polymerization reaction occurs for the polymerized monomer
Original solution directly as the polyamic acid solution.
17. the solution of polyamic acid as claimed in claim 10, which is characterized in that the solution of the polyamic acid is by described poly-
The solid of amic acid is dissolved in solvent and is made.
18. the solution of polyamic acid as claimed in claim 17, which is characterized in that the solvent is selected from by N, N- dimethyl methyl
Amide (DMF), n,N-dimethylacetamide (DMAc), N- methyl arsenic pyrrolidone (NMP), N- ethyl arsenic pyrrolidone (NEP), diformazan
Base sulfoxide (DMSO), the group of hexamethyl phosphoramide (HMPA) and combinations thereof composition.
19. a kind of solution of the polyamic acid as heat-proof polyimide presoma, the polyamic acid is poly- via polymerized monomer
Conjunction obtains, and the polymerized monomer includes 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydrides (BPDA), 1,2,4,5- pyromellitic acid anhydride
(PMDA) and p-phenylenediamine (pPDA)；The viscosity of the solution of the polyamic acid is 3000-5000 centipoise, and solid content is
10%-30% weight percent, which is characterized in that after by the polymerized monomer polymerization reaction occurs for the solution of the polyamic acid
The original solution solid that obtains polyamic acid through precipitating reagent be dissolved in polyamic acid solution obtained in solvent and obtain.
20. the solution of polyamic acid as claimed in claim 19, wherein the precipitating reagent selects Free water, isopropanol, methanol, second
Alcohol, acetone, the group of MIBK and combinations thereof composition.
21. the solution of polyamic acid as claimed in claim 19, wherein the solvent is selected from by n,N-Dimethylformamide
(DMF), n,N-dimethylacetamide (DMAc), N- methyl arsenic pyrrolidone (NMP), N- ethyl arsenic pyrrolidone (NEP), dimethyl are sub-
Sulfone (DMSO), the group of hexamethyl phosphoramide (HMPA) and combinations thereof composition.
22. a kind of solution by any one of the claim 1-21 polyamic acid is dried through film, it is made after high-temperature heat treatment
Kapton.
23. Kapton as claimed in claim 22, which is characterized in that heat of the Kapton in nitrogen
Decomposition temperature is greater than 500 DEG C.
24. Kapton as claimed in claim 22, which is characterized in that the drawing of the Kapton at room temperature
Modulus is stretched greater than 8GPa, and tensile strength is greater than 300MPa, and tension fracture elongation rate is greater than 10%.
25. Kapton as claimed in claim 22, which is characterized in that the thermal expansion coefficient of the Kapton
In room temperature to being less than 10ppm/ DEG C between 400 DEG C.
26. a kind of display base plate of the preparation of the Kapton as described in any one of claim 22-25.
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| CN201710749230 | 2017-08-28 | ||
| CN2017107492301 | 2017-08-28 |
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| WO2021035907A1 (en) * | 2019-08-26 | 2021-03-04 | 武汉华星光电半导体显示技术有限公司 | Fluorine-group-containing polyimide and preparation method therefor, flexible substrate and display device |
| CN113737213A (en) * | 2021-09-01 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flexible polyimide carbon cloth composite electrode material, product and application thereof |
| CN113831570A (en) * | 2021-10-13 | 2021-12-24 | 无锡顺铉新材料有限公司 | Polyimide composite film for special cable and preparation method thereof |
| CN114752074A (en) * | 2022-05-16 | 2022-07-15 | 北京化工大学常州先进材料研究院 | Blended polyamic acid solution, blended polyimide adhesive, battery pole piece and preparation method thereof |
| CN114805806A (en) * | 2022-05-10 | 2022-07-29 | 上海华谊三爱富新材料有限公司 | Method for reducing viscosity of polyamic acid solution and preparation method of polyimide film |
| CN115505262A (en) * | 2021-06-07 | 2022-12-23 | 达迈科技股份有限公司 | Polymer film and method for producing same |
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| CN113831570A (en) * | 2021-10-13 | 2021-12-24 | 无锡顺铉新材料有限公司 | Polyimide composite film for special cable and preparation method thereof |
| CN114805806A (en) * | 2022-05-10 | 2022-07-29 | 上海华谊三爱富新材料有限公司 | Method for reducing viscosity of polyamic acid solution and preparation method of polyimide film |
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| CN114752074A (en) * | 2022-05-16 | 2022-07-15 | 北京化工大学常州先进材料研究院 | Blended polyamic acid solution, blended polyimide adhesive, battery pole piece and preparation method thereof |
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| CN115975233A (en) * | 2023-02-23 | 2023-04-18 | 上海继尔新材料科技有限公司 | Polyimide-based electromagnetic shielding film with pearl layered structure and preparation method and application thereof |
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