CN110372899A - A kind of colorless and transparent heat-proof polyimide film of high hydrophobicity and preparation method thereof - Google Patents
A kind of colorless and transparent heat-proof polyimide film of high hydrophobicity and preparation method thereof Download PDFInfo
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- 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
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- 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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Abstract
The invention discloses colorless and transparent heat-proof polyimide films of a kind of high hydrophobicity and preparation method thereof.First with two kinds of diamine monomers of a certain proportion of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer, with include 4, dianhydride monomer including 4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids carries out polymerisation in solution, generate polyamic acid copolymer, casting film-forming on a glass, high temperature goes solvent, and imidization, and the colorless and transparent heat-proof polyimide film of high hydrophobicity can be obtained.The method of the present invention is easy to operate, application easy to promote large-scale, and Kapton obtained is not only colorless and transparent, also has excellent heat resistance and hydrophobicity, can be preferably applied in flexible display device.
Description
Technical field
The present invention relates to a kind of polyimide material and preparation method thereof, in particular to a kind of high hydrophobicity transparency and heat-proof is poly-
Acid imide material and preparation method, belong to technical field of polymer materials.
Background technique
In recent years, flexible electronic and flexible display technologies are grown rapidly in electronic information field, develop with lightweight, can
Bending, foldable or even rollable characteristic flexible electronic product have become the target of Flexible Displays industry competitively effort.It is soft
Property substrate is the important component of entire flexible display device, and performance has the quality of flexible display device with the service life
There is important influence.And polyimides is due to its heat resistance outstanding, chemical stability, excellent mechanical performance and good
The features such as dielectric properties, becomes the preferred material of flexible display device substrate.
But because containing imide ring in polyimide structures, and in strand often containing ether, oxygen, sulfide linkage, carbonyl etc.
Hydrophilic functional group causes the water imbibition of PI material and wetability larger, has seriously affected the insulation performance and dielectric of material
Performance limits its application in Flexible Displays industry.
Display medium in flexible display device, when being exposed in water vapour environment, performance meeting rapid degradation, therefore it is flexible
Substrate will have hydrophobicity as high as possible.And common colorless and transparent PI water absorption rate is 2.0% or so, therefore, PI substrate is in reality
It must apply on its surface in the application process of border and block water oxidation prevention layer, and the step of addition for the oxidation prevention layer that blocks water not only increases technique
And processing cost, the practical application that also will affect flexible display device.In simple terms, the degree of the water suction of polyimides determines
Polymer property and its application in the work environment.Therefore to meet the application requirement of flexible base board, prepare high hydrophobicity without
Color transparency and heat-proof polyimide material is imperative.
Method currently used for polyimides hydrophobically modified mainly has introducing flexible structure polymerization hydrophobic, thin containing fluorine structure
Water, containing silicon structure is hydrophobic, overlay coating modified hydrophobic and a variety of methods and with hydrophobic.
If Chinese patent application 201611168382.4 is by dispersed preferable oxygen fluorinated graphene doped polyimide material
Material, has been made a kind of hydrophobic oxygen fluorinated graphene compound polyimide powdery paints.This powdery paints has hydrophobic well
Property, leakage resistance is strong, and surface strength is high, and good toughness, comprehensive performance is superior, but color is not suitable for colourless transparent material more deeply
Preparation.Chinese patent application 201711413756.9 introduces fluoro-containing group and pyrrole by MOLECULE DESIGN in the main chain of polyimides
Phenazine ring, the dissolubility resistent for improving polymer can and maintain its mechanical performance, thermal stability, and it is sub- that the fluorine-containing polyamides of novel hot setting is made
Amine polymer, glass transition temperature are 346 DEG C, T5%Thermal weight loss temperature is 575 DEG C, T10%Thermal weight loss temperature is 602 DEG C, is connect
Feeler is lower than 95 °, although excellent heat resistance, hydrophobic performance is excellent not enough.Chinese patent application 201710574815.4 is logical
It crosses fluorine-containing dianhydride 6FDA and fluorinated diamine TFDB and has synthesized a kind of high transparency and low dielectric Kapton, maximum transmission degree is super
91% is crossed, dielectric constant is less than 3, and tensile strength is higher than 150MPa, and contact angle is between 72 ~ 74 °, although realizing high transparency
And low-dielectric, but hydrophobic performance need to be improved.
Require polyimides imines material that there is better transparency, higher heat resistance and dredge in field of flexible display
Aqueous, clear polyimides currently on the market are difficult to have both these features.
Summary of the invention
The purpose of the present invention is to provide a kind of high hydrophobicity transparency and heat-proof Kaptons and preparation method thereof.
Realize that the technical solution of the object of the invention is as follows:
A kind of colorless and transparent heat-proof polyimide film of high hydrophobicity and preparation method thereof, by 2- (4- aminophenyl) -5- amino
The diamine monomer of benzimidazole and X monomer composition, and include the dianhydride monomer hair including 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids
Raw polycondensation reaction obtains polyamic acid copolymer solution, after which to be coated on to the glass plate of clean dried, goes molten
Agent and imidization, wherein X monomer structure is as follows:
。
Further, the polycondensation reaction carries out in the presence of an organic, and the organic solvent is selected from N, N- bis-
One of methylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, acetone, butanone, N-Methyl pyrrolidone are several
Kind.
Further, polycondensation reaction temperature is 0 ~ 20 DEG C, and polycondensation reaction time is 3 ~ 24 hours.
Further, the total moles of diamine monomer and dianhydride monomer are than control in 1.07:1 ~ 1:1.07, more preferable 1:1.01
~1:1.03。
Further, the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer is 3:7 ~ 7:3.
Further, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids account for 50% or more of dianhydride monomer moles total number.
Further, the dianhydride monomer further includes pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, 2,
One or more of 3 ', 3,4 '-biphenyltetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride.
Further, dissolving agent process is gone to complete under 60 DEG C ~ 150 DEG C of temperature programming in 1 ~ 5 hour.
Further, imidization is completed under 150 DEG C ~ 400 DEG C of temperature programming in 1 ~ 5 hour.
Further, before coating, the solid content of polyamic acid copolymer solution is adjusted to 10 ~ 25%.
Compared with prior art, advantages of the present invention is as follows:
The present invention is with 2- (4- aminophenyl) -5- aminobenzimidazole, X monomer and 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids
Raw material includes a large amount of fluorine atom and hexafluoro isopropyl structure in polyimide molecule obtained, has film obtained excellent
Different colorless and transparent property, ultraviolet permeability (500nm) are greater than 90%;Simultaneously as the presence of benzimidazole structure, so that thin
Film has high hydrophobicity, and for water absorption rate less than 0.1%, contact angle is greater than 110 °;And the rigidity of structure enables its glass transition temperature
It is maintained at 350 DEG C or more, it is heat-resist.
Specific embodiment
Detailed description are as follows for the embodiment of the present invention, and the present invention is not limited to scope of embodiments.
The preparation method of the colorless and transparent heat-proof polyimide film of high hydrophobicity, the specific steps are as follows:
Step 1, by 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer, (letter moistens the limited public affairs of peaceful new material science and technology in Nanjing
Department, trade name: fluorinated monomer ZHJH-07) composition diamine monomer add band flow back and inflated with nitrogen mechanically stirred reactor
In, it being dissolved in organic solvent, constant temperature stirs at 25 ~ 60 DEG C, after diamine monomer is completely dissolved, reaction temperature is down to 0 ~
It 20 DEG C, is then added portionwise comprising the dianhydride monomer including 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, it is completely molten to dianhydride monomer
After solution, polycondensation reaction 3 ~ 24 hours under constant temperature obtain polyamic acid copolymer solution.
Step 2, the solid content of the polyamic acid copolymer solution is adjusted to 10 with the organic solvent that uses when polycondensation ~
25%, then solution is coated on the glass plate of clean dried, membrane glass plate is dry in 60 DEG C ~ 150 DEG C, then
150 DEG C ~ 400 DEG C imidizations arrive the colorless and transparent heat-proof polyimide film of high hydrophobicity after cooling demoulding.
Embodiment 1:
In the mechanically stirred reactor with reflux and inflated with nitrogen, by 2- (4- aminophenyl) -5- amino benzo miaow of 0.05mol
The X monomer of azoles and 0.05mol are dissolved in n,N-dimethylacetamide, and constant temperature stirs at 30 DEG C, after monomer is completely dissolved,
Reaction temperature is down to 10 DEG C, then by the equal benzene of 4, the 4'- of 0.051mol (hexafluoro isopropyl alkene) two anhydride phthalic acids and 0.051mol
5 additions of tetracarboxylic acid dianhydride point, every minor tick 1 hour.Isothermal reaction 10 hours, obtain polyamic acid after dianhydride monomer adds
Copolymer solution.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer is 5:5;(hexafluoro is different by 4,4'-
Propylene) the two total dianhydride monomers of anhydride phthalic acid Zhan molar ratio 50%;The total moles of diamine monomer and dianhydride monomer ratio is 1:1.02.
The solid content of the polyamic acid copolymer solution is adjusted to 15% with n,N-dimethylacetamide, is coated in clean dry
On dry glass plate, thickness control is at 25 μm, by the plate after film 90 DEG C in vacuum drying oven, 120 DEG C, 150 DEG C of each dryings 1
Hour, it is then heat-treated in Muffle furnace according to following temperature program: 180 DEG C, 210 DEG C, 240 DEG C, 270 DEG C, 300
DEG C, 330 DEG C, 360 DEG C, 390 DEG C each drying 0.5 hour, be cooled to room temperature rear demoulding, it is poly- that high hydrophobicity transparency and heat-proof can be obtained
Imide membrane.
Gained film is colorless and transparent, and the uv transmittance at 500nm is 90.93%, water absorption rate 4.7 × 10-4;Contact
Angle is 111.31 °, 355.0 DEG C of glass transition temperature (test of DSC method).
Embodiment 2:
The specific steps are the same as those in embodiment 1 for embodiment 2, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.07mol, and the dosage of X monomer is 0.03mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol,
The dosage of pyromellitic dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
For 7:3;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer
Total moles ratio is 1:1.02.
Uv transmittance of the gained film at 500nm is 90.07%, water absorption rate 5.2 × 10-4;Contact angle is
110.09 °, 358.2 DEG C of glass transition temperature (test of DSC method).
Embodiment 3:
The specific steps are the same as those in embodiment 1 for embodiment 3, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.03mol, and the dosage of X monomer is 0.07mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol,
The dosage of pyromellitic dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
For 3:7;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer
Total moles ratio is 1:1.02.
Uv transmittance of the gained film at 500nm is 91.27%, water absorption rate 4.5 × 10-4;Contact angle is
111.78 °, 351.3 DEG C of glass transition temperature (test of DSC method).
Embodiment 4:
In the mechanically stirred reactor with reflux and inflated with nitrogen, by 2- (4- aminophenyl) -5- amino benzo miaow of 0.05mol
The X monomer of azoles and 0.05mol are dissolved in n,N-Dimethylformamide, and constant temperature stirs at 25 DEG C, after monomer is completely dissolved,
Reaction temperature is down to 6 DEG C, then by the 3,3 ', 4 of 4, the 4'- of 0.06mol (hexafluoro isopropyl alkene) two anhydride phthalic acids and 0.04mol,
4 '-biphenyltetracarboxylic dianhydride point, 6 additions, every minor tick 1 hour.Isothermal reaction 24 hours, are gathered after dianhydride monomer adds
Amic acid copolymer solution.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer is 5:5;4,4'-
The 60% of the molar ratio of (hexafluoro isopropyl alkene) two total dianhydride monomer of anhydride phthalic acid Zhan;The total moles of diamine monomer and dianhydride monomer ratio is
1:1。
The solid content of the polyamic acid copolymer solution is adjusted to 20% with n,N-Dimethylformamide, is coated in clean dry
On dry glass plate, thickness control is at 25 μm, by the plate after film 80 DEG C in vacuum drying oven, 100 DEG C, 120 DEG C of each dryings 1
Hour, it is then heat-treated in Muffle furnace according to following temperature program: 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350
DEG C, 400 DEG C each drying 0.5 hour, be cooled to room temperature rear demoulding, high hydrophobicity transparency and heat-proof Kapton can be obtained.
Gained film is colorless and transparent, and the uv transmittance at 500nm is 91.55%, water absorption rate 4.5 × 10-4;Contact
Angle is 111.92 °, 352.2 DEG C of glass transition temperature (test of DSC method).
Embodiment 5:
5 specific steps of embodiment are with embodiment 4, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.05mol, and the dosage of X monomer is 0.05mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.1mol, 3,
The dosage of 3 ', 4,4 '-biphenyltetracarboxylic dianhydride is 0mol.That is: 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer rub
You are than being 5:5;The 100% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride
The total moles ratio of monomer is 1:1.
Uv transmittance of the gained film at 500nm is 92.01%, water absorption rate 4.1 × 10-4;Contact angle is
112.11 °, 350.7 DEG C of glass transition temperature (test of DSC method).
Comparative example 1:
The specific steps are the same as those in embodiment 1 for comparative example 1, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.08mol, and the dosage of X monomer is 0.02mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol,
The dosage of pyromellitic dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
For 8:2;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer
Total moles ratio is 1:1.02.
Uv transmittance of the gained film at 500nm is 88.63%, water absorption rate 5.2 × 10-4;Contact angle is
109.13 °, 360.1 DEG C of glass transition temperature (test of DSC method).
Comparative example 2:
The specific steps are the same as those in embodiment 1 for comparative example 2, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.02mol, and the dosage of X monomer is 0.08mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol,
The dosage of pyromellitic dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
For 2:8;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer
Total moles ratio is 1:1.02.
Uv transmittance of the gained film at 500nm is 91.31%, water absorption rate 4.3 × 10-4;Contact angle is
111.79 °, 337.3 DEG C of glass transition temperature (test of DSC method).
Comparative example 3:
The specific steps are the same as those in embodiment 1 for comparative example 3, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.1mol, and the dosage of X monomer is 0mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol, equal benzene four
The dosage of formic acid dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer is 10:
0;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer always rub
You are than being 1:1.02.
Uv transmittance of the gained film at 500nm is 87.35%, water absorption rate 6.2 × 10-4;Contact angle is
107.99 °, 361.3 DEG C of glass transition temperature (test of DSC method).
Comparative example 4:
The specific steps are the same as those in embodiment 1 for comparative example 4, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0mol, and the dosage of X monomer is 0.1mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.051mol, equal benzene four
The dosage of formic acid dianhydride is 0.051mol.That is: the molar ratio of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer is 0:
10;The 50% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride monomer it is total
Molar ratio is 1:1.02.
Uv transmittance of the gained film at 500nm is 91.54%, water absorption rate 4.9 × 10-4;Contact angle is
114.18 °, 320.9 DEG C of glass transition temperature (test of DSC method).
Comparative example 5:
5 specific steps of comparative example are with embodiment 4, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.05mol, and the dosage of X monomer is 0.05mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0.04mol, 3,
The dosage of 3 ', 4,4 '-biphenyltetracarboxylic dianhydride is 0.06mol.That is: 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
Molar ratio is 5:5;The 40% of the molar ratio of the two total dianhydride monomer of anhydride phthalic acid Zhan of 4,4'- (hexafluoro isopropyl alkene);Diamine monomer and dianhydride
The total moles ratio of monomer is 1:1.
Uv transmittance of the gained film at 500nm is 87.72%, water absorption rate 5.6 × 10-4;Contact angle is
111.32 °, 353.6 DEG C of glass transition temperature (test of DSC method).
Comparative example 6:
6 specific steps of comparative example are with embodiment 4, the difference lies in that the use of 2- used (4- aminophenyl) -5- aminobenzimidazole
Amount is 0.05mol, and the dosage of X monomer is 0.05mol, and the dosage of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids is 0mol, 3,3 ',
The dosage of 4,4 '-biphenyltetracarboxylic dianhydride is 0.1mol.That is: mole of 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
Than for 5:5;The 0% of the molar ratio of 4,4'- (hexafluoro isopropyl alkene) the two total dianhydride monomers of anhydride phthalic acid Zhan, i.e., only with 3,3 ', 4,4 '-connection
Acid dianhydride;The total moles of diamine monomer and dianhydride monomer ratio is 1:1.
Uv transmittance of the gained film at 500nm is 79.31%, water absorption rate 5.9 × 10-4;Contact angle is
110.41 °, 355.1 DEG C of glass transition temperature (test of DSC method).
Claims (10)
1. a kind of preparation method of the colorless and transparent heat-proof polyimide film of high hydrophobicity, which is characterized in that by 2- (4- aminobenzene
Base) -5- aminobenzimidazole and X monomer composition diamine monomer, and comprising 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids including
Dianhydride monomer occurs polycondensation reaction and obtains polyamic acid copolymer solution, which is coated on to the glass of clean dried
After plate, solvent and imidization are gone, wherein X monomer structure is as follows:
。
2. the method as described in claim 1, which is characterized in that the polycondensation reaction carries out in the presence of an organic.
3. method according to claim 2, which is characterized in that the organic solvent is selected from n,N-Dimethylformamide, N,
One or more of N- dimethyl acetamide, dimethyl sulfoxide, acetone, butanone, N-Methyl pyrrolidone.
4. the method as described in claim 1, which is characterized in that polycondensation reaction temperature be 0 ~ 20 DEG C, polycondensation reaction time be 3 ~
24 hours.
5. the method as described in claim 1, which is characterized in that the total moles of diamine monomer and dianhydride monomer exist than control
1.07:1 ~ 1:1.07, more preferable 1:1.01 ~ 1:1.03.
6. the method as described in claim 1, which is characterized in that 2- (4- aminophenyl) -5- aminobenzimidazole and X monomer
Molar ratio is 3:7 ~ 7:3.
7. the method as described in claim 1, which is characterized in that 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids account for dianhydride monomer and rub
50% or more of that total amount.
8. method as claimed in claim 1 or 7, which is characterized in that the dianhydride monomer further include pyromellitic acid anhydride,
One or more of 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydride, 2,3 ', 3,4 '-biphenyltetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride.
9. the method as described in claim 1, which is characterized in that before coating, by the solid content tune of polyamic acid copolymer solution
It saves to 10 ~ 25%.
10. the colorless and transparent heat-proof polyimide film of high hydrophobicity prepared by the method as described in claim 1-9 is any.
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CN111647270A (en) * | 2020-05-29 | 2020-09-11 | 浙江中科玖源新材料有限公司 | Insulating polyimide film and preparation method thereof |
CN112430323A (en) * | 2020-11-26 | 2021-03-02 | 深圳瑞华泰薄膜科技股份有限公司 | Transparent polyimide film with excellent performance and preparation method thereof |
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CN105461923A (en) * | 2015-12-25 | 2016-04-06 | 南京理工大学 | Polyimide film and preparation method thereof |
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CN105461923A (en) * | 2015-12-25 | 2016-04-06 | 南京理工大学 | Polyimide film and preparation method thereof |
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CN111647270A (en) * | 2020-05-29 | 2020-09-11 | 浙江中科玖源新材料有限公司 | Insulating polyimide film and preparation method thereof |
CN112430323A (en) * | 2020-11-26 | 2021-03-02 | 深圳瑞华泰薄膜科技股份有限公司 | Transparent polyimide film with excellent performance and preparation method thereof |
CN112430323B (en) * | 2020-11-26 | 2021-05-11 | 深圳瑞华泰薄膜科技股份有限公司 | Transparent polyimide film with excellent performance and preparation method thereof |
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