CN111732747B - Polyimide film with good insulating and bonding properties and preparation method thereof - Google Patents
Polyimide film with good insulating and bonding properties 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- 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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- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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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
- 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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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- 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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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
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- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a polyimide film with good insulating and bonding properties, which sequentially comprises the following components: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer film is a polyimide porous film. The invention also discloses a preparation method of the polyimide film with good insulating and bonding properties. The invention has good insulativity and good cohesiveness with the copper foil.
Description
Technical Field
The invention relates to the technical field of polyimide films, in particular to a polyimide film with good insulating and bonding properties and a preparation method thereof.
Background
Polyimide is widely applied to microelectronics and photoelectric industries due to excellent thermal stability, good mechanical properties and electrical properties. The dielectric constant of polyimide is about 3.0 to 4.0, and with the development demand for high integration in the microelectronics industry, polyimide is required to have a lower dielectric constant.
At present, fluorine is often introduced into polyimide to reduce the dielectric constant of the polyimide, but fluorine-containing monomers are high in price and can reduce the adhesion between the polyimide and a copper foil.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a polyimide film with good insulating and bonding properties and a preparation method thereof.
The invention provides a polyimide film with good insulating and bonding properties, which sequentially comprises: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer film is a polyimide porous film.
Preferably, the raw material of the polyimide porous membrane includes: hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane), wherein the molar ratio of hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride and 4,4' -diaminodiphenyl ether is 0.5.
Preferably, the dianhydride monomers of the polyimide flat film are 4,4- (4,4-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4' -biphenyl ether dianhydride.
Preferably, the molar ratio of 4,4- (4,4-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4' -biphenyl ether dianhydride is 0.5 to 0.6.
Preferably, the diamine monomer of the polyimide flat film is aminopropyl terminated polydimethylsiloxane, 4,4' -diaminodiphenyl ether.
Preferably, the molar ratio of aminopropyl terminated polydimethylsiloxane 4,4' -diaminodiphenyl ether is 0.6 to 0.7.
Preferably, the molar ratio of the diamine monomer and the dianhydride monomer of the polyimide flat film is 1.
Preferably, the upper film and the lower film each have a thickness of 15 to 20 μm.
Preferably, the intermediate film has a thickness of 4 to 8 μm.
The invention also provides a preparation method of the polyimide film with good insulating and bonding properties, which comprises the following steps:
s1, reacting a raw material of a polyimide flat membrane in N, N-dimethylacetamide in an inert gas atmosphere to obtain a polyamic acid glue solution 1;
s2, reacting a raw material of a polyimide porous membrane in N, N-dimethylacetamide in an inert gas atmosphere to obtain a polyamic acid glue solution 2, imidizing, and crushing to obtain intermediate powder; uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane to obtain a solution 3; ultrasonically and uniformly mixing the intermediate solution and water to obtain emulsion 4;
and S3, defoaming the polyamic acid glue solution 1, coating the polyamic acid glue solution on the surface of a substrate, imidizing to obtain a lower layer film, coating the emulsion 4 on the surface of the lower layer film, drying to obtain a middle layer film, coating the polyamic acid glue solution 1 on the surface of the middle layer film, and imidizing to obtain an upper layer film to obtain the polyimide film with good insulating and bonding properties.
Preferably, in S2, the weight ratio of the intermediate powder, the hexadecyl trimethyl ammonium bromide and the trichloromethane is 1.
Preferably, in S2, the volume ratio of chloroform to water is 100 to 150.
Has the advantages that:
the invention selects proper proportion of aminopropyl terminated polydimethylsiloxane, 4,4 '-diaminodiphenyl ether, 4,4- (4,4-isopropylidenediphenoxy) bis (phthalic anhydride) and 4,4' -diphenyl ether dianhydride as polymerization monomers, embeds bulky side groups and dimethyl polysiloxane chain segments in polyimide, reduces stacking density of molecular chains, thereby reduces dielectric constants of an upper layer film and a lower layer film, improves insulating property, and can also reduce water absorption of the upper layer film and the lower layer film due to embedding of the dimethyl polysiloxane chain segments, and the adhesion of the upper layer film and the lower layer film with copper foil is good; selecting hexafluoro dianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane) for polymerization and imidization to obtain intermediate powder, namely fluorine-containing polyimide, reducing the content of fluorine element, reducing the cost, improving the adhesiveness of the intermediate powder with an upper layer membrane and a lower layer membrane, then uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane, uniformly mixing the intermediate powder with a small amount of water to form a water-in-oil emulsion, dispersing water in the emulsion in the form of tiny droplets, coating the emulsion on the surface of the lower layer membrane, and drying the trichloromethane and the water to obtain the polyimide membrane with a micropore structure, wherein micropores are matched with the fluorine element and the octa (aminophenyltrioxasilane) to ensure that the middle layer membrane has good insulating property; and finally, coating polyamic acid glue solution 1, imidizing, and tightly connecting the three layers of films, so that the copper foil-clad laminate has good insulativity and is easy to bond with a copper foil.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A polyimide film with good insulating and bonding properties sequentially comprises: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer membrane is a polyimide porous membrane; the thicknesses of the upper layer film and the lower layer film are both 15 mu m, and the thickness of the middle layer film is 4 mu m;
the raw material of the polyimide porous membrane comprises: hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane), wherein the molar ratio of hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride and 4,4' -diaminodiphenyl ether is 0.5;
the dianhydride monomers of the polyimide flat film are 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride), 4,4 '-diphenyl ether dianhydride, 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride) and 4,4' -diphenyl ether dianhydride in a molar ratio of 0.6;
the diamine monomer of the polyimide flat film is aminopropyl terminated polydimethylsiloxane, 4,4 '-diaminodiphenyl ether, and the molar ratio of the aminopropyl terminated polydimethylsiloxane to 4,4' -diaminodiphenyl ether is 0.6;
the molar ratio of diamine monomer and dianhydride monomer of the polyimide flat film is 1:1.
The preparation method of the polyimide film with good insulating and bonding properties comprises the following steps:
s1, in an inert gas atmosphere, taking a raw material of a polyimide flat membrane to react in N, N-dimethylacetamide to obtain a polyamic acid glue solution 1 with the solid content of 15 wt%;
s2, reacting a raw material of a polyimide porous membrane in N, N-dimethylacetamide in an inert gas atmosphere to obtain a polyamic acid glue solution 2, imidizing, and crushing to obtain intermediate powder; uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane to obtain a solution 3; ultrasonically and uniformly mixing the intermediate solution and water to obtain an emulsion 4, wherein the weight ratio of the intermediate powder to the hexadecyl trimethyl ammonium bromide to the trichloromethane is 1;
and S3, defoaming the polyamic acid glue solution 1, coating the polyamic acid glue solution on the surface of a substrate, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain a lower layer film, coating the emulsion 4 on the surface of the lower layer film, drying at 105 ℃ to obtain a middle layer film, coating the polyamic acid glue solution 1 on the surface of the middle layer film, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain an upper layer film, and thus obtaining the polyimide film with good insulating and bonding properties.
Example 2
A polyimide film with good insulating adhesion sequentially comprises: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer membrane is a polyimide porous membrane; the thicknesses of the upper layer film and the lower layer film are both 20 mu m, and the thickness of the middle layer film is 8 mu m;
the raw material of the polyimide porous membrane comprises: hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane), wherein the molar ratio of hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride and 4,4' -diaminodiphenyl ether is 0.5;
the dianhydride monomers of the polyimide flat film are 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride), 4,4 '-diphenyl ether dianhydride, 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride) and 4,4' -diphenyl ether dianhydride in a molar ratio of 0.5;
the diamine monomer of the polyimide flat film is aminopropyl terminated polydimethylsiloxane, 4,4 '-diaminodiphenyl ether, and the molar ratio of the aminopropyl terminated polydimethylsiloxane to 4,4' -diaminodiphenyl ether is 0.7;
the molar ratio of the diamine monomer to the dianhydride monomer of the polyimide flat film is 1.
The preparation method of the polyimide film with good insulating and bonding properties comprises the following steps:
s1, in an inert gas atmosphere, taking a raw material of a polyimide flat membrane to react in N, N-dimethylacetamide to obtain a polyamic acid glue solution 1 with a solid content of 15 wt%;
s2, reacting a raw material of a polyimide porous membrane in N, N-dimethylacetamide in an inert gas atmosphere to obtain a polyamic acid glue solution 2, imidizing, and crushing to obtain intermediate powder; uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane to obtain a solution 3; ultrasonically and uniformly mixing the intermediate solution and water to obtain an emulsion 4, wherein the weight ratio of the intermediate powder to the hexadecyl trimethyl ammonium bromide to the trichloromethane is (1);
and S3, defoaming the polyamic acid glue solution 1, coating the polyamic acid glue solution on the surface of a substrate, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain a lower layer film, coating the emulsion 4 on the surface of the lower layer film, drying at 105 ℃ to obtain a middle layer film, coating the polyamic acid glue solution 1 on the surface of the middle layer film, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain an upper layer film, and thus obtaining the polyimide film with good insulating and bonding properties.
Example 3
A polyimide film with good insulating and bonding properties sequentially comprises: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer membrane is a polyimide porous membrane; the thicknesses of the upper layer film and the lower layer film are both 17 mu m, and the thickness of the middle layer film is 6 mu m;
the raw material of the polyimide porous membrane comprises: hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane), wherein the molar ratio of hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride and 4,4' -diaminodiphenyl ether is 0.5;
the dianhydride monomers of the polyimide flat film are 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride), 4,4 '-diphenyl ether dianhydride, 4,4- (4,4-isopropylidene diphenoxy) bis (phthalic anhydride) and 4,4' -diphenyl ether dianhydride in a molar ratio of 0.55;
the diamine monomer of the polyimide flat film is aminopropyl terminated polydimethylsiloxane, 4,4 '-diaminodiphenyl ether, and the molar ratio of the aminopropyl terminated polydimethylsiloxane to 4,4' -diaminodiphenyl ether is 0.65;
the molar ratio of the diamine monomer to the dianhydride monomer of the polyimide flat film is 1.
The preparation method of the polyimide film with good insulating and bonding properties comprises the following steps:
s1, in an inert gas atmosphere, taking a raw material of a polyimide flat membrane to react in N, N-dimethylacetamide to obtain a polyamic acid glue solution 1 with a solid content of 15 wt%;
s2, in an inert gas atmosphere, taking a raw material of the polyimide porous membrane to react in N, N-dimethylacetamide to obtain a polyamic acid glue solution 2, then imidizing and crushing to obtain intermediate powder; uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane to obtain a solution 3; ultrasonically and uniformly mixing the intermediate solution and water to obtain an emulsion 4, wherein the weight ratio of the intermediate powder to the hexadecyl trimethyl ammonium bromide to the trichloromethane is 1;
and S3, defoaming the polyamic acid glue solution 1, coating the polyamic acid glue solution on the surface of a substrate, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain a lower layer film, coating the emulsion 4 on the surface of the lower layer film, drying at 105 ℃ to obtain a middle layer film, coating the polyamic acid glue solution 1 on the surface of the middle layer film, keeping the temperature for 30min at 140 ℃, heating to 360 ℃, keeping the temperature for 20min for imidization to obtain an upper layer film, and thus obtaining the polyimide film with good insulating and bonding properties.
Comparative example 1
A polyimide film prepared from the same intermediate film as in example 3; and (3) obtaining a polyamic acid glue solution 2 by referring to the operation in the step S2 in the embodiment 3, coating the polyamic acid glue solution on the surface of the substrate, keeping the temperature at 140 ℃ for 30min, then heating to 360 ℃, and keeping the temperature for 20min for imidization to obtain the polyamic acid film.
The films of examples 1 to 3 and comparative example 1 were tested for dielectric constant, and after corona-treated, they were thermally pressed with copper foil at 140 ℃ to prepare single-sided laminates, and the adhesion of the films to the copper foil was tested, the results are shown in the following table:
| detecting items | Dielectric constant 1MHz | Adhesive strength N/cm |
| Example 1 | 2.47 | 8.9 |
| Example 2 | 2.45 | 9.0 |
| Example 3 | 2.40 | 9.3 |
| Comparative example 1 | 2.8 | 4.0 |
As can be seen from the above table, the invention has better insulation and good adhesion with the copper foil.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The polyimide film with good insulating and bonding properties is characterized by sequentially comprising: the film comprises an upper layer film, a middle layer film and a lower layer film, wherein the upper layer film and the lower layer film are polyimide flat films; the middle layer membrane is a polyimide porous membrane;
the preparation method of the polyimide film with good insulating and bonding properties comprises the following steps:
s1, in an inert gas atmosphere, taking a raw material of a polyimide flat membrane to react in N, N-dimethylacetamide to obtain a polyamic acid glue solution 1;
s2, reacting a raw material of a polyimide porous membrane in N, N-dimethylacetamide in an inert gas atmosphere to obtain a polyamic acid glue solution 2, imidizing, and crushing to obtain intermediate powder; uniformly mixing the intermediate powder, hexadecyl trimethyl ammonium bromide and trichloromethane to obtain a solution 3; ultrasonically and uniformly mixing the solution 3 with water to obtain emulsion 4;
s3, defoaming the polyamic acid glue solution 1, coating the defoamed polyamic acid glue solution on the surface of a substrate, imidizing to obtain a lower layer film, coating the emulsion 4 on the surface of the lower layer film, drying to obtain an intermediate layer film, coating the polyamic acid glue solution 1 on the surface of the intermediate layer film, and imidizing to obtain an upper layer film to obtain the polyimide film with good insulation and adhesion properties;
in S2, the weight ratio of the intermediate powder, the hexadecyl trimethyl ammonium bromide and the trichloromethane is (1); in S2, the volume ratio of the trichloromethane to the water is 100-150;
the raw material of the polyimide porous membrane comprises: hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride, 4,4' -diaminodiphenyl ether and octa (aminophenyltrioxasilane), wherein the molar ratio of hexafluorodianhydride, 4,4 '-diphenyl ether dianhydride and 4,4' -diaminodiphenyl ether is 0.5.
2. The polyimide film having good insulating and adhesive properties according to claim 1, wherein the dianhydride monomer of the polyimide flat film is 4,4- (4,4-isopropylidenediphenoxy) bis (phthalic anhydride) or 4,4' -biphenyl ether dianhydride.
3. The polyimide film having good insulating and adhesive properties according to claim 2, wherein the molar ratio of 4,4- (4,4-isopropylidenediphenoxy) bis (phthalic anhydride) to 4,4' -biphenyl ether dianhydride is 0.5 to 0.6.
4. The polyimide film having good insulating adhesion according to claim 1, wherein the diamine monomer of the polyimide flat film is aminopropyl terminated polydimethylsiloxane, 4,4' -diaminodiphenyl ether.
5. The polyimide film having good insulating adhesion according to claim 1, wherein the molar ratio of the diamine monomer to the dianhydride monomer of the polyimide flat film is 1.
6. The polyimide film having good insulating adhesion according to claim 1, wherein the upper film and the lower film each have a thickness of 15 to 20 μm.
7. The polyimide film having good insulating adhesion according to claim 1, wherein the thickness of the interlayer film is 4 to 8 μm.
8. The polyimide film having excellent insulating adhesion according to claim 4, wherein the molar ratio of aminopropyl terminated polydimethylsiloxane to 4,4' -diaminodiphenyl ether is from 0.6 to 0.7.
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| JP2008265027A (en) * | 2007-04-16 | 2008-11-06 | Kaneka Corp | Laminate and printed wiring board |
| CN101372534B (en) * | 2007-08-24 | 2012-04-11 | 东丽纤维研究所（中国）有限公司 | Low dielectric coefficient polyimide/oligomeric silsesquioxane nano hybrid film and preparation thereof |
| CN101993535B (en) * | 2009-08-21 | 2013-07-17 | 东丽纤维研究所（中国）有限公司 | Polyamide/oligomeric silsesquioxane nano-hybrid material and preparation method thereof |
| US9365756B1 (en) * | 2010-02-26 | 2016-06-14 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Low-melt poly(amic acids) and polyimides and their uses |
| CN106084271A (en) * | 2016-07-13 | 2016-11-09 | 哈尔滨理工大学 | New method prepared by three layers of laminated film of nanoparticle/polyimides |
| JP7119290B2 (en) * | 2017-05-30 | 2022-08-17 | 住友ベークライト株式会社 | Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board and semiconductor device |
| JP2019001875A (en) * | 2017-06-14 | 2019-01-10 | 東レ株式会社 | Temporary adhesive, support substrate for temporary adhesion, temporary adhesive tape, and method for producing electronic component using the same |
| CN108329689B (en) * | 2018-03-08 | 2020-09-15 | 哈尔滨理工大学 | Low-dielectric-constant polyimide porous film and preparation method thereof |
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