CN114805806B - Method for reducing viscosity of polyamic acid solution and method for producing polyimide film - Google Patents
Method for reducing viscosity of polyamic acid solution and method for producing polyimide film Download PDFInfo
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- CN114805806B CN114805806B CN202210506320.9A CN202210506320A CN114805806B CN 114805806 B CN114805806 B CN 114805806B CN 202210506320 A CN202210506320 A CN 202210506320A CN 114805806 B CN114805806 B CN 114805806B
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- dianhydride
- polyamic acid
- anhydride
- monomer
- acid solution
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- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229920001721 polyimide Polymers 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 150000004985 diamines Chemical class 0.000 claims abstract description 37
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims abstract description 33
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 3
- -1 hexafluoroisopropylidene Chemical group 0.000 claims description 3
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- IWFSADBGACLBMH-UHFFFAOYSA-N 4-[4-[4-[4-amino-2-(trifluoromethyl)phenoxy]phenyl]phenoxy]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC(N)=CC=3)C(F)(F)F)=CC=2)C=C1 IWFSADBGACLBMH-UHFFFAOYSA-N 0.000 claims description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 239000010408 film Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Disclosed are a method for reducing the viscosity of a polyamic acid solution and a method for producing a polyimide film. The method for reducing the viscosity of the polyamic acid solution comprises adding alcohol in the process of polymerizing anhydride monomers and diamine monomers to generate polyamic acid through condensation reaction; the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda); the alcohol is selected from C 1‑6 Alkanols and sugar alcohols, the alcohols being added in an amount of from 4 to 15 mol%, based on the total mole of anhydride monomers.
Description
Technical Field
The present invention relates to a method for producing a polyamic acid solution and a method for producing a polyimide film. More particularly, the present invention relates to a method for reducing the viscosity of a polyamic acid solution. The method can flexibly regulate and control the viscosity of the polyamic acid solution, thereby better utilizing the polyamic acid solution to prepare various polyimide films.
Background
As the demand for flexible and wearable devices has increased, the demands on the manufacturing materials of the corresponding display devices have also become increasingly diverse. In terms of substrate materials, conventional glass substrates themselves are thick, heavy and fragile, limiting the design and versatility of display products.
The polymer material has small specific gravity, good flexibility, difficult breakage, easy film preparation, and better suitability for flexible electronic device manufacture compared with glass substrate materials. However, the common polymer material is difficult to bear the high temperature process of more than 400 ℃ in the processing of the display device due to the most hydrocarbon composition. In particular for top-emitting OLED devices, the flexible polymer used as the substrate material in the production process must be able to withstand the harsh conditions during the device fabrication process.
In addition, some of the key requirements that need to be met include:
1) The polymer solution has good leveling property on the glass substrate, and the formed film has good adhesion with the substrate and has a flat surface;
2) The heat-resistant polymer has extremely high heat-resistant stability, so that the pollution to devices caused by micromolecules generated by thermal decomposition in the high-temperature processing process is avoided, and the product yield is influenced;
3) Good mechanical properties, such as very high tensile strength and high elongation at break, make the devices made thinner and more gentle;
4) Has good dimensional stability and has a Coefficient of Thermal Expansion (CTE) similar to that of the glass substrate or semiconductor material to prevent bending, delamination and interfacial stress of the substrate due to the CTE mismatch.
Polyimide (PI) materials, which are known as a classical heat-resistant polymer material with excellent thermal/mechanical properties, are considered as the best candidates for substrate materials for fabricating flexible OLEDs. In the classical preparation process, aromatic dianhydride and aromatic diamine react in aprotic dipolar solvent to form soluble precursor polyamide acid, which is used for casting film and imidized at high temperature to complete the preparation of polyimide film.
Among various polyimide varieties, polymers prepared from biphenyl dianhydride BPDA, pyromellitic dianhydride PMDA and p-phenylenediamine pPDA have excellent mechanical properties and extremely low CTE. These properties should be related to their rigid and linear macromolecular structure. The wholly aromatic structure also makes it have higher thermal decomposition temperature.
However, the BPDA/PMDA/pda-based polyamic acid generally exhibits a large solution viscosity, which makes the film-making process difficult. In general, it is difficult to process a polymer solution having a viscosity of more than 15000 centipoise in a solution viscosity of a coating line for preparing a substrate material. Although it has been reported that the viscosity of the solution can be controlled by reducing the molecular weight, it is generally believed that low molecular weight will result in reduced performance of the film product, particularly with respect to mechanical properties, thermal stability, and coefficient of thermal expansion, which are greatly affected and difficult to achieve with stringent requirements for high mechanical properties, thermal stability, and low coefficient of thermal expansion; in addition, the solution of polyamic acid having a high molecular weight of BPDA/PMDA/pda can also be reduced in solution viscosity by reducing the solid content, but this results in a significant increase in the amount of solvent removed during the film formation process, and a decrease in the film formation efficiency, further resulting in an increase in the film formation cost, pollution and energy consumption.
Accordingly, there remains a need in the art to develop a method for reducing the viscosity of polyamic acid solutions that advantageously produce a variety of polyimide films.
The field also needs to develop a method for preparing polyimide film.
Disclosure of Invention
An object of the present invention is to provide a method for reducing the viscosity of a polyamic acid solution, by which a polyamic acid solution can be advantageously produced into various polyimide films.
Another object of the present invention is to provide a method for producing a polyimide film.
Accordingly, one aspect of the present invention is directed to a method for reducing the viscosity of a polyamic acid solution comprising adding an alcohol during the polymerization of an anhydride monomer and a diamine monomer to form a polyamic acid by a condensation reaction;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA);
the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 Alkanols and sugar alcohols, the alcohols being added in an amount of from 4 to 15 mol%, based on the total mole of anhydride monomers.
Another aspect of the invention relates to a method of preparing a polyamic acid solution comprising polymerizing an anhydride monomer and a diamine monomer in an alcohol solution to form a polyamic acid by a condensation reaction;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 Alkanols and sugar alcohols, the alcohols being added in an amount of from 4 to 15 mol%, based on the total mole of anhydride monomers.
In still another aspect, the present invention relates to a method for preparing a polyimide film, comprising:
(i) Polymerizing anhydride monomer and diamine monomer in alcohol solution through condensation reaction to produce polyamic acid;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 An alkanol and a sugar alcohol, the alcohol being added in an amount of 4 to 15 mole% based on the total mole of anhydride monomers;
(ii) The polyamic acid solution is coated on a substrate and imidized by heating.
Still another aspect of the invention relates to C 1-6 Use of alkanols and sugar alcohols to reduce the viscosity of a polyamic acid solution, the anhydride monomers of the polyamic acid comprising 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); diamine monomers include p-phenylenediamine (pda).
Detailed Description
The inventors of the present invention have found that, for the polyamic acid mainly comprising BPDA/PMDA/pPDA, if alcohols, particularly C, are added during the reaction 1-6 Alkanols and sugar alcohols as additives can reduce the viscosity of high solids polyamic acid solutions while efficiently producing them. At the same time, a polyimide film having good mechanical properties and a very low Coefficient of Thermal Expansion (CTE) can be obtained based on the solution of the polyamic acid having a high concentration and a low apparent viscosity, and the polyimide film has a very good heat resistance and shows a very high thermal decomposition temperature. The present invention has been completed based on this finding.
Method for reducing polyimide solution concentration
Accordingly, the method of reducing the viscosity of a polyamic acid solution according to the present invention comprises adding an alcohol during the polymerization of an acid anhydride monomer and a diamine monomer to form a polyamic acid by a condensation reaction;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 The alkanol and sugar alcohol are added in an amount of 4 to 15 mol%, preferably 4.5 to 13 mol%, more preferably 5 to 11 mol%, based on the total mole of the anhydride monomers.
In one example of the present invention, the C 1-6 Non-limiting examples of alkanols are, for example, methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerol, mixtures of one or more thereof, or mixtures of one or more thereof with sugar alcohols.
The viscosity of the polyamic acid solution can be reduced to 2000-20000 cps, preferably 3000-18000 cps, more preferably 4000-16000 cps under the condition of 20% solid content.
In one embodiment of the present invention, the polyamic acid may include other optional anhydride and/or diamine monomers in addition to the dianhydride and diamine monomers described above.
Non-limiting examples of suitable optional anhydride monomers are, for example: monoether dianhydrides such as 3,3'4,4' -diphenyl ether dianhydride (ODPA); hexafluorodianhydride such as 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA); diphenyl sulfone dianhydrides such as 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA); bisphenol a diether dianhydrides such as 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (bisda); benzophenone dianhydrides such as 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), or combinations of two or more thereof formed in any ratio.
In one embodiment of the invention, the amount of said optional monomer is not more than 10%, preferably not more than 8%, more preferably not more than 5% based on the total molar amount of anhydride monomers.
Non-limiting examples of suitable diamine monomers are, for example, m-phenylenediamine (mPDA), 4' -diaminodiphenyl ether (ODA), 3,4' -diaminodiphenyl ether (3, 4' -ODA), 4' -diaminodiphenyl sulfone (DDS) 3,3' -diaminodiphenyl ether (3, 3' -DDS), 2' -dimethyl-4, 4' -diaminodiphenyl ether (oTOL), 4' -diaminodiphenyl Methane (MDA), 4' -diaminobenzophenone 4,4' -diaminodiphenyl-2, 2-hexafluoropropane, 9-bis- (4-aminophenyl) fluorene, 9-bis- (3-fluoro-4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (PFMB), bis- (2-trifluoromethyl-4-aminophenoxy) biphenyl, or a combination of two or more thereof formed in any ratio.
In one embodiment of the present invention, the optional diamine monomer is added at a ratio of no greater than 20%, preferably no greater than 15%, more preferably no greater than 10% based on the total moles of diamine monomer.
In one embodiment of the present invention, the mole number of BPDA in the polyamic acid solution is 30 to 90%, preferably 35 to 85%, more preferably 40 to 70%, and preferably 45 to 65% of the total mole number of dianhydride monomers.
Preparation method of polyimide solution
The process for preparing the polyamic acid solution of the present invention comprises polymerizing an acid anhydride monomer and a diamine monomer in an alcohol solution by a condensation reaction to form a polyamic acid, and the process conditions of the preparation process may be conventional process conditions known in the art.
The anhydride monomer, diamine monomer, alcohol and the amounts thereof are as described above.
In one embodiment of the present invention, the polymerization temperature may be controlled between 30℃and 80℃and preferably between 35℃and 75℃and more preferably between 40℃and 70 ℃.
In one embodiment of the invention, one of the forward and reverse feeding sequences can be selected as the feeding method according to the reactivity of dianhydride or diamine monomers in the polymerization process. In the normal feed sequence, one or more diamine monomers and alcohol are first dissolved in the reaction solvent, followed by the addition of one or more dianhydride monomers to initiate the polycondensation reaction. In the back-feed sequence, one or more dianhydride monomers and alcohol are added preferentially to the amount of solvent, followed by the desired diamine monomer.
In some embodiments of the invention, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), dimethylsulfoxide (DMSO), hexamethylphosphoramide (HMPA), and combinations thereof.
In one example of the present invention, a solvent (e.g., NMP), BPDA, PMDA, pPDA and alcohol are charged into a reaction vessel equipped with a stirrer, inert gas protection and condensing means. The reaction was then carried out at room temperature under an inert gas flow.
Polyimide film
The method for preparing the polyimide film by coating the polyamic acid solution of the present invention is not particularly limited, and may be any conventional method known in the art. In one example of the present invention, the method includes coating the polyamic acid solution on a substrate, drying, and thermally treating the polyimide film.
The applicable solution coating method is not particularly limited and may be any conventional method known in the art. In one example of the present invention, the coating method is selected from brushing, casting, knife coating, and the like.
The substrate to be used is not particularly limited, and may be a conventional substrate known in the art, and it may be, for example, a plastic substrate, a metal substrate, a glass substrate, or the like, preferably a glass substrate.
The applicable high-temperature heat treatment method is not particularly limited and may be a conventional method known in the art. For example, imidization can be performed by an isothermal gradient method (see "synthesis of polyamic acid and imidization process of polyamic acid" by Infeifei et al (university of Industrial university, vol. 27, fourth edition, 12 th year 2008)).
The polyimide film prepared by the method has the thermal decomposition temperature of more than 500 ℃ in nitrogen, the tensile modulus of more than 8GPa at room temperature, the tensile strength of more than 400MPa and the tensile elongation at break of more than 20%; the coefficient of thermal expansion is less than 10 ppm/DEG C between room temperature and 400 ℃.
The solution of polyamic acid obtained by polymerizing the polymerization monomer has a viscosity of 2000-20000 cps and a solid content of 10% -30% by weight. The solution of the polyamide acid has lower viscosity and higher solid content, is easy to process into a film, and the polyimide film prepared by the film coating, drying and high-temperature heat treatment has good heat resistance, mechanical property and dimensional stability, and is suitable for being used as a substrate material of a flexible display.
The thin film prepared from the polyamic acid solution according to the present invention exhibits excellent heat resistance and dimensional stability over a wide high temperature range. Starting from the polyamic acid with BPDA/PMDA/pda as the polymer host, the resulting polyimide film still exhibits good thermal/mechanical properties by the viscosity control method described in this patent, even with solutions based on low viscosity, high solids polyamic acid. This provides a practical solution for preparing polyimide films from solutions of high solids low viscosity polyamic acids. The polyimide film with excellent characteristics can be used as a substrate material to manufacture a flexible OLED device.
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
Examples
Unless otherwise indicated, the viscosities in the present invention are volume viscosities. Unless otherwise indicated, the solids content in the present invention refers to the polyamic acid.
Solution viscosity test:
solution viscosity was measured using a Brookfield DV-type I viscometer at 25 ℃.
Film forming performance test:
pouring the sample solution on a glass substrate, drying with hot air to remove residual solvent, and then heating at a high temperature (400-500 ℃) to obtain the polyimide film. Whether or not there were protrusions, inhomogeneities, cracks, powdering, etc. was evaluated by observation. Films in which no defects were observed were evaluated as excellent, and films in which defects were observed were evaluated as inferior.
Thermal stability test:
the thermal stability of the film was measured by a thermogravimetric analyzer (TGA) model TA-Q50, and the sample was heated at a rate of 20 ℃ per minute under a nitrogen atmosphere from room temperature to 800 ℃, preferably 500 ℃ or higher and 500 ℃ or lower.
Dimensional stability test:
the change in film size with temperature was measured by a thermo-mechanical analyzer (TMA) model TA-Q400. The sample was heated from 0 ℃ to 500 ℃ in a nitrogen atmosphere at a rate of 10 ℃/min. Between room temperature and 400 ℃, CTE <10ppm/°c is preferred, CTE >10ppm/°c is inferior.
Mechanical property test:
the mechanical properties of the films were measured by an INSTRON stretcher INSTRON 5969 series. Film samples of 10 to 20 microns thickness were stretched at room temperature at a stretch rate of 10 millimeters per minute with an initial length of 25.4 millimeters. The tensile modulus is more than 8GPa, the tensile strength is more than 300MPa, the elongation is more than 10 percent, three items are qualified and are excellent, and one of the three items does not reach the standard and is inferior.
Example 1
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 87.28 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 4.80 mmol of methanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 21000 cps and the solid content was 20.0%. The solution has proper viscosity, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film.
Comparative example 1
87.43 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA, and 60.00 mmol of pPDA are charged into a flask equipped with stirrer, stirring blades, nitrogen protection and condensing means. The reaction was carried out at room temperature, and then the reaction time was 5 hours under a nitrogen stream. The apparent viscosity of the resulting reaction solution was more than 600000 cps (limit of the range of the viscometer), and the solid content was 20.0%. Because the solution viscosity is too high, a flat film is difficult to form, and the requirement of high solid content and low viscosity is not met. Because it is difficult to form a flat film, the physical parameters of the film cannot be characterized.
Comparative example 2
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 87.39 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 1.20 mmol of methanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 200000 cps and the solid content was 20.0%. The solution viscosity was significantly reduced compared to comparative example 1, but still at a higher level, and it was difficult to form a flat film, which did not meet the requirements of high solids content and low viscosity. Because it is difficult to form a flat film, the physical parameters of the film cannot be characterized.
Comparative example 3
87.33 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pPDA and 3 mmol of methanol are introduced into a flask equipped with a stirrer, stirring blades, nitrogen protection and condensing means. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 55000 cps and the solid content was 20.0%. The apparent viscosity was significantly reduced compared to comparative examples 1-2, and the coating process was possible using conventional coating equipment. However, the viscosity of the reaction solution is still high, so that uneven and bubbling phenomena exist on the film surface, and the viscosity of the polymer solution is not required to be further reduced.
Example 2
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 87.22 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 6.60 mmol of methanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The resulting reaction solution had an apparent viscosity of 12400 cps and a solids content of 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 3
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 87.14 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of methanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 4000 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 4
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 87.01 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of ethanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 4500 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 5
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 86.89 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of n-propanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 4800 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 6
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 86.89 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of isopropyl alcohol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 5000 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 7
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 86.87 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of ethylene glycol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 3500 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Example 8
Into a flask equipped with a stirrer, stirring blade, nitrogen protection, and condensing device, 86.89 g of NMP,30.00 mmol of BPDA,30.00 mmol of PMDA,60.00 mmol of pda, and 9.00 mmol of isopropanol were charged. The reaction was then carried out under a nitrogen stream at room temperature for 5 hours.
The apparent viscosity of the resulting reaction solution was 4000 cps and the solid content was 20.0%. The solution has proper viscosity under high solid content, is easy to form a film, and has excellent thermal stability, excellent dimensional stability and excellent mechanical property of the polyimide film corresponding to the solution.
Referring to comparative examples 1 to 3, it can be seen from examples 1 to 8 above that polyimide solutions having lower viscosity and higher solid content can be prepared by adding alcohol additives to polyamic acid having BPDA/PMDA/pPDA as a polymer main body during the reaction. The solution is easy to process into a film, and the polyimide film prepared by the solution after film coating, drying and high-temperature heat treatment has good heat resistance, mechanical property and dimensional stability, and is suitable for being used as a substrate material of a flexible display. The polyamic acid solution-prepared film exhibits excellent heat resistance, dimensional stability and mechanical properties over a wide high temperature range.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (18)
1. A method for reducing the viscosity of a polyamic acid solution comprising adding an alcohol during the polymerization of an anhydride monomer and a diamine monomer to form a polyamic acid by a condensation reaction;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA);
the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 Alkanols and sugar alcohols, the alcohols being added in an amount of from 4 to 15 mol%, based on the total mole of anhydride monomers.
2. A preparation method of a polyamic acid solution comprises the steps of polymerizing an anhydride monomer and a diamine monomer in an alcohol solution through a condensation reaction to generate polyamic acid;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 Alkanols and sugar alcohols, the alcohols being added in an amount of from 4 to 15 mol%, based on the total mole of anhydride monomers.
3. A method for producing a polyimide film, comprising:
(i) Polymerizing anhydride monomer and diamine monomer in alcohol solution through condensation reaction to produce polyamic acid;
the acid anhydride monomers include 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); the diamine monomer comprises p-phenylenediamine (pda);
the alcohol is selected from C 1-6 An alkanol and a sugar alcohol, the alcohol being added in an amount of 4 to 15 mole% based on the total mole of anhydride monomers;
(ii) The polyamic acid solution is coated on a substrate and imidized by heating.
4. A method according to any one of claims 1-3, characterized in that C 1-6 The alkanol is selected from methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerol, a mixture of one or more of them, or a mixture of one or more of them with sugar alcohol, or sugar alcohol.
5. A method according to any one of claims 1 to 3, wherein the polyamic acid solution has a viscosity in the range of 2000 to 20000 centipoise at 20% solids.
6. A method according to any one of claims 1 to 3, wherein the polyamic acid solution has a viscosity in the range of 3000 to 18000 centipoise at 20% solids.
7. A method according to any one of claims 1 to 3, wherein the polyamic acid solution has a viscosity in the range of 4000 to 16000 centipoise at 20% solids.
8. A method according to any one of claims 1 to 3, wherein the polyamic acid may comprise, in addition to the dianhydride and diamine monomers described above, other optional anhydride and/or diamine monomers.
9. The method of claim 8, wherein the optional anhydride monomer is selected from the group consisting of monoether dianhydride, hexafluorodianhydride, diphenyl sulfone dianhydride, bisphenol a diether dianhydride, benzophenone dianhydride, and combinations of two or more thereof in any ratio;
the optional diamine monomer is selected from m-phenylenediamine (mPDA), 4' -diaminodiphenyl ether (ODA), 3,4' -diaminodiphenyl ether (3, 4' -ODA), 4' -diaminodiphenyl sulfone (DDS) 3,3' -diaminodiphenyl ether (3, 3' -DDS), 2' -dimethyl-4, 4' -diaminodiphenyl ether (oTOL), 4' -diaminodiphenyl Methane (MDA), 4' -diaminobenzophenone 4,4' -diaminodiphenyl-2, 2-hexafluoropropane, 9-bis- (4-aminophenyl) fluorene, 9-bis- (3-fluoro-4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl (PFMB), bis- (2-trifluoromethyl-4-aminophenoxy) biphenyl, or a combination of two or more thereof formed in any ratio.
10. The method of claim 8 wherein the optional anhydride monomer is selected from the group consisting of 3,3'4,4' -diphenyl ether dianhydride (ODPA), 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA), 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride (DSDA), 4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride (bisda), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), or a combination of two or more thereof formed in any ratio.
11. The process of claim 8, wherein the amount of the optional anhydride monomer is no more than 10% based on the total moles of anhydride monomers;
the optional diamine monomer comprises no more than 20% by total moles of diamine monomer.
12. The process of claim 8, wherein the amount of the optional anhydride monomer is no more than 8% based on the total moles of anhydride monomers;
the optional diamine monomer comprises no more than 15% by total moles of diamine monomer.
13. The process of claim 8, wherein the amount of the optional anhydride monomer is no more than 5% based on the total moles of anhydride monomers;
the optional diamine monomer comprises no more than 10% by total moles of diamine monomer.
14. A method according to any one of claims 1 to 3, wherein the moles of BPDA in the polyamic acid solution are 30% to 90% of the total moles of dianhydride monomers.
15. A method according to any one of claims 1 to 3, wherein the molar amount of BPDA in the polyamic acid solution is 35% to 85% of the total molar amount of dianhydride monomer, based on the total molar amount of dianhydride monomer.
16. A method according to any one of claims 1 to 3, wherein the molar amount of BPDA in the polyamic acid solution is 40% to 70% based on the total molar amount of dianhydride monomer.
17. A method according to any one of claims 1 to 3, wherein the moles of BPDA in the polyamic acid solution are 45 to 65% of the total moles of dianhydride monomer, based on the total moles of dianhydride monomer.
18.C 1-6 Use of alkanols and sugar alcohols for reducing the viscosity of solutions of polyamic acids whose anhydride monomer units include 3,3', 4' -biphenyltetramethylAcid dianhydride (BPDA) and 1,2,4, 5-pyromellitic dianhydride (PMDA); diamine monomer units include p-phenylenediamine (pda).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663728A (en) * | 1968-07-25 | 1972-05-16 | Gen Electric | Process for producing polyamide acid and polyimides |
| US6222007B1 (en) * | 1998-05-29 | 2001-04-24 | The United States Of America As Represented By The National Aeronautics And Space Administration | Films, preimpregnated tapes and composites made from polyimide “Salt-like” Solutions |
| CN109422876A (en) * | 2017-08-28 | 2019-03-05 | 苏州聚萃材料科技有限公司 | Solution, Kapton and its application of polyamic acid |
| WO2019160218A1 (en) * | 2018-02-19 | 2019-08-22 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid composition having improved storage stability, manufacturing method for polyimide film using same, and polyimide film manufactured by means of same |
| WO2020091432A1 (en) * | 2018-10-31 | 2020-05-07 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition for enhancing adhesiveness of polyimide film and polyimide film manufactured therefrom |
| CN112341929A (en) * | 2019-08-07 | 2021-02-09 | 苏州聚萃材料科技有限公司 | Polyamide acid solution primer, preparation method and application thereof |
-
2022
- 2022-05-10 CN CN202210506320.9A patent/CN114805806B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663728A (en) * | 1968-07-25 | 1972-05-16 | Gen Electric | Process for producing polyamide acid and polyimides |
| US6222007B1 (en) * | 1998-05-29 | 2001-04-24 | The United States Of America As Represented By The National Aeronautics And Space Administration | Films, preimpregnated tapes and composites made from polyimide “Salt-like” Solutions |
| CN109422876A (en) * | 2017-08-28 | 2019-03-05 | 苏州聚萃材料科技有限公司 | Solution, Kapton and its application of polyamic acid |
| WO2019160218A1 (en) * | 2018-02-19 | 2019-08-22 | 에스케이씨코오롱피아이 주식회사 | Polyamic acid composition having improved storage stability, manufacturing method for polyimide film using same, and polyimide film manufactured by means of same |
| WO2020091432A1 (en) * | 2018-10-31 | 2020-05-07 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition for enhancing adhesiveness of polyimide film and polyimide film manufactured therefrom |
| CN112341929A (en) * | 2019-08-07 | 2021-02-09 | 苏州聚萃材料科技有限公司 | Polyamide acid solution primer, preparation method and application thereof |
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