CN116217929A - Polyimide resin, film and preparation method thereof, flexible copper-clad plate and electronic device - Google Patents
Polyimide resin, film and preparation method thereof, flexible copper-clad plate and electronic device Download PDFInfo
- Publication number
- CN116217929A CN116217929A CN202211565684.0A CN202211565684A CN116217929A CN 116217929 A CN116217929 A CN 116217929A CN 202211565684 A CN202211565684 A CN 202211565684A CN 116217929 A CN116217929 A CN 116217929A
- Authority
- CN
- China
- Prior art keywords
- dianhydride
- polyimide
- formula
- polyimide resin
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 193
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 133
- 150000004985 diamines Chemical class 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011889 copper foil Substances 0.000 claims abstract description 23
- 125000004185 ester group Chemical group 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 122
- 239000011521 glass Substances 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 50
- 239000004952 Polyamide Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 30
- 229920002647 polyamide Polymers 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000013007 heat curing Methods 0.000 claims description 24
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 23
- 125000005591 trimellitate group Chemical group 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 239000004642 Polyimide Substances 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 hexafluoroisopropyl Chemical group 0.000 claims description 8
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 97
- 238000003756 stirring Methods 0.000 description 57
- 239000000243 solution Substances 0.000 description 30
- 229920000642 polymer Polymers 0.000 description 23
- 238000010345 tape casting Methods 0.000 description 23
- 238000001816 cooling Methods 0.000 description 19
- 238000005530 etching Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZZEXDXUCUBHXGE-UHFFFAOYSA-N [4-[4-(1,3-dioxo-2-benzofuran-5-carbonyl)oxy-3-phenylphenyl]-2-phenylphenyl] 1,3-dioxo-2-benzofuran-5-carboxylate Chemical group C=1C=C2C(=O)OC(=O)C2=CC=1C(=O)OC1=CC=C(C=2C=C(C(OC(=O)C=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 ZZEXDXUCUBHXGE-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical group C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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)
- Microelectronics & Electronic Packaging (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides polyimide resin, a film, a preparation method, a flexible copper-clad plate and an electronic device. The polyimide resin contains structural units shown in a formula I and a formula II,
Description
Technical Field
The invention relates to the field of polyimide film preparation, in particular to polyimide resin, a film, a preparation method, a flexible copper-clad plate and an electronic device.
Background
Polyimide film (PIF for short) has excellent heat resistance, mechanical, electrical insulation and chemical resistance, and is widely applied to manufacturing flexible copper-clad plates, and plays a role in mechanical support and insulation of electronic circuits. Common polyimide films have dielectric constants of about 3.3 and dielectric losses of about 0.025. With the increase of the application frequency of electronic products, the frequency spectrum is widened, and higher requirements on the dielectric constant and heat resistance of the material are put forward. For example, 4G has low dielectric property requirement on the material because the transmission rate is lower than 1Gbps, and the dielectric constant of the material is smaller than 4.5, so that the material can meet the property requirement. However, with the research of 5G, in order to reduce the transmission delay, the high signal transmission rate is maintained, the energy loss and the signal distortion in the modulation process are reduced, and the dielectric performance of the material is more demanding. If the transmission rate is higher than 15Gbps, the dielectric constant of the material is required to be less than 3.0, and the dielectric loss is required to be less than 0.005. At present, the common polyimide film is difficult to meet the requirement of the electronic industry in the future 5G age on the dielectric property of the material. Therefore, development of polyimide films with dielectric constants less than 3.0 and dielectric losses less than 0.005 has become a hot point of research.
According to reports in the literature, there are mainly several methods for lowering the dielectric constant of PI films: 1) Fluorine-containing substituents are introduced into the PI molecular structure. The introduction of fluorine generally reduces the dielectric constant to 2.3-2.9. It was found that symmetrical fluoro substituents can reduce the node constant by decreasing electron polarization and increasing free volume; 2) Polyimide inorganic hybrid composite materials. Inorganic particles commonly used for modifying PI are carbon nanotubes, graphite, molecular sieves, nano glass fibers, silica particles, montmorillonite and the like; 3) And macromolecular groups are connected to the side chains, so that the free volume of the molecular chains is increased. Introducing large-volume groups such as fluorene groups, triphenylamine and the like into the PI side chain can form gaps among molecular chains, so that the free volume of the PI molecular chains is increased; 4) Polyimide porous material. The polyimide is modified by the low dielectric property of air by introducing a porous structure into the PI film by adding a porous filler.
In patent application CN 109648970A, a multilayer polyimide film is described, which is formed by compounding a surface polyimide with good thermocompression bonding capability and a high-rigidity structural core polyimide with good dimensional stability, and finally a polyimide film with low dielectric loss, high bonding strength and good thermal dimensional stability is obtained. However, there is no mention of flatness problems caused by differences in thermal expansion coefficients of the surface layer and the core layer, and the preparation process of the composite film is relatively complex.
At present, the conventional PI film can reduce the peeling strength by introducing fluorine-containing groups for reducing the dielectric constant, and the thermal expansion coefficient can be increased by introducing flexible monomers for improving the peeling strength, so that the dimensional stability of the subsequent process is affected, and the problem of the thermal expansion coefficient can be solved by the performance complementation of the multilayer composite film, but the preparation process is more complex.
Disclosure of Invention
The invention mainly aims to provide polyimide resin, a film and a preparation method thereof, a flexible copper-clad plate and an electronic device, so as to solve the problem that the polyimide film in the prior art is difficult to have low dielectric constant, high peel strength and proper thermal expansion coefficient.
In order to achieve the above object, according to one aspect of the present invention, there is provided a polyimide resin comprising structural units represented by formula I and formula II,
in the formula I, n represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R a ～R d Each of which is a single pieceIndependently represents a hydrogen atom, a halogen atom, C 1 ～C 5 Alkyl, C of (2) 1 ～C 4 Any one of the alkoxy groups of (a); ar (Ar) 1 Is the residue of a first dianhydride, and Ar 1 Contains ester groups;
in the formula II, y represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom; ar (Ar) 2 The second dianhydride is a residue of a second dianhydride selected from any one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4 '-biphenyl ether dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropyl) diphthalic dianhydride.
Further, the mol ratio of the structural unit shown in the formula I is 10% -40%, and the mol ratio of the structural unit shown in the formula II is 90% -60%;
preferably, the first dianhydride has the structure of formula V,
in V, R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3;
more preferably, formula I has the structure
Further, R 1 ～R 4 At least one of them is a fluorine atom or a trifluoromethyl group; preferably, R 1 ～R 4 Are all selected from fluorine atoms, or R 3 Is trifluoromethyl, and R 1 、R 2 、R 4 Is a hydrogen atom.
According to another aspect of the present application, there is provided a polyimide film containing any one of the polyimide resins described above, preferably, the polyimide film has a thickness of 12 to 50 μm.
According to still another aspect of the present application, there is provided a method for preparing a polyimide film, the method comprising:
step S1, reacting first dianhydride and first diamine in a solvent to obtain a first precursor solution of polyamide acid resin; wherein the first dianhydride contains ester groups and the first diamine has a structure shown in a formula III;
in formula III, R a ～R d Each independently represents a hydrogen atom, a halogen atom, or C 1 ～C 5 Alkyl and C of (C) 1 ～C 4 Any one of the alkoxy groups of (a);
step S2, sequentially adding a second diamine monomer and a second dianhydride monomer into the first precursor solution to react to obtain a second precursor solution of polyimide resin, wherein the second dianhydride comprises one or more selected from 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4 '-biphenyl ether dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropyl) diphthalic dianhydride, and the second diamine has a structure shown in a formula IV:
in the formula IV, R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom;
and step S3, coating the second precursor solution on a carrier, and drying and curing to obtain the polyimide film attached to the carrier.
Further, the reaction temperature in the step S1 and/or the step S2 is controlled to be 10-30 ℃;
preferably, the strong polar solvent in step S1 is selected from any one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and m-cresol;
preferably, the molar ratio of the first dianhydride to the first diamine is from 0.95 to 1.05 and/or the molar ratio of the second dianhydride to the second diamine is from 0.95 to 1.05;
preferably, the first dianhydride has the structure of formula V,
in V, R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3;
more preferably, the first dianhydride is p-phenyl bis (trimellitate) dianhydride and the first diamine is p-phenylenediamine;
preferably, the second diamine is selected from any one or more of 4,4' -diaminooctafluorobiphenyl and 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl.
Further, step S2 includes: adding a second diamine monomer into the first precursor solution, reacting for 1-3 h, adding a second dianhydride monomer, and reacting for 6-8 h to obtain a second precursor solution of the polyamide acid resin;
preferably, the second dianhydride monomer is added in more than two portions.
Further, step S3 includes: step S31, coating the second precursor solution on a carrier, and drying at 80-150 ℃ until the content of the solvent is 25-35wt% to obtain a polyimide precursor dry film layer; in step S32, the precursor dry film layer is thermally cured at 350 to 400 ℃ to obtain a polyimide film attached to a carrier, preferably for 5 to 15 minutes.
Further, the preparation method further comprises the following steps: s4, separating the polyimide film from the carrier to obtain the polyimide film; preferably, the polyimide film is separated from the carrier by a water boiling method; preferably, the carrier is selected from any one of a glass plate, a copper foil, and an aluminum foil.
According to still another aspect of the present application, there is provided a flexible copper clad laminate comprising the polyimide film described above or a polyimide film prepared by any one of the above methods.
According to still another aspect of the present application, there is provided an electronic device including the flexible copper-clad laminate described above.
Further, the electronic device includes aerospace equipment, navigation equipment, aircraft instruments, military guidance systems, mobile phones, digital cameras, digital video cameras, automobile satellite direction positioning devices, liquid crystal televisions, notebook computers, automobile interior lights, neon lights and the like.
By applying the technical scheme of the invention, ester groups are introduced into polyimide resin, and a specific block copolymer structure is formed by selecting the combination of dianhydride and diamine with specific structures, so that the polyimide resin has lower dielectric constant and higher peeling strength, has good matching property with the coefficient of thermal expansion CTE of copper foil, and is favorable for the smoothness and dimensional stability of the polyimide resin applied to the copper foil.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background of the present application, the polyimide film in the prior art has the problem that it is difficult to have low dielectric constant, high peel strength and suitable thermal expansion coefficient, and in order to solve the problem, the present application provides a polyimide resin, a film and a preparation method, a flexible copper-clad plate and an electronic device.
According to an exemplary embodiment of the present application, there is provided a polyimide resin comprising structural units represented by formula I and formula II,
in the formula I, n represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R a ～R d Each independently represents a hydrogen atom, a halogen atom, or C 1 ～C 5 Alkyl, C of (2) 1 ～C 4 Any one of the alkoxy groups of (a); ar (Ar) 1 Is the residue of a first dianhydride, and Ar 1 Contains ester groups; in the formula II, y represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom; ar (Ar) 2 The second dianhydride is selected from any one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 4 '-biphenyl ether dianhydride (ODPA), bisphenol A type diether dianhydride, 4' - (hexafluoroisopropyl) diphthalic dianhydride (6 FDA).
The polyimide resin disclosed by the application introduces ester groups, and a specific block copolymer structure is formed by selecting the combination of dianhydride and diamine with specific structures, so that the polyimide resin has lower dielectric constant and higher peeling strength, has good matching property with the coefficient of thermal expansion CTE of the copper foil, and is favorable for the smoothness and dimensional stability of the polyimide resin applied to the copper foil.
The structural units represented by the above formula I and formula II may form a diblock, triblock, tetrablock or more polyimide resin, preferably a diblock, triblock. In some embodiments of the present application, the molar ratio of structural units of formula I is 10% to 40%, and the molar ratio of structural units of formula II is 90% to 60%. In the present application In some preferred embodiments, the first dianhydride has a structure of formula V, wherein R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3.
More preferably, formula I has the structure
The polyimide resin formed by the amide with the structure and the polyimide with the structure of the formula II not only has lower dielectric constant and higher peeling strength, but also has better matching property with the coefficient of thermal expansion CTE of copper foil, and the prepared polyimide film has better comprehensive performance.
In some preferred embodiments, R 1 ～R 4 At least one of them is fluorine atom or trifluoromethyl, which can further reduce the dielectric constant of polyimide resin and better meet the transmission requirement under high frequency condition. More preferably, R 1 ～R 4 Are all selected from fluorine atoms, or R 3 Is trifluoromethyl, and R is 1 、R 2 、R 4 Is a hydrogen atom, when R in formula II 1 ～R 4 When the structure is satisfied, the peeling strength, the thermal expansion coefficient and the dielectric property can be better balanced.
According to another exemplary embodiment of the present application, there is provided a polyimide film containing any one of the polyimide resins described above, preferably, the polyimide film has a thickness of 12 to 50um.
The polyimide film has the advantages of lower dielectric constant and higher peeling strength due to the adoption of the polyimide resin, and good matching property with the coefficient of thermal expansion CTE of the copper foil, thereby being beneficial to the flatness and the dimensional stability of the polyimide film applied to the copper foil.
According to still another exemplary embodiment of the present application, there is provided a method for preparing a polyimide film as described above, the method comprising: step S1, reacting first dianhydride and first diamine in a solvent to obtain a first precursor solution of polyamide acid resin; wherein the first dianhydride contains ester groups and the first diamine has a structure shown in a formula III; step S2, sequentially adding a second diamine monomer and a second dianhydride monomer into the first precursor solution to react to obtain a second precursor solution of polyimide resin, wherein the second dianhydride comprises any one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 4 '-biphenyl ether dianhydride (ODPA), bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropyl) diphthalic dianhydride (6 FDA), and the second diamine has a structure shown in a formula IV; and step S3, coating the second precursor solution on a carrier, and drying and curing to obtain the polyimide film attached to the carrier.
In formula III, R a ～R d Each independently represents a hydrogen atom, a halogen atom, or C 1 ～C 5 Alkyl, C of (2) 1 ～C 4 Any one of the alkoxy groups of (a);
in the formula IV, R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom.
The preparation method utilizes the reactivity between different dianhydride and diamine compounds to control the feeding sequence, so that a block polymer is formed in the polymerization process of the polyamide acid resin, and the thermal expansion coefficient is reduced by utilizing the ordering of the block polymer, so that the prepared polyimide film has good matching property with the CTE of the copper foil, and the requirements of subsequent process procedures on flatness and dimensional stability are met. The polyimide film prepared by the method does not need to be coated with a thermoplastic layer, has a single-layer structure, can be prepared by adopting a traditional tape casting method, has simple process, is easy to industrialize, and has good application value.
In some preferred embodiments of the present application, the reaction temperature in the step S1 and/or the step S2 is controlled to be 10-30 ℃, and the reaction temperature is controlled to be lower, which is beneficial to reducing the exchange reaction between molecular chains, and obtaining the block polymer with better CTE matching with the copper foil.
The strong polar solvent in step S1 may be selected from the prior art, and preferably, the above strong polar solvent is selected from any one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and m-cresol.
The molar ratio of the first dianhydride to the first diamine in step S1 and the second dianhydride to the second diamine in step S2 may be determined according to a stoichiometric ratio, preferably the molar ratio of the first dianhydride to the first diamine is 0.95 to 1.05 and/or the molar ratio of the second dianhydride to the second diamine is 0.95 to 1.05. Since the second diamine having a biphenyl group has poor reactivity with the first dianhydride having an ester group, the first dianhydride preferentially reacts with the first diamine having a p-phenyl group, thereby obtaining the above-mentioned block polyimide.
Preferably, the first dianhydride has a structure of formula V, wherein R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3. More preferably, the first dianhydride is p-phenyl bis (trimellitate) dianhydride, and the first diamine is p-phenylenediamine.
In some preferred embodiments of the present application, the second diamine is selected from any one or more of 4,4' -diaminooctafluorobiphenyl and 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, and the resulting block copolymer is more effective.
In some exemplary embodiments of the present application, the step S2 includes: adding a second diamine monomer into the first precursor solution, reacting for 1-3 h, adding a second dianhydride monomer, and reacting for 6-8 h to obtain a second precursor solution of the polyamide acid resin; preferably, the second dianhydride monomer is added in two or more times, which is favorable for controlling the temperature of the reaction system and avoiding gel generation caused by rapid increase of the viscosity of the polyamide acid resin due to the excessively rapid temperature rise of one-time addition.
The second precursor solution described above may be dried according to the prior art method, desolventized, and then cured to obtain a polyimide film attached to a carrier. In some exemplary embodiments of the present application, the step S3 includes: step S31, coating the second precursor solution on a carrier, and drying at 80-150 ℃ until the content of the solvent is 25-35wt% to obtain a polyimide precursor dry film layer; in step S32, the precursor dry film layer is thermally cured at 350 to 400 ℃ to obtain a polyimide film attached to a carrier, preferably for 5 to 15 minutes.
In some embodiments of the present application, the above preparation method further comprises: s4, separating the polyimide film from the carrier to obtain the polyimide film; the above carrier may be selected from the prior art, for example, the carrier is selected from any one of a glass plate, a copper foil, and an aluminum foil, and a person skilled in the art may separate the carrier from the polyimide film according to a method of the prior art, for example, by a water boiling method.
According to still another exemplary embodiment of the present application, a flexible copper-clad laminate is provided, which contains the polyimide film described above or is prepared by the preparation method described above. The flexible copper-clad plate has good comprehensive performance due to the adoption of the polyimide film, and is good in flatness and dimensional stability due to the fact that the expansion coefficient of the polyimide film is close to that of the copper foil, and the subsequent process is facilitated to be smoothly carried out.
The preparation method of the flexible copper-clad plate can be referred to as the preparation method of the polyimide film, and the copper foil is used as a carrier. In some preferred embodiments of the present application, the flexible copper clad laminate is prepared by the following steps: 1) Sequentially preparing a first precursor solution and a second precursor solution of polyimide resin, controlling the temperature of the solutions to be 10-30 ℃, and reacting to obtain the precursor solution of polyimide resin; wherein the molar ratio of dianhydride to diamine is 0.95-1.05; 2) Coating the precursor solution of the polyimide resin prepared in the step 1) on a copper foil; the polyimide precursor resin can be coated by one polyimide precursor resin, or can be coated by a plurality of polyimide precursor resins in a mode of layering coating, simultaneous extrusion coating and the like; the film thickness of the polyimide resin after final curing is 12-50um; volatilizing at 80-150deg.C to make the content of strong polar solvent be 15-25wt% to obtain precursor dry film layer of polyimide resin; 3) The copper foil coated with the precursor dry film layer of polyimide resin is cured to form a polyimide film layer through a continuous nitrogen drying tunnel, so that a single-sided glue-free flexible copper-clad plate product is obtained; the temperature at the inlet of the nitrogen drying tunnel is 120-180 ℃, the temperature is gradually increased, the imidization reaction is slowly carried out, the highest temperature is 350-400 ℃, and the temperatures of all sections are reasonably set according to the temperature gradient; the residence time of the product in the drying tunnel from entering the entrance of the drying tunnel to leaving the drying tunnel is 4-10min.
According to yet another exemplary embodiment of the present application, there is provided an electronic device including the flexible copper-clad laminate described above.
In some embodiments of the present application, the electronic device includes an aerospace device, a navigation device, an aircraft instrument, a military guidance system and mobile phone, a digital camera, a digital video camera, an automobile satellite positioning device, a liquid crystal television, a notebook computer, an automobile interior light, a neon light, and the like.
The advantages that can be achieved by the present application will be further described below in connection with examples and comparative examples.
Example 1
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 4.71g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 8.72g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 2
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 7.06g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 6.98g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 3
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 9.41g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 5.23g of pyromellitic acid dianhydride was continuously charged into the flask, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 4
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 11.77g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 5
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 1.73g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 7.33g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 7.06g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 8.72g of pyromellitic dianhydride was continuously charged into the flask, followed by stirring for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 6
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 1.73g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 7.33g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 9.41g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was charged into the three-necked flask, and stirred for 1 hour, 6.98g of pyromellitic acid dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 7
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 1.73g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 7.33g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 11.77g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 5.23g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 8
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 1.73g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 7.33g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 14.12g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 9
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 7.46g of 4,4 '-diphenyl ether dianhydride (ODPA) was charged into the three-necked flask, and stirred for 1 hour, 14.21g of 4,4' - (hexafluoroisopropyl) diphthalic dianhydride (6 FDA) was continuously charged, and stirred for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 10
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 11.89g of 2,2 '-dimethyl-4, 4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring to react for 0.5h; then, 4.71g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 8.72g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the precursor dry film layer of polyimide resin is solidified to form a polyimide film layer;
example 11
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 11.89g of 2,2 '-dimethyl-4, 4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring to react for 0.5h; then, 7.06g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 6.98g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 12
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 9.41g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 12.55g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was continuously charged, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) The polyamide acid resin is evenly coated on a smooth glass plate by a knife coating method, and is placed in a baking oven at 120 ℃ for 30min to volatilize the solvent, so as to obtain a precursor dry film layer of the polyimide resin.
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 13
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) At a temperature of 10 ℃, 9.41g of 3,3', 4' -biphenyl tetracarboxylic dianhydride and 5.23g of pyromellitic dianhydride are put into a three-neck flask under stirring, and stirred for 7 hours, wherein the molar ratio of the total diamine to the total dianhydride is controlled to be 1:1, a step of;
(3) The polyamide acid resin is evenly coated on a smooth glass plate by a knife coating method, and is placed in a baking oven at 120 ℃ for 30min to volatilize the solvent, so as to obtain a precursor dry film layer of the polyimide resin.
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 14
(1) Setting the water bath temperature at 40 ℃, adding 1.73g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 7.33g of p-phenyl bis (trimellitate) dianhydride was added to the three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 40 ℃, and stirring and reacting for 0.5h; then, 14.12g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 15
(1) Setting the water bath temperature at 40 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 40 ℃, and stirring and reacting for 0.5h; then, 11.77g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 16
(1) Setting the water bath temperature at 40 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 11.77g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 17
(1) Setting the water bath temperature at 30 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 30 ℃, and stirring and reacting for 0.5h; then, 11.77g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask, and stirred for 1 hour, 3.49g of pyromellitic dianhydride was continuously charged, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Example 18
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 16.464G of 4,4 '-bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-ylcarbonyloxy) -3,3' -diphenyl biphenyl (denoted as G18) was added to a three-necked flask and stirred for 1 hour to prepare a precursor resin having a structure represented by formula (I);
(2) Adding 17.93g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 9.41g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 5.23g of pyromellitic acid dianhydride was continuously charged into the flask, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Comparative example 1
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then 7.06g of 3,3', 4' -biphenyl tetracarboxylic dianhydride is put into a three-neck flask and stirred for 1h to obtain polyamic acid solution;
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 12.21g of pyromellitic dianhydride was charged into the three-necked flask, and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled to be 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Comparative example 2
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then 5.23g of pyromellitic dianhydride is put into a three-neck flask and stirred for 1h to obtain polyamic acid solution;
(2) Adding 20.49g of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl into the polymer obtained in the step (1) at the temperature of 10 ℃, and stirring and reacting for 0.5h; then, 16.48g of 3,3', 4' -biphenyltetracarboxylic dianhydride was charged into the three-necked flask and stirred for 6 hours, and the molar ratio of the total diamine to the total dianhydride was controlled to be 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Comparative example 3
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is put into a three-neck flask and stirred for 8 hours to obtain a polyamic acid solution;
(2) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(3) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the polyimide resin precursor dry film layer is cured to form a polyimide film layer.
Comparative example 4
(1) Setting the temperature of a low-temperature cooling circulating pump to 10 ℃, adding 2.60g of p-phenylenediamine and 220g of N-methylpyrrolidone into a three-neck flask, and stirring for 0.5h; then, 11.00g of p-phenyl bis (trimellitate) dianhydride is added into a three-neck flask and stirred for 1h to prepare a precursor resin with a structure shown in a formula (I);
(2) Adding 11.21g of diaminodiphenyl ether into the polymer obtained in the step (1) at the temperature of 10 ℃ and stirring for reaction for 0.5h; then, 9.41g of 3,3', 4' -biphenyltetracarboxylic acid dianhydride was charged into the three-necked flask, followed by stirring for 1 hour, 5.23g of pyromellitic acid dianhydride was continuously charged into the flask, followed by stirring for 6 hours, and the molar ratio of the total amount of diamine to the total amount of dianhydride was controlled at 1:1, a step of;
(3) Uniformly coating polyamide acid resin on a smooth glass plate by a knife coating method, and placing the smooth glass plate in a baking oven at 120 ℃ for 30min to volatilize a solvent to obtain a precursor dry film layer of the polyimide resin;
(4) Directly placing the glass plate coated with the polyimide resin precursor dry film layer into a 370 ℃ oven for heat curing; the total time is 10min; the precursor dry film layer of polyimide resin is solidified to form a polyimide film layer;
The molar ratios of the diamine monomer and the dianhydride monomer in the above examples and comparative examples are specifically shown in table 1 below.
TABLE 1
The performance of the films prepared from the polyimides prepared in each of the examples and comparative examples was measured, and the measurement results are shown in the following table 2, and the specific performance indexes were measured as follows:
dielectric constant (DK) and dielectric loss (Df):
1) Preparation of samples
The polyimide films prepared in the examples and the comparative examples were laminated with copper foil, and samples of (10 cm x 10 cm) size were taken, and metallic copper was completely etched with an etching solution at a temperature of no more than 45 ℃. After etching, cleaning with clear water, and airing the sample at room temperature; is not pressed in the etching, cleaning and airing processes. The composition of the etching solution used is saturated FeCl 3 The aqueous solution was adjusted to pH 1 using hydrochloric acid.
The samples were treated in a 150 ℃ circulation oven for 2 hours and then placed in a dryer for cooling.
2) Testing of samples
Taking out the cooled sample, testing the thickness of the sample by using a micrometer, fixing the sample by using a resonant cavity clamp, testing the dielectric constant (Dk) and dielectric loss (Df) of the sample by using a network analyzer, and recording the test result.
Coefficient of expansion (CTE):
1) Sample etching treatment
Laminating the polyimide film prepared in the examples and comparative examples with copper foil to obtain >5.0cm by 5.0 cm) and the sample is completely etched with an etching solution, the temperature of the etching solution is not more than 45 ℃. After etching, cleaning with clear water, and airing the sample at room temperature; is not pressed in the etching, cleaning and airing processes. The composition of the etching solution used is saturated FeCl 3 The aqueous solution was adjusted to pH 1 using hydrochloric acid.
The mixture is stabilized for 24 hours under the environment of 23+/-2 ℃ and 50+/-5% of humidity. If statistics on a given line show that the stabilization time is supported to be shortened, the stabilization time can be shortened.
2) Testing of samples
Cutting the completely etched sample into a rectangular sample with the width of 2-3mm by using a blade, loading the sample into a TMA stretching clamp, heating the TMA to 300 ℃ at a temperature of 30 ℃/min, keeping the temperature for 10min, finally reducing the temperature to 100 ℃ at a temperature of 5 ℃/min, and finally reading the CTE value from the final curve.
3) Repeated testing of results
The same test sample was taken and repeated according to the second test procedure.
The data error of the two tests is not more than 2ppm/K; and taking the average value as a final accurate value.
If the error of the two tests exceeds 2ppm/K, the sample is prepared again and the test is performed.
The coefficient of expansion of the copper foil, cte=17.5 ppm/K, as measured by this method.
Peel strength:
1) Treatment of initial samples
And (3) taking samples with the size of 7.5cm and 50cm from the polyimide film layers prepared in the examples and the comparative examples, adhering photosensitive dry films with the size of 3.2mm and 228.6mm to the copper foil surfaces of the samples by using the photosensitive dry films which are cut in advance, setting the number of the photosensitive dry films to be not less than 5, curing the samples adhered with the dry films for 0.5-1min by using an exposure machine, and taking out the samples.
2) Sample etching treatment
The sample was completely etched with an etching solution at a temperature of 45 ℃ or less. After etching, cleaning with clear water, and airing the sample at room temperature; is not pressed in the etching, cleaning and airing processes.
The etched sample requires the copper wire edge to be neat and burr-free, uniform in width and high in parallelism.
The composition of the etching solution used is saturated FeCl 3 The aqueous solution was adjusted to pH 1 using hydrochloric acid.
The mixture is stabilized for 24 hours under the environment of 23+/-2 ℃ and 50+/-5% of humidity. If statistics on a given line show that the stabilization time is supported to be shortened, the stabilization time can be shortened.
3) Testing of samples
The etched sample was stuck to a glass plate prepared in advance with a double-sided tape, and then the actual width of the copper wire was measured with a two-dimensional imager and data was recorded.
Then, the peel strength is tested by a tensile tester, the test speed is 50.8mm/min, and the copper wire and the polyimide film always keep 90 degrees. During the stripping process, a minimum of 57.2mm was stripped, the initial 6.4mm was ignored, and the stripping data was recorded.
TABLE 2
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the polyimide film can still be matched with copper foil in thermal expansion coefficient under the condition of ensuring the peeling strength, has low dielectric property, and can meet the signal transmission requirement under the high-frequency condition.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A polyimide resin comprising structural units represented by the formulas I and II,
in the formula I, n represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R a ～R d Each independently represents a hydrogen atom, a halogen atom, or C 1 ～C 5 Alkyl and C of (C) 1 ～C 4 Any one of the alkoxy groups of (a); ar (Ar) 1 Is the residue of a first dianhydride, and Ar 1 Contains ester groups;
in the formula II, y represents the repetition number of the structural unit and is an integer greater than or equal to 1; r is R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom; ar (Ar) 2 Is the residue of a second dianhydride selected from any one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4 '-biphenyl ether dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropyl) diphthalic dianhydride.
2. The polyimide resin according to claim 1, wherein the molar ratio of the structural unit represented by formula I is 10% to 40%, and the molar ratio of the structural unit represented by formula II is 90% to 60%;
preferably, the first dianhydride has the structure of formula V,
in V, R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3;
more preferably, the structure of formula I is
3. The polyimide resin according to claim 1, wherein R 1 ～R 4 At least one of them is a fluorine atom or a trifluoromethyl group;
preferably, said R 1 ～R 4 Are each selected from fluorine atoms, or R is 3 Is trifluoromethyl, and R is 1 、R 2 And R is 4 Is a hydrogen atom.
4. A polyimide film comprising the polyimide resin according to any one of claims 1 to 3, preferably having a thickness of 12 to 50um.
5. A method for producing a polyimide film, comprising:
step S1, reacting first dianhydride and first diamine in a solvent to obtain a first precursor solution of polyamide acid resin; the first dianhydride contains ester groups, and the first diamine has a structure shown in a formula III;
in formula III, R a ～R d Each independently represents a hydrogen atom, a halogen atom, or C 1 ～C 5 Alkyl and C of (C) 1 ～C 4 Any one of the alkoxy groups of (a);
step S2, sequentially adding a second diamine monomer and a second dianhydride monomer into the first precursor solution to react to obtain a second precursor solution of polyimide resin, wherein the second dianhydride comprises any one or more selected from 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4 '-biphenyl ether dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropyl) diphthalic dianhydride, and the second diamine has a structure shown in a formula IV:
In the formula IV, R 1 ～R 4 Each independently is a hydrogen atom, a fluorine atom, a trifluoromethyl group, C 1 ～C 10 Alkyl, C of (2) 2 ～C 4 Alkenyl and C of (C) 1 ～C 8 And R is any one of alkoxy groups of (C) 1 ～R 4 At least one of which is not a hydrogen atom;
and step S3, coating the second precursor solution on a carrier, and drying and curing to obtain the polyimide film attached to the carrier.
6. The preparation method according to claim 5, wherein the reaction temperature in the step S1 and/or the step S2 is controlled to be 10 to 30 ℃;
preferably, the strong polar solvent in the step S1 is selected from any one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and m-cresol;
preferably, the molar ratio of the first dianhydride to the first diamine is from 0.95 to 1.05, and/or the molar ratio of the second dianhydride to the second diamine is from 0.95 to 1.05;
preferably, the first dianhydride has the structure of formula V,
in V, R 5 And R is 6 Each independently is C 1 ～C 6 Alkyl and C of (C) 1 ～C 6 S represents an integer of 0 to 4, q represents an integer of 0 to 4, and m represents an integer of 1 to 3;
more preferably, the first dianhydride is p-phenyl bis (trimellitate) dianhydride and the first diamine is p-phenylenediamine;
Preferably, the second diamine is selected from any one or more of 4,4' -diaminooctafluorobiphenyl and 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl.
7. The method according to claim 5, wherein the step S2 comprises: adding the second diamine monomer into the first precursor solution, reacting for 1-3 h, adding the second dianhydride monomer, and reacting for 6-8 h to obtain a second precursor solution of the polyamide acid resin;
preferably, the second dianhydride monomer is added in two or more portions.
8. The method according to claim 5, wherein the step S3 comprises:
step S31, coating the second precursor solution on a carrier, and drying at 80-150 ℃ until the content of the solvent is 25-35wt% to obtain a precursor dry film layer of polyimide;
and step S32, performing heat curing on the precursor dry film layer at 350-400 ℃ to obtain the polyimide film attached to the carrier, wherein the heat curing time is preferably 5-15min.
9. The method according to claim 5, further comprising step S4 of separating the polyimide film from the carrier to obtain a polyimide film;
Preferably, the polyimide film is separated from the carrier by a water boiling method;
preferably, the carrier is selected from any one of glass plate, copper foil and aluminum foil.
10. A flexible copper clad laminate characterized in that it contains the polyimide film of claim 4 or a polyimide film produced by the method of any one of claims 5 to 9.
11. An electronic device comprising the flexible copper-clad laminate of claim 10.
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| CN117384406A (en) * | 2023-12-08 | 2024-01-12 | 苏州尊尔光电科技有限公司 | Transparent polyimide film with high cohesiveness, preparation method and application |
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