CN115505125B - Polyimide composition, polymer, film and product containing same - Google Patents
Polyimide composition, polymer, film and product containing same Download PDFInfo
- Publication number
- CN115505125B CN115505125B CN202211360886.1A CN202211360886A CN115505125B CN 115505125 B CN115505125 B CN 115505125B CN 202211360886 A CN202211360886 A CN 202211360886A CN 115505125 B CN115505125 B CN 115505125B
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- Prior art keywords
- acid
- polyimide
- compound
- diamine
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 122
- 239000004642 Polyimide Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 6
- -1 diamine compounds Chemical class 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 23
- 230000001681 protective effect Effects 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 8
- 125000006159 dianhydride group Chemical class 0.000 claims description 7
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 2
- KOBXDXPRULUSCC-UHFFFAOYSA-N 3-phenylbenzene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O KOBXDXPRULUSCC-UHFFFAOYSA-N 0.000 claims description 2
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 40
- 238000002834 transmittance Methods 0.000 abstract description 17
- 125000005462 imide group Chemical group 0.000 description 17
- 239000009719 polyimide resin Substances 0.000 description 16
- 125000000524 functional group Chemical group 0.000 description 15
- 125000003368 amide group Chemical group 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 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 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 229920002647 polyamide Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FZLHLGUYHAXYNA-UHFFFAOYSA-N 2-fluoro-3,3-bis(fluorooxycarbonyl)-2-(trifluoromethyl)butanedioic acid Chemical compound OC(=O)C(F)(C(F)(F)F)C(C(O)=O)(C(=O)OF)C(=O)OF FZLHLGUYHAXYNA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 239000010981 turquoise 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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)
Abstract
The application relates to the technical field of polyimide film materials, in particular to a polyimide composition, a polymer and a film prepared from the composition, a flexible copper-clad plate using the film, a flexible circuit board containing the flexible copper-clad plate and a corresponding display module. The polyimide composition is added with a protection auxiliary agent composed of a compound with carboxylic acid functional groups, and the polyimide material prepared by the polyimide composition has the characteristics of light color and high light transmittance, can greatly reduce the influence on the color display of a light-emitting device, and can also improve the para-position accuracy in the FPC processing process and the processing yield.
Description
Technical Field
The application relates to the technical field of polyimide film materials, in particular to a polyimide composition, a polymer and a film prepared from the composition, a flexible copper-clad plate using the film, a flexible circuit board containing the flexible copper-clad plate and a corresponding display module.
Technical Field
The flexible printed circuit board FPC is an indispensable component part in electronic products such as digital cameras, digital video cameras, automobile navigation instruments, computer accessories and the like, and is also widely used as a circuit board of an LED lamp/lamp strip, a circuit board of a neon lamp/atmosphere lamp, a backlight board of a display screen and the like. Polyimide is used as a high-performance polymer resin and is a key raw material for FPC and electronic circuit industry. When the polyimide film is applied to the display field, polyimide materials used by corresponding FPCs can refer to a polyimide film disclosed in China patent application publication No. CN 113831533A of the applicant, so that the defects of foaming and bubbling can be effectively avoided, and the polyimide film has the advantage of high production efficiency.
However, in practical applications, the polyimide film material is also required to have high light transmittance and a lighter color, so as to avoid the influence of the polyimide material on the color display of the light emitting device. In addition, the transmittance of the polyimide material is improved, the color is lightened, the alignment accuracy in the FPC processing process can be improved, and the processing yield is improved. The benzene ring functional group and the imide ring functional group in the polyimide material are luminescent groups, and color can be displayed in a visible light region due to pi-pi transition of electrons on conjugated benzene rings/double bonds. Polyimide materials can exhibit different colors such as yellow, turquoise, brown, and the like, according to different polyimide molecular chain structures and different ratios of benzene ring functional groups to imide functional groups, and different energy of pi-pi transition. Such colors are among the colors of polyimide materials themselves, and are difficult to remove by other means than adjusting the molecular chain structure.
The prior art adds other non-conjugated functional groups to reduce the color of polyimide materials, such as CN201910214276.2, by reducing the ratio of benzene ring functional groups to imide ring functional groups in the polyimide molecular chain structure. In addition, atoms/functional groups such as carbon, oxygen, nitrogen, isopropyl, ester groups and the like are added between the two benzene ring functional groups, so that the conjugation between the benzene ring functional groups is reduced, pi-pi transition is weakened, and the color of the polyimide material can be greatly adjusted. However, the non-benzene ring functional groups, such as aliphatic molecular chains and alicyclic molecular chains, have poor heat resistance, and the introduction of the non-benzene ring functional groups into the polyimide molecular main chain causes a decrease in heat resistance of the polyimide material.
In addition, some of the prior art has been proposed to neutralize the color of a polyimide material by adding a white inorganic filler to the polyimide material, thereby achieving the purpose of lightening the color. However, the inorganic filler can cause the decrease of the light transmittance of the polyimide material, and influence the color display of the light-emitting component and the circuit alignment in the FPC manufacturing process; the addition of the inorganic filler also causes the mechanical property of the polyimide material to be reduced, and influences the performance of the FPC device.
In addition to this, the color of the polyimide material is also related to its preparation process, such as CN202011033864.5. Although polyimide materials have high temperature resistance, dianhydride/diamine raw materials and polyamic acid intermediates are easily attacked by surrounding oxygen atoms before polyimide is completely generated by reaction, so that the functional groups in the raw materials/intermediates undergo oxidation reaction, and the color is deepened. Diamine raw materials are easily oxidized by oxygen molecules, and quickly change from white to pink in air, and amino groups are converted into nitro groups and other dark functional groups. Polymerization using the diamine raw material after powdering will introduce a dark nitro functional group into the polyimide molecular chain, resulting in darkening of the polyimide material. Also, in the polyamic acid intermediate, the amino group whose terminal is not reacted with the anhydride group is also easily oxidized by oxygen, deepening the color of the final polyimide material. In the polyamic acid intermediate, carboxylic acid and amide groups generated by the reaction of anhydride groups and amino groups also undergo reverse reaction and become anhydride groups and amino groups again; or hydrolyzing to generate amino and dicarboxylic acid groups under the participation of the reaction of water molecules. In any event, the amino groups generated by the polyamic acid intermediate are also easily oxidized by surrounding oxygen molecules, thereby darkening the color of the final polyimide material.
According to the principle of deepening the color of the polyimide material, researchers basically adopt nitrogen protection to isolate oxidation and hydrolysis of raw materials/polyamide acid intermediates by oxygen molecules, water molecules and the like in the environment in the raw material polymerization stage and the polyamide acid molecular chain growth stage. However, pure nitrogen protection is difficult to completely isolate the existence of oxygen molecules and water molecules; because of the high reactivity of amino groups, the oxidation of amino groups can also occur due to the ppm level of molecular oxygen content in the surrounding environment.
Disclosure of Invention
In order to solve the above technical problems, the present inventors have analyzed the preparation process of polyimide materials, further designed/improved the process route and process parameters of polymerization and chain growth, so as to further lighten the color of the polyimide material and maximize the light transmittance thereof, and have further devised a polyimide composition, a polymer and a film made of the composition, a flexible copper-clad laminate using the film, a flexible circuit board comprising the flexible copper-clad laminate, and a corresponding light-emitting device.
The specific technical scheme is as follows:
a polyimide composition comprising:
monomers and solvents;
the monomer comprises dianhydride compounds and diamine compounds, wherein the molar ratio of the dianhydride compounds to the diamine compounds is (0.8-1.0): 1.0; the solvent is a polar solvent;
preferably, the solvent is any one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and r-butyrolactone, and the solvent accounts for 80-90% of the total weight of the solution; preferably an amide-based strongly polar solvent;
the dianhydride compound is a compound with a structure shown in a formula I:
in formula I, ar comprises C 6 ～C 40 Any one or more of tetravalent substituted aryl groups of (a);
the diamine compound comprises p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, compound with structure shown in formula II, compound with structure shown in formula III and C 13 ～C 30 Any one or more of fluorenyl diamine-containing compounds:
in formula II, R 1 ～R 8 Each independently selected from-H, -CF 3 、C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 R is any one of alkoxy, R 9 Selected from-O-, -NH-, -CH 2 -, -CONH-, phenylene, -COO-, -SO 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-O-Ar 2 -O-、-COO-Ar 3 -OOC-、-CONH-Ar 4 -NHOC-any one of said Ar 2 、Ar 3 、Ar 4 Each independently selected from C 6 ～C 20 A substituted or unsubstituted divalent substituted aryl group, said C 6 ～C 20 The substituents in the substituted divalent substituted aryl group of (a) are selected from the group consisting of-H, -CF 3 、C 1 ～C 6 Any one of alkyl groups and halogen atoms;
in formula III, R 10 ～R 17 Each independently selected from-H, -CF 3 、C 1 ～C 6 Any one of the alkyl groups of (a);
the polyimide composition also comprises a protection auxiliary agent;
the protective auxiliary agent is a compound with carboxylic acid functional groups, wherein the molar ratio of the carboxylic acid groups to the amino groups in the diamine compound is (0.01-0.6) (1.0).
The protective auxiliary comprises benzoic acid, 2-naphthoic acid, 2-anthranilic acid, phthalic acid, terephthalic acid, 2 '-biphthalic acid, 4' -biphthalic acid, 1, 8-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 1,2, 4-benzene tricarboxylic acid, 2,4 '-biphenyl tricarboxylic acid, pyromellitic acid, 3',4,4 '-biphenyltetracarboxylic acid, 2, 3',4 '-biphenyltetracarboxylic acid, 3',4,4 '-diphenyl ether tetracarboxylic acid, 5' -oxidized isophthalic acid, 3',4' -benzophenone tetracarboxylic acid, 5 '-carbonylbisisophthalic acid, 3', a composition of one or more of 4,4 '-bisphenol a-type diether tetracarboxylic acid, 1,2,3, 4-cyclobutane tetracarboxylic acid, 1,2,4, 5-cyclohexane tetracarboxylic acid, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane, and mellitic acid.
Preferably, the amounts of the substances of carboxylic acid groups in the dianhydride-type compound, the diamine-type compound and the protection aid satisfy the following relation:
1.0≤(2b+c):2a≤1.3；
wherein a is the amount of the diamine compound, b is the amount of the dianhydride compound, and c is the amount of the carboxylic acid group protecting agent.
In the polymerization stage of preparing the polyimide polymer, the composition of the technical scheme adds the protection auxiliary agent into the polymerization reaction liquid, so that amino groups on a molecular chain can be fully protected, the oxidation of the amino groups is avoided, further, the generation of dark nitro functional groups is avoided, the color of a final polyimide material is lightened, and the purpose of controlling the color of the polyimide material is achieved.
Further, the inventors found that: in the imidization process at high temperature, carboxyl and amino in the compound with carboxylic acid functional groups can generate amide groups or imide groups at high temperature, so that on one hand, the molecular chain is prolonged, and the stability of the molecular chain is improved; on the other hand, oxidation of the amino groups is also directly avoided. Therefore, the protective aid is preferably a compound having a carboxylic acid functional group, and specifically may be any one or more of a monocarboxylic acid functional group compound, a dicarboxylic acid functional group compound, a tricarboxylic acid functional group compound, a tetracarboxylic acid functional group compound, and a hexacarboxylic acid functional group compound.
Further, the inventors found that: the tetracarboxylic acid functional group compound can react with two terminal amino groups to form a long-chain high polymer, namely, two imide ring structures are formed after the imidization temperature is high, the two imide ring structures serve as linking units of a molecular main chain and have an effect of promoting the growth of a final polyimide molecular chain, and the formed imide ring has the same structure as other imide rings obtained by reacting dianhydride/diamine functional groups on the polyimide molecular main chain, so that the mechanical property, the dimensional stability, the heat resistance and the like of the polyimide material prepared by the technical scheme are not influenced.
Thus, the protective aid is preferably a composition of any one or more of the tetracarboxylic acid functional compounds, in particular pyromellitic acid, 3',4' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 3', a composition of one or more of 4,4' -diphenyl ether tetracarboxylic acid, 3',4' -benzophenone tetracarboxylic acid, bisphenol a type diether tetracarboxylic acid, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane tetracarboxylic acid, 1,2,4, 5-cyclohexane tetracarboxylic acid.
The composition according to any of the above embodiments can be used for preparing polyimide polymers by imidization.
In the present application, a typical reaction process for reacting a dianhydride and a diamine to form a polyimide precursor resin is as follows:
the process of reacting a protective auxiliary (carboxylic acid compound) with a polyimide precursor resin to obtain an internal salt is as follows, the exposed amino groups are protected:
subsequently, under high temperature conditions (over 200 ℃), the amidic acid groups undergo a dehydration reaction to give an imide ring, typical of polyimide resins; the inner salt functional group with the function of protecting the amino group can also carry out high-temperature dehydration reaction to obtain the amide group. The reaction process is as follows:
the carboxyl and amino groups generate inner salt functional groups, and the inner salt functional groups generate amide groups at high temperature, so that terminal/redundant amino groups in the reaction process of polyimide precursor resin and the high-temperature generation process of polyimide resin are not decomposed at high temperature and oxidized by free oxygen molecules, and meanwhile, the molecular chain of the polyimide resin can be prolonged through the generation of the amide groups, and the thermal stability, mechanical property and the like of the polyimide resin are improved.
The preparation process of the polyimide polymer in the present application can be described as follows:
(1) Adding a strong polar amide solvent into a sealable container, and using high-purity nitrogen to replace oxygen in the reaction container and dissolved oxygen in the solvent for 0.5-4 hours; the temperature of the reaction solution is controlled to be 0-50 ℃. Then adding a proper amount of protective auxiliary agent, and completely dissolving; adding diamine compound into the solution, and dissolving completely. Then, dianhydride compound is added in three batches, the addition amount of each batch is 60%, 30% and 10%, and the reaction is carried out. The reaction time is controlled between 4 and 48 hours. In the reaction process, except for a short period of material feeding, nitrogen needs to be introduced in the whole process, and the oxygen content in the gas of the reaction system is controlled below 1000ppm so as to eliminate the influence of oxygen on reactants and products.
(2) The protective auxiliary is added before the diamine compound is added, so that the protection can be provided before the amino groups in the diamine compound are oxidized by residual oxygen; nitrogen is continuously introduced in the reaction process, and the oxidation of residual oxygen to amino groups can be eliminated. After the reaction is finished and the continuous introduction of nitrogen is stopped, the protective auxiliary agent and the residual amino/terminal amino form inner salt or form intermolecular hydrogen bond acting force, so as to protect the redundant residual amino/terminal amino from being oxidized by residual oxygen in the gas of the reaction system.
(3) The polyimide precursor resin solution obtained by the reaction has no residual amino/terminal amino exposed, can not contact and react with residual oxygen in the gas of the reaction system, can not introduce dark functional groups such as nitro functional groups and the like on the polyimide molecular main chain, and can control the color of the final polyimide resin or polymer product to the shallowest degree.
When the protective auxiliary agent used in (4-1) is a monocarboxyl compound, the carboxyl group and the amino group react to generate an amide group, and the protective auxiliary agent has a blocking effect on the molecular chain of the polyimide resin. In the process, the thermal decomposition of amino and the reaction of amino and oxygen are avoided, so that the color of the polyimide resin is not influenced by dark groups such as nitro and the like. The reaction process can be as follows:
when the protective auxiliary agent used in (4-2) is a dicarboxylic compound (two carboxyl groups are in ortho positions), one carboxyl group reacts with an amino group to generate an inner salt, and the other carboxyl group can react with the inner salt functional group under high temperature conditions (more than 200 ℃) to obtain an imide group. The thermal stability of the imide group is higher than that of the amide group, so that the dicarboxyl compound is used as a protection auxiliary agent, and the thermal stability of the prepared polyimide resin is improved. The reaction process can be as follows:
the protective auxiliary used in (4-3) is a dicarboxylic compound (the two carboxyl groups are not in ortho positions), and the reaction process is greatly different from that in (4-2). Because of steric hindrance, two carboxyl groups can react with two amino groups respectively to generate inner salt, and then the inner salt reacts at high temperature to obtain an amide group; therefore, the molecular chain main chain of the finally obtained polyimide resin is prolonged, the molecular weight is remarkably increased, and the mechanical properties and the like are improved. Of course, the two carboxyl groups may also react with only one amino group, and the imide ring (the non-most stable 5-membered ring structure) is finally obtained with reference to the reaction process of (4-2). The thermal stability of the molecular main chain obtained in both cases will be weaker than that of the polyimide resin obtained in (4-2). The reaction process at this time can be illustrated as follows:
the case where the protective auxiliary used in (4-4) is a tricarboxyl compound or a tetracarboxylic acid compound will be relatively similar to those in (4-2) and (4-3); the difference is that tricarboxy compounds or tetracarboxylic compounds can obtain polyimide molecular chain backbones (even network structures) with a plurality of amide groups linked; polyimide molecular chain backbones can also be obtained in which the amide groups and imide groups together act as linking units. However, due to the increase of carboxyl functional groups, both the amide groups and the imide groups can be used as linking units, so that not only is the heat resistance of the polyimide molecular chain improved through the generation of the imide ring groups, but also the main chain of the polyimide molecular chain is prolonged, the molecular weight is increased, the thermal stability of the polyimide resin is improved, and meanwhile, the mechanical properties of the polyimide resin and other mechanical properties are enhanced. In particular, in the case of the tetracarboxylic acid compound having four carboxyl groups in the ortho-position state, the molecular chain structure obtained by the formation of the inner salt and the formation of the imide ring under the condition of high Wen Tiao is consistent with the imide ring obtained by the reaction of the dianhydride compound and the diamine compound. The polyimide molecular chain main chain obtained at this time does not contain an amide group, and the molecular chain is prolonged to the maximum extent, and heat resistance, mechanical properties and the like are preferable. The reaction process may be exemplified as follows:
the composition according to any one of the above technical schemes is prepared to form a polyimide film.
The thickness of the polyimide film is between 5 and 50 mu m.
The polyimide film in any one of the above technical schemes can be used as at least part of base materials for forming the flexible copper clad laminate, and the thickness of the copper foil is 9-70um.
The flexible copper clad laminate according to any one of the above technical schemes can be used as a component of a flexible circuit board.
The flexible circuit board according to any of the above technical solutions may be used as a component of a display module, such as an OLED display panel, an automotive interior light circuit board, a neon light circuit board, and the like.
In summary, the technical scheme of the application has the following main beneficial effects:
the polyimide material prepared by the polyimide composition has the characteristics of light color and high light transmittance, and can greatly reduce the influence on the color display of the light-emitting device;
in addition, the polyimide film material can also improve the para-position precision in the FPC processing process and improve the processing yield.
Further or more detailed benefits will be described in connection with specific embodiments.
Detailed Description
The application is further illustrated by the following examples:
the core technical problem faced by the technical scheme of the embodiment of the application is derived from the adverse effect of the color display and the light transmittance of the polyimide material on the color display of the light emitting device and on the FPC processing yield.
Therefore, on the basis of the prior art, how to further lighten the color of the polyimide material and improve the light transmittance of the polyimide material is a technical problem to be solved by the inventor.
The solution of the technical problem is benefited by the deep analysis of the polyimide material forming process by the inventor, and based on the deep analysis, the inventor can select a proper protection auxiliary agent to complete the technical task faced by the application.
It should be noted that, the embodiments do not limit the scope of the claims of the present application, and according to the technical concepts provided/proven by the embodiments, those skilled in the art can reasonably expect technical solutions to be covered in the scope of the claims of the present application.
The examples are detailed below:
the preparation method of the polyimide film in the embodiment and the comparative example of the application is as follows:
(1) Preparing polyimide precursor resin solution: under the nitrogen atmosphere, adding a strong polar amide solvent into a container, introducing nitrogen into the solvent for treatment for 0.5-4h, and fully removing dissolved oxygen in the solvent; dissolving the corresponding protection auxiliary agent in a solvent while stirring, wherein the total mole number of carboxyl groups in the protection auxiliary agent is c mole; then adding a mole of diamine compound, and completely dissolving to make the mass percentage of the diamine compound in the solution be 5% -13%; b, controlling the temperature of the solution to be 0-50 ℃ under the nitrogen atmosphere, and adding b moles of dianhydride compounds into the solution for three times, wherein the addition amount of each time is 60%, 30% and 10% of the total weight of the dianhydride compounds respectively; continuously reacting for 4-48h under nitrogen atmosphere, controlling the temperature of the solution at 0-50 ℃, and obtaining polyimide precursor resin solution after the reaction; wherein b is more than or equal to 0.8 and less than or equal to 1.0, c is more than or equal to 0.01 and less than or equal to 0.6, and preferably (2b+c) is more than or equal to 1.0 and less than or equal to 1.3; introducing nitrogen in the whole reaction process, and controlling the oxygen content in the gas to be below 1000 ppm;
(2) Coating the polyimide precursor resin solution prepared in the step (1) on a carrier, so that the thickness of a film layer of the dried polyimide precursor resin is 5-70 mu m; then volatilizing and removing the solvent in a nitrogen atmosphere at 80-150 ℃ to ensure that the solvent content is 10-40wt% so as to obtain a dry film layer of polyimide precursor resin;
(3) Thermally curing the carrier coated with the polyimide precursor resin dry film layer in a nitrogen atmosphere (oxygen content is below 500 ppm) at a temperature of 280-350 ℃; the polyimide precursor resin dry film layer is cured to form a polyimide resin film base layer;
(4) Cooling to room temperature, and removing the polyimide resin film base layer in the step (3) from the surface of the carrier by a water boiling method to obtain a high-light-transmission polyimide resin film;
(5) When the carrier is copper foil, cooling to room temperature after the step (3) to obtain the flexible copper-clad plate product of the high-light-transmittance polyimide resin.
Examples 1-30 the preparation methods were as described in (1) - (5) above,reference is made to the preparation methods of comparative examples 1-7Above it In the steps (1) to (5), the nitrogen gas is not introduced in the steps (1) to (2), and only the atmosphere of air is maintained.
Table 1 raw material numbers and names used in examples and comparative examples
The formulations of the polyimide compositions corresponding to examples 1 to 30 and comparative examples 1 to 7 are shown in tables 2 to 9, in which the molar ratio of each example is merely used to compare the magnitudes of the molar contents of the components in the same example, and the actual addition amounts are referred to the parameters of the mass column.
TABLE 2 formulation of polyimide compositions corresponding to examples 1 to 5
TABLE 3 formulation of polyimide compositions corresponding to examples 6-10
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TABLE 4 formulation of polyimide compositions corresponding to examples 11 to 15
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TABLE 5 formulation of polyimide compositions corresponding to examples 16-20
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TABLE 6 formulation of polyimide compositions corresponding to examples 21-25
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TABLE 7 formulation of polyimide compositions corresponding to examples 26 to 30
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Table 8 formulations of polyimide compositions corresponding to comparative examples 1 to 5
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Table 9 formulations of polyimide compositions corresponding to comparative examples 6 and 7
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The performance parameters of the polyimide film materials formed in examples 1 to 30 and comparative examples 1 to 7 are shown in Table 10:
TABLE 10 Performance parameters of polyimide film materials formed in examples 1-30 and comparative examples 1-7
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The test method of the performance parameters in table 10 is:
transmittance @550nm, transmittance average @500-760nm, cut-off wavelength: and (3) using an ultraviolet spectrophotometer as transmission spectrum characterization, and recording the light transmittance of 550nm wavelength, the average light transmittance of 500-760nm wavelength and the cut-off wavelength respectively.
Thermal decomposition temperature: the thermogravimetric profile was tested using a thermogravimetric analyzer (TA Q50) at a 20 ℃/min ramp rate and the temperatures at 1% and 5% mass loss were recorded, respectively.
Tensile strength: the method is carried out on a universal testing tensile machine, specifically, a polyimide film sample is cut into strips with the width of 1cm, the thickness is measured, and the strips are placed on a clamp of the tensile machine. The tensile machine selects a clamp with proper measuring range, the stretching speed of the clamp is 50.8mm/min, and the clamping interval of the breaking elongation clamp is 5cm. According to the standard test process and data processing of the tensile machine, the corresponding tensile strength is directly read from the instrument.
As can be seen from table 10, in general, the light transmittance properties of examples 1 to 30 are overall better than those of comparative examples 1 to 7, in which no protective aid was added, while the addition of the protective aid had no adverse effect on the thermal stability and mechanical properties.
Since dianhydride and dianhydride monomer types may affect the light transmittance of the polyimide film, the light transmittance at 550nm is 64% when the additive amount of the protective aid is 0, and the light transmittance increases as the (carboxyl: diamine) ratio increases, compared with comparative example 7 using examples 26 to 30, for the single variable principle.
The dianhydride and diamine monomers used in examples 1 to 3 were the same, but the light transmittance values in examples 1 to 3 were successively decreased because the addition amount of the protective aid in example 3 was small and the addition amount of the protective aid in example 1 was largest.
The dianhydride and diamine monomers used in examples 4-7 were the same, but the values of the addition amount of the protective aid (carboxylic acid: diamine) were successively decreased, and the thermal decomposition temperature and tensile strength values also tended to decrease, indicating that the addition of a certain amount of carboxylic acid compound could improve the thermal and mechanical properties of the polyimide film.
In example 14, the diamine dianhydride monomer type and the amount added were the same as those in example 15, and the amount of the protective aid was the same, but in example 14, the tetracarboxylic acid compound was added, the thermal stability and mechanical properties were better than in example 15, in which the dicarboxylic acid compound was added.
In the description of the present specification, reference to the terms "embodiment," "base embodiment," "preferred embodiment," "other embodiments," "example," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A polyimide composition characterized in that:
comprises the following steps:
monomers and solvents;
the monomer comprises dianhydride compounds and diamine compounds, wherein the molar ratio of the dianhydride compounds to the diamine compounds is (0.8-1.0): 1.0; the solvent is a polar solvent;
the polyimide composition also comprises a protection auxiliary agent;
the protection auxiliary agent comprises a compound with carboxyl, wherein the molar ratio of the carboxyl to the amino group in the diamine compound is (0.01-0.6): 1.0;
the dianhydride compound is a compound with a structure shown in a formula I:
；
in formula I, ar comprises C 6 ~C 40 Any one or more of tetravalent substituted aryl groups of (a);
the diamine compound comprises p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, compound with structure shown in formula II, compound with structure shown in formula III and C 13 ~C 30 Any one or more of fluorenyl diamine-containing compounds:
，/>；
in formula II, R 1 ~R 8 Each independently selected from-H, -CF 3 、C 1 ~C 6 Alkyl, C of (2) 1 ~C 6 R is any one of alkoxy, R 9 Selected from-O-, -NH-, -CH 2 -, -CONH-, phenylene, -COO-, -SO 2 -、-C（CH 3 ） 2 -、-C（CF 3 ） 2 -、-O-Ar 2 -O-、-COO-Ar 3 -OOC-、-CONH-Ar 4 -NHOC-any one of said Ar 2 、Ar 3 、Ar 4 Each independently selected from C 6 ~C 20 A substituted or unsubstituted divalent substituted aryl group, said C 6 ~C 20 The substituents in the substituted divalent substituted aryl group of (a) are selected from the group consisting of-H, -CF 3 、C 1 ~C 6 Any one of alkyl groups and halogen atoms;
in formula III, R 10 ~R 17 Each independently selected from-H, -CF 3 、C 1 ~C 6 Any one of the alkyl groups of (a);
the amounts of the substances of carboxylic acid groups in the dianhydride compound, the diamine compound and the protection aid satisfy the following relational expression:
1.01 ≤ ( 2b + c ) : 2a ≤ 1.3；
wherein a is the amount of the diamine compound, b is the amount of the dianhydride compound, and c is the amount of the carboxylic acid group protecting agent.
2. The polyimide composition according to claim 1, characterized in that: the protective auxiliary comprises benzoic acid, 2-naphthoic acid, 2-anthranilic acid, phthalic acid, terephthalic acid, 2 '-biphthalic acid, 4' -biphthalic acid, 1, 8-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 1,2, 4-benzene tricarboxylic acid, 2,4 '-biphenyl tricarboxylic acid, pyromellitic acid, 3',4,4 '-biphenyltetracarboxylic acid, 2, 3',4 '-biphenyltetracarboxylic acid, 3',4,4 '-diphenyl ether tetracarboxylic acid, 5' -oxidized isophthalic acid, 3',4' -benzophenone tetracarboxylic acid, 5 '-carbonylbisisophthalic acid, 3', a composition of one or more of 4,4 '-bisphenol a-type diether tetracarboxylic acid, 1,2,3, 4-cyclobutane tetracarboxylic acid, 1,2,4, 5-cyclohexane tetracarboxylic acid, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane, and mellitic acid.
3. The polyimide composition according to claim 1, characterized in that: the protection aid comprises any one or more of a monocarboxylic acid compound, a dicarboxylic acid compound and a tetracarboxylic acid compound.
4. The polyimide composition according to claim 1, characterized in that: the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and r-butyrolactone, and accounts for 80-90% of the total weight of the solution.
5. The polyimide composition according to claim 1, characterized in that: in the process of preparing polyimide polymer by the polyimide composition, the following steps are included: except for a short feeding time period, nitrogen is required to be introduced in the whole process, and the oxygen content in the gas of the reaction system is controlled below 1000 ppm; and adding a protective auxiliary before adding the diamine compound.
6. A polyimide polymer characterized in that: prepared from the composition of any one of claims 1-5.
7. Polyimide film, its characterized in that: formed from the polyimide composition of any one of claims 1 to 5.
8. The flexible copper-clad plate is characterized in that: comprising the polyimide film according to claim 7 and a copper foil; the thickness of the polyimide film is 5-50 um, and the thickness of the copper foil is 9-70um.
9. The flexible circuit board, its characterized in that: comprising the flexible copper-clad plate according to claim 8.
10. Display module assembly, its characterized in that: a flexible circuit board comprising the device of claim 9.
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020091432A1 (en) * | 2018-10-31 | 2020-05-07 | 에스케이씨코오롱피아이 주식회사 | Polyimide precursor composition for enhancing adhesiveness of polyimide film and polyimide film manufactured therefrom |
| CN110317339A (en) * | 2019-07-31 | 2019-10-11 | 武汉柔显科技股份有限公司 | Polyimide precursor, Kapton and the display device including the film |
| CN112500569A (en) * | 2021-02-04 | 2021-03-16 | 武汉柔显科技股份有限公司 | Polyimide precursor composition, polyimide film, laminated film, and display device |
| CN113831533A (en) * | 2021-07-30 | 2021-12-24 | 杭州福斯特电子材料有限公司 | Polyimide composition, polyimide polymer, polyimide film and flexible copper clad laminate |
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