CN117004362A - Adhesive and preparation method and application thereof - Google Patents
Adhesive and preparation method and application thereof Download PDFInfo
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- CN117004362A CN117004362A CN202311016117.4A CN202311016117A CN117004362A CN 117004362 A CN117004362 A CN 117004362A CN 202311016117 A CN202311016117 A CN 202311016117A CN 117004362 A CN117004362 A CN 117004362A
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- Prior art keywords
- adhesive
- dianhydride
- integer
- stirring
- residue
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- 239000000853 adhesive Substances 0.000 title claims abstract description 122
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 diamine compound Chemical class 0.000 claims abstract description 50
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 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 26
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 10
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012346 acetyl chloride Substances 0.000 claims description 5
- 238000004377 microelectronic Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- SAVPSRHNNQVBLW-UHFFFAOYSA-N 3,5-diethylpyridine Chemical compound CCC1=CN=CC(CC)=C1 SAVPSRHNNQVBLW-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 claims description 4
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 claims description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 claims description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 49
- 229920002647 polyamide Polymers 0.000 abstract description 49
- 239000012458 free base Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- 239000010949 copper Substances 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000002253 acid Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 229920001721 polyimide Polymers 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000523 sample Substances 0.000 description 15
- 239000004642 Polyimide Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002998 adhesive polymer Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- NFSQGQXKVFGKSO-UHFFFAOYSA-N 3-(2-phenylphenoxy)aniline Chemical group NC1=CC=CC(OC=2C(=CC=CC=2)C=2C=CC=CC=2)=C1 NFSQGQXKVFGKSO-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, and provides an adhesive, a preparation method and application thereof. The structure of the adhesive is shown as a structural formula I:wherein x is an integer from 1 to 500, y is an integer from 1 to 500, n is an integer from 1 to 500, ar is the residue of a primary diamine, A is the residue of a tetracarboxylic dianhydride, and B is the residue of a tetracarboxylic dianhydride. The preparation method of the adhesive comprises the following steps: step (1): mixing a diamine compound and a dianhydride compound with a solvent under inert atmosphere, and stirring to obtain a viscous solution; and (2) adding an auxiliary agent into the viscous solution, and stirring to obtain the adhesive. The adhesive prepared by the invention introduces diamine compound 2- (2-aminofuranyl) in the formula5-aminobenzimidazole (2-AFBM), and copolymerizing the 2-AFBM with other diamine compounds and dianhydride compounds to obtain the polyamide adhesive. The adhesive can be used for preparing FCCL materials with high peel strength and corrosion-free base materials.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an adhesive, a preparation method and application.
Background
Polyamide acid is a precursor for synthesizing polyimide and is generally obtained by stepwise polymerization of diamine and dicarboxylic anhydride in solution. The slurry of polyamic acid may be used for bonding of metals (e.g., titanium, copper, aluminum, steel, etc.), non-metals (e.g., silicate, silicon wafer, silicon nitride, etc.), and polymeric substrates. The polyamide acid adhesive generally comprises polyamide acid resin, a solvent and an auxiliary agent, wherein the polyamide acid resin is generated in situ through solution polymerization, and the addition of the auxiliary agent can adjust the performances such as viscosity, drying speed, imidization speed and the like of the slurry.
In general, a polyamide adhesive is applied by a high Wen Tuorong and imidization process to convert the solute polyamide into polyimide. The polyamide acid and polyimide main chain contain rich carbonyl groups, and the characteristic structure imide ring is strong in polarity, so that the polyamide acid and polyimide main chain are sources of good adhesive performance. Polyimide after imidization of the polyamic acid adhesive has many advantages such as high strength, low CTE value, excellent heat resistance and chemical resistance, and the like.
As the monomer is rich in variety and source, the polyamide acid adhesive can be suitable for various application scenes by adjusting the chemical structure. Taking the bonding metal substrate as an example, the bonding metal substrate can be classified into a polyamide/polyimide adhesive for copper foil or aluminum foil bonding and a high temperature resistant polyamide/polyimide adhesive for bonding titanium alloy. The former is mainly used in the field of integrated circuits, and the latter is mainly used for bonding aircraft and structural members thereof.
With the development of the integrated circuit field, the high dielectric constant and high adhesion to copper of polyimide materials have led to their widespread use in the preparation of flexible printed circuit boards (FCCLs). However, in the process of preparing the copper-clad plate by using the precursor polyamide acid adhesive and the copper foil, carboxyl in the polyamide acid interacts with the copper foil, and generated copper ions diffuse into the polyamide acid layer, so that the electrical property of the polyamide acid layer serving as a dielectric layer is reduced. At the same time, copper and cuprous ions diffused into the dielectric layer further aggravate degradation and oxidation side reaction of the polyamide acid adhesive in the heat curing process, so that the peeling strength and thermal and mechanical properties of the dielectric layer are further reduced.
In order to avoid the diffusion and oxidation phenomena of copper, early researchers proposed the use of polyamide esters and polyisoimides without acidity instead of polyamide acids, but these prepolymers were more cumbersome to synthesize and had inferior adhesion to copper than to polyamide acids. More methods are applied to build up a barrier layer at the interface of polyimide and copper, in which methods imidazole and its derivative polymers are commonly used to make such barrier layers: for example, (1) Jang et al use a copolymer of vinylimidazole and vinyltrimethoxysilane as a barrier for polyimide with copper, jang J, earmme T.Polymer,2001,42:2871; (2) Yu et al used Polyaryletherbenzimidazole (PAEBI) as a primer for copper foil to improve the adhesion of BPDA/PPD to copper, but phase separation occurred when polyamide ester was used resulting in reduced peel strength, yu J, reeM, shin T J, park Y H, cai W, zhou D, lee K W.macromol.chem.Phys.,2000,201:491; (3) Liang et al, using a Kapton film impregnated with Si-imidazole to combine with a copper plate, found a 1.5 fold increase in peel strength to copper, and found a failure mainly between the Si-imidazole layer and the Kapton film during peeling, liang G, fan J.J.appl.Polym.Sci.,1999,73:1645; (4) Kim et al used a polymer containing imidazole and silanol in its pendant groups as primer to improve the adhesion of polyimide films to copper, kim H, jang J.J.appl.Polym.Sci.,2000,78:2518.
As described above, in order to solve the diffusion and oxidation phenomena of copper, the original method uses the complexation of imidazole ring and copper in the barrier layer to isolate the diffusion of copper ions to the polyimide layer and increase the adhesion of the adhesive and copper. However, the adhesion between the polymer layers is insufficient due to the difference of chemical structure and solubility parameters between the barrier layer and the polyimide layer, and phase separation occurs during preparation in severe cases, so that the peeling strength of the coating is affected. The difference of linear thermal expansion Coefficients (CTE) of the barrier layer and the polyimide layer can lead the copper-clad plate to warp or lead the film to generate internal stress in the preparation process, thereby damaging the structure of the copper-clad plate workpiece. Meanwhile, the process for preparing the copper-clad plate with the barrier layer is relatively complicated. Thus, this method is not currently being used on a large scale in the industry.
At present, the production path for preparing the FCCL by coating the polyamide acid slurry on other substrates, aminating and stripping the polyimide film with high Wen Ya content to obtain the self-supporting polyimide film, and then compositing the polyimide film and the copper foil under the high-temperature condition is generally adopted in the industry, so that the corrosion of the polyamide acid to the metal substrate can be avoided to a certain extent. However, with this route, the film does not react with the substrate sufficiently because of not imidization in situ on the copper foil, resulting in limited peel strength of the film in FCCL. Meanwhile, in order to ensure that the modulus of the polyimide film is rapidly reduced under high temperature and pressure conditions, forming a resin with a certain viscoelasticity, it is necessary to use a flexible monomer which greatly reduces Tg of the product, which adversely affects tensile strength, CTE and heat-resistant temperature of the product.
In view of the above, in the field of base materials in the microelectronics industry, there is a lack of polyamic acid adhesives that can achieve high peel strength by direct coating without corroding the substrate.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an adhesive and a preparation method and application thereof. The diamine compound 2- (2-amino furyl) -5-amino benzimidazole (2-AFBM) is introduced into the formula of the adhesive, and the polyamide adhesive is obtained by copolymerizing the 2-AFBM with other diamine compounds and dianhydride compounds. The adhesive can be used for preparing FCCL materials with high peel strength and corrosion-free base materials.
In a first aspect, the present invention provides an adhesive, where the adhesive structure is shown in structural formula I:
wherein,
x is selected from an integer between 1 and 500,
y is selected from an integer between 1 and 500,
n is selected from an integer between 1 and 500,
ar is a residue of a primary diamine, and A, B is independently a residue selected from tetrahydric dianhydride, and A, B may be the same or different.
As a specific embodiment of the invention, x is selected from integers between 1 and 50, y is selected from integers between 1 and 50, and n is selected from integers between 1 and 200.
As a specific embodiment of the present invention, the residue of the primary diamine is selected from one or more of the following groups:
as a specific embodiment of the present invention, the residue of the tetracarboxylic dianhydride is selected from one or more of the following groups:
in a second aspect, the invention provides a preparation method of an adhesive, wherein the preparation process of the adhesive adopts the following raw materials: diamine compounds, dianhydride compounds, solvents and adjuvants; the preparation method of the adhesive comprises the following steps:
step (1): mixing a diamine compound and a dianhydride compound with a solvent under inert atmosphere, and stirring to obtain a viscous solution;
step (2): and adding an auxiliary agent into the viscous solution, and stirring to obtain the adhesive.
As a specific embodiment of the present invention, the inert atmosphere may be N 2 。
As a specific embodiment of the present invention, the stirring conditions in step (1) include: stirring for 1-240 min at-15 to-10 deg.C, stirring for 1-240 min at-5 deg.C, stirring for 1-240 min at 5-15 deg.C, stirring for 1-240 min at 35-45 deg.C.
As a specific embodiment of the present invention, the sum of the mass of the diamine compound and the dianhydride compound in the step (1) is 10 to 20% of the total mass of the viscous solution.
As a specific embodiment of the present invention, the stirring conditions in step (2) include: the stirring time is 1-240 min.
As a specific implementation of the present invention, the diamine compound comprises at least 2- (2-aminofuranyl) -5-aminobenzimidazole;
preferably, the diamine compound further comprises one or more of p-phenylenediamine, m-phenylenediamine, 4 '-diaminophenyl ether, 4' -biphenyldiamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-diaminobenzophenone, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 4' -bis (3-aminophenoxy) biphenyl;
as specific embodiments of the present invention, the dianhydride compound is selected from one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride;
as a specific embodiment of the present invention, the molar ratio of the diamine compound to the dianhydride compound is 1: (0.95-1.05).
The adhesive prepared by copolymerizing the 2-AFBM and the rest diamine compounds and dianhydride compounds serving as monomers can achieve the following purposes after being coated on the surface of a substrate:
(1) The adhesive is obtained through copolymerization of monomers, the uniformity of the adhesive formula and CET can be ensured to be the same as possible, and the problems of phase separation between the adhesive and the barrier layer caused by non-uniform adhesive formula and internal stress of the adhesive coating caused by different CTE values in the existing research are eliminated;
(2) Compared with the prior art, the adhesive prepared by the method has the advantages that firstly, the adhesive is coated on other substrates, and then the substrate is peeled off and then conforms to the method on the substrate to be coated, and compared with the method on the substrate to be coated, the adhesive prepared by the method can be directly coated, so that the locking effect and the contact area between the adhesive and the uneven substrate can be maximized, and the peeling strength is increased; the "latch effect" in the present invention refers to the interaction force generated between the adhesive and the substrate due to chemical bond, intermolecular force, etc.
(3) Alkaline imidazole and furan rings are introduced into the main chain of the structural formula I of the adhesive, so that the pH value of the polyamic acid solution can be regulated, the corrosion effect of carboxyl groups on the polyamic acid on copper at high temperature is weakened, and the complexation of the imidazole can increase the peel strength and capture diffused copper ions;
(4) In the prior art, furan derivatives are used in the preparation of the 2-AFBM monomer, most of the furan derivatives are derived from furfural prepared from corncobs which are non-grain biomass sources, so that the use proportion of renewable raw materials in the adhesive can be improved;
(5) N-H in the 2- (2-amino furyl) -5-amino benzimidazole can form a stable hydrogen bond with furan ring O atoms on a nearby polymer chain to block the thermal movement of a polymer chain segment, regulate and control the linear thermal expansion coefficient of a product, prevent the FCCL product from warping, and improve the tensile strength and softening temperature of the product to a certain extent.
As specific embodiments of the present invention, the solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and gamma-butyrolactone;
as specific embodiments of the invention, the auxiliary agent comprises one or more of acetyl chloride, acetic anhydride, benzoic acid, trifluoroacetic anhydride, triethylamine, imidazole, benzimidazole, pyridine, 3-methylpyridine, 3, 5-diethylpyridine, quinoline and isoquinoline.
Preferably, the molar amount of the auxiliary agent is 0.1% -40% of the sum of the molar amounts of the diamine compound and the dianhydride compound;
preferably, the molar amount of the auxiliary agent is 10 to 30% of the sum of the molar amounts of the diamine compound and the dianhydride compound.
In a third aspect, the present invention provides an adhesive according to the first aspect of the present invention and an application of the adhesive according to the second aspect of the present invention in a microelectronic composite material.
Preferably, the method is applied to the field of flexible copper-clad plates.
In a fourth aspect, the present invention provides a method for using the adhesive provided in the first aspect of the present invention and the adhesive prepared by the preparation method provided in the second aspect of the present invention, including: coating the adhesive on the surface of a substrate, attaching a material to be bonded on the surface of the adhesive to obtain a bonding object, and performing desolventizing treatment and heat treatment on the bonding object to obtain a bonded device.
Preferably, the desolventizing conditions include: the temperature is 40-200 ℃ and the time is 1-4 h. Coating the adhesive on the surface of a substrate to be bonded, attaching a material to be bonded on the surface of the adhesive, applying a certain pressure to obtain a bonding object, placing the bonding object in a desolventizing device at 40-200 ℃, and treating for 1-4 h to remove the solvent. The coating mode in the invention can be one of casting, spin coating, dipping or spraying.
Preferably, the heat treatment conditions include: the temperature is 250-350 ℃ and the time is 2-8 h. Transferring the adhesive after solvent removal to an explosion-proof vacuum drying device, an air blast drying device or a sintering furnace, and performing heat treatment for 2-8 hours at the temperature of 250-350 ℃ to ensure that the characteristic chemical structure of the adhesive is converted from the structural formula I to the structural formula II.
As a specific embodiment of the invention, the adhesive after heat treatment is shown in the structural formula II:
wherein the method comprises the steps of，
x is selected from an integer between 1 and 500,
y is selected from an integer between 1 and 500,
n is selected from an integer between 1 and 500,
ar is the residue of a primary diamine, A is the residue of a tetracarboxylic dianhydride, and B is the residue of a tetracarboxylic dianhydride.
Preferably, x is selected from integers between 1 and 50, y is selected from integers between 1 and 50, and n is selected from integers between 1 and 200.
Preferably, the residue of the primary diamine is selected from one or more of the following groups:
preferably, the residues of the tetracarboxylic dianhydride are selected from one or more of the following groups:
in the invention, 2- (2-aminofuryl) -5-aminobenzimidazole, a diamine compound and two dianhydride compounds are subjected to polymerization reaction to obtain the adhesive with the structure I, and the reaction process of the structural formula II obtained by desolventizing and heat-treating the adhesive with the structural formula I is schematically shown in figure 1.
Compared with the prior art, the invention has the following beneficial effects.
(1) Imidazole groups are introduced into the main chain of the adhesive polymer, and can capture metal ions generated when the metal substrate is corroded through metal-organic complexation reaction, so that the metal ions are prevented from diffusing into the adhesive to change electrical properties, and the peeling strength of the adhesive can be increased.
(2) The furan derivative used in the preparation of the 2-AFBM monomer is a biomass source, so that the use proportion of non-renewable raw materials in the adhesive can be reduced.
(3) N-H in the 2- (2-amino furyl) -5-amino benzimidazole can form a stable hydrogen bond with O atoms on adjacent furan rings, can prevent thermal movement of an adhesive polymer chain segment, regulate and control the linear thermal expansion coefficient of the adhesive, prevent the FCCL product from warping, and improve the tensile strength and softening temperature of the product to a certain extent.
(4) Compared with a method for pre-coating polymer primer containing imidazole side groups, when the composite material in the microelectronic field such as a flexible copper-clad plate is prepared, the imidazole ring is introduced in a copolymerization mode, so that the uniformity of the adhesive formula can be ensured, and the problems of phase separation between the adhesive and the polymer primer and internal stress of the adhesive coating caused by different CTE values in the existing research are solved.
(5) Compared with the FCCL industrialized method of film formation and then compounding, the direct coating method can maximize the latch effect and the contact area between the polyimide layer and the uneven substrate, thereby increasing the peeling strength.
Drawings
In FIG. 1, the reaction of the adhesive and the adhesive desolventizing and heat treating process is schematically shown by polymerizing the monomers.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
The raw materials used in the examples of the present invention were all commercially available.
The performance test method or standard of the product in the embodiment of the invention is as follows:
(1) Inherent viscosity: according to GB/T1632.3-1993, the test is carried out using an Ubbelohde viscometer. 0.125g of the dried polyamide acid sample (accurate to 0.1 mg) is weighed into a 25mL volumetric flask, about 15mL of solvent is added, the solvent is shaken to be completely dissolved, the solvent is added to a position about 0.5cm below the scale mark, and the solution is placed in a constant-temperature water bath at the temperature of (35+/-0.1) ℃ for 15 minutes and then the volume is fixed to the scale mark. In the test, firstly, blank test is carried out, the solvent is poured into an Ubbelohde viscometer, and after the solution is placed in a constant temperature water bath with the temperature of (35+/-0.1) DEG C for 15 minutes, the outflow time t is measured 0 . After the blank test solution is poured out, a small amount of sample solution is used for cleaning the viscometer, then the sample solution is poured into a constant temperature water bath for 15 minutes at the temperature of 35+/-0.1 ℃,the time t required for the test sample to flow out.
The calculation formula is as follows:
wherein: η (eta) inK Is the inherent viscosity, dL/g;
t 0 is blank solvent run-off time, seconds;
t is the sample solution outflow time, seconds;
c is the sample concentration, g/dL.
(2) Glass transition temperature (Tg) test method: according to GB/T19466.2-2004, a scanning differential calorimeter (DSC) is used. N (N) 2 Under protection, the sample is filled into an aluminum crucible, an automatic temperature rise measurement program is set, and the temperature rise rate is 20 ℃/min. And automatically calculating according to the slope change of the curve to obtain the glass transition temperature.
(3) Coefficient of linear thermal expansion (CTE) test method: according to GB/T1036.1-2008, a linear expansion coefficient meter is adopted for testing. And spin-coating the polyamide adhesive to be tested on the surface of glass, drying and imidizing, and stripping to obtain the transparent film. After the film is put into a sample testing platform, the film is heated at a certain linear temperature rising rate, and a curve of the dimensional change (namely absolute expansion) of the sample along with the change of temperature is obtained.
The calculation formula is as follows:
wherein: alpha is linear thermal expansion coefficient, 10 -6 K -1 ；
L 0 Is the initial length of the sample, mm;
deltaT is the temperature interval under investigation, K;
Δl is the amount of dimensional change, i.e., absolute expansion, in mm, of the sample over this temperature interval.
(4) Tensile strength and elongation at break test method: according to GB/T1040.3-2018, a tensile tester is used. The tensile sample is a strip sample with the thickness of less than 1mm, the width of 10-25mm and the length of not less than 150 mm. And (3) installing the test sample in a clamp, applying a tensile force until the material breaks, recording the maximum tensile stress of the test sample until the test sample breaks as tensile strength, and recording the ratio of the deformation quantity at the moment of breaking to the initial length of the test as elongation at break.
(5) Peel strength test method: according to GB/T2791-1995, the peel strength tester was used. The non-glued ends of the flexible test piece are respectively clamped in the device. The tester was started to separate the upper and lower grippers at a rate of 100.+ -.10 mm/min. The glass length is at least 125mm, and the recording device simultaneously draws a peeling load curve. The average value of the peel force was estimated by the peel curve.
The calculation formula is as follows:
wherein: sigma (sigma) T Is peel strength, N/cm;
f is the stripping force, N;
b is the width of the sample, cm.
Example 1
In this example, 2- (2-aminofuryl) -5-aminobenzimidazole (2-AFBM), paraphenylenediamine (PDA) and metaphenylene diamine (MPD) were used as the polyamide adhesive diamine compound, and 3,3', 4' -biphenyltetracarboxylic dianhydride (S-BPDA), pyromellitic dianhydride (PMDA) and 4,4' -oxydiphthalic anhydride (ODPA) were used as the dianhydride compound.
The preparation method comprises the following steps:
step 1: room temperature, N 2 Under the atmosphere, 4.28g (20 mmol) of 2-AFBM, 6.48g (60 mmol) of PDA and 2.16g (20 mmol) of MPD are dissolved in 300mL of N-methylpyrrolidone (NMP) solvent, then 20.58g (70 mmol) of S-BPDA, 5.45g (25 mmol) of PMDA and 0.93g (3 mmol) of ODPA are added in portions, the mixture is cooled to-10 ℃ for stirring reaction for 30 minutes, 0 ℃ for stirring reaction for 90 minutes, 10 ℃ for stirring reaction for 90 minutes and 40 ℃ for stirring reaction for 10 minutes, and a viscous solution is obtained;
step 2: 2.04g (20 mmol) of acetic anhydride and 1.87g (20 mmol) of a mixed auxiliary agent of 3, 5-diethyl pyridine are added into the viscous solution, and the mixture is stirred for 10 minutes, so as to obtain the polyamide acid adhesive.
The polyamide adhesive obtained in example 1 was subjected to performance test.
The inherent viscosity of the polyamide adhesive obtained in test example 1 was 0.57dL/g;
desolventizing the polyamide adhesive obtained in example 1 at 60 ℃ for 1 hour, desolventizing at 120 ℃ for 1 hour, desolventizing at 180 ℃ for 1 hour, and carrying out vacuum oven heat treatment at 320 ℃ for 6 hours to obtain a film, wherein the glass transition temperature of the film is tested to have no signal in DSC;
the tensile strength of the test film is 178MPa, the elongation at break is 18 percent, and the CTE value at-30 ℃ to 30 ℃ is 19.10 -6 K -1 The 90℃peel strength to copper was 17.52N/cm.
Example 2
The polyamide acid adhesive diamine compound adopts 2- (2-amino furyl) -5-amino benzimidazole
(2-AFBM), 4' -diaminophenyl ether (ODA) and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), wherein the dianhydride compound is 3,3', 4' -biphenyl tetracarboxylic dianhydride (S-BPDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and bisphenol A type diether dianhydride (BPADA), and the auxiliary agent is acetyl chloride, 3-methylpyridine and triethylamine. The preparation method comprises the following steps:
step 1: room temperature, N 2 6.42g (30 mmol) of 2-AFBM, 2.00g (10 mmol) of ODA and 24.60g (60 mmol) of BAPP are dissolved in 500mL of N, N-dimethylacetamide (DMAc) solvent under atmosphere, then 5.88g (20 mmol) of S-BPDA, 16.75g (52 mmol) of BTDA and 15.6g (30 mmol) of BPADA are added in portions, cooled to-10 ℃ and stirred for 15 minutes, 0 ℃ and stirred for 120 minutes, 10 ℃ and stirred for 60 minutes, and 40 ℃ and reacted for 30 minutes to obtain a viscous solution;
step 2: 2.41g (20 mmol) of acetyl chloride, 1.64g (20 mmol) of 3-methylpyridine and 0.51g (5 mmol) of triethylamine as a mixed auxiliary agent are added into the viscous solution, and the mixture is stirred for 10 minutes to obtain the polyamide adhesive.
The polyamide adhesive obtained in example 2 was subjected to performance test.
The inherent viscosity of the polyamide adhesive obtained in test example 2 was 0.76dL/g.
The polyamic acid adhesive obtained in example 2 was desolventized at 80℃for 1 hour, at 140℃for 1 hour, at 180℃for 1 hour, and the resultant film was heat-treated in a vacuum oven at 300℃for 6 hours, and the glass transition temperature was measured at 328 ℃.
The tensile strength of the test film is 147MPa, the elongation at break is 44%, and the CTE value at-30 ℃ to 30 ℃ is 43.10 -6 K -1 The 90℃peel strength to copper was 9.74N/cm.
Example 3
The polyamide acid adhesive diamine compound adopts 2- (2-aminofuryl) -5-aminobenzimidazole (2-AFBM), 4 '-Diaminobenzophenone (DABP), 1, 3-di (4-aminophenoxy) benzene (TPE-R), 1, 4-di (3-aminophenoxy) benzene (TPE-M) and 4,4' -di (3-aminophenoxy) biphenyl (BAPB), and the dianhydride compound adopts pyromellitic dianhydride (PMDA).
The preparation method comprises the following steps:
step 1: room temperature, N 2 6.42g (30 mmol) of 2-AFBM, 4.24g (20 mmol) of DABP, 2.92g (10 mmol) of TPE-R, 2.92g (10 mmol) of TPE-M and 11.40g (30 mmol) of BAPB are dissolved in 300mL of N, N-Dimethylformamide (DMF) solvent under atmosphere, 21.15g (97 mmol) of PMDA is added, the mixture is cooled to-10 ℃ and stirred for 30 minutes, 0 ℃ and stirred for 120 minutes, 10 ℃ and stirred for 20 minutes, and a viscous solution is obtained;
step 2: 4.20g (20 mmol) of trifluoroacetic anhydride and 2.58g (20 mmol) of isoquinoline are added into the viscous solution, and the mixture is stirred for 30 minutes to obtain the polyamide adhesive.
The polyamide adhesive obtained in example 3 was subjected to performance test.
The inherent viscosity of the polyamide adhesive obtained in test example 3 was 0.47dL/g.
Desolventizing at 40 ℃ for 1 hour, desolventizing at 100 ℃ for 1 hour, desolventizing at 170 ℃ for 1 hour, vacuum oven heat-treating at 250 ℃ for 6 hours to obtain a film, and testing the glass transition temperature of the film at 264 ℃.
The tensile strength of the test film is 106MPa, the elongation at break is 75 percent, and CT at-30 ℃ to 30 DEG CE value 58.10 -6 K -1 The 90℃peel strength to copper was 8.80N/cm.
Comparative example 1
In comparison to example 1, the 2-AFBM was removed from the formulation and the other diamines from the original formulation were used to make up the same total equivalent of diamine as in example 1. The preparation method comprises the following steps:
step 1: room temperature, N 2 7.56g (70 mmol) of PDA and 3.24g (30 mmol) of MPD are dissolved in 300mL of N-methylpyrrolidone (NMP) solvent under the atmosphere, 20.58g (70 mmol) of S-BPDA, 5.45g (25 mmol) of PMDA and 0.93g (3 mmol) of ODPA are added in portions, the temperature is reduced to-10 ℃ and the mixture is stirred and reacted for 30 minutes, the mixture is stirred and reacted for 90 minutes at 0 ℃, the mixture is stirred and reacted for 90 minutes at 10 ℃ and the mixture is stirred and reacted for 10 minutes at 40 ℃ to obtain a viscous solution;
step 2: 2.04g (20 mmol) of acetic anhydride and 1.87g (20 mmol) of a mixed auxiliary agent of 3, 5-diethyl pyridine are added into the viscous solution, and the mixture is stirred for 10 minutes, so as to obtain the polyamide acid adhesive.
The polyamide adhesive obtained in comparative example 1 was subjected to performance test.
The comparative example 1 was tested to give a polyamide adhesive with an inherent viscosity of 0.62dL/g.
The polyamic acid adhesive obtained in comparative example 1 was desolventized at 60℃for 1 hour, at 120℃for 1 hour, at 180℃for 1 hour, and after heat treatment in a vacuum oven at 320℃for 6 hours, the film was obtained, and the glass transition temperature of the film was tested to have no signal in DSC.
The tensile strength of the test film is 183MPa, the elongation at break is 16%, and the CTE value at-30 ℃ to 30 ℃ is 23.10 -6 K -1 The 90℃peel strength to copper was 14.25N/cm.
Comparative example 2
In comparison to example 2, the 2-AFBM was removed from the formulation and the other diamines from the original formulation were used to make up the same total equivalent of diamine as in example 2. The preparation method comprises the following steps:
step 1: room temperature, N 2 Under an atmosphere, 4.00g (20 mmol) of ODA and 32.80g (80 mmol) of BAPP were dissolved in 500mL of N, N-dimethylacetamide (DMAc) solvent, followed by addition of 5.88g (20 mmol) of S-BPDA, 16.75g (52 mm) in portionsMol) BTDA and 15.6g (30 mmol) BPADA, cooling to-10deg.C, stirring and reacting for 15 min, stirring and reacting for 120 min at 0deg.C, stirring and reacting for 60 min at 10deg.C, stirring and reacting for 30 min at 40deg.C to obtain viscous solution;
step 2: 2.41g (20 mmol) of acetyl chloride, 1.64g (20 mmol) of 3-methylpyridine and 0.51g (5 mmol) of triethylamine as a mixed auxiliary agent are added into the viscous solution, and the mixture is stirred for 10 minutes to obtain the polyamide adhesive.
The polyamide adhesive obtained in comparative example 2 was subjected to performance test.
The comparative example 2 was tested to give a polyamide adhesive with an inherent viscosity of 0.79dL/g.
Desolventizing the polyamide adhesive obtained in comparative example 2 at 80℃for 1 hour, at 140℃for 1 hour, at 180℃for 1 hour, and vacuum oven heat-treating at 300℃for 6 hours to obtain a film having a glass transition temperature of 322℃and a film tensile strength of 136MPa, an elongation at break of 51%, and CTE values of 47.10 at-30℃to 30 ℃of -6 K -1 The 90℃peel strength to copper was 8.37N/cm.
Comparative example 3
In comparison to example 3, the 2-AFBM was removed from the formulation and the other diamines from the original formulation were used to make up the same total equivalent of diamine as in example 3. The preparation method comprises the following steps:
step 1: room temperature, N 2 6.36g (30 mmol) of DABP, 4.38g (15 mmol) of TPE-R, 4.38g (15 mmol) of TPE-M and 15.20g (40 mmol) of BAPB are dissolved in 300mLN, N-Dimethylformamide (DMF) solvent under atmosphere, 21.15g (97 mmol) of PMDA is added, the temperature is reduced to-10 ℃ and stirred for 30 minutes, the temperature is 0 ℃ and stirred for 120 minutes, the temperature is 10 ℃ and stirred for 20 minutes, and a viscous solution of a polyamic acid intermediate is obtained;
step 2: 4.20g (20 mmol) of trifluoroacetic anhydride and 2.58g (20 mmol) of isoquinoline are added into the viscous solution, and the mixture is stirred for 30 minutes to obtain the polyamide adhesive.
The polyamide adhesive obtained in comparative example 3 was subjected to performance test.
The comparative example 3 was tested to give a polyamide adhesive with an inherent viscosity of 0.55dL/g.
The polyamide adhesive obtained in comparative example 3 was desolventized at 40℃for 1 hour, desolventized at 100℃for 1 hour, desolventized at 170℃for 1 hour, heat-treated in a vacuum oven at 250℃for 6 hours, and the glass transition temperature of the film was measured at 251 ℃.
The tensile strength of the test film is 97MPa, the elongation at break is 92%, and the CTE value at-30 ℃ to 30 ℃ is 68.10 -6 K -1 The 90℃peel strength to copper was 7.83N/cm.
The test results according to the above examples and comparative examples are summarized in table 1:
TABLE 1 results of the performance tests for examples 1-3 and comparative examples 1-3
| Sample of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| η inK (dL/g) | 0.57 | 0.76 | 0.47 | 0.62 | 0.79 | 0.55 |
| Tensile Strength (MPa) | 178 | 147 | 106 | 183 | 136 | 97 |
| Elongation at break (%) | 18 | 44 | 75 | 16 | 51 | 92 |
| CTE(10 -6 K -1 ) | 19 | 43 | 58 | 23 | 47 | 68 |
| Tg(℃) | Not measured | 328 | 264 | Not measured | 322 | 251 |
| Peel strength (N/cm) | 17.52 | 9.74 | 8.80 | 14.25 | 8.37 | 7.83 |
From the inherent viscosity of the adhesive prepared in example 1 of the present invention, the adhesive prepared in the present invention has a desired molecular weight, i.e., all the monomers used are involved in the reaction to form the adhesive structure of the following "structural formula I", and it can be deduced that the x, y, n values of the adhesive structure in the present invention are within a given range according to the Mark-Houwink equation:
wherein,
x is selected from an integer between 1 and 50,
y is selected from an integer between 1 and 50,
n is selected from an integer between 1 and 200,
ar is the residue of a primary diamine, A is the residue of a tetracarboxylic dianhydride, B is the residue of a tetracarboxylic dianhydride, and A and B can be the same or different.
As can be seen from the table, after copolymerization of the 2- (2-aminofuryl) -5-aminobenzimidazole monomer introduced in examples 1-3, three different formulation examples were all superior to the comparative examples without this monomer in 90℃peel strength of the adhesive to copper, which resulted from complexation of the imidazole ring in the copolymer backbone to copper. The CTE values are reduced to some extent because the monomers increase the polymer backbone stiffness and intermolecular forces, which are critical for warpage tuning of metal-adhesive film composites. Whether the tensile strength and the elongation at break increase or decrease are mainly determined by the structure of the polymer chain other than 2- (2-aminofuryl) -5-aminobenzimidazole is not significantly regulated.
In conclusion, the important parameters such as the peeling strength, CTE value, tensile strength and the like of the polyamide acid adhesive can be adjusted by introducing the 2- (2-aminofuryl) -5-aminobenzimidazole comonomer into the adhesive, and the adhesive is expected to be widely applied to the microelectronic fields such as flexible copper-clad plates and the like.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (11)
1. The adhesive is characterized in that the structure of the adhesive is shown as a structural formula I:
wherein,
x is selected from an integer between 1 and 500,
y is selected from an integer between 1 and 500,
n is selected from an integer between 1 and 500,
ar is a residue of a primary diamine, and A and B are each independently selected from the group consisting of the residues of a tetracarboxylic dianhydride.
2. The adhesive of claim 1, wherein x is selected from an integer between 1 and 50, y is selected from an integer between 1 and 50, and n is selected from an integer between 1 and 200.
3. The adhesive according to claim 1 or 2, wherein the residue of the primary diamine is selected from one or more of the following groups:
4. an adhesive according to any one of claims 1 to 3, wherein the residues of the tetracarboxylic dianhydride are selected from one or more of the following groups:
5. a method for preparing an adhesive according to any one of claims 1 to 4, wherein the adhesive is prepared from the following raw materials: the preparation method of the adhesive comprises the following steps of:
step (1): mixing a diamine compound and a dianhydride compound with a solvent under inert atmosphere, and stirring to obtain a viscous solution;
step (2): and adding an auxiliary agent into the viscous solution, and stirring to obtain the adhesive.
6. The method of preparing an adhesive according to claim 5, wherein the stirring conditions in the step (1) include: stirring for 1-240 min at minus 15 to minus 10 ℃, stirring for 1-240 min at minus 5 to 5 ℃, stirring for 1-240 min at 5 to 15 ℃, and stirring for 1-240 min at 35 to 45 ℃;
and/or, the mass sum of the diamine compound and the dianhydride compound in the step (1) is 10-20% of the total mass of the viscous solution;
and/or, the stirring conditions in the step (2) comprise: the stirring time is 1-240 min.
7. The method for preparing an adhesive according to claim 5 or 6, wherein the diamine compound comprises at least 2- (2-aminofuryl) -5-aminobenzimidazole;
preferably, the diamine compound further comprises one or more of p-phenylenediamine, m-phenylenediamine, 4 '-diaminophenyl ether, 4' -biphenyldiamine, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 4 '-diaminobenzophenone, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, and 4,4' -bis (3-aminophenoxy) biphenyl;
and/or the dianhydride compound is selected from one or more of 3,3', 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 4' -oxydiphthalic anhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and bisphenol A type diether dianhydride;
and/or the molar ratio of the diamine compound to the dianhydride compound is 1: (0.95-1.05).
8. The method for preparing an adhesive according to claim 6 or 7, wherein,
the solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and gamma-butyrolactone;
and/or the auxiliary agent comprises one or more of acetyl chloride, acetic anhydride, benzoic acid, trifluoroacetic anhydride, triethylamine, imidazole, benzimidazole, pyridine, 3-methylpyridine, 3, 5-diethylpyridine, quinoline and isoquinoline;
preferably, the molar amount of the auxiliary agent is 0.1% to 40% of the sum of the molar amounts of the diamine compound and the dianhydride compound;
preferably, the molar amount of the auxiliary agent is 10% to 30% of the sum of the molar amounts of the diamine compound and the dianhydride compound.
9. Use of the adhesive of any one of claims 1-4 or prepared by the method of preparation of the adhesive of any one of claims 5-8 in microelectronic composites; preferably, the method is applied to the field of flexible copper-clad plates.
10. An adhesive according to any one of claims 1 to 4 or a method for using the adhesive according to any one of claims 5 to 8, wherein the adhesive is coated on the surface of a substrate, a material to be bonded is attached to the surface of the adhesive to obtain a bonded object, and the bonded object is subjected to desolventizing treatment and heat treatment to obtain a bonded device;
preferably, the desolventizing treatment conditions include: the temperature is 40-200 ℃ and the time is 1-4 h;
preferably, the heat treatment conditions include: the temperature is 250-350 ℃ and the time is 2-8 h.
11. The method of claim 10, wherein the heat treated adhesive has a structure according to formula II:
wherein the method comprises the steps of
x is selected from an integer between 1 and 500,
y is selected from an integer between 1 and 500,
n is selected from an integer between 1 and 500,
ar is the residue of a primary diamine, A is the residue of a tetracarboxylic dianhydride, and B is the residue of a tetracarboxylic dianhydride;
preferably, x is selected from integers between 1 and 50, y is selected from integers between 1 and 50, and n is selected from integers between 1 and 200;
preferably, the residue of the primary diamine is selected from one or more of the following groups:
preferably, the residue of the tetracarboxylic dianhydride is selected from one or more of the following groups:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311016117.4A CN117004362A (en) | 2023-08-11 | 2023-08-11 | Adhesive and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311016117.4A CN117004362A (en) | 2023-08-11 | 2023-08-11 | Adhesive and preparation method and application thereof |
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| CN117004362A true CN117004362A (en) | 2023-11-07 |
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| CN202311016117.4A Pending CN117004362A (en) | 2023-08-11 | 2023-08-11 | Adhesive and preparation method and application thereof |
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| CN (1) | CN117004362A (en) |
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- 2023-08-11 CN CN202311016117.4A patent/CN117004362A/en active Pending
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