CN116875243B - High-flexibility, impact-resistant and low-temperature quick-curing underfill and preparation method thereof - Google Patents
High-flexibility, impact-resistant and low-temperature quick-curing underfill and preparation method thereof Download PDFInfo
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- CN116875243B CN116875243B CN202310872890.4A CN202310872890A CN116875243B CN 116875243 B CN116875243 B CN 116875243B CN 202310872890 A CN202310872890 A CN 202310872890A CN 116875243 B CN116875243 B CN 116875243B
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- epoxy resin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 131
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 131
- 229920005989 resin Polymers 0.000 claims abstract description 104
- 239000011347 resin Substances 0.000 claims abstract description 104
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 73
- 239000000945 filler Substances 0.000 claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 70
- 239000000805 composite resin Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000011342 resin composition Substances 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 163
- 238000001723 curing Methods 0.000 claims description 95
- 238000000034 method Methods 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 50
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000013335 mesoporous material Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000004381 surface treatment Methods 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 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 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 150000008064 anhydrides Chemical group 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 abstract description 30
- 230000001070 adhesive effect Effects 0.000 abstract description 24
- 239000000853 adhesive Substances 0.000 abstract description 23
- 230000001976 improved effect Effects 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000005452 bending Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 14
- 238000004806 packaging method and process Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- HIVRNXYEWIPOMU-UHFFFAOYSA-N 1,3-dimethyl-9h-carbazole Chemical compound C1=CC=C2C3=CC(C)=CC(C)=C3NC2=C1 HIVRNXYEWIPOMU-UHFFFAOYSA-N 0.000 description 3
- APYQRKDHRDGCBK-UHFFFAOYSA-N 1,4-dimethyl-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(C)=CC=C2C APYQRKDHRDGCBK-UHFFFAOYSA-N 0.000 description 3
- MEFATMTVUAOEJH-UHFFFAOYSA-N 1,6-dinitro-9h-carbazole Chemical compound C1=CC=C2C3=CC([N+](=O)[O-])=CC=C3NC2=C1[N+]([O-])=O MEFATMTVUAOEJH-UHFFFAOYSA-N 0.000 description 3
- VYOKOQDVBBWPKO-UHFFFAOYSA-N 1-nitro-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C([N+](=O)[O-])=CC=C2 VYOKOQDVBBWPKO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- -1 diethylene triaminopropyl triethoxysilane Chemical compound 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000007712 rapid solidification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 description 2
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000004985 diamines Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000004880 explosion Methods 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- DKMJSUBUAMUZAJ-UHFFFAOYSA-N 1,4,8-trimethyl-9h-carbazole Chemical compound N1C2=C(C)C=CC(C)=C2C2=C1C(C)=CC=C2 DKMJSUBUAMUZAJ-UHFFFAOYSA-N 0.000 description 1
- TXUDHVSAPSIPLF-UHFFFAOYSA-N 10-bromo-7H-benzo[a]carbazole Chemical compound C1C=CC(=C2C1=C3C=CC4=CC=CC=C4C3=N2)Br TXUDHVSAPSIPLF-UHFFFAOYSA-N 0.000 description 1
- RVCKCEDKBVEEHL-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzyl alcohol Chemical compound OCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl RVCKCEDKBVEEHL-UHFFFAOYSA-N 0.000 description 1
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 1
- IMKMEPLAEXUGBU-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-ol Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCO IMKMEPLAEXUGBU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QBPAUIDFWFXLKB-UHFFFAOYSA-N 9h-carbazol-1-ol Chemical compound N1C2=CC=CC=C2C2=C1C(O)=CC=C2 QBPAUIDFWFXLKB-UHFFFAOYSA-N 0.000 description 1
- RIUUHLXAZCECMM-UHFFFAOYSA-N 9h-carbazol-1-ylboronic acid Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2B(O)O RIUUHLXAZCECMM-UHFFFAOYSA-N 0.000 description 1
- TZXYZCGWHFCFDX-UHFFFAOYSA-N 9h-carbazole-3,6-dicarbonitrile Chemical compound C1=C(C#N)C=C2C3=CC(C#N)=CC=C3NC2=C1 TZXYZCGWHFCFDX-UHFFFAOYSA-N 0.000 description 1
- APYLNYCULQUSLG-UHFFFAOYSA-N 9h-carbazole-3-carbonitrile Chemical compound C1=CC=C2C3=CC(C#N)=CC=C3NC2=C1 APYLNYCULQUSLG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- MXLBKVCGLRNKBW-UHFFFAOYSA-N C(=C)OO[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C Chemical compound C(=C)OO[Si](C(C)(C)C)(C(C)(C)C)C(C)(C)C MXLBKVCGLRNKBW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting and a preparation method thereof, wherein the underfill adhesive comprises the following components in parts by mass based on 100 parts by mass: 40-60 parts of resin composition, 10-30 parts of filler, 10-20 parts of diluent, 1-5 parts of coupling agent, 5-10 parts of curing agent, 1-5 parts of curing accelerator and 0.1-1 part of pigment. The resin composition is composite resin particles with a core-shell structure formed by epoxy resin and bismaleimide resin, wherein the epoxy resin is a shell layer, and the bismaleimide resin is an inner core. The invention adopts the coating technology to prepare the composite resin particles with the core-shell structure taking the epoxy resin as the shell layer and the bismaleimide resin as the inner core, and the composite resin particles are taken as the resin matrix of the underfill, so that the bending strength and the impact strength of the colloid can be effectively improved, and the colloid is convenient to clean.
Description
Technical Field
The invention belongs to the technical field of filling glue, and relates to high-flexibility, impact-resistant and low-temperature fast-curing underfill and a preparation method thereof.
Background
Because of the demands of wireless communication, portable computers, broadband internet products and automobile navigation electronic products, the integration level of electronic devices is higher and higher, the chip area is enlarged continuously, the pin count of integrated circuits is increased continuously, meanwhile, the chip packaging size is required to be further miniaturized and miniaturized, the integrated circuits are developed towards the directions of light, thin and small, and the integration level, density and performance of the integrated circuits are gradually improved, so that a plurality of new packaging technologies and packaging forms are developed.
Packaging is to put on a 'garment' on a chip, protect the chip from damage caused by physical, chemical and other environmental factors, enhance the heat dissipation performance of the chip, and realize standard formatting and facilitate connection of an I/O port of the chip to a component-level or system-level printed circuit board, a glass substrate and the like so as to realize electrical connection and ensure normal operation of a circuit.
With the progress of integration technology, the improvement of equipment and the use of deep submicron technology, the integration level of a silicon single chip is continuously improved, the requirements on the packaging of integrated circuits are more strict, the number of I/O pins is rapidly increased, and the power consumption is also increased. In order to meet the development requirement, a new packaging mode, ball grid array packaging, is added on the basis of the original packaging variety, and is called BGA (Ball Grid Array Package) for short.
The I/O terminals of the BGA package are distributed under the package in the form of circular or columnar welding points according to an array, and the BGA technology has the advantages that the number of I/O pins is increased, but the pin spacing is not reduced but is increased, so that the assembly yield is improved; although its power consumption is increased, BGA can be soldered by a controlled collapse chip method, so that its electrothermal performance can be improved; the thickness and the weight are reduced compared with the prior packaging technology; parasitic parameters (when the current changes greatly, the output voltage disturbance is caused) are reduced, the signal transmission delay is small, and the use frequency is greatly improved; the assembly can be realized by coplanar welding, and the reliability is high.
The underfill is a filling material suitable for the BGA packaging mode, is simply referred to as underfill, and is conventionally defined as underfilling a chip in the BGA packaging mode by using chemical glue (mainly comprising epoxy resin), filling a large area (generally covering more than 80 percent) of a gap at the bottom of the BGA by using a heated curing mode, thereby achieving the purpose of reinforcement and enhancing the anti-drop performance between the chip in the BGA packaging mode and the PCBA.
Since the gap between the chip and the substrate is small, the viscosity of the underfill is required to be extremely low, and after dispensing, the underfill is cured in an oven or a reflow oven, and the curing time and temperature of the underfill are required to be greatly reduced due to the limitation of the heat-resistant temperature of the IC element.
However, most of the existing underfill have the problems of high curing temperature, low curing speed, poor storage stability and the like, and the existing underfill is difficult to meet the process use requirements aiming at the actual requirements of high speed and high efficiency of electronic production. Therefore, there is a need to provide an underfill that meets the low temperature rapid cure requirements.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the underfill adhesive with high flexibility, impact resistance and low-temperature quick fixation and the preparation method thereof, wherein the composite resin particles with the core-shell structure and the core-shell structure are prepared by adopting a coating process, and the composite resin particles with the epoxy resin as a shell layer and the bismaleimide resin as an inner core are used as a resin matrix of the underfill adhesive, so that the bending strength and the impact resistance of the adhesive can be effectively improved, and the adhesive is convenient to clean.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an underfill adhesive which is high in flexibility, impact-resistant and quick-setting at a low temperature, and comprises the following components in parts by mass, based on 100 parts by mass of the underfill adhesive:
40-60 parts of resin composition, 10-30 parts of filler, 10-20 parts of diluent, 1-5 parts of coupling agent, 5-10 parts of curing agent, 1-5 parts of curing accelerator and 0.1-1 part of pigment.
The resin composition is composite resin particles with a core-shell structure formed by epoxy resin and bismaleimide resin, wherein the epoxy resin is a shell layer, and the bismaleimide resin is an inner core.
Wherein the mass part of the resin composition may be 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts or 60 parts, the mass part of the filler may be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts or 30 parts, the mass part of the diluent may be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, the mass part of the coupling agent may be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, the curing agent may be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts, the curing accelerator may be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, the colorant may be 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part, but the present invention is not limited to the exemplified values, and other non-exemplified values in the range of values are equally applicable.
The bismaleimide resin is a most commonly used resin matrix of the advanced resin matrix composite material, has heat resistance superior to that of epoxy resin, but has the technical properties inferior to that of epoxy resin, and has the characteristics of moisture and heat resistance, radiation resistance, small thermal expansion coefficient, good electrical property, wear resistance and the like. The glass transition temperature of the bismaleimide resin is above 220 ℃, and the glass transition temperature of the epoxy resin is in the range of 150-170 ℃. In order to integrate the advantages of the bismaleimide resin and the epoxy resin, the invention adopts a coating process to prepare the composite resin particles with the core-shell structure by taking the epoxy resin as a shell layer and the bismaleimide resin as a core, and the composite resin particles are taken as a resin matrix of the underfill, so that the bending strength and the impact strength of the colloid can be effectively improved, and the colloid is convenient to clean.
The composite resin particles provided by the invention have the advantages that:
(1) The bending strength of the underfill is improved: the epoxy resin is used for coating the bismaleimide resin, so that the bending strength of the composite resin particles is greatly improved, and at the coating interface of the bismaleimide resin and the epoxy resin, the chain segment of the epoxy resin participates in the curing reaction between the bismaleimide resin and the curing agent, so that the space between crosslinking points is increased, the crosslinking density in a system is reduced, the molecular activity is improved, a coating interface system formed between the bismaleimide resin and the epoxy resin is in a flexible curing network structure with a rigid curing network and a flexible network coexisting, and when the external force acts, the flexible curing network structure can well generate a stress relaxation and flexibility relaxation effect, effectively resist the cracking resistance of the system, and enable the system to present higher bending strength.
(2) Impact strength of the underfill is improved: the impact strength of the underfill can also be improved by coating the bismaleimide resin with the epoxy resin. Since the cured product of the pure bismaleimide resin is a highly crosslinked polymer, the crosslinking density is high, and when the cured product is impacted by external force, the movement of a molecular chain segment is difficult, and the generated stress is not dispersed sufficiently, the impact strength of the underfill which simply adopts the bismaleimide resin as a resin matrix is low. When the bismaleimide resin is coated by the epoxy resin, the epoxy group is arranged in the molecular structure of the epoxy resin, so that the epoxy group can react with the surface of the material containing active hydrogen to generate a chemical bond, and the flexibility of the molecular chain of the bismaleimide resin before curing is improved; in addition, when the coating is carried out with the bismaleimide resin, a copolymerization reaction is carried out on the bismaleimide resin main chain, the final result of the copolymerization reaction is that a cross-linked network is formed, and the bismaleimide resin main chain is also partially chain-extended by diamine and epoxy chain links, so that the cross-linked density of the bismaleimide resin is reduced. When the underfill is subjected to impact energy, the flexible chains of the epoxy resin can act as stress dispersion and stress bearing, so that the toughness of the system is improved.
It is noted that the term "cross-linking" as referred to hereinabove refers to bridging of two or more oligomers or longer polymer chains by an element, molecular group, compound or another oligomer or polymer. Crosslinking may occur under conditions of heat or light, etc., and some crosslinking processes may also occur at room temperature or lower. As the crosslink density increases, the properties of the material may change from thermoplastic to thermosetting.
(3) Under the low temperature condition, the shell is epoxy resin cured at low temperature, so that the curing agent and the shell of the epoxy resin undergo a crosslinking polymerization reaction, the shell of the composite resin particles is cured first, and the curing time of the underfill is shortened. After the shell is solidified, the bismaleimide resin of the inner core part is in a micro-dispersion state due to the high-temperature solidification characteristic and higher glass transition temperature, and is uniformly dispersed in the colloid, when the chip needs to be repaired, the colloid is heated at high temperature to reach the glass transition temperature of the inner core, so that the solidified underfill adhesive becomes soft, and the colloid can be easily removed under the action of external force.
(4) Epoxy resins have great adhesion to a variety of substrates. Most substrates (e.g., metals, minerals, glass, and ceramics) have a relatively high surface energy due to their inherent polarity and the presence of an oxide layer, which is a potential bonding site for epoxy resins, and thus have better adhesion properties to high surface energy substrates. The surface energy of the bismaleimide adopted in the invention is far lower than that of the epoxy resin, so that the bismaleimide and the low-surface-energy substrate have better adhesive property. By combining the high strength polar forces of epoxy resins with the van der waals forces of bismaleimide resins, adhesion of substrates having different surface energies can be addressed.
In summary, the invention adopts the composite resin particles formed by coating the bismaleimide resin with the epoxy resin as the resin matrix of the underfill, and can effectively improve the bending strength and the impact strength of the underfill.
It should be noted that the type of the diluent is not particularly limited and may include, by way of non-limiting example: butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, dodecyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, and trimethylol triglycidyl ether.
The bottom filling glue is used for filling the bottom of the chip, filling the bottom gap of the chip, and curing after heating, so that the purpose of reinforcing the chip is achieved. In addition, the underfill material may help mechanically interlock the chip to the substrate, and thus it is desirable that the underfill exhibit good adhesion to both the chip and the substrate. In order to improve the adhesive properties of the underfill, a coupling agent is required.
It should be noted that the kind of the coupling agent is not particularly limited and the present invention is not particularly limited, and some examples of the coupling agent include silane, titanate, zirconate, aluminate, silicate, metal acrylate or methacrylate, a compound containing a chelating ligand (e.g., phosphine, thiol, acetoacetate) and/or a mixture thereof. Certain coupling agents, such as titanates and zirconates, can also catalyze the curing reaction of the epoxy resin, thereby lowering the cure initiation temperature and increasing the viscosity of the underfill during low temperature storage.
Some specific non-limiting examples of coupling agents are: any one or a combination of at least two of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysiloxane, gamma-methacrylate propyl trimethoxysiloxane, gamma-thiol propyl trimethoxysiloxane, vinyl tri-tert-butyl peroxy silane, beta-hydroxyethyl-gamma-aminopropyl triethoxysilane, aniline methyl triethoxysilane or diethylene triaminopropyl triethoxysilane.
It should be noted that the terms "underfill", "underfill composition" and "underfill material" in the present invention are used interchangeably to refer to an adhesive agent using resin as a main material, and are generally used to fill a gap between a semiconductor component (e.g., a semiconductor chip) and a substrate. "underfill" refers to a process in which an underfill is applied to the interface of a semiconductor component and a substrate, thereby filling the gap between the underfill and the substrate.
As a preferable technical scheme of the invention, the mass ratio of the epoxy resin to the bismaleimide resin is 1 (0.1-0.5), for example, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:4, 1:0.45 or 1:0.5, but the invention is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The higher the crosslinking density of the cured product, the more heat-resistant rigid groups such as aromatic rings, ester rings, and heterocyclic rings on the molecular chain, the higher the heat distortion temperature of the cured product, and the higher the high-temperature mechanical properties, the better the heat resistance. However, an increase in crosslink density affects the size of the space between the crosslinks, resulting in a decrease in molecular activity. In order to balance the crosslinking density, heat resistance and molecular activity in the system at the same time, the invention particularly limits the mass ratio of the epoxy resin to the bismaleimide resin to be 1 (0.1-0.5).
When the surface of the maleimide resin is coated with the epoxy resin, the chain segments of the epoxy resin participate in the curing reaction, so that the space between the crosslinking points is increased, the crosslinking density in the system is reduced, and the molecular activity of the bismaleimide resin is improved. However, as the epoxy resin content continues to increase, the flexible network in the system increases, resulting in a decrease in the proportion of the rigid network, and thus the effect of improving the bending strength of the underfill is not obvious.
In addition, the main chain molecule of the bismaleimide resin contains a benzene ring structure, the carbon skeleton in the benzene ring is connected through conjugated pi-pi bonds, the molecular structure is stable, and the ring opening is not easy to occur due to external factors, so that when the temperature of the system is increased, the benzene ring structure is not easy to be influenced, and meanwhile, the benzene ring structure belongs to a rigid group, so that the bismaleimide resin has excellent heat resistance and can ensure the heat resistance strength of the system. After the epoxy resin is coated, the mechanical property of the crosslinked network is improved, but the proportion of the benzene ring structure in the system is reduced along with the increase of the addition amount of the epoxy resin, and the heat resistance is also reduced, so that the thermal deformation temperature is reduced.
The epoxy resin is any one or the combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin or epoxy phenol resin.
Examples of the epoxy resin used in the present invention include resins having two or more epoxy groups in the molecule thereof. An alternative example is a bisphenol epoxy resin, such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol a type epoxy resin, cycloaliphatic epoxy resin, or epoxidized phenol resin. Among the epoxy resins exemplarily provided above, any one or a combination of at least two of bisphenol a type epoxy resins, bisphenol F type epoxy resins, or alicyclic epoxy resins is preferable because bisphenol a type epoxy resins and bisphenol F type epoxy resins can produce a cured product having a low linear expansion ratio and have excellent meltability at low temperatures. Among them, bisphenol F type epoxy resin has lower viscosity, good heat resistance and excellent electrical properties. The aliphatic epoxy resin has lower chloride ion content and lower viscosity.
Furthermore, the shell can be formed by compounding various epoxy resins, such as bisphenol F epoxy resin, alicyclic epoxy resin and epoxidized phenol resin, and the three epoxy resins have synergistic effect, so that the viscosity of the system is ensured to be lower, and the flowability is good. The alicyclic epoxy resin has good heat resistance and chemical corrosion resistance, the resin before curing has low viscosity and good fluidity, and the cured resin has good bonding effect, and does not generate chemical corrosion to microcircuits and environmental pollution and human body damage due to the fact that the alicyclic epoxy resin does not contain organic chlorine and free chloride ions. Therefore, the three epoxy resins are used in combination so that the glass transition temperature of the finally prepared underfill adhesive is not excessively high.
Mesoporous materials are dispersed in the shell formed by the epoxy resin.
As a preferred embodiment of the present invention, the filler includes a first filler and a second filler, and the mass ratio of the first filler to the second filler is 1 (1-5), for example, may be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The particle size of the first filler is larger than the particle size of the second filler.
The particle size of the first filler may be, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The particle size of the second filler is 30 to 50nm, and may be, for example, 30nm, 32nm, 34nm, 36nm, 38nm, 40nm, 42nm, 44nm, 46nm, 48nm or 50nm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention adopts the fillers with different particle sizes to be mixed into the colloid, can be filled into the gap between the chip and the substrate, and can inhibit the influence of the surface area of the filler on the colloid fluidity by adjusting the mass ratio between the particle sizes, thereby obtaining good colloid fluidity, so that the filler can enter into the deep part of the gap under the permeation of the colloid, realize the mechanical engagement between the chip and the substrate after solidification, and improve the fixing effect of the chip.
The first filler and the second filler are each independently selected from SiO 2 、TiO 2 、Al 2 O 3 Or ZnO, or any one or a combination of at least two thereof.
As a preferable technical scheme of the invention, the curing agent is anhydride oligomer.
The molecular weight of the curing agent is 1500-1600Da, for example, 1500Da, 1510Da, 1520Da, 1530Da, 1540Da, 1550Da, 1560Da, 1570Da, 1580Da, 1590Da or 1600Da, but the curing agent is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
The invention is particularly limited to the use of polyfunctional anhydride oligomers (molecular weight in the range 1500-1600 Da) as curing agents for the underfill. The use of low molecular weight anhydride oligomers can effectively reduce volatilization of the resin composition, promote the resin curing process, and thus reduce the porosity of the underfill.
In addition, anhydride oligomers having R groups are used in the underfill, which can react with the epoxy matrix to form a crosslinked matrix, by substituting different R groups, to reduce the viscosity, hygroscopicity, volatility, and modulus of the underfill, improve the mechanical properties of the underfill, and enhance adhesion. The R group may be any one or a combination of at least two of nitroso group, carboxyl group, alcoholic hydroxyl group, ester group or nitrile group. Specifically, alternative examples of the curing agent provided by the present invention include: any one or a combination of at least two of styrene/maleic anhydride, cyclohexane/maleic anhydride or norbornene/maleic anhydride copolymers.
As a preferable embodiment of the present invention, the curing accelerator is selected from any one or a combination of at least two of tertiary amine curing accelerators, imidazole curing accelerators, phosphorus curing accelerators and boron curing accelerators.
The invention can promote the curing of epoxy resin and bismaleimide resin by adding a curing accelerator into the underfill. The present invention is particularly limited to the curing accelerator added in an amount of 1 to 5 parts by mass, and in this mass range, it is possible to ensure a shorter curing time for the heat treatment and also to ensure a superior preservability of the resin composition. In addition, in the invention, an imidazole curing accelerator is preferably adopted, and bubbles generated in the curing and heating process of the colloid can be effectively prevented by adding a specific mass part of the imidazole curing accelerator. The specific action mechanism is as follows:
the reaction initiation temperature of the existing underfill in the curing temperature rising process is higher, small molecules in the underfill volatilize due to untimely reaction in the temperature rising process, and the underfill reacts vigorously in a high temperature area to generate bubbles or gaps, so that the cured system has defects. According to the invention, after research, the imidazole curing accelerator with specific content is added into a colloid system, so that the reaction initial temperature of the underfill is reduced, the underfill is ensured to react slowly at a lower temperature, bubbles generated by the explosion polymerization of the underfill at a high temperature are avoided, small molecules are enabled to start to react in advance at the lower reaction initial temperature, the small molecules in the underfill are ensured to react fully in the slow temperature rising process, and the generation of bubbles and gaps is effectively avoided.
In summary, the present invention particularly preferably employs an imidazole-based curing accelerator for promoting the curing of the colloid while preventing the generation of bubbles in the colloid during high-temperature curing. Through screening the action and effect of a plurality of imidazole curing accelerators, the imidazole curing accelerators preferably adopted by the invention are as follows: 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole. At least one of 1, 6-dinitrocarbazole, 3, 6-dicyanocarbazole, 3-cyanocarbazole, 10-bromo-7H-benzocarbazole, 5-bromo-7H-benzocarbazole, 12H-benzofuran [2,3-A ] carbazole, 1, 4-dimethylcarbazole, 1,4, 8-trimethylcarbazole, 1, 3-dimethylcarbazole, 1-nitrocarbazole, carbazole-1-ylboronic acid, 1-hydroxycarbazole, or 2, 7-dicarboxylic carbazole.
In a second aspect, the present invention provides a method for preparing the underfill adhesive with high flexibility, impact resistance and low temperature fast solidification according to the first aspect, the method comprising:
putting the resin composition, the diluent and the pigment into stirring equipment, and stirring and dispersing uniformly in a vacuum environment;
(II) putting the curing accelerator, the first filler, the second filler and the coupling agent into stirring equipment, and stirring and dispersing uniformly in a vacuum environment;
And (III) putting the curing agent into stirring equipment, and stirring and dispersing uniformly in a vacuum environment to obtain the underfill.
In a preferred embodiment of the present invention, in the step (I), first, composite resin particles composed of an epoxy resin and a bismaleimide resin are prepared, and then, the composite resin particles, a diluent and a coloring material are mixed, followed by sequentially performing the first stirring and the second stirring.
The rotating speed of the first stirring process is larger than that of the second stirring process, and the temperature of the first stirring process is larger than that of the second stirring process.
The rotation speed of the first stirring is controlled to be 1200-1300r/min, for example, 1200r/min, 1210r/min, 1220r/min, 1230r/min, 1240r/min, 1250r/min, 1260r/min, 1270r/min, 1280r/min, 1290r/min or 1300r/min; the stirring time is 0.5-1.5h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h; the temperature of the first stirring step is maintained within the range of 50 to 60 ℃, and may be, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, or 60 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The rotation speed of the second stirring is controlled to be 400-500r/min, for example, 400r/min, 410r/min, 420r/min, 430r/min, 440r/min, 450r/min, 460r/min, 470r/min, 480r/min, 490r/min or 500r/min; the stirring time is 0.5-1.5h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h; the temperature of the second stirring step is maintained within the range of 30 to 40 ℃, and may be, for example, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃, but is not limited to the values recited, and other values not recited in the range are equally applicable.
As a preferable technical scheme of the invention, the preparation process of the composite resin particles comprises the following steps:
mixing deionized water, epoxy resin, mesoporous material and emulsifier, and heating until the epoxy resin is completely dissolved to obtain resin emulsion; adding initiator into resin emulsion, dropping bismaleimide resin monomer at 50-100 deg.c to perform heat insulating polymerization reaction, such as 50 deg.c, 60 deg.c, 70 deg.c, 80 deg.c, 90 deg.c or 100 deg.c, cooling to room temperature after the reaction, and filtering to obtain composite resin particle.
The mesoporous material is added in the preparation of the composite resin particles, so that the mesoporous material is dispersed in the epoxy resin shell coated on the surface of the bismaleimide resin. According to the invention, the storage capacity of mesoporous materials is utilized, epoxy resin is used as a repairing agent, the mixing and heating process is carried out in a vacuum environment, the viscosity of the heated epoxy resin is reduced and is injected into the pore canal of the mesoporous materials, after the epoxy resin is completely dissolved, the epoxy resin is restored to normal pressure, the viscosity of the epoxy resin injected into the pore canal is increased and cannot be discharged out of the pore canal, and meanwhile, other liquid substances are difficult to further diffuse into the pore canal; and then dropwise adding a bismaleimide resin monomer, polymerizing the bismaleimide resin monomer under the action of an initiator to form bismaleimide resin, wrapping the bismaleimide resin with epoxy resin, and filtering to form the composite resin particles with the core-shell structure.
In the coating process of the epoxy resin, maleimide resin monomer reacts with the epoxy resin which does not permeate into the pore canal of the mesoporous material to generate a polymer, and the polymer forms barriers on the periphery and the surface of the pore canal of the mesoporous material, so that the blocking of the pore canal of the mesoporous material is realized, the exudation of the epoxy resin in the pore canal is inhibited, and the epoxy resin can be kept in the pore canal of the mesoporous material. The epoxy resin blocked in the pore canal is completely isolated from the external environment, so that the epoxy resin cannot react with the curing agent and the curing agent accelerator which are added subsequently, and therefore, the epoxy resin can be polymerized and cured at a very high temperature, and therefore, the epoxy resin blocked in the pore canal can still keep certain chemical reactivity in a low-temperature environment. When the colloid is solidified and formed, and cracks are generated in the using process, the mesoporous material is extruded and broken, so that the epoxy resin in the pore canal is released, and the epoxy resin is polymerized under the action of the curing agent in the external environment, so that the cracks are bonded and repaired, and the purpose of recovering the colloid performance is achieved.
It should be noted that the invention does not make specific requirements and special choices on the material of the mesoporous material, and the mesoporous material optionally comprises SiO 2 、TiO 2 、Al 2 O 3 Or ZnO, or any one or a combination of at least two thereof.
In the step (ii), the first filler and the second filler are subjected to surface treatment before being added;
the surface treatment process comprises the following steps:
mixing the silane coupling agent with an organic solvent to obtain a dilute solution, adding the first filler and the second filler into the dilute solution, and performing ultrasonic dispersion for 0.5-1.5h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h; the mixture is then dried at 50-60℃for use, for example, 50℃51℃52℃53℃54℃55℃56℃57℃58℃59℃60℃but not limited to the values recited, and other values not recited in the range are equally applicable.
The silane coupling agent is 0.5 to 1% of the total mass of the first filler and the second filler, and may be 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.7%, 0.8%, 0.85%, 0.9% or 1%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the step (II), the stirring speed is 1300-1400r/min, for example, 1300r/min, 1310r/min, 1320r/min, 1330r/min, 1340r/min, 1350r/min, 1360r/min, 1370r/min, 1380r/min, 1390r/min or 1400r/min, but not limited to the values listed, and other values not listed in the range are equally applicable.
The temperature during the stirring may be maintained at 20 to 30℃and may be, for example, 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃or 30℃respectively, but the stirring is not limited to the values listed, and other values not listed in the range are equally applicable.
The stirring time is 0.5 to 1.5 hours, and may be, for example, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours or 1.5 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, in the step (iii), the stirring speed is 1300-1400r/min, for example 1300r/min, 1310r/min, 1320r/min, 1330r/min, 1340r/min, 1350r/min, 1360r/min, 1370r/min, 1380r/min, 1390r/min or 1400r/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
The temperature during the stirring may be maintained at 20 to 30℃and may be, for example, 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃or 30℃respectively, but the stirring is not limited to the values listed, and other values not listed in the range are equally applicable.
The stirring time is 0.5 to 1.5 hours, and may be, for example, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours or 1.5 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The invention provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick solidification, which comprises the following steps:
(1) Mixing deionized water, epoxy resin, mesoporous material and emulsifier, and heating until the epoxy resin is completely dissolved to obtain resin emulsion; adding an initiator into the resin emulsion, dropwise adding a bismaleimide resin monomer at the temperature of 50-100 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1 (0.1-0.5) after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) Mixing 40-60 parts of composite resin particles, 10-20 parts of diluent and 0.1-1 part of pigment, and sequentially carrying out first stirring and second stirring; wherein the rotation speed of the first stirring is 1200-1300r/min, the stirring time is 0.5-1.5h, and the temperature of the first stirring process is maintained within the range of 50-60 ℃; the rotation speed of the second stirring is 400-500r/min, the stirring time is 0.5-1.5h, and the temperature of the second stirring process is maintained within the range of 30-40 ℃;
(3) Mixing a silane coupling agent and an organic solvent to obtain a dilute solution, adding a first filler with the particle size of 10-20 mu m and a second filler with the particle size of 30-50nm into the dilute solution, performing ultrasonic dispersion for 0.5-1.5h, and then drying at the temperature of 50-60 ℃ for later use; wherein the silane coupling agent accounts for 0.5-1% of the total mass of the first filler and the second filler;
(4) Carrying out the step (2), continuously adding the first filler subjected to surface treatment, the second filler subjected to surface treatment, the curing accelerator and the coupling agent into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1300-1400r/min, the stirring time is 0.5-1.5h, and the temperature in the stirring process is maintained at 20-30 ℃; wherein the mass ratio of the first filler to the second filler is 1 (1-5), the total mass part of the first filler and the second filler is 10-30 parts, the addition amount of the curing accelerator is 5-10 parts, and the addition amount of the coupling agent is 1-5 parts;
(5) And (4) carrying out the step of continuously adding 5-10 parts of curing agent into the stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1300-1400r/min, the stirring time is 0.5-1.5h, the temperature in the stirring process is maintained at 20-30 ℃, and the underfill is obtained after the stirring is completed.
It should be noted that, all the chemical substances related in the invention are commercial products except self-made products, and the chemical properties of the components, the formula, the molecular formula and the like are disclosed in the prior art.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the composite resin particles with the core-shell structure and the core-shell structure are prepared by adopting a coating process, wherein the epoxy resin is taken as a shell layer, the bismaleimide resin is taken as a core, and the composite resin particles are taken as a resin matrix of the underfill, so that the bending strength and the impact strength of the colloid can be effectively improved, and the colloid is convenient to clean;
(2) The epoxy resin is used for coating the bismaleimide resin, so that the bending strength of the composite resin particles is greatly improved, and at the coating interface of the bismaleimide resin and the epoxy resin, the chain segments of the epoxy resin participate in the curing reaction between the bismaleimide resin and the curing agent, so that the space between crosslinking points is increased, the crosslinking density in a system is reduced, the molecular activity is improved, a coating interface system formed between the bismaleimide resin and the epoxy resin is in a flexible curing network structure with a rigid curing network and a flexible network coexisting, and when the external force acts, the flexible curing network structure can well generate a stress relaxation and flexibility relaxation effect, the anti-cracking capability of the system is effectively resisted, and the system presents higher bending strength;
(3) According to the invention, the impact strength of the underfill can be improved by coating the bismaleimide resin with the epoxy resin. Because the epoxy group is arranged in the molecular structure of the epoxy resin, the epoxy group can react with the surface of the material containing active hydrogen to generate a chemical bond, so that the flexibility of the molecular chain of the bismaleimide resin before curing is improved; in addition, when the coating is carried out with the bismaleimide resin, a copolymerization reaction is carried out on the bismaleimide resin main chain, the final result of the copolymerization reaction is that a cross-linked network is formed, and the bismaleimide resin main chain is also partially chain-extended by diamine and epoxy chain links, so that the cross-linked density of the bismaleimide resin is reduced. When the underfill is subjected to impact energy, the flexible chain of the epoxy resin can play a role in stress dispersion and stress bearing, so that the toughness of the system is improved;
(4) Under the low temperature condition, the shell is epoxy resin cured at low temperature, so that the curing agent and the shell of the epoxy resin undergo a crosslinking polymerization reaction, the shell of the composite resin particles is cured first, and the curing time of the underfill is shortened. After the shell is solidified, the bismaleimide resin of the inner core part is in a micro-dispersion state due to the high-temperature solidification characteristic and higher glass transition temperature, and is uniformly dispersed in the colloid, when the chip needs to be repaired, the colloid is heated at high temperature to reach the glass transition temperature of the inner core, so that the solidified underfill adhesive becomes soft, and the colloid can be easily removed under the action of external force;
(5) The invention adopts the fillers with different particle sizes to be mixed into the colloid, can be filled into the gap between the chip and the substrate, and can inhibit the influence of the surface area of the filler on the colloid mobility by adjusting the mass ratio between the different particle sizes, thereby obtaining good colloid mobility, so that the filler can enter into the deep part of the gap under the permeation effect of the colloid, realize the mechanical engagement between the chip and the substrate after solidification, and improve the fixing effect of the chip;
(6) The invention adopts the anhydride oligomer with multiple functional groups as the curing agent, can effectively reduce the volatilization of the resin composition, and promote the resin curing process, thereby reducing the porosity of the underfill;
(7) The imidazole curing accelerator is adopted, so that not only can the curing of colloid be promoted, but also the reaction initial temperature of the underfill can be reduced, the underfill can be ensured to react slowly at a lower temperature, bubbles generated by the explosion polymerization of the underfill at a high temperature are avoided, the small molecules are enabled to start to react in advance at the lower reaction initial temperature, the small molecules in the underfill are ensured to react fully in the slow temperature rising process, and the generation of bubbles and gaps is effectively avoided;
(8) According to the invention, the repair of colloid cracks can be realized by dispersing mesoporous materials in the epoxy resin shell, in the coating process of epoxy resin, maleimide resin monomer reacts with epoxy resin which does not permeate into the pore channels of the mesoporous materials to generate polymers, and the polymers form barriers on the periphery and the surface of the pore channels of the mesoporous materials, so that the pore channels of the mesoporous materials are blocked, the exudation of epoxy resin in the pore channels is inhibited, and the epoxy resin can be kept in the pore channels of the mesoporous materials. The epoxy resin blocked in the pore canal is completely isolated from the external environment, so that the epoxy resin cannot react with the curing agent and the curing agent accelerator which are added subsequently, and therefore, the epoxy resin can be polymerized and cured at a very high temperature, and therefore, the epoxy resin blocked in the pore canal can still keep certain chemical reactivity in a low-temperature environment. When the colloid is solidified and formed, and cracks are generated in the using process, the mesoporous material is extruded and broken, so that the epoxy resin in the pore canal is released, and the epoxy resin is polymerized under the action of the curing agent in the external environment, so that the cracks are bonded and repaired, and the purpose of recovering the colloid performance is achieved.
Detailed Description
The technical scheme of the invention is described in detail below with reference to specific embodiments. The examples described herein are specific embodiments of the present invention for illustrating the concept of the present invention; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the invention in its aspects. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims of the present application and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting, which comprises the following steps:
(1) Deionized water, bisphenol A epoxy resin and SiO 2 Mixing mesoporous material (particle diameter of 20 μm, pore diameter of 5 nm) with emulsifier, and heating until epoxy resin is completely dissolved to obtain resin emulsion; adding an initiator potassium persulfate into the resin emulsion, dropwise adding a bismaleimide resin monomer at the temperature of 50 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1:0.1 after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) Mixing 40 parts of composite resin particles, 10 parts of diluent butyl glycidyl ether and 1 part of pigment, and sequentially carrying out first stirring and second stirring; wherein the rotation speed of the first stirring is 1200r/min, the stirring time is 1.5h, and the temperature of the first stirring process is maintained within the range of 50 ℃; the rotation speed of the second stirring is 400r/min, the stirring time is 1.5h, and the temperature of the second stirring process is maintained within the range of 30 ℃;
(3) Mixing silane coupling agent KH550 with organic solvent acetone to obtain diluted solution, and mixing first filler SiO with particle diameter of 10 μm 2 And a second filler TiO having a particle size of 30nm 2 Adding the mixture into a dilute solution, performing ultrasonic dispersion for 0.5h, and then drying at 50 ℃ for later use; wherein, the silane coupling agent KH550 is SiO 2 And TiO 2 0.5% of the total mass;
(4) The receiving step (2) is carried out, and SiO after surface treatment is continuously added into the stirring equipment 2 Surface-treated TiO 2 Uniformly stirring and dispersing the curing accelerator 1, 6-dinitrocarbazole and the coupling agent gamma-aminopropyl triethylsiloxane in a vacuum environment, wherein the stirring speed is 1300r/min, the stirring time is 0.5h, and the temperature in the stirring process is maintained at 20 ℃; wherein 19 parts of SiO after surface treatment is added 2 10 parts of surface-treated TiO 2 5 parts of 1, 6-dinitrocarbazole and 5 parts of gamma-aminopropyl triethylsiloxane;
(5) And (4) carrying out the receiving step, continuously adding 10 parts of curing agent cyclohexane/maleic anhydride copolymer into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1300r/min, the stirring time is 1.5h, the temperature in the stirring process is maintained at 20 ℃, and the underfill with the viscosity of 20.26 Pa.S is obtained after the stirring is completed.
Example 2
The embodiment provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting, which comprises the following steps:
(1) Deionized water, bisphenol F type epoxy resin and TiO 2 Mixing mesoporous material (particle size of 22 μm, pore diameter of 6 nm) with emulsifier, and heating until epoxy resin is completely dissolved to obtain resin emulsion; addition of initiation to resin emulsionDropwise adding bismaleimide resin monomer into potassium persulfate at the temperature of 60 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1:0.2 after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) 45 parts of composite resin particles, 20 parts of diluent phenyl glycidyl ether and 0.5 part of pigment are mixed, and the first stirring and the second stirring are sequentially carried out; wherein the rotating speed of the first stirring is 1230r/min, the stirring time is 1.2h, and the temperature of the first stirring process is maintained within the range of 52 ℃; the rotation speed of the second stirring is 420r/min, the stirring time is 1.2h, and the temperature of the second stirring process is maintained within the range of 32 ℃;
(3) Mixing silane coupling agent KH550 with organic solvent acetone to obtain diluted solution, and mixing first filler SiO with particle diameter of 12 μm 2 And a second filler Al having a particle diameter of 35nm 2 O 3 Adding the mixture into a dilute solution, performing ultrasonic dispersion for 0.8h, and then drying at 52 ℃ for later use; wherein, the silane coupling agent KH550 is SiO 2 And Al 2 O 3 0.6% of the total mass;
(4) The receiving step (2) is carried out, and SiO after surface treatment is continuously added into the stirring equipment 2 Surface-treated Al 2 O 3 Uniformly stirring and dispersing the curing accelerator 2-phenyl-4, 5-dihydroxymethylimidazole and the coupling agent gamma-glycidoxypropyl trimethoxysiloxane in a vacuum environment, wherein the stirring speed is 1320r/min, the stirring time is 0.8h, and the temperature in the stirring process is maintained at 23 ℃; wherein 12 parts of SiO after surface treatment is added 2 8 parts of surface-treated Al 2 O 3 5.5 parts of 2-phenyl-4, 5-dihydroxymethylimidazole and 4 parts of gamma-glycidoxypropyl trimethoxysiloxane;
(5) And (4) carrying out the receiving step, continuously adding 5 parts of curing agent styrene/maleic anhydride copolymer into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1320r/min, the stirring time is 1.2h, the temperature in the stirring process is maintained at 23 ℃, and the underfill with the viscosity of 18.59 Pa.S is obtained after the stirring is completed.
Example 3
The embodiment provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting, which comprises the following steps:
(1) Deionized water, epoxy phenol resin and Al 2 O 3 Mixing mesoporous material (particle diameter of 25 μm, pore diameter of 7 nm) with emulsifier, and heating until epoxy resin is completely dissolved to obtain resin emulsion; adding an initiator potassium persulfate into the resin emulsion, dropwise adding a bismaleimide resin monomer at the temperature of 80 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1:0.3 after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) 50 parts of composite resin particles, 12 parts of diluent benzyl glycidyl ether and 0.1 part of pigment are mixed, and the first stirring and the second stirring are sequentially carried out; wherein the rotation speed of the first stirring is 1250r/min, the stirring time is 1h, and the temperature of the first stirring process is maintained within the range of 55 ℃; the rotation speed of the second stirring is 450r/min, the stirring time is 1h, and the temperature of the second stirring process is maintained within the range of 35 ℃;
(3) Mixing silane coupling agent KH550 with organic solvent ethanol to obtain diluted solution, and adding first filler TiO with particle diameter of 15 μm 2 Adding a second filler ZnO with the particle size of 40nm into the dilute solution, performing ultrasonic dispersion for 1h, and then drying at 55 ℃ for later use; wherein, the silane coupling agent KH550 is TiO 2 And 0.7% of the total mass of ZnO;
(4) Carrying out the bearing step (2), and continuously adding the TiO subjected to the surface treatment into the stirring equipment 2 Uniformly stirring and dispersing ZnO subjected to surface treatment, curing accelerator 1, 3-dimethyl carbazole and coupling agent vinyl tri-tert-butyl silane peroxide in a vacuum environment, wherein the stirring speed is 1350r/min, the stirring time is 1h, and the temperature in the stirring process is maintained at 25 ℃; wherein 15 parts of TiO after surface treatment is added 2 8 parts of ZnO after surface treatment, 6 parts of 1, 3-dimethyl carbazole and 3-vinyl tri-tert-butyl silane peroxide;
(5) And (4) carrying out the receiving step, continuously adding 5.9 parts of curing agent norbornene/maleic anhydride copolymer into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1350r/min, the stirring time is 1h, the temperature in the stirring process is kept at 25 ℃, and the underfill with the viscosity of 13.47 Pa.S is obtained after the stirring is completed.
Example 4
The embodiment provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting, which comprises the following steps:
(1) Mixing deionized water, bisphenol A epoxy resin, znO mesoporous material (particle diameter is 28 μm, aperture is 8 nm) and emulsifier, and heating until the epoxy resin is completely dissolved to obtain resin emulsion; adding an initiator potassium persulfate into the resin emulsion, dropwise adding a bismaleimide resin monomer at the temperature of 90 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1:0.4 after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) Mixing 55 parts of composite resin particles, 10 parts of diluent 4-tert-butylphenyl glycidyl ether and 0.4 part of pigment, and sequentially carrying out first stirring and second stirring; wherein the rotating speed of the first stirring is 1270r/min, the stirring time is 0.8h, and the temperature of the first stirring process is maintained within the range of 58 ℃; the rotation speed of the second stirring is 480r/min, the stirring time is 0.8h, and the temperature of the second stirring process is maintained within 38 ℃;
(3) Mixing silane coupling agent KH550 with organic solvent ethanol to obtain diluted solution, and mixing first filler Al with particle diameter of 18 μm 2 O 3 Adding a second filler ZnO with the particle size of 45nm into the dilute solution, performing ultrasonic dispersion for 1.2 hours, and then drying at 58 ℃ for later use; wherein, the silane coupling agent KH550 is Al 2 O 3 And 0.8% of the total mass of ZnO;
(4) Carrying out the bearing step (2), and continuously adding the Al subjected to the surface treatment into the stirring equipment 2 O 3 ZnO after surface treatment, 1-nitrocarbazole as a curing accelerator and gamma-aminopropyl triethyl as a coupling agentSiloxane is stirred and dispersed uniformly in a vacuum environment, the stirring speed is 1380r/min, the stirring time is 1.2h, and the temperature in the stirring process is maintained at 28 ℃; wherein 12 parts of surface-treated Al is added 2 O 3 6 parts of ZnO after surface treatment, 10 parts of 1-nitrocarbazole and 1 part of gamma-aminopropyl triethylsiloxane;
(5) And (4) carrying out the receiving step, continuously adding 5.6 parts of curing agent cyclohexane/maleic anhydride copolymer into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1380r/min, the stirring time is 0.8h, the temperature in the stirring process is maintained at 28 ℃, and the bottom filling glue with the viscosity of 15.36 Pa.S is obtained after the stirring is completed.
Example 5
The embodiment provides a preparation method of an underfill adhesive with high flexibility, impact resistance and low-temperature quick-setting, which comprises the following steps:
(1) Deionized water, bisphenol F type epoxy resin and SiO 2 Mixing mesoporous material (particle diameter of 30 μm, pore diameter of 10 nm) with emulsifier, and heating to dissolve epoxy resin completely to obtain resin emulsion; adding an initiator potassium persulfate into the resin emulsion, dropwise adding a bismaleimide resin monomer at the temperature of 100 ℃ for thermal insulation polymerization reaction, and controlling the mass ratio of the obtained epoxy resin to the bismaleimide resin to be 1:0.5 after the reaction is finished; cooling to room temperature after the reaction is completed, and filtering to obtain composite resin particles for later use;
(2) Mixing 60 parts of composite resin particles, 12 parts of a diluent of trimethylol triglycidyl ether and 0.5 part of a colorant, and sequentially performing first stirring and second stirring; the rotation speed of the first stirring is 1300r/min, the stirring time is 0.5h, and the temperature of the first stirring process is maintained within the range of 60 ℃; the rotation speed of the second stirring is 500r/min, the stirring time is 0.5h, and the temperature of the second stirring process is maintained within the range of 40 ℃;
(3) Mixing silane coupling agent KH550 with organic solvent ethanol to obtain diluted solution, mixing first filler ZnO with particle diameter of 20 μm and second filler TiO with particle diameter of 50nm 2 Adding into dilute solution to carry out ultrasonic dispersion for 1.5h, drying at 60 ℃ for later use; wherein the silane coupling agent KH550 is ZnO and TiO 2 1% of the total mass;
(4) The receiving step (2) is that ZnO after surface treatment and TiO after surface treatment are continuously added into the stirring equipment 2 The curing accelerator 1, 4-dimethyl carbazole and the coupling agent gamma-aminopropyl triethylsiloxane are stirred and dispersed uniformly in a vacuum environment, the stirring speed is 1400r/min, the stirring time is 1.5h, and the temperature in the stirring process is maintained at 30 ℃; wherein 10 parts of ZnO after surface treatment and 5 parts of TiO after surface treatment are added 2 5 parts of 1, 4-dimethyl carbazole and 1.5 parts of gamma-aminopropyl triethylsiloxane;
(5) And (4) carrying out the receiving step, continuously adding 6 parts of curing agent styrene/maleic anhydride copolymer into stirring equipment, stirring and dispersing uniformly in a vacuum environment, wherein the stirring speed is 1400r/min, the stirring time is 0.5h, the temperature in the stirring process is maintained at 30 ℃, and the underfill with the viscosity of 17.49 Pa.S is obtained after the stirring is completed.
Comparative example 1
The present embodiment provides a method for preparing an underfill having high flexibility, impact resistance and low temperature rapid solidification, which is different from embodiment 3 in that step (1) is omitted and the composite resin particles added in step (2) are replaced with equal parts by mass of epoxy resin.
Other operating parameters and process steps were exactly the same as in example 1, the final underfill having a viscosity of 68.48 Pa.S.
Comparative example 2
The present embodiment provides a method for preparing an underfill having high flexibility, impact resistance and low temperature rapid solidification, which is different from embodiment 3 in that step (1) is omitted and the composite resin particles added in step (2) are replaced with the bismaleimide resin of equal mass parts.
Other operating parameters and process steps were exactly the same as in example 1, the final underfill having a viscosity of 58.69 Pa.S.
Comparative example 3
The present embodiment provides a method for preparing an underfill having high flexibility, impact resistance and low temperature rapid solidification, which is different from embodiment 3 in that step (1) is omitted, and the composite resin particles added in step (2) are replaced with a dispersion system formed by epoxy resin and bismaleimide resin, i.e., the epoxy resin and the bismaleimide resin are not formed into a core-shell structure, but are directly put into a stirring device according to a mass ratio to be mixed with a diluent and a pigment.
Other operating parameters and process steps were exactly the same as in example 1, the final underfill having a viscosity of 55.16 Pa.S.
The underfill adhesives prepared in examples 1 to 5 and comparative examples 1 to 5 were subjected to curing tests at different temperatures for curing times at different temperatures, and the test results are shown in Table 1.
TABLE 1
| Curing temperature | 70℃ | 100℃ | 120℃ | 150℃ |
| Example 1 | 8.5min | 7.6min | 4.8min | 2.5min |
| Example 2 | 7.8min | 6.0min | 4.2min | 1.3min |
| Example 3 | 5.5min | 4.3min | 2.3min | 1.0min |
| Example 4 | 6.3min | 4.8min | 3.8min | 1.5min |
| Example 5 | 8.9min | 5.0min | 4.5min | 2.3min |
| Comparative example 1 | — | 16.3min | 14.6min | 13.9min |
| Comparative example 2 | — | 18.5min | 15.3min | 13.5min |
| Comparative example 3 | 12.5min | 10.6min | 9.3min | 8.5min |
In the table "-" means that it is not cured after more than 20 minutes.
As can be seen from the data in table 1, the underfill adhesives prepared in examples 1-5 provided by the invention adopt a core-shell structure formed by cladding, so that the prepared underfill adhesive has better low-temperature curing performance and fluidity, is relatively suitable for the underfill for packaging such as large-size chip packaging (CSP), ball grid array packaging (BGA) and the like, and greatly increases the packaging efficiency, reliability and long-term usability.
The underfill adhesives prepared in examples 1 to 5 and comparative examples 1 to 5 were tested for elongation at break, breaking strength and shear strength, and the test results are shown in Table 2.
As can be seen from the data in table 2,
| elongation at break (%) | Breaking strength (MPa) | Shear strength (MPa) | |
| Example 1 | 18.6 | 20.5 | 15.6 |
| Example 2 | 19.8 | 23.6 | 16.7 |
| Example 3 | 20.3 | 25.1 | 18.3 |
| Example 4 | 17.7 | 24.3 | 17.6 |
| Example 5 | 16.5 | 19.2 | 14.6 |
| Comparative example 1 | 5.3 | 10.5 | 11.3 |
| Comparative example 2 | 6.8 | 12.7 | 12.5 |
| Comparative example 3 | 8.7 | 13.6 | 10.4 |
As can be seen from the data in Table 2, the elongation at break, the breaking strength and the shearing strength of the underfill prepared in examples 1-5 provided by the present invention are significantly higher than those of comparative examples 1-3, which demonstrates that the underfill prepared by the preparation method provided by the present invention has excellent flexibility and impact resistance.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (9)
1. The high-flexibility, impact-resistant and low-temperature fast-curing underfill is characterized in that the underfill comprises the following components in parts by mass based on 100 parts by mass of the underfill:
40-60 parts of resin composition, 10-30 parts of filler, 10-20 parts of diluent, 1-5 parts of coupling agent, 5-10 parts of curing agent, 1-5 parts of curing accelerator and 0.1-1 part of pigment;
the resin composition is composite resin particles with a core-shell structure formed by epoxy resin and bismaleimide resin, wherein the epoxy resin is a shell layer, and the bismaleimide resin is an inner core;
the preparation process of the composite resin particles comprises the following steps:
mixing deionized water, epoxy resin, mesoporous material and emulsifier, and heating until the epoxy resin is completely dissolved to obtain resin emulsion; adding an initiator into the resin emulsion, dropwise adding a bismaleimide resin monomer in the temperature environment of 50-100 ℃ for thermal insulation polymerization reaction; and cooling to room temperature after the reaction is completed, and filtering to obtain the composite resin particles.
2. The underfill of claim 1, wherein the mass ratio of the epoxy resin to the bismaleimide resin is 1 (0.1-0.5);
The epoxy resin is any one or the combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin or epoxy phenol resin;
mesoporous materials are dispersed in the shell formed by the epoxy resin.
3. The underfill according to claim 1 or 2, wherein the filler comprises a first filler and a second filler, the mass ratio of the first filler to the second filler being 1 (1-5);
the particle size of the first filler is larger than that of the second filler;
the particle size of the first filler is 10-20 mu m, and the particle size of the second filler is 30-50nm; the first filler and the second filler are each independently selected from SiO 2 、TiO 2 、Al 2 O 3 Or ZnO, or any one or a combination of at least two thereof.
4. The underfill according to claim 1 or 2, wherein the curing agent is an anhydride oligomer;
the molecular weight of the curing agent is 1500-1600Da.
5. The underfill according to claim 1 or 2, wherein the curing accelerator is selected from any one or a combination of at least two of tertiary amine curing accelerators, imidazole curing accelerators, phosphorus curing accelerators or boron curing accelerators.
6. A method of preparing a highly flexible, impact resistant, low temperature fast setting underfill according to claim 3, comprising:
putting the resin composition, the diluent and the pigment into stirring equipment, and stirring and dispersing uniformly in a vacuum environment;
(II) putting the curing accelerator, the first filler, the second filler and the coupling agent into stirring equipment, and stirring and dispersing uniformly in a vacuum environment;
and (III) putting the curing agent into stirring equipment, and stirring and dispersing uniformly in a vacuum environment to obtain the underfill.
7. The method according to claim 6, wherein in the step (I), first composite resin particles composed of an epoxy resin and a bismaleimide resin are prepared, and then the composite resin particles, a diluent and a coloring material are mixed, followed by first stirring and second stirring in this order; the rotating speed of the first stirring process is higher than that of the second stirring process, and the temperature of the first stirring process is higher than that of the second stirring process;
the rotation speed of the first stirring is controlled to be 1200-1300r/min, the stirring time is 0.5-1.5h, and the temperature of the first stirring process is maintained within the range of 50-60 ℃;
The rotation speed of the second stirring is controlled to be 400-500r/min, the stirring time is 0.5-1.5h, and the temperature of the second stirring process is maintained within the range of 30-40 ℃.
8. The method according to claim 6, wherein in the step (ii), the first filler and the second filler are subjected to surface treatment before the first filler and the second filler are added;
the surface treatment process comprises the following steps:
mixing the silane coupling agent and the organic solvent to obtain a dilute solution, adding the first filler and the second filler into the dilute solution, performing ultrasonic dispersion for 0.5-1.5h, and then drying at 50-60 ℃ for later use; wherein the silane coupling agent accounts for 0.5-1% of the total mass of the first filler and the second filler;
in the step (II), the stirring rotating speed is 1300-1400r/min;
the temperature in the stirring process is maintained at 20-30 ℃;
the stirring time is 0.5-1.5h.
9. The process according to claim 6, wherein in step (III), the stirring speed is 1300-1400r/min;
the temperature in the stirring process is maintained at 20-30 ℃;
the stirring time is 0.5-1.5h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560167A (en) * | 2004-03-10 | 2005-01-05 | 四川大学 | Epoxy resin adhesive containing bismaleimide and preparation method thereof |
| CN104152116A (en) * | 2014-09-09 | 2014-11-19 | 北京宇田相变储能科技有限公司 | Phase change energy storage composite microsphere and preparation method thereof |
| CN106317982A (en) * | 2016-08-17 | 2017-01-11 | 烟台长盈电子科技有限公司 | Low-hydroscopicity composite epoxy resin adhesive |
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| CN119978723A (en) * | 2018-12-12 | 2025-05-13 | 松下知识产权经营株式会社 | Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board |
| CN113248917B (en) * | 2020-02-13 | 2023-02-03 | 台光电子材料(昆山)有限公司 | A kind of resin composition and its products |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560167A (en) * | 2004-03-10 | 2005-01-05 | 四川大学 | Epoxy resin adhesive containing bismaleimide and preparation method thereof |
| CN104152116A (en) * | 2014-09-09 | 2014-11-19 | 北京宇田相变储能科技有限公司 | Phase change energy storage composite microsphere and preparation method thereof |
| CN106317982A (en) * | 2016-08-17 | 2017-01-11 | 烟台长盈电子科技有限公司 | Low-hydroscopicity composite epoxy resin adhesive |
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