CN116855211A - Low-viscosity low-dielectric-constant underfill adhesive and preparation method and application thereof - Google Patents
Low-viscosity low-dielectric-constant underfill adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN116855211A CN116855211A CN202311020360.3A CN202311020360A CN116855211A CN 116855211 A CN116855211 A CN 116855211A CN 202311020360 A CN202311020360 A CN 202311020360A CN 116855211 A CN116855211 A CN 116855211A
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- CN
- China
- Prior art keywords
- low
- underfill
- epoxy resin
- parts
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 14
- 230000001070 adhesive effect Effects 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 71
- 239000004593 Epoxy Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011256 inorganic filler Substances 0.000 claims abstract description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims abstract description 25
- 239000012745 toughening agent Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 5
- -1 alkylene alkyl compound Chemical class 0.000 claims description 50
- 239000013067 intermediate product Substances 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000003444 phase transfer catalyst Substances 0.000 claims description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 238000006467 substitution reaction Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 13
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000005821 Claisen rearrangement reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 244000226021 Anacardium occidentale Species 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 claims description 3
- 235000020226 cashew nut Nutrition 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 241000894007 species Species 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 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 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000013466 adhesive and sealant Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000000203 mixture Substances 0.000 description 28
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- 125000002723 alicyclic group Chemical group 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 6
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LLSFRMPDWAMQAU-UHFFFAOYSA-N C(C)(C)P(C(C)C)C(C)C.B(F)(F)F Chemical compound C(C)(C)P(C(C)C)C(C)C.B(F)(F)F LLSFRMPDWAMQAU-UHFFFAOYSA-N 0.000 description 1
- KHQZSBGSWULCNS-UHFFFAOYSA-N C(C)P(CC)CC.B(F)(F)F Chemical compound C(C)P(CC)CC.B(F)(F)F KHQZSBGSWULCNS-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- ZXUJYIQZKNWLQN-UHFFFAOYSA-N [3-(7-oxabicyclo[4.1.0]heptan-3-ylmethyl)-7-oxabicyclo[4.1.0]heptan-3-yl] formate Chemical compound C(=O)OC1(CC2C(CC1)O2)CC1CC2C(CC1)O2 ZXUJYIQZKNWLQN-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Classifications
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3218—Carbocyclic compounds
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- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the field of adhesives and sealants, and relates to a low-viscosity low-dielectric-constant underfill, a preparation method and application thereof. The high temperature-resistant underfill comprises an alkoxyl phenyl tri-epoxy monomer, epoxy resin, a toughening agent, a curing agent, an accelerator, a coupling agent, an inorganic filler and optional auxiliary agents; the weight ratio of the alkoxy phenyl tri-epoxy monomer to the epoxy resin is 1 (0.5-1.75); the alkoxyphenyl trioxymethylene monomer has the following formulaA structure represented by formula (I); the epoxy resin is an epoxy resin comprising at least bisphenol F diglycidyl ether. The invention adopts the reasonable collocation of the epoxy resin at least comprising bisphenol F diglycidyl ether and the alkoxyl phenyl tri-epoxy monomer with three epoxy functional groups, and has low dielectric constant and good heat resistance on the basis of low viscosity and good fluidity. The underfill with low viscosity and low dielectric constant has wide application prospect in the underfilling of chips and PCB substrates.
Description
Technical Field
The invention belongs to the field of adhesives and sealants, and particularly relates to a low-viscosity low-dielectric-constant underfill adhesive, and a preparation method and application thereof.
Background
The integrated circuit industry is constantly producing microelectronic elements with higher integration, packaging density and power density, and electronic packaging materials are used to package these microelectronic elements together, to help dissipate heat, redistribute stresses, and to protect the entire system from the environment, which plays an important role in ensuring the performance and reliability of electronic devices. Epoxy-based underfills are often used in flip-chip packaging in a variety of packaging materials. Epoxy adhesives polymerize to amorphous and highly crosslinked materials, and their microstructure has many advantages such as multiple curing modes, small shrinkage during curing, good wettability, adhesion to most substrates, good adhesion properties, high corrosion resistance, high mechanical strength, chemical resistance and good heat resistance.
The development of high integration and high performance of electronic chips has put higher demands on the performance of underfill. According to the process and the application properties, the underfill needs to have the basic characteristics of easy operation, fast flow, fast curing, long service life, high adhesion strength and low modulus, while satisfying the filling property, compatibility, reworkability and the like. Although existing underfill has high heat resistance, generally the viscosity is high, and how to achieve low viscosity is a key to ensuring easy operability of the underfill. In addition, the underfill material should have a low dielectric constant to ensure a high signal propagation speed to avoid shorting. However, the existing underfill has to be balanced and optimized in terms of high performance such as low viscosity, low dielectric constant, good heat resistance, etc. Therefore, how to obtain an underfill having low viscosity and low dielectric constant and to ensure good heat resistance has become a problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects of higher heat resistance but higher viscosity and dielectric constant of the existing underfill, and provides an underfill with low viscosity, low dielectric constant and good heat resistance, and a preparation method and application thereof.
Specifically, the invention provides a low-viscosity low-dielectric-constant underfill adhesive, which contains an alkoxyphenyl tri-epoxy monomer, an epoxy resin, a toughening agent, a curing agent, an accelerator, a coupling agent, an inorganic filler and optional auxiliary agents; the weight ratio of the alkoxy phenyl tri-epoxy monomer to the epoxy resin is 1 (0.5-1.75);
the alkoxyl phenyl tri-epoxy monomer has a structure shown in the following formula (I):
in the formula (I), R 1 Is C 1 ～C 5 Alkyl of R 2 、R 3 And R is 4 Each independently is C 1 ～C 5 An alkylene group of (a);
the epoxy resin is an epoxy resin comprising at least bisphenol F diglycidyl ether.
In a preferred embodiment, the content of the alkoxyphenyl tri-epoxy monomer is 20 to 35 parts by mass, the content of the epoxy resin is 10 to 35 parts by mass, the content of the toughening agent is 10 to 20 parts by mass, the content of the curing agent is 29 to 50 parts by mass, the content of the accelerator is 0.5 to 2.5 parts by mass, the content of the coupling agent is 0.2 to 5 parts by mass, the content of the inorganic filler is 40 to 80 parts by mass, and the content of the auxiliary agent is 0.1 to 10 parts by mass.
In a preferred embodiment, the alkoxyphenyl tri-epoxy monomer is prepared according to a process comprising the steps of:
step one: carrying out substitution reaction on 2-alkoxy-4-alkylene alkylphenol with a structure shown in a formula (II) and a first alkylene alkyl compound with a structure shown in a formula (III) in the presence of a first phase transfer catalyst and in a first alkaline medium, and purifying to obtain a colorless first intermediate product in a liquid state;
step two: heating the first intermediate product to high temperature for claisen rearrangement reaction, and purifying to obtain a liquid colorless or yellow second intermediate product;
step three: carrying out substitution reaction on the second intermediate product and a second alkyl compound with a structure shown in a formula (III) in a second alkaline medium in the presence of a second phase transfer catalyst, and purifying to obtain a liquid colorless or yellow third intermediate product;
step four: oxidizing the third intermediate product in the presence of an oxidant, and purifying to obtain a colorless or yellow low-viscosity liquid product, namely the alkoxyl phenyl trioxymethylene monomer;
in the formula (II), R 5 Is C 1 ～C 5 Alkyl of R 6 Is C 1 ～C 5 An alkylene group of (a);
in the formula (III), R 7 Is C 1 ～C 5 X is a halogen atom.
In a preferred embodiment, in step one, the molar ratio of 2-alkoxy-4-alkenalkyl phenol to the first alkenalkyl compound employed during the substitution reaction is 1 (2.5-3.5).
In a preferred embodiment, in step one, the first alkaline medium is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
In a preferred embodiment, in step one, the molar ratio of said 2-alkoxy-4-alkenoyl phenol to the first basic medium is 1 (2.5 to 3.5).
In a preferred embodiment, in the first step, the first phase transfer catalyst is selected from at least one of cyclic crown ethers, polyethers and ammonium.
In a preferred embodiment, in step one, the molar ratio of the 2-alkoxy-4-alkenoyl phenol to the first phase transfer catalyst is 1 (0.1 to 0.3).
In a preferred embodiment, in step one, the conditions of the substitution reaction include a temperature of 50 to 90 ℃ for a period of 8 to 15 hours.
In a preferred embodiment, in the second step, the claisen rearrangement reaction conditions include a temperature of 180 to 220 ℃ for a period of 8 to 12 hours.
In a preferred embodiment, in step three, the molar ratio of the second intermediate product to the second alkyl compound employed during the substitution reaction is 1 (2.5-3.5).
In a preferred embodiment, in step three, the second alkaline medium is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide.
In a preferred embodiment, in step three, the molar ratio of the second intermediate product to the second alkaline medium is 1 (2.5-3.5).
In a preferred embodiment, in step three, the second phase transfer catalyst is selected from at least one of cyclic crown ethers, polyethers and ammonium.
In a preferred embodiment, in step three, the molar ratio of the second intermediate product to the second phase transfer catalyst is 1 (0.1 to 0.3).
In a preferred embodiment, in the third step, the conditions of the substitution reaction include a temperature of 50 to 90 ℃ for 8 to 15 hours.
In a preferred embodiment, in the fourth step, the oxidizing agent is peroxide and/or hydrogen peroxide.
In a preferred embodiment, in step four, the molar ratio of the third intermediate product to the oxidizing agent used in the oxidation reaction is 1 (4.0 to 5.0).
In a preferred embodiment, in the fourth step, the oxidation reaction conditions include a temperature of 30 to 50 ℃ for 48 to 96 hours.
In a preferred embodiment, the epoxy resin is a combination of bisphenol F diglycidyl ether and cycloaliphatic epoxy resin in a weight ratio of 1 (0.1-0.4).
In a preferred embodiment, the toughening agent is selected from at least one of silicone hybrid epoxy, epoxy oligomeric silsesquioxane, liquid nitrile rubber, liquid polybutadiene, liquid polysulfide rubber, neoprene, cashew shell liquid modified phenolic resin, polyester resin, epoxy reactive toughening agent, SBS thermoplastic elastomer, polyvinyl formal, polyethersulfone, polyimide, polyetherimide, polyetheretherketone, polyetherdiol, and polyether triol.
In a preferred embodiment, the curing agent is selected from one or more of an amine curing agent, an anhydride curing agent, a phenolic curing agent, an imidazole curing agent and a latent curing agent.
In a preferred embodiment, the ratio of the total epoxy equivalent to the reactive functional equivalent of the curing agent in the alkoxyphenyl tri-epoxy monomer and epoxy resin is 1 (0.8 to 1.2), the term "reactive functional" referring to the reactive group capable of participating in the curing reaction.
In a preferred embodiment, the accelerator is selected from at least one of imidazole-based compounds, amine-based compounds, and phosphorus-based compounds.
In a preferred embodiment, the coupling agent is selected from at least one of gamma-methacryloxypropyl trimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, phenylmethyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and gamma-ureidopropyl triethoxysilane.
In a preferred embodiment, the inorganic filler is spherical silica particles.
In a preferred embodiment, the inorganic filler has an average particle size of 0.1 to 1. Mu.m.
In a preferred embodiment, the auxiliary agent is selected from one or more of stabilizers, polymerization inhibitors, antioxidants, flame retardants, diluents, adhesion promoters, dyes, pigments, defoamers, leveling agents and ion capturing agents.
The invention also provides a preparation method of the low-viscosity low-dielectric-constant underfill adhesive, which comprises the following steps: and uniformly mixing the alkoxyphenyl tri-epoxy monomer, the epoxy resin, the toughening agent, the curing agent, the accelerator, the coupling agent, the inorganic filler and optional auxiliary agents to obtain the low-viscosity low-dielectric-constant underfill adhesive.
In a preferred embodiment, the mixing means comprises the steps of: uniformly mixing an alkoxyphenyl tri-epoxy monomer, epoxy resin, a toughening agent, a curing agent, an accelerator, a coupling agent and optional auxiliary agents to obtain an epoxy resin compound; and adding the inorganic filler into the epoxy resin compound, continuously and uniformly mixing, grinding for 1-5 times after passing through 1-5 rollers, stirring for 10-50 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill adhesive.
In addition, the invention also provides application of the low-viscosity low-dielectric-constant underfill adhesive in underfilling of chips and PCB substrates (printed circuit boards).
The key point of the invention is that epoxy resin at least comprising bisphenol F diglycidyl ether and alkoxyl phenyl tri-epoxy monomer with three epoxy functional groups are reasonably matched according to a specific proportion, and then are cooperated with a toughening agent, a curing agent, an accelerator, a coupling agent, an inorganic filler and optional auxiliary agents to form the low-viscosity low-dielectric-constant underfill, so that the obtained low-viscosity low-dielectric-constant underfill has the high-performance requirements of low viscosity, low dielectric constant and good heat resistance.
Drawings
FIG. 1 is a nuclear magnetic mass spectrum of a methoxyphenyl trioxymethylene monomer.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments. The parts are by weight in the examples below, unless otherwise indicated.
The low-viscosity low-dielectric-constant underfill provided by the invention contains alkoxyl phenyl tri-epoxy monomer, epoxy resin, toughening agent, curing agent, accelerator, coupling agent and inorganic filler, and can further contain optional auxiliary agents. The content of the alkoxyphenyl trioxymethylene monomer is 20-35 parts, such as 20, 22, 25, 27, 30, 32, 35 parts or any value between the two; the content of the epoxy resin is 10-35 parts, such as 10, 15, 20, 25, 30, 35 parts or any value between the two; the content of the toughening agent is 10-20 parts, such as 10, 12, 14, 16, 18, 20 parts or any value between the two; the content of the curing agent is 29 to 50 parts, such as 29, 33, 35, 38, 40, 43, 46, 50 parts or any value between the two parts; the content of the accelerator is 0.5 to 2.5 parts, such as 0.5, 0.7, 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5 parts or any value between the two; the content of the coupling agent is 0.2-5 parts, such as 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 parts or any value between the two; the content of the inorganic filler is 40-80 parts, such as 40, 45, 50, 55, 60, 65, 70, 75, 80 parts or any value between the two; the content of the auxiliary agent is 0.1-10 parts, such as 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts or any value between the two parts.
In the present invention, the alkoxyphenyl tri-epoxy monomer has a structure represented by the following formula (I):
in the formula (I), R 1 Is C 1 ～C 5 Alkyl of R 2 、R 3 And R is 4 Each independently is C 1 ～C 5 Alkylene groups of (a). The C is 1 ～C 5 Specific examples of alkyl groups of (a) include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl. The C is 1 ～C 5 Specific examples of alkylene groups include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene or neopentylene.
In the present invention, the epoxy resin is preferably an epoxy resin including at least bisphenol F diglycidyl ether. The bisphenol F diglycidyl ether epoxy resin can be obtained commercially or prepared according to various methods known in the art.
In the present invention, the weight ratio of the alkoxyphenyl tri-epoxy monomer to the epoxy resin is preferably 1 (0.5 to 1.75), such as 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5, 1:1.75 or any value therebetween. The inventor of the present invention has found, after intensive and extensive studies, that an epoxy resin comprising at least bisphenol F diglycidyl ether is reasonably matched with an alkoxyphenyl tri-epoxy monomer having three epoxy functional groups, and the weight ratio of the alkoxyphenyl tri-epoxy monomer to the epoxy resin is controlled to 1 (0.5 to 1.75), thereby simultaneously achieving low viscosity, low dielectric constant and good heat resistance.
In the present invention, the alkoxyphenyl tri-epoxy monomer is preferably prepared according to a method comprising the steps of:
step one: carrying out substitution reaction on 2-alkoxy-4-alkylene alkylphenol with a structure shown in a formula (II) and a first alkylene alkyl compound with a structure shown in a formula (III) in the presence of a first phase transfer catalyst and in a first alkaline medium, and purifying to obtain a colorless first intermediate product in a liquid state;
step two: heating the first intermediate product to high temperature for claisen rearrangement reaction, and purifying to obtain a liquid colorless or yellow second intermediate product;
step three: carrying out substitution reaction on the second intermediate product and a second alkyl compound with a structure shown in a formula (III) in a second alkaline medium in the presence of a second phase transfer catalyst, and purifying to obtain a liquid colorless or yellow third intermediate product;
step four: oxidizing the third intermediate product in the presence of an oxidant, and purifying to obtain a colorless or yellow low-viscosity liquid product, namely the alkoxyl phenyl trioxymethylene monomer;
in the formula (II), R 5 Is C 1 ～C 5 Alkyl of R 6 Is C 1 ～C 5 An alkylene group of (a); in the formula (III), R 7 Is C 1 ～C 5 X is a halogen atom. Wherein the C 1 ～C 5 Specific examples of alkyl groups of (a) include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl. The C is 1 ～C 5 Specific examples of alkylene groups include, but are not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene or neopentylene. The halogen atom may be fluorine, chlorine, bromine or iodine.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the first step, the molar ratio of the 2-alkoxy-4-alkenoyl phenol to the first alkenoyl compound used in the substitution reaction process is preferably 1 (2.5-3.5), such as 1:2.5, 1:2.7, 1:3.0, 1:3.2, 1:3.5 or any value therebetween.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the first step, specific examples of the first alkaline medium include, but are not limited to: at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide. Wherein the molar ratio of the 2-alkoxy-4-alkenoyl phenol to the first basic medium is preferably 1 (2.5-3.5), such as 1:2.5, 1:2.7, 1:3.0, 1:3.2, 1:3.5 or any value in between.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the first step, the first phase transfer catalyst is preferably at least one selected from cyclic crown ethers, polyethers and ammonium species, such as at least one of 18-crown-6, dibenzo-18-crown-6, 15-crown-5, etc. Wherein the molar ratio of the 2-alkoxy-4-alkylene phenol to the first phase transfer catalyst is preferably 1 (0.1 to 0.3): such as 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, or any value therebetween.
In the preparation process of the alkoxyphenyl trioxymethylene monomer, in the first step, the substitution reaction is preferably performed in the following manner: dissolving 2-alkoxy-4-alkene alkylphenol in an organic solvent, adding a first alkaline medium to provide alkaline conditions, adding a first phase transfer catalyst, heating to 50-90 ℃ under the protection of inert gas, stirring, adding a first alkene alkyl compound, reacting for 8-15 hours, filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with deionized water, extracting with ethyl acetate, collecting an organic phase, and evaporating to dryness to obtain a liquid colorless first intermediate product.
In the preparation of the above alkoxyphenyl trioxymethylene monomer, in the first step, the conditions for the substitution reaction include a temperature of preferably 50 to 90℃such as 50℃55℃60℃65℃70℃75℃80℃85℃90℃or any value therebetween; the time is preferably 8 to 15 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any value therebetween.
In the preparation process of the alkoxyphenyl trioxymethylene monomer, in the second step, the claisen rearrangement reaction is preferably performed in the following manner: the first intermediate product is placed in a round bottom flask, and is heated to 180-220 ℃ under the protection of inert gas to react for 8-12 hours, so as to obtain a liquid colorless or yellow second intermediate product.
In the preparation of the above alkoxyphenyl trioxymethylene monomer, in the second step, the condition of the claisen rearrangement reaction includes a temperature of preferably 180 to 220 ℃, such as 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or any value therebetween; the time is preferably 8 to 12 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or any value therebetween.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the third step, the molar ratio of the second intermediate product to the second alkyl compound used in the substitution reaction process is preferably 1 (2.5-3.5), such as 1:2.5, 1:2.7, 1:3.0, 1:3.2, 1:3.5 or any value therebetween.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the third step, specific examples of the second alkaline medium include, but are not limited to: at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide. Wherein the molar ratio of the second intermediate product to the second alkaline medium is preferably 1 (2.5-3.5), such as 1:2.5, 1:2.7, 1:3.0, 1:3.2, 1:3.5 or any value therebetween.
In the preparation of the above-mentioned alkoxyphenyl trioxymethylene monomer, in the third step, the second phase transfer catalyst is preferably at least one selected from cyclic crown ethers, polyethers and ammonium species, such as at least one of 18-crown-6, dibenzo-18-crown-6, 15-crown-5, etc. Wherein the molar ratio of the second intermediate product to the second phase transfer catalyst is preferably 1 (0.1 to 0.3): such as 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, or any value therebetween.
In the preparation process of the alkoxyphenyl trioxymethylene monomer, in the third step, the substitution reaction is preferably performed as follows: dissolving the second intermediate product in an organic solvent, adding a second alkaline medium to provide alkaline conditions, adding a second phase transfer catalyst, heating to 50-90 ℃ under the protection of inert gas, stirring, adding a second alkyl compound, reacting for 8-12 hours, filtering the reaction solution, distilling the filtrate under reduced pressure to remove the solvent, washing with deionized water, extracting with ethyl acetate, collecting an organic phase, and evaporating to dryness to obtain a liquid colorless or yellow third intermediate product.
In the preparation of the above alkoxyphenyl trioxymethylene monomer, in the third step, the conditions for the substitution reaction include a temperature of preferably 50 to 90℃such as 50℃55℃60℃65℃70℃75℃80℃85℃90℃or any value therebetween; the time is preferably 8 to 15 hours, such as 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any value therebetween.
In the preparation process of the alkoxyphenyl trioxymethylene monomer, in the fourth step, the oxidant is preferably peroxide and/or hydrogen peroxide. Specific examples of the peroxide include, but are not limited to: at least one of m-chloroperoxybenzoic acid, allyl chloride, peracetic acid and the like. The molar ratio of the third intermediate product to the oxidizing agent employed during the oxidation reaction is preferably 1 (4.0 to 5.0), such as 1:4.0, 1:4.2, 1:4.4, 1:4.6, 1:4.8, 1:5.0 or any value therebetween.
In the preparation process of the alkoxyphenyl trioxymethylene monomer, in the fourth step, the oxidation reaction is preferably performed in the following manner: the oxidation reaction mode is that a third intermediate product is dissolved in ethyl acetate, an oxidant is dissolved in ethyl acetate, a reaction system is slowly added dropwise, after the dropwise addition is finished, the temperature is raised to 30-50 ℃ for reaction for 48-96 hours, the solvent is removed by reduced pressure distillation, the solution is washed by 8-15% of sodium carbonate solution, then the solution is washed by saturated saline solution, the solution is extracted by dichloromethane, and an organic phase is collected and evaporated to dryness to obtain a colorless or yellow low-viscosity liquid product, namely the alkoxyl phenyl trioxymethylene monomer. The terms "first," "second," and "third" are used merely for convenience of distinction and description and have no other special meaning.
In the preparation of the above alkoxyphenyl trioxymethylene monomer, in the fourth step, the conditions for the oxidation reaction include a temperature of preferably 30 to 50℃such as 30℃C, 33℃C, 36℃C, 39℃C, 42℃C, 45℃C, 48℃C, 50℃C or any value therebetween; the time is preferably 48 to 96 hours, such as 48 hours, 54 hours, 60 hours, 66 hours, 72 hours, 78 hours, 84 hours, 90 hours, 96 hours or any value therebetween.
In the preparation process of the above alkoxyphenyl trioxymethylene monomer, in the fourth step, the mass concentration of the sodium carbonate solution is preferably 8% to 15%, such as 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or any value therebetween.
In the present invention, specific examples of the organic solvents used in the first and third steps include, but are not limited to: at least one of methanol, ethanol, diethyl ether, chloroform, acetone, methyl formate, methyl acetate and ethyl acetate.
In the present invention, the epoxy resin is a combination of bisphenol F diglycidyl ether and a cycloaliphatic epoxy resin. Wherein the weight ratio of bisphenol F diglycidyl ether to cycloaliphatic epoxy resin in the epoxy resin is preferably 1 (0.1-0.4), such as 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4 or any value therebetween. When the epoxy resin is a composition of bisphenol F diglycidyl ether and alicyclic epoxy resin with a weight ratio of 1 (0.1-0.4), the functions of enhancing the thermal performance of the obtained underfill and reducing the viscosity and dielectric constant of the underfill can be achieved to a certain extent. Specific examples of the alicyclic epoxy resin include, but are not limited to: at least one of cyclohexane diglycidyl ether, cyclohexene diglycidyl ether, dicyclopentadiene diglycidyl ether, cyclohexanedimethanol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 3-ethyl-3-oxetane methanol, 3, 4-epoxycyclohexyl methacrylate, bis (7-oxabicyclo [4.1.0] 3-heptylmethyl) adipate, and 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate. Further, the epoxy equivalent weights of the bisphenol F diglycidyl ether and the alicyclic epoxy resin are each independently preferably 70 to 500g/eq, more preferably 80 to 250g/eq, such as 80g/eq, 90g/eq, 100g/eq, 120g/eq, 150g/eq, 180g/eq, 200g/eq, 220g/eq, 250g/eq, or any value therebetween.
The type of the toughening agent is not particularly limited, and may be any of various conventional ones which can reduce brittleness of the material and improve impact resistance and impart better toughness. Specific examples of the toughening agent include, but are not limited to: at least one of silicone hybrid epoxy resins, epoxy oligomeric silsesquioxanes, liquid nitrile rubber, liquid polybutadiene, liquid polysulfide rubber, neoprene, cashew shell liquid modified phenolic resins, polyester resins, epoxy resin reactive tougheners, SBS thermoplastic elastomers, polyvinyl formal, polyether sulfones, polyimides, polyetherimides, polyether ether ketones, polyether diols, and polyether triols.
In the present invention, specific examples of the curing agent include, but are not limited to: amine curing agents, anhydride curing agents, phenolic curing agents, imidazole curing agents and latent curing agents. Wherein the ratio of the total epoxy group equivalent in the alkoxyphenyl tri-epoxy monomer and the epoxy resin to the active functional group equivalent of the curing agent is preferably 1 (0.8-1.2), such as 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2 or any value therebetween. The inventors of the present invention have found, after intensive and extensive studies, that controlling the equivalent ratio of the total epoxy groups of the resin contained in the underfill material to the active functional groups of the curing agent to about 1 can allow the underfill material to be cured most sufficiently, thereby improving T g . The term "reactive functional group" refers to a reactive group capable of participating in a curing reaction.
In the present invention, specific examples of the accelerator include, but are not limited to: at least one of an imidazole compound, an amine compound and a phosphorus compound. Specific examples of the imidazole-based compound accelerator include, but are not limited to: at least one of organic acid dihydrazide, 2-ethyl-4-methylimidazole and imidazole salt complex prepared by reacting imidazole with inorganic salts such as copper chloride and the like; specific examples of the amine-based compound accelerator include, but are not limited to: ext> atext> leastext> oneext> ofext> anext> HDGext> -ext> Aext> /ext> Bext> epoxyext> curingext> acceleratorext>,ext> triethylamineext>,ext> triethanolamineext> andext> 1ext>,ext> 8ext> -ext> diazabicycloext> [ext> 5.4.0ext> ]ext> undecext> -ext> 7ext> -ext> eneext>;ext> Specific examples of the phosphorus-based compound accelerator include, but are not limited to: at least one of boron trifluoride triethylphosphine, boron trifluoride triisopropylphosphine, trimethylphosphine, triphenylphosphine and its derivatives, cyclotriphosphorus and phosphoramine compounds.
In the present invention, specific examples of the coupling agent include, but are not limited to: at least one of gamma-methacryloxypropyl trimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, phenylmethyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and gamma-ureidopropyl triethoxysilane.
In the present invention, the inorganic filler is preferably spherical silica particles. Wherein the average particle diameter of the inorganic filler is preferably 0.1 to 1. Mu.m, such as 0.1. Mu.m, 0.2. Mu.m, 0.3. Mu.m, 0.4. Mu.m, 0.5. Mu.m, 0.6. Mu.m, 0.7. Mu.m, 0.8. Mu.m, 0.9. Mu.m, 1.0. Mu.m, or any value therebetween.
In the present invention, specific examples of the auxiliary agent include, but are not limited to: one or more of stabilizers, polymerization inhibitors, antioxidants, flame retardants, diluents, adhesion promoters, dyes, pigments, defoamers, leveling agents, and ion capturing agents.
The preparation method of the low-viscosity low-dielectric-constant underfill provided by the invention comprises the following steps: and uniformly mixing the alkoxyphenyl tri-epoxy monomer, the epoxy resin, the toughening agent, the curing agent, the accelerator, the coupling agent, the inorganic filler and optional auxiliary agents to obtain the low-viscosity low-dielectric-constant underfill adhesive. The mixing mode may be mixing all the raw materials together after feeding all the raw materials simultaneously, or may be mixing part of the raw materials in any order, and then adding the rest of the raw materials for continuous mixing, without any particular limitation.
In the above preparation method of the low-viscosity low-dielectric-constant underfill, the mixing method is preferably performed according to the following steps: uniformly mixing an alkoxyphenyl tri-epoxy monomer, epoxy resin, a toughening agent, a curing agent, an accelerator, a coupling agent and optional auxiliary agents to obtain an epoxy resin compound; and adding the inorganic filler into the epoxy resin compound, continuously and uniformly mixing, grinding for 1-5 times after passing through 1-5 rollers, stirring for 10-50 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill adhesive.
In the above-mentioned method for producing a low-viscosity low-dielectric-constant underfill, the number of grinding is preferably 1 to 5 times, such as 1 time, 2 times, 3 times, 4 times, 5 times, or any value therebetween; the stirring time is preferably 10 to 50 minutes, such as 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes or any value therebetween.
In addition, the invention also provides application of the low-viscosity low-dielectric-constant underfill adhesive in underfilling of chips and PCB substrates (printed circuit boards).
The raw materials and sources used in the following examples and comparative examples are as follows:
bisphenol F diglycidyl ether was purchased from Mitsubishi chemical corporation under the designation jER806 and an epoxy equivalent of 160g/eq; cycloaliphatic epoxy resins are available from large cellophane under the designation Celloxide 2021P; the toughening agent is oligomeric silsesquioxane resin, and is purchased from Hybird Plastics in the United states, and the trademark is EP0409; the curing agent is methyl hexahydrophthalic anhydride, which is purchased from Xin Japanese physicochemical with the brand of MH-700G; the accelerator was 1, 8-diazabicyclo [5.4.0] undec-7-ene available from San-Apro, japan under the designation DBU; the coupling agent is gamma- (2, 3-glycidoxy) propyl trimethoxy silane, which is purchased from Shin-Etsu Chemical company of Japan and has the brand name KBM-403; the inorganic filler is graded spherical silica particles with the average particle diameter of 0.5 mu m; the auxiliary agent is carbon BLACK, which is purchased from cabot corporation under the brand name BLACK PEARLS1000.
Preparation example 1
The invention provides a preparation method of a methoxy phenyl tri-epoxy Monomer (MEUTG), which comprises the following specific reaction flow charts and steps:
step one: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 41.05g (0.25 mol) of 2-methoxy-4-allylphenol was dissolved in 300mL of acetone, 103.65g (0.75 mol) of potassium carbonate was added to provide alkaline conditions, 13.22g (0.05 mol) of 18-crown-6 as a phase transfer catalyst was added, then the mixture was stirred at 70℃for 60 minutes, 90.74g (0.75 mol) of allyl bromide was then added, the reaction mixture was filtered after 10 hours of reaction, the solvent was distilled off from the filtrate under reduced pressure, washed with deionized water three times and extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give a first intermediate product a as a liquid colorless product, about 50.05g, yield 98%.
Step two: 50.05g (0.245 mol) of the first intermediate product a are placed in a 250mL round-bottomed flask under inert gas N 2 The temperature is raised to 200 ℃ under protection, the claisen rearrangement reaction is carried out for 10 hours, and a second intermediate product b which is liquid pale yellow is obtained, about 47.54g, and the yield is 95%.
Step three: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 47.54g (0.233 mol) of the second intermediate b was dissolved in 300mL of acetone, 96.51g (0.700 mol) of potassium carbonate was added to provide alkaline conditions, 12.3g (0.046 mol) of 18-crown-6 as a phase transfer catalyst was added, then the mixture was stirred at 70℃for 60 minutes, 84.48g (0.70 mol) of allyl bromide was then added to react for 10 hours, the reaction solution was filtered, the filtrate was distilled off under reduced pressure to remove the solvent, washed with deionized water three times and extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give a third intermediate c as a liquid colorless product, about 54.59g, in 96% yield.
Step four: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 54.59g (0.224 mol) of a third intermediate product c is dissolved in 100mL of ethyl acetate, 173.52g (1.006 mol) of 3-chloroperoxybenzoic acid (m-CPBA) is dissolved in 200mL of ethyl acetate, an oxidant is slowly added dropwise to the reaction system, after the dropwise addition is completed, the temperature is raised to 40 ℃ for 72 hours, the solvent is removed by distillation under reduced pressure, the reaction system is washed twice with 10% sodium carbonate solution, the reaction system is washed three times with saturated saline solution, the reaction system is extracted with dichloromethane, and an organic phase is collected and evaporated to dryness to obtain a yellowish viscous liquid product, namely a methoxyphenyl trioxymonomer, about 55.52g (0.19 mol) and the yield is 85%.
The total yield of the methoxyphenyl trioxymethylene monomer is 75.97%, and the nuclear magnetic spectrum of the material is shown in figure 1. In the nuclear magnetic resonance mass spectrum of FIG. 1, 7.26ppm (CDCl) 3 Reference peak), 6.70ppm (Ar, 2H), 4.23 and 4.89ppm (-O-CH) 2 -,2H)，3.83ppm(CH 3 -O-, 3H), 3.32ppm (glycidyl ether linked to phenyl via ether linkage-CH, 1H), 3.16, 3.13ppm (glycidyl ether linked to phenyl-CH, 2H), 2.51-2.95ppm (Ar-CH) 2 4H; of-O-CH in epoxy groups 2 -, 6H). It is assumed that the methoxyphenyl trioxymethylene monomer has a structure represented by the formula (I), wherein R 1 Is methyl, R 2 、R 3 And R is 4 Are both methylene groups.
Preparation example 2
The preparation method of the methoxy phenyl tri-epoxy monomer provided by the invention comprises the following specific steps:
step one: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 41.05g (0.25 mol) of 2-methoxy-4-allylphenol was dissolved in 300mL of acetone, 103.65g (0.75 mol) of potassium carbonate was added to provide alkaline conditions, 13.22g (0.05 mol) of 18-crown-6 as a phase transfer catalyst was added, then the mixture was stirred at 50℃for 60 minutes, 90.74g (0.75 mol) of allyl bromide was then added, the reaction mixture was filtered after 8 hours of reaction, the solvent was distilled off from the filtrate under reduced pressure, washed with deionized water three times and extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give a first intermediate product a, about 45.96g, which was colorless in liquid state, in 90% yield.
Step two: 45.96g (0.225 mol) of the first intermediate a are placed in a 250mL round-bottomed flask under inert gas N 2 The temperature is raised to 180 ℃ under protection, and the claisen rearrangement reaction is carried out for 8 hours, so that a second intermediate product b which is in a liquid pale yellow state is obtained, about 40.45g, and the yield is 88%.
Step three: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 40.45g (0.198 mol) of the second intermediate b was dissolved in 300mL of acetone, 82.1g (0.594 mol) of potassium carbonate was added to provide alkaline conditions, 10.46g (0.039 mol) of 18-crown-6 was added as a phase transfer catalyst, followed by heating to 50℃and stirring for 60 minutes, then 71.86g (0.594 mol) of allyl bromide was added to react for 8 hours, then the reaction solution was filtered, the solvent was distilled off under reduced pressure, washed with deionized water three times, extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give the third intermediate c as a liquid colorless product, about 39.67g, yield 82%.
Step four: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 39.67g (0.162 mol) of a third intermediate product c was dissolved in 100mL of ethyl acetate, 126.08g (0.731 mol) of 3-chloroperoxybenzoic acid (m-CPBA) was dissolved in 200mL of ethyl acetate, an oxidant was slowly added dropwise to the reaction system, after the completion of the dropwise addition, the temperature was raised to 30 ℃ for 48 hours, the solvent was distilled off under reduced pressure, and the mixture was washed twice with 10% sodium carbonate solution, washed three times with saturated brine, extracted with dichloromethane, and the organic phase was collected and evaporated to dryness to give a pale yellow viscous liquid product, namely, methoxyphenyl trioxymonomer, about 33.223g (0.114 mol) was obtained in 70% yield.
The overall yield of the methoxyphenyl trioxymethylene monomer was 45.46%. As can be seen from the nuclear magnetic mass spectrum, the methoxyphenyl trioxymethylene monomer has a structure shown as a formula (I), wherein R 1 Is methyl, R 2 、R 3 And R is 4 Are both methylene groups.
Preparation example 3
The preparation method of the methoxy phenyl tri-epoxy monomer provided by the invention comprises the following specific steps:
step one: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 41.05g (0.25 mol) of 2-methoxy-4-allylphenol was dissolved in 300mL of acetone, 103.65g (0.75 mol) of potassium carbonate was added to provide alkaline conditions, 13.22g (0.05 mol) of 18-crown-6 as a phase transfer catalyst was added, then the mixture was stirred at 90℃for 60 minutes, 90.74g (0.75 mol) of allyl bromide was then added, the reaction mixture was filtered after 12 hours of reaction, the solvent was distilled off from the filtrate under reduced pressure, washed with deionized water three times and extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give a first intermediate product a as a liquid colorless product, about 47.49g, yield 93%.
Step two: 47.49g (0.233 mol) of first intermediate a are placed in a 250mL round-bottomed flask under inert gas N 2 The temperature is raised to 220 ℃ under protection, the claisen rearrangement reaction is carried out for 12 hours, and a second intermediate product b which is in a liquid pale yellow state is obtained, about 37.99g, and the yield is 80%.
Step three: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 37.99g (0.186 mol) of the second intermediate b was dissolved in 300mL of acetone, 77.12g (0.558 mol) of potassium carbonate was added to provide alkaline conditions, 9.83g (0.037 mol) of 18-crown-6 as a phase transfer catalyst was added, then the mixture was stirred at 90℃for 60 minutes, 67.50g (0.558 mol) of allyl bromide was then added to react for 12 hours, the reaction solution was filtered, the filtrate was distilled off under reduced pressure to remove the solvent, washed with deionized water three times and extracted with ethyl acetate, and the organic phase was collected and evaporated to dryness to give a third intermediate c as a liquid colorless product, about 41.36g, yield 91%.
Step four: three pumping operations were performed using a 500mL three-necked flask equipped with a rotor, a constant pressure dropping funnel, and a spherical condenser, and a nitrogen atmosphere was ensured in the three-necked flask. 41.36g (0.169 mol) of a third intermediate product c is dissolved in 100mL of ethyl acetate, 131.44g (0.762 mol) of 3-chloroperoxybenzoic acid (m-CPBA) is dissolved in 200mL of ethyl acetate, an oxidant is slowly added into the reaction system in a dropwise manner, after the dropwise addition is finished, the temperature is raised to 50 ℃ for 96 hours, the solvent is removed by reduced pressure distillation, the mixture is washed twice with 10% sodium carbonate solution, the mixture is washed three times with saturated saline solution, the mixture is extracted with dichloromethane, and an organic phase is collected and evaporated to dryness to obtain a yellowish viscous liquid product, namely a methoxyphenyl trioxymonomer, about 39.09g (0.134 mol) is obtained, and the yield is 79%.
The overall yield of the methoxyphenyl trioxymethylene monomer was 53.48%. As can be seen from the nuclear magnetic mass spectrum, the methoxyphenyl trioxymethylene monomer has a structure shown as a formula (I), wherein R 1 Is methyl, R 2 、R 3 And R is 4 Are both methylene groups.
Example 1
25 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 20 parts of bisphenol F diglycidyl ether (jeR 806), 5 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 36 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 10 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 2
20 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 2, 16 parts of bisphenol F diglycidyl ether (jeR 806), 4 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 29 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 20 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 3
35 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 3, 28 parts of bisphenol F diglycidyl ether (jeR 806), 7 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 50 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 30 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 4
22 parts of a methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 18 parts of bisphenol F diglycidyl ether (jeR 806), 4 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 31 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of an accelerator (DBU), 3 parts of a coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 40 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 5
33 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 26 parts of bisphenol F diglycidyl ether (jeR 806), 7 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 47 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of spherical silica particles (average particle size of 0.5 μm) into the epoxy resin compound, continuously mixing uniformly, grinding for three times after three rollers, stirring for 50 minutes again, vacuumizing, defoaming, filtering, and discharging to obtain the low-viscosity low-dielectric-constant underfill adhesive.
Example 6
28 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 10 parts of bisphenol F diglycidyl ether (jeR 806), 4 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 32 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 20 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 7
22 parts of a methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 30 parts of bisphenol F diglycidyl ether (jeR 806), 3 parts of a cycloaliphatic epoxy resin (Celloxide 2021P), 15 parts of an oligomeric silsesquioxane resin (EP 0409), 37 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of an accelerator (DBU), 3 parts of a coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 30 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 8
20 parts of a methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 28 parts of bisphenol F diglycidyl ether (jeR 806), 7 parts of a cycloaliphatic epoxy resin (Celloxide 2021P), 15 parts of an oligomeric silsesquioxane resin (EP 0409), 37 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of an accelerator (DBU), 3 parts of a coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 40 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Example 9
25 parts of the methoxyphenyl trioxymethylene Monomer (MEUTG) obtained in preparation example 1, 5 parts of bisphenol F diglycidyl ether (jeR 806), 20 parts of alicyclic epoxy resin (Celloxide 2021P), 15 parts of oligomeric silsesquioxane resin (EP 0409), 38 parts of methyl hexahydrophthalic anhydride (MH-700G), 1.5 parts of accelerator (DBU), 3 parts of coupling agent (KBM-403) and 0.5 part of carbon BLACK (BLACK PEARLS 1000) are added into a dispersing and mixing device and uniformly mixed to obtain an epoxy resin compound; and adding 55 parts of inorganic filler into the spherical silicon dioxide particles (average particle size of 0.5 mu m) to uniformly mix, grinding for three times after three rollers, stirring for 10 minutes again, and finally carrying out vacuumizing and defoaming treatment on the obtained mixture, filtering and discharging to obtain the low-viscosity low-dielectric-constant underfill.
Comparative example 1
An epoxy adhesive was prepared as in example 1, except that the content of Methoxyphenyltrioxymonomer (MEUTG) was 0 parts, the content of bisphenol F diglycidyl ether (jER 806) was 45 parts, the content of alicyclic epoxy resin (Celloxide 2021P) was 5 parts, the content of methylhexahydrophthalic anhydride (MH-700G) was 28 parts, and the remaining condition ratios were unchanged.
Comparative example 2
An epoxy adhesive was prepared as in example 1, except that the content of Methoxyphenyltrioxymonomer (MEUTG) was 0 part, the content of bisphenol F diglycidyl ether (jER 806) was 50 parts, the content of alicyclic epoxy resin (Celloxide 2021P) was 0 part, the content of methylhexahydrophthalic anhydride (MH-700G) was 27 parts, and the remaining condition ratios were unchanged.
Comparative example 3
An epoxy adhesive was prepared as in example 1, except that the content of Methoxyphenyltrioxymonomer (MEUTG) was 25 parts, the content of bisphenol F diglycidyl ether (jER 806) was 0 part, the content of alicyclic epoxy resin (Celloxide 2021P) was 25 parts, the content of methylhexahydrophthalic anhydride (MH-700G) was 38 parts, and the remaining condition ratios were unchanged.
Test case
(1) Glass transition temperature (T) g ): q-800 type using a TA Instrument in the United statesTesting by dynamic thermo-mechanical analysis tester (DMA), preparing the cured epoxy gel into a film with the thickness of 42mm multiplied by 8mm multiplied by 0.3mm, measuring the change rule of loss factor (tan delta) with temperature in the liquid nitrogen atmosphere and film stretching mode in the temperature range of-40-250 ℃, wherein the heating rate is 10 ℃/min, the testing frequency is 10Hz, thereby determining the glass transition temperature T of the resin composition after curing g The results are shown in Table 1.
(2) Viscosity: the underfill obtained in each example and comparative example was tested using a HAAKE rheometer using a 20mm flat rotor at 25℃and a rotational speed of 40s -1 The average of the three replicates was taken as the final viscosity and the results are detailed in table 1.
(3) Dielectric constant measurement: the samples of the above examples were tested for dielectric constant using a radio frequency impedance material analyzer at a test frequency of 106Hz according to the GB/T1409 2006 test standard, and the results are detailed in table 1.
Table 1 underfill performance comparison
| Numbering device | T g (℃) | Viscosity (mPa. S) | Dielectric constant |
| Example 1 | 169 | 5417 | 2.3 |
| Example 2 | 165 | 5479 | 2.5 |
| Example 3 | 167 | 5496 | 2.8 |
| Example 4 | 164 | 5483 | 2.6 |
| Example 5 | 166 | 5489 | 2.7 |
| Example 6 | 163 | 5501 | 2.5 |
| Example 7 | 159 | 6760 | 2.4 |
| Example 8 | 160 | 6421 | 2.6 |
| Example 9 | 152 | 5750 | 2.4 |
| Comparative example 1 | 138 | 12500 | 3.8 |
| Comparative example 2 | 132 | 15740 | 3.7 |
| Comparative example 3 | 144 | 5020 | 3.6 |
As can be seen from the results of Table 1, the epoxy resin comprising at least bisphenol F diglycidyl ether was reasonably combined with alkoxyphenyl tri-epoxy monomer having three epoxy functional groups, and the weight ratio of alkoxyphenyl tri-epoxy monomer to epoxy resin was controlled to 1 (0.5-1.75), which was able to simultaneously have low viscosity, low dielectric constant and good heat resistance. As can be seen from a comparison of example 1 with comparative examples 1 to 2, when the alkoxyphenyl trioxymonomer having the structure represented by formula (I) is not present, T of the resulting underfill is obtained g Lower and higher in both viscosity and dielectric constant. As can be seen from the comparison of example 1 with comparative example 3, when bisphenol F diglycidyl ether epoxy resin is not present, the resulting underfill has a higher dielectric constant and poor heat resistance.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (16)
1. A low viscosity low dielectric constant underfill comprising an alkoxyphenyl tri-epoxy monomer, an epoxy resin, a toughening agent, a curing agent, an accelerator, a coupling agent, and an inorganic filler, and optionally an auxiliary agent; the weight ratio of the alkoxy phenyl tri-epoxy monomer to the epoxy resin is 1 (0.5-1.75);
the alkoxyl phenyl tri-epoxy monomer has a structure shown in the following formula (I):
in the formula (I), R 1 Is C 1 ～C 5 Alkyl of R 2 、R 3 And R is 4 Each independently is C 1 ～C 5 An alkylene group of (a);
the epoxy resin is an epoxy resin comprising at least bisphenol F diglycidyl ether.
2. The underfill adhesive of claim 1, wherein the alkoxyphenyl tri-epoxy monomer is present in an amount of 20 to 35 parts by mass, the epoxy resin is present in an amount of 10 to 35 parts by mass, the toughening agent is present in an amount of 10 to 20 parts by mass, the curing agent is present in an amount of 29 to 50 parts by mass, the accelerator is present in an amount of 0.5 to 2.5 parts by mass, the coupling agent is present in an amount of 0.2 to 5 parts by mass, the inorganic filler is present in an amount of 40 to 80 parts by mass, and the auxiliary agent is present in an amount of 0.1 to 10 parts by mass.
3. The low viscosity low dielectric constant underfill of claim 1, wherein said alkoxyphenyl tri-epoxy monomer is prepared by a process comprising the steps of:
step one: carrying out substitution reaction on 2-alkoxy-4-alkylene alkylphenol with a structure shown in a formula (II) and a first alkylene alkyl compound with a structure shown in a formula (III) in the presence of a first phase transfer catalyst and in a first alkaline medium, and purifying to obtain a colorless first intermediate product in a liquid state;
step two: heating the first intermediate product to high temperature for claisen rearrangement reaction, and purifying to obtain a liquid colorless or yellow second intermediate product;
step three: carrying out substitution reaction on the second intermediate product and a second alkyl compound with a structure shown in a formula (III) in a second alkaline medium in the presence of a second phase transfer catalyst, and purifying to obtain a liquid colorless or yellow third intermediate product;
step four: oxidizing the third intermediate product in the presence of an oxidant, and purifying to obtain a colorless or yellow low-viscosity liquid product, namely the alkoxyl phenyl trioxymethylene monomer;
in the formula (II), R 5 Is C 1 ～C 5 Alkyl of R 6 Is C 1 ～C 5 An alkylene group of (a);
in the formula (III), R 7 Is C 1 ～C 5 X is a halogen atom.
4. The low viscosity, low dielectric constant underfill of claim 3 wherein in step one, the molar ratio of the 2-alkoxy-4-alkenalkyl phenol to the first alkenalkyl compound employed in the substitution reaction is 1 (2.5-3.5);
preferably, the first alkaline medium is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide;
preferably, the molar ratio of the 2-alkoxy-4-alkylene phenol to the first alkaline medium is 1 (2.5-3.5);
preferably, the first phase transfer catalyst is selected from at least one of cyclic crown ethers, polyethers, and ammonium;
preferably, the molar ratio of the 2-alkoxy-4-alkylene phenol to the first phase transfer catalyst is 1 (0.1-0.3);
preferably, the conditions of the substitution reaction include a temperature of 50 to 90 ℃ for 8 to 15 hours.
5. The low viscosity low dielectric constant underfill according to claim 3, wherein the claisen rearrangement reaction conditions in step two comprise a temperature of 180 to 220 ℃ for a period of 8 to 12 hours.
6. The low viscosity, low dielectric constant underfill according to claim 3, wherein in step three, the molar ratio of the second intermediate to the second alkyl compound used in the substitution reaction is 1 (2.5-3.5);
preferably, the second alkaline medium is selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide;
preferably, the molar ratio of the second intermediate product to the second alkaline medium is 1 (2.5-3.5);
preferably, the second phase transfer catalyst is selected from at least one of cyclic crown ethers, polyethers, and ammonium species;
preferably, the molar ratio of the second intermediate product to the second phase transfer catalyst is 1 (0.1-0.3);
preferably, the conditions of the substitution reaction include a temperature of 50 to 90 ℃ for 8 to 15 hours.
7. The low viscosity low dielectric constant underfill according to claim 3, wherein in step four, the oxidizing agent is peroxide and/or hydrogen peroxide;
preferably, the molar ratio of the third intermediate product to the oxidant used in the oxidation reaction process is 1 (4.0-5.0);
preferably, the conditions of the oxidation reaction include a temperature of 30 to 50 ℃ and a time of 48 to 96 hours.
8. The low viscosity, low dielectric constant underfill according to any one of claims 1 to 7, wherein the epoxy resin is a combination of bisphenol F diglycidyl ether and cycloaliphatic epoxy resin in a weight ratio of 1 (0.1 to 0.4).
9. The low viscosity, low dielectric constant underfill of any one of claims 1 to 7, wherein the toughening agent is selected from at least one of silicone hybrid epoxy resins, epoxy oligomeric silsesquioxanes, liquid nitrile rubbers, liquid polybutadiene, liquid polysulfide rubbers, neoprene rubbers, cashew shell liquid modified phenolic resins, polyester resins, epoxy resin reactive toughening agents, SBS thermoplastic elastomers, polyvinyl formal, polyethersulfones, polyimides, polyetherimides, polyetheretherketones, polyetherdiols, and polyethertriols.
10. The low viscosity, low dielectric constant underfill according to any one of claims 1 to 7, wherein the curing agent is selected from one or more of an amine curing agent, an anhydride curing agent, a phenolic curing agent, an imidazole curing agent, and a latent curing agent; the ratio of the equivalent of the total epoxy groups in the alkoxy phenyl tri-epoxy monomer and the epoxy resin to the equivalent of the active functional groups of the curing agent is 1 (0.8-1.2).
11. The low-viscosity low-dielectric-constant underfill according to any one of claims 1 to 7, wherein the accelerator is at least one selected from the group consisting of imidazole-based compounds, amine-based compounds and phosphorus-based compounds.
12. The low viscosity, low dielectric constant underfill of any one of claims 1 to 7, wherein the coupling agent is selected from at least one of gamma-methacryloxypropyl trimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane, phenylmethyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and gamma-ureidopropyl triethoxysilane.
13. The low viscosity, low dielectric constant underfill according to any one of claims 1 to 7, wherein the inorganic filler is spherical silica particles; the average particle diameter of the inorganic filler is 0.1-1 mu m.
14. The low viscosity, low dielectric constant underfill according to any one of claims 1 to 7, wherein the adjuvant is selected from one or more of stabilizers, polymerization inhibitors, antioxidants, flame retardants, diluents, adhesion promoters, dyes, pigments, defoamers, leveling agents, and ion capturing agents.
15. A method of preparing the low viscosity low dielectric constant underfill according to any one of claims 1 to 13, comprising: and uniformly mixing the alkoxyphenyl tri-epoxy monomer, the epoxy resin, the toughening agent, the curing agent, the accelerator, the coupling agent, the inorganic filler and optional auxiliary agents to obtain the low-viscosity low-dielectric-constant underfill adhesive.
16. Use of the low viscosity low dielectric constant underfill of any one of claims 1-13 in underfilling of chips and PCB substrates.
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| CN202311020360.3A CN116855211A (en) | 2023-08-14 | 2023-08-14 | Low-viscosity low-dielectric-constant underfill adhesive and preparation method and application thereof |
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