CN118451123A - Resin composition, semiconductor device, and method for producing same - Google Patents
Resin composition, semiconductor device, and method for producing same Download PDFInfo
- Publication number
- CN118451123A CN118451123A CN202280086025.0A CN202280086025A CN118451123A CN 118451123 A CN118451123 A CN 118451123A CN 202280086025 A CN202280086025 A CN 202280086025A CN 118451123 A CN118451123 A CN 118451123A
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- China
- Prior art keywords
- resin composition
- epoxy resin
- filler
- cured product
- resin
- 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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- 239000011342 resin composition Substances 0.000 title claims abstract description 152
- 239000004065 semiconductor Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 142
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 142
- 239000000945 filler Substances 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 229920001971 elastomer Polymers 0.000 claims description 31
- 239000005060 rubber Substances 0.000 claims description 31
- 239000011258 core-shell material Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 24
- 238000001723 curing Methods 0.000 description 69
- 238000012360 testing method Methods 0.000 description 64
- 230000035882 stress Effects 0.000 description 46
- 238000000034 method Methods 0.000 description 27
- -1 naphthylene ether Chemical compound 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010191 image analysis Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000012856 packing Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- 241001075517 Abelmoschus Species 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 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 3
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 3
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 3
- WGCKYCGUJYPRCV-UHFFFAOYSA-N 4,5-dimethyl-7-(2-methylprop-1-enyl)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC(C)=CC1C=C(C)C(C)C2C(=O)OC(=O)C12 WGCKYCGUJYPRCV-UHFFFAOYSA-N 0.000 description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000000644 propagated effect Effects 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical class C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LPVHVQFTYXQKAP-YFKPBYRVSA-N (4r)-3-formyl-2,2-dimethyl-1,3-thiazolidine-4-carboxylic acid Chemical compound CC1(C)SC[C@@H](C(O)=O)N1C=O LPVHVQFTYXQKAP-YFKPBYRVSA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- GTZHDRRNFNIFTL-UHFFFAOYSA-N 1-[4-(2-amino-2-methylpropyl)piperazin-1-yl]-2-methylpropan-2-amine Chemical compound CC(C)(N)CN1CCN(CC(C)(C)N)CC1 GTZHDRRNFNIFTL-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NQJNUYZIKYERSC-UHFFFAOYSA-N 2-(cyclohexylmethyl)oxirane Chemical compound C1CCCCC1CC1CO1 NQJNUYZIKYERSC-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UVYLEXYRTBDZNM-UHFFFAOYSA-N 4,4-diethyloxane-2,6-dione Chemical class CCC1(CC)CC(=O)OC(=O)C1 UVYLEXYRTBDZNM-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
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- HMALAVIDTOCZBY-UHFFFAOYSA-N C(C(=C)C)(=O)CO[Si](OC)(OC)CCCCCCCC Chemical compound C(C(=C)C)(=O)CO[Si](OC)(OC)CCCCCCCC HMALAVIDTOCZBY-UHFFFAOYSA-N 0.000 description 1
- WMSNOIUMOVYXSR-UHFFFAOYSA-N C(C1CO1)OCO[Si](OC)(OC)CCCCCCCC Chemical compound C(C1CO1)OCO[Si](OC)(OC)CCCCCCCC WMSNOIUMOVYXSR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 241001446276 Helia <angisperm> Species 0.000 description 1
- 241000976416 Isatis tinctoria subsp. canescens Species 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZGACYOKNEKDSNK-UHFFFAOYSA-N ac1mjht3 Chemical compound C1CC2(C)C3C(=O)OC(=O)C3C1(C(C)C)C=C2 ZGACYOKNEKDSNK-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
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- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- OZEHOHQZIRILDX-UHFFFAOYSA-N ctk1b7797 Chemical compound O=C1OC(=O)C2C1C1(C)CC2CC1 OZEHOHQZIRILDX-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000005496 eutectics Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical class O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a resin composition used as an underfill material (CUF) capable of further reducing the occurrence of fillet cracks. There is provided a resin composition comprising: an epoxy resin, (B) a curing agent, and (C) a filler. The cured product of the resin composition has a fatigue crack propagation lower limit stress expansion coefficient range DeltaK th of 0.55MPa m 0.5 or more.
Description
Technical Field
The present disclosure relates to a resin composition. And more particularly, to a resin composition for use as a semiconductor sealing material, particularly an underfill material (CUF: CAPILLARY UNDERFILL), a semiconductor device using the resin composition, a method of manufacturing the semiconductor device, and a method of manufacturing the resin composition.
Background
In flip chip connection, BGA (Ball GRID ARRAY) or CSP (Chip Size Package) mounting, stress or strain due to curing may be accumulated in the exposed portions (fillets) of the underfill material or in bump bonding portions in the peripheral portions of the semiconductor element or other electronic components. In this case, peeling and cracking may occur due to deformation or the like associated with thermal shock, thermal expansion and contraction, moisture absorption, heat treatment, and the like. Therefore, the following problems occur: peeling or cracking caused by the rounded corner portion or the bump bonding portion is very relevant to connection reliability between bump bonding portions and the like.
Further, the solder forming the bump is replaced with lead-free solder. Therefore, the reflow temperature at the time of mounting becomes higher, so that the thermal stress increases. The mechanical strength of the lead-free solder is inferior to that of the eutectic solder. On this basis, the adoption of the copper pillar bump leads to a reduction in the coating volume of the lead-free solder. Therefore, the mechanical strength is further lowered.
In light of the above, existing underfill materials create the following problems: peeling and cracking of the fillet portion and peeling and cracking of the bump bonding portion are likely to occur.
Further, as the number of bumps increases, the bump pitch and the bump height become smaller. The result is that narrow gapping is underway. In addition, with high integration, a large-sized chip is employed. Therefore, characteristics that enable a large area flow even in a narrow gap are demanded for the underfill material (CUF).
In order to cope with such problems, attempts have been made to reduce the stress and increase the toughness of the underfill (CUF) (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-163747
Disclosure of Invention
Technical problem to be solved by the invention
Recently, with respect to the underfill material, it is further required to suppress the occurrence of the above-described corner cracks. That is, there is a need for an underfill material that has excellent round-foot crack resistance (resistance).
The prior art does not sufficiently satisfy the characteristics required above. Therefore, further improvement is required.
In order to cope with the problems in the prior art described above, an object of the present disclosure is to provide a resin composition that is used as an underfill material (CUF) having more excellent fillet crack resistance. Further, an object of the present disclosure is to provide a semiconductor device using the resin composition, a method for manufacturing the semiconductor device, and a method for manufacturing the resin composition.
Technical means for solving the technical problems
In order to achieve the above object, the resin composition of the present embodiment includes:
(A) An epoxy resin,
(B) A curing agent,
(C) The filler is used for filling the filler,
The cured product of the resin composition has a fatigue crack propagation lower limit stress expansion coefficient range DeltaK th of 0.55MPa m 0.5 or more.
The resin composition of the present embodiment preferably has a glass transition temperature (Tg) of 100 ℃ or higher.
The resin composition of the present embodiment preferably contains the epoxy resin (a) in a liquid state.
The resin composition of the present embodiment preferably contains at least one epoxy resin selected from the group consisting of bisphenol F type epoxy resin, bisphenol a type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin and cyclohexane type epoxy resin.
The resin composition of the present embodiment preferably has a content of the filler (C) of 40 to 80 parts by mass based on 100 parts by mass of the total of all components of the resin composition.
In the resin composition of the present embodiment, the filler (C) preferably has an average particle diameter of 0.1 to 20.0. Mu.m.
The resin composition of the present embodiment preferably has the filler (C) surface-treated with a silane coupling agent.
The resin composition of the present embodiment may further comprise (D) a core-shell rubber.
The cured product of the resin composition of the present embodiment preferably satisfies the requirement 1 described below.
The cured product of the resin composition of the present embodiment preferably satisfies the requirement 2 described below.
The semiconductor device of the present embodiment includes a substrate, a semiconductor element disposed on the substrate, and a cured product of the resin composition of the present embodiment sealing the semiconductor element.
The method for manufacturing a semiconductor device according to the present embodiment includes filling a void between a substrate and a semiconductor element disposed on the substrate with the resin composition according to the present embodiment, and curing the resin composition.
The method for producing a resin composition according to the present embodiment is the method for producing a resin composition, and the method for producing a resin composition according to the present embodiment includes mixing the epoxy resin (a), the curing agent (B), and the filler (C) by using a roll mill, wherein the pressure between rolls of the roll mill is 3.0MPa or more.
Advantageous effects
The underfill material (CUF) using the resin composition of the present embodiment has more excellent fillet crack resistance.
Drawings
FIG. 1A plan view of a test piece for measuring the fatigue crack propagation lower limit stress expansion coefficient range DeltaK th.
FIG. 2 is a diagram for explaining a method of analyzing an image of a cross section of a test piece.
Detailed Description
The resin composition of the present embodiment will be described in detail below.
The resin composition of the present embodiment contains the following components (a) to (C) as essential components.
(A) Epoxy resin
The epoxy resin as the component (a) is a component that becomes a main component of the resin composition of the present embodiment.
From the viewpoints of viscosity, injectability, and the like, the epoxy resin of component (a) preferably contains a liquid epoxy resin that is liquid at ordinary temperature (25 ℃). The following epoxy resins may be suitably used: the epoxy resin is solid at normal temperature, but when used together with a liquid epoxy resin, the epoxy resin is in a liquid state as a mixture.
As an example of the component (a) epoxy resin, examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisxylenol type epoxy resin, cyclohexane type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, t-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin having an aromatic structure, glycidylester type epoxy resin having an aromatic structure, and cresol novolac type epoxy resin, a bearing polymer, a biphenyl type epoxy resin, a linear aliphatic epoxy resin having an aromatic structure, an epoxy resin having a butadiene structure, an alicyclic epoxy resin having an aromatic structure, a heterocyclic epoxy resin, an epoxy resin having an aromatic structure containing a spiro ring, a cyclohexanedimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, a tetraphenyl methane type epoxy resin, an aminophenol type epoxy resin, and an organosilicon modified epoxy resin.
The epoxy resin of the component (a) is preferably at least one resin selected from the group consisting of bisphenol F type epoxy resin, bisphenol a type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin and cyclohexane type epoxy resin.
Specific examples of the liquid epoxy resin include: the materials include "YDF8170" (bisphenol F epoxy resin), "YDF8125" (bisphenol a epoxy resin), "ZX1658", "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane) manufactured by dada company; "HP-4032", "HP-4032D", "HP-4032SS" (naphthalene type epoxy resin) manufactured by DIC; "jER828US", "jER828EL" (bisphenol a type epoxy resin), "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "jER630", "jER630LSD" (aminophenol type epoxy resin), "YX7400" (high resilience epoxy resin) manufactured by mitsubishi chemical company; "ZX1059" manufactured by Nitro-Kagaku chemical Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by the Uk company; and "setback 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by the dow company.
Specific examples of the solid epoxy resin include "HP-4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "dicyclopentadiene type epoxy resin)," EXA7311"," EXA7311-G3"," EXA7311-G4S "and" HP6000 "(naphthalene ether type epoxy resin) manufactured by DIC; "EPPN-502H" (triphenol type epoxy resin), "NC-7000-L" (naphthol novolac type epoxy resin), "NC-3000-H", "NC-3000-L", "NC-3100" (biphenyl type epoxy resin) manufactured by Kagaku corporation; the "ESN475V" (naphthol type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by the company of helia; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bisxylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi chemical corporation; the parts of the medicine "PG-100", "CG-500" manufactured by Osaka, inc.; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (solid bisphenol a type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "jER157S70" (bisphenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "YX4000HK" (Bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi chemical corporation; the parts of the medicine "PG-100", "CG-500" manufactured by Osaka, inc.; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company.
The epoxy resin as component (A) may be used alone. Alternatively, 2 or more kinds of epoxy resins may be used in combination.
The amount of the epoxy resin component (a) is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, based on 100 parts by mass of the total of all the components of the resin composition.
(B) Curing agent
The curing agent of the component (B) is not particularly limited as long as it is a curing agent of an epoxy resin. Well-known curing agents may be used. Examples of the component (B) curing agent include amine curing agents, acid anhydride curing agents, phenol curing agents, hydrazide curing agents, polythiol curing agents, and lewis acid-amine complexes.
The component (B) curing agent is preferably at least one curing agent selected from the group consisting of amine curing agents, acid anhydride curing agents and phenol curing agents.
Examples of the amine-based curing agent include aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophorone diamine, 1, 3-diaminomethyl cyclohexane, bis (4-aminocyclohexyl) methane, norbornene diamine, and 1, 2-diaminocyclohexane; piperazine-type heterocyclic aliphatic amines such as N-aminoethylpiperazine and 1, 4-bis (2-amino-2-methylpropyl) piperazine; aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoluenediamine, trimethylene bis (4-aminobenzoate), polytetramethylene oxide-bis-p-aminobenzoate, and 4,4 '-diamino-3, 3' -diethyldiphenylmethane.
Of these, 4 '-diamino-3, 3' -diethyldiphenylmethane, diethyltoluenediamine and dimethylthiotoluenediamine are preferred.
The acid anhydride-based curing agent is not particularly limited. Examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, tatamiable acid anhydride, methylnorbornene dianhydride, alkene-substituted succinic anhydride, and glutaric anhydride.
In particular, 3, 4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1, 2-dicarboxylic anhydride, 3, 4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3, 6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2] oct-5-ene-2, 3-dicarboxylic anhydride, norbornane-2, 3-dicarboxylic anhydride, methyl norbornane-2, 3-dicarboxylic anhydride, hydrogenated methylnadic anhydride, alkenyl-substituted succinic anhydride, and diethylglutaric anhydride are preferred.
Phenolic curing agents refer to all monomers, oligomers and polymers having phenolic hydroxyl groups. Examples of the phenolic curing agent include phenol novolac resins and alkyls or allylates thereof, cresol novolac resins, phenol aralkyl (containing phenylene and biphenylene backbones) resins, naphthol aralkyl resins, triphenol methane resins, and dicyclopentadiene type phenolic resins. Among them, allylphenol novolac resins are preferable.
The component (B) curing agent may be used alone. Alternatively, 2 or more kinds of curing agents may be used in combination.
The component (B) curing agent is blended so that the stoichiometric equivalent ratio (curing agent equivalent/epoxy group equivalent) of the component (B) curing agent to the component (a) epoxy resin is preferably 0.5 to 1.5, more preferably 0.8 to 1.2.
In the case where the curing agent is a compound having active hydrogen such as an amine-based curing agent, the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy resin (active hydrogen equivalent/epoxy equivalent) is preferably within the above-mentioned range.
(C) Packing material
The filler of component (C) is not particularly limited as long as it has an effect of reducing the linear expansion coefficient by addition.
Examples of the component (C) filler include silica (diacylated compound) filler, alumina (acidified) filler, and aluminum nitride filler. In particular, silica (diacid compound) fillers are preferred from the standpoint of being able to increase the amount of filler.
The filler of component (C) may be surface-treated with, for example, a silane coupling agent.
The average particle diameter of the filler of component (C) is preferably 0.1 μm to 20.0. Mu.m, more preferably 0.3 μm to 10.0. Mu.m.
In order to adjust the viscosity of the resin composition according to the present embodiment, 2 or more fillers having different average particle diameters may be used in combination.
The shape of the filler of component (C) is not particularly limited. The filler of component (C) may be in any of spherical, amorphous, phosphorus flake and the like.
The filler of component (C) may be used alone. Alternatively, 2 or more fillers may be used in combination.
The amount of the filler of the component (C) to be blended is preferably 40 to 80 parts by mass, more preferably 40 to 75 parts by mass, based on 100 parts by mass of the total of all the components of the resin composition.
The resin composition of the present embodiment may contain the following components as needed in addition to the components (a) to (C).
(D) : core-shell rubber
The resin composition of the present embodiment may contain a core-shell rubber as the component (D).
In the resin composition of the present embodiment, the core-shell rubber as the component (D) is used in order to suppress occurrence and propagation of fillet cracks when the resin composition is used as an underfill (CUF).
Specifically, when the resin composition of the present embodiment is used as an underfill material (CUF), the elastic modulus decreases by containing the component (D) (core-shell rubber). Thereby, stress generated in the rounded portion is reduced. Therefore, the occurrence of fillet cracks can be suppressed.
In addition, when a fillet crack occurs, the component (D) core-shell rubber functions as a stress relaxation agent. Therefore, the propagation of the fillet crack can be suppressed.
In the present specification, the core-shell rubber means a rubber material having a multilayer structure composed of rubber particles serving as a core and one or more shell layers covering the core. As described later, the core portion of the core-shell rubber may be composed of a material excellent in flexibility. Meanwhile, the shell layer of the core-shell rubber may be composed of a material excellent in affinity for components other than the component (D) contained in the resin composition (particularly, the epoxy resin as the component (a)). Thus, the rubber component can be blended to achieve low modulus of elasticity and good dispersibility in the resin composition.
As a constituent material of the rubber particles serving as the core portion, a material excellent in flexibility is used. Examples of the constituent materials include silicone rubber, butadiene rubber, styrene rubber, acrylic rubber, polyolefin rubber, and silicone/acrylic composite rubber.
On the other hand, as a constituent material of the shell layer, a material having excellent affinity for other components (particularly, an epoxy resin as the component (a)) other than the component (D) contained in the resin composition of the present embodiment is used.
Examples of the constituent materials include acrylic resins, and epoxy resins such as bisphenol a type epoxy resins and bisphenol F type epoxy resins.
Specific examples of the core-shell rubber include "カネエースMX-153"、"カネエースMX-257"、"カネエースMX-154"、"カネエースMX-960"、"カネエースMX-136"、"カネエースMX-137"、"カネエースMX-965"、"カネエースMX-217"、"カネエースMX-227M75"、"カネエースMX-334M75"、"カネエースMX-416" and "cover glass MX-451" manufactured by Proc, inc.; the components include, but are not limited to, "tard C-223A," "tard C-140A," "tard E-860A," "tard E-870A," "tard E-875A," "tard S-2100," "tard S-2200" and "tard S-2260" manufactured by mitre company; the methods include "faerie IM-203", "faerie IM-401", "faerie IM-601", "faerie AC3355" and "faerie AC3816" manufactured by faara industrial corporation; and "cartridge BPA328" and "cartridge BPF307" of japan catalyst of the corporation. In particular, silicone-based and butadiene-based cores are suitably used from the viewpoints of toughness, heat resistance, durability and crack resistance.
Component (D) core-shell rubber may be used alone. Alternatively, 2 or more core-shell rubbers may be used in combination.
The blending amount of the component (D) core-shell rubber is preferably 0.3 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, relative to 100 parts by mass of the total of all the components of the resin composition.
(E) : curing accelerator
The resin composition of the present embodiment may contain a curing accelerator as component (E).
The curing accelerator of the component (E) is not particularly limited as long as it is a curing accelerator of an epoxy resin. Well-known curing accelerators may be used.
The curing accelerator as component (E) imparts an appropriate curing rate to the epoxy resin as component (A).
Examples of the curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole. Examples of the commercial products include 2-phenyl-4-methylimidazole (trade name: 2P4MZ, manufactured by Shimadzu corporation) and 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine (trade name: 2MZA, manufactured by Shimadzu corporation).
In addition, encapsulated imidazoles known as microencapsulated imidazoles or epoxy-adduct imidazoles may also be used. Examples of the encapsulated imidazole include HX3941HP, HXA3942HP, HXA3922HP, HXA3792, HX3748, HX3721, HX3722, HX3088, HX3741, HX3742, and HX3613 (all manufactured by the chemical industry, trade name); PN-23J, PN-40J and PN-50 (trade name, manufactured by Weichang access company); FXR-1121 (trade name, manufactured by Fuji chemical Co., ltd.).
The curing accelerator of component (E) may be used alone. Alternatively, 2 or more curing accelerators may be used in combination.
The blending amount of the component (E) curing accelerator is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, relative to 100 parts by mass of the total of all components of the resin composition.
(Other compounding agent)
The resin composition of the present embodiment may further contain components other than the above components (a) to (E) as other compounding agents, if necessary. Examples of such complexing agents include coupling agents, ion capturing agents, leveling agents, antioxidants, defoamers, flame retardants, colorants, and reactive diluents. The amount of each compounding agent can be determined according to a usual method.
Examples of the coupling agent include silane coupling agents such as vinyl-based, glycidoxy-based, methacrylic-based, amino-based, mercapto-based, and imidazole-based; titanium coupling agents such as alkoxide-based, chelate-based and acylate-based; and various coupling agents such as glycidoxy octyl trimethoxy silane and methacryloyl octyl trimethoxy silane as long-chain spacer coupling agents.
The coupling agent may be used alone. Alternatively, 2 or more kinds of coupling agents may be used in combination.
(Preparation of resin composition)
The resin composition of the present embodiment can be produced by a conventional method.
For example, the above-mentioned resin composition is prepared by mixing the components (A) to (C) and, if necessary, the component (D), the component (E) or the above-mentioned other compounding agents.
When the epoxy resin component (a) is in a solid form, it is preferable to mix the component (a) which is liquefied or fluidized by heating or the like with other components. In the case where it is difficult to uniformly disperse the component (C) filler in the component (A) epoxy resin, the component (A) epoxy resin and the component (C) filler may be mixed first, and then the remaining components may be mixed.
When mixing the components, the components may be mixed simultaneously. Alternatively, a part of the components may be mixed first, and then the remaining components may be mixed.
The method for mixing the components (A) to (C) is not particularly limited. Well-known mixing methods may be employed. Among them, a roll mill is preferably used from the viewpoint of easy adjustment of Δk th described later. Specifically, the components (a) to (C) and, if necessary, the component (D), the component (E) and the other compounding agents are mixed by using a roll mill. Thus, the resin composition can be suitably produced.
The roll mill is preferably composed of 3 or more rolls.
The inter-roll pressure in the roll mill is not particularly limited. From the viewpoint of easy adjustment of Δk th to a predetermined range, the inter-roll pressure is preferably 2MPa or more, more preferably 3MPa or more. The upper limit of the pressure between the rolls is not particularly limited. In many cases, the upper limit of the pressure between the rolls is 30MPa or less. In more cases, the upper limit of the pressure between the rolls is 20MPa or less.
The characteristics of the resin composition according to the present embodiment will be described below.
(Fatigue crack propagation lower limit stress expansion coefficient range DeltaK th)
The fatigue crack propagation lower limit stress expansion coefficient range ΔK th is known as an index for evaluating the fatigue crack propagation performance (lower limit coating extension large coefficient Fan K th, simple and convenient method guan, yikenken, kokungkoku, kagaku, vol.35, no. 4, p149-153 (2017), japanese patent application laid-open No. 6-82353).
In the fatigue crack propagation test, a crack propagation speed da/dN is given as a function of the stress expansion coefficient amplitude Δk, wherein the crack propagation speed da/dN is obtained from the relationship between the number of repetitions N of the load of the repetitive load and the crack length a.
The stress expansion coefficient K is expressed by the following formula.
K＝f(a/W)σ(πa)1/2
Here, W: width of the test piece; a: crack length; sigma: load stress; f: a constant determined by the ratio of a to W.
In addition, the above f is specifically calculated by the following formula.
[ 1]
The fatigue crack growth test may be performed according to the steps described later. The relationship between the crack propagation velocity da/dN and the stress expansion coefficient amplitude Δk obtained from the test results was plotted, and if the stress expansion coefficient amplitude Δk was equal to or smaller than a specific value, the crack propagation velocity da/dN was 0, and it was considered that the fatigue crack did not grow. This particular value is generally defined as the fatigue crack propagation lower limit stress expansion coefficient range Δk th. If the stress expansion coefficient amplitude DeltaK is greater than or equal to the fatigue crack propagation lower limit stress expansion coefficient range DeltaK th, the crack propagation speed da/dN increases with the increase of the stress expansion coefficient amplitude DeltaK. At this time, logda/dN is almost a straight line with respect to log.DELTA.K. Further, regarding this relationship, it is known that the case law shown in the following formula holds.
da/dN＝C·ΔK'
In this disclosure, Δk at da/dn=1.0×10 -9 m/cycle is defined as the fatigue crack propagation lower limit stress expansion coefficient range Δk th.
The fatigue crack propagation lower limit stress expansion coefficient range Δk th of the cured product of the resin composition of the present embodiment is 0.55mpa·m 0.5 or more. If ΔK th is 0.55 MPa.m 0.5 or more, the fillet crack resistance is improved. Among them, ΔK th is preferably 0.56 MPa.m 0.5 or more, more preferably 0.60 MPa.m 0.5 or more. The upper limit of Δk th is not particularly limited. In many cases, the upper limit is 0.9 MPa.m 0.5 or less. In more cases, the upper limit is 0.8 MPa.m 0.5 or less.
For example, Δk th can be adjusted by the items described in (1) to (5) below. Further, Δk th may be adjusted by only 1 of the following (1) to (5). Alternatively, Δk th may be adjusted by combining 2 or more items.
(1) Glass transition temperature (Tg) of cured product of resin composition
Δk th can be adjusted by the glass transition temperature (Tg) of the cured product of the resin composition. The Δk th tends to be larger as the glass transition temperature (Tg) of a cured product of the resin composition described later is lower (for example, refer to example 1 and example 6 described later). The Tg decreases so that the crosslink density of the resin backbone decreases. Thus, flexibility is increased. As a result, the stress acting on the cured product of the resin composition can be relaxed more. This is considered to increase Δk th.
The appropriate range of the glass transition temperature (Tg) of the cured product of the resin composition will be described later.
(2) The amount of the filler of component (C)
Δk th can be adjusted by the amount of the filler of component (C). The amount of the filler of component (C) tends to be larger as Δk th increases (for example, refer to examples 1 and 2 described later). By blending a large amount of filler, the elastic modulus and strength of the cured product of the resin composition are improved. Therefore, the energy required for crack growth per unit area becomes large. This is considered to increase Δk th.
(3) Compounding of component (D) core-shell rubber
The Δk th may be adjusted by blending the component (D) core-shell rubber. If component (D) is blended into the core-shell rubber, ΔK th tends to be large (for example, refer to examples 4 and 9 described later). It is considered that Δk th can be increased by relaxing the stress acting on the cured product of the resin composition by the core-shell rubber.
(4) Epoxy resin having soft skeleton is used as the component (A) epoxy resin
Δk th can also be adjusted by using an epoxy resin having a soft skeleton as the component (a) epoxy resin. If an epoxy resin having a soft skeleton is used as the epoxy resin of the component (a), Δk th tends to be large (for example, refer to examples 1 and 7 described later). It is considered that Δk th can be increased by relaxing the stress acting on the cured product of the resin composition by the soft skeleton in the epoxy resin.
The soft skeleton herein refers to a molecular skeleton having a structure that is easy to move among molecular skeletons such as alkyl chains and siloxanes. Examples of the epoxy resin having a soft skeleton include (poly) alkylene glycol-modified epoxy resins such as (poly) ethylene glycol-modified epoxy resin, (poly) propylene glycol-modified epoxy resin, (poly) tetramethylene glycol-modified epoxy resin and (poly) hexamethylene glycol-modified epoxy resin. Further, as other examples, there may be mentioned epoxy resins having a siloxane skeleton such as bis (2- (3, 4-epoxycyclohexyl) ethyl) polydimethylsiloxane and polydimethylsiloxane diglycidyl ether, and polyisobutylene diglycidyl ether.
(5) Uniformity of resin composition
Δk th can also be adjusted by uniformity of composition in the resin composition. When kneading a resin composition, if kneading is performed with a 3-roll mill at a strong pressure, Δk th tends to be large (for example, refer to example 3 and comparative example 5 described later). If the composition in the resin composition is not uniform, stress concentrates somewhere in the cured product of the resin composition. Thus, the crack is easily propagated from the portion. By making the composition uniform in the resin composition, stress is uniformly transmitted to the inside of the cured product of the resin composition. Thus, it is considered that the strength of the cured product of the resin composition can be maximally exerted.
When the Δk th is measured, the resin composition of the present embodiment is first subjected to a curing treatment. Thus, a test piece was obtained. In the curing treatment, the coated resin composition was heat-treated at 165℃for 2 hours.
Test pieces were produced by the above-mentioned heat treatment. The dimensions of the test piece were 20mm (L). Times.2 mm (W). Times.0.5 mm (T). The test piece was subjected to preliminary crack formation (length: 0.3 mm). More specifically, fig. 1 is a top view of test strip 10. In fig. 1, a surface composed of a length L and a width W is observed. As shown in fig. 1, a crack 12 extending from one side to the other side is formed in the center of the length L of the test piece 10. The direction in which the crack 12 extends is parallel to the width direction of the test piece 10. The crack 12 was produced so as to penetrate the test piece in the thickness direction. In the test described later, stress was applied to the test piece in the direction indicated by the arrow.
A minute load tester (LMH 207-10 manufactured by Lung palace manufacturing) was used to repeatedly apply a load (stress). In the crack observation, a microscope (SZX-16), a moving image, and a still image are used to obtain a system for a long time. The load waveform of the micro load testing machine is sine wave. The frequency was 2Hz. However, in order to determine crack growth behavior under minute stress, it is preferable to conduct a test with low stress in terms of the characteristics of the fatigue crack propagation lower limit stress expansion coefficient range Δk th. Moreover, the test stress can be gradually increased as long as the crack does not propagate.
Therefore, as a test, first, under a load condition of one cycle in which the load waveform is a sine wave, the frequency is 2Hz, the minimum stress is 0 (N), and the maximum stress is X (N), the load is repeatedly applied to the test piece while changing the value of X. Thus, the value of X was found when a crack of 1 μm or more did not propagate after 20000 cycles. Next, the value of X was increased by 0.1N each time from the found value of X, and the load was repeatedly applied to the test piece. Then, the minimum value (hereinafter also referred to as "value Y") was obtained from the value of X at the time of crack growth of 1 μm or more after 20000 cycles.
For example, first, in the above-described load conditions, a load is repeatedly applied to the test piece at a maximum stress X of 14 (N). Then, when a crack of 1 μm or more did not propagate after 20000 cycles, the test piece was repeatedly loaded under the loading conditions described above with a maximum stress X of 14.1 (N) which was increased by 0.1 (N) from this value. Then, it was confirmed whether or not a crack of 1 μm or more was propagated after 20000 cycles. In the case where the crack did not propagate, the same test was further performed with a maximum stress X of 14.2 (N) increased by 0.1 (N) from this value. The test was repeated with the maximum stress X increased by 0.1 (N) each time until crack growth of 1 μm or more was confirmed after 20000 cycles. Thus, the minimum value Y of the maximum stress X can be obtained.
Then, the test piece was repeatedly loaded under the condition that X was the value Y. At this time, the propagation of the crack was confirmed on the surface composed of the length L and the width W of the test piece. The crack length Lc (see fig. 1) was measured. Then, the crack propagation velocity da/dN is plotted against the stress expansion coefficient amplitude Δk. Here, Δk at da/dn=1.0×10 -9 m/cycle is defined as Δk th.
The stress expansion coefficient range Δk corresponds to the difference between the maximum value Δk max and the minimum value Δk min of the stress expansion coefficient K in one cycle. In the above measurement, the minimum value Δk min of stress in 1 cycle is 0. Thus, a relationship of Δk=Δk max is obtained.
(Glass transition temperature (Tg))
The glass transition temperature (Tg) of the cured product of the resin composition of the present embodiment is preferably 100 ℃ or higher. The underfill material preferably has good bump crack resistance in addition to good fillet crack resistance. If Tg is 100 ℃ or higher, bump crack resistance is improved. The Tg of the cured product of the resin composition of the present embodiment is more preferably 103℃or higher, and still more preferably 105℃or higher. The upper limit of Tg of the cured product of the resin composition of the present embodiment is not particularly limited. In many cases, the upper limit of Tg is 200℃or lower. In more cases, the upper limit of Tg is 180℃or lower.
In measuring the glass transition temperature, first, a test piece is obtained by curing the resin composition of the present embodiment. As the curing treatment, the applied resin composition was heat-treated at 165℃for 2 hours. The film thickness of the cured product was adjusted to a range of 2000.+ -.100. Mu.m.
Then, the glass transition temperature of the obtained cured product can be determined by a double support bending method (two-layer casting method) using a dynamic thermo-mechanical measuring Device (DMA) under conditions of a frequency of 1Hz and a temperature rise rate of 3 ℃/min at a temperature in the range of-20 ℃ to 260 ℃. The glass transition temperature (Tg) is determined from the peak temperature of the loss tangent (tan. Delta.) which is determined from the loss elastic modulus (E ')/storage elastic modulus (E').
(Viscosity)
The resin composition of the present embodiment has a low viscosity. Therefore, when the resin composition is used as an underfill material (CUF), injectability by capillary flow is good.
Specifically, the viscosity is preferably 100 pas or less, more preferably 80 pas or less, when measured at 25 ℃ and a rotational speed of 50rpm using a rotational viscometer. The lower limit is not particularly limited. In many cases, the lower limit is 1pa·s or more. In more cases, the lower limit is 10 Pa.s or more.
(Essential element 1)
The cured product of the resin composition of the present embodiment preferably satisfies the following requirement 1.
Element 1: when the area (μm 2) occupied by each of the 6 regions of the filler (the 6 regions are randomly selected 6 horizontal (horizontal) 37.8 μm×vertical ((vertical)) 18.9 μm regions in the cross section of the cured product of the resin composition) was calculated, the standard deviation of the area (filler area) of each of the 6 obtained fillers was 0.36 μm 2 or less. Here, regarding the filler area, the cross section of the cured product of the resin composition was observed at 1000 times magnification by a scanning electron microscope, thereby obtaining the filler area.
The following describes the element 1 in detail.
In the element 1, the standard deviation of the filler area in the cross section of the cured product of the resin composition is calculated. The smaller the value of the standard deviation means that the more uniform the size of the filler and/or the distribution of the filler contained in the resin composition. That is, a small standard deviation means that the uniformity of the composition of the resin composition is high. That is, the standard deviation is related to the uniformity of the above (5) resin composition. Therefore, the smaller the standard deviation calculated in element 1, the larger Δk th. The standard deviation calculated in the element 1 is preferably 0.36 μm 2 or less, more preferably 0.27 μm 2 or less. The lower limit of the standard deviation is not particularly limited. In many cases, the standard deviation is 0 μm 2 or more. In more cases, the standard deviation is 0.02 μm 2 or more.
An example of a method for calculating the standard deviation of the area occupied by the filler in element 1 will be described in detail below.
First, a test piece was obtained by curing the resin composition of the present embodiment. Specifically, first, a glass plate was fixed on an organic substrate (FR-4 substrate) with a gap of 100 μm therebetween. Then, the above organic substrate having the glass plate fixed thereon was placed on a hot plate set to 110 ℃. Then, the resin composition of the present embodiment is injected into the gap. The implantation width was 10mm. The injection length was 20mm. Then, as a curing treatment, the injected resin composition was heat-treated at 165℃for 2 hours.
Then, the obtained test piece (cured product of the resin composition) was cut. Then, a cross section exposed at an injection distance site of 10mm was observed. The observation was performed using a scanning electron microscope (Hitachi-pass electron Xuan micro-mirror device S-3400N). The observation magnification was 1000 times. The size of the image when observed was 122.4. Mu.m, 93.4. Mu.m, in the horizontal direction. The resolution is 1280×960.
Then, the obtained observation image was subjected to image analysis using image analysis software windof 2018 (ver4.5.5, san francisco). The range of image analysis is a range of 113.4 μm in the horizontal direction and 37.8 μm in the vertical direction in the obtained observation image. The number of pixels is 1200×400. As a specific step of image analysis, the above software was used, and a cross-sectional view image of the cured product was subjected to a filter process using a median filter (5×5 pixels), thereby reducing noise. Further, the observation image is subjected to a monochromatic imaging process, and then to a binarization process. In the binarization processing, an image having a depth that does not reach a predetermined threshold is cut off. The image is processed by taking 1 as an image having a depth equal to or greater than the threshold value and taking 0 as an image having a depth less than the threshold value. Binarization was performed by the method of Otsu (discriminant analysis).
Then, the filler area (μm 2) in the region of 37.8 μm in the horizontal direction by 18.9 μm in the vertical direction in the binarized observation image was calculated. The region of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction corresponds to a region (region indicated by a in fig. 2) of 400×200 pixels in the binarized observation image 20 in fig. 2. Specifically, the number of pixels contained in the filler selected from one of the regions a to F in fig. 2 is calculated. Then, the number of pixels is multiplied by the area of 1 pixel. The resulting value is defined as the packing area. The packing area in each selected region was determined as described above. Further, an average of these 6 filler areas was calculated. The calculated average value is defined as the average area of the filler (μm 2).
By the above-described processing, the filler areas of the areas (the areas indicated as a to F in fig. 2) at 6 in the binarized observation image 20 shown in fig. 2 were calculated. The standard deviation was calculated using the obtained values of 6 filler areas. When the obtained value is not more than 0.36 μm 2, the requirement 1 is satisfied.
In the above, when the standard deviation is calculated, binarization processing is performed in a range larger than the area of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction. Among these, the region itself of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction selected from the regions A to F may be subjected to binarization treatment. The packing area of the selected region can then also be calculated by the above-described process. The standard deviation may be obtained by performing such processing on the different points 6.
The randomly selected 6 regions corresponding to the standard deviation obtained above mean 6 regions that do not overlap with each other.
The number of pixels contained in the filler in each region of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction can be calculated. Then, the standard deviation of the number of pixels (hereinafter, also referred to as "standard deviation of the number of pixels") contained in the filler of each region can be calculated. In this case, the standard deviation of the number of pixels is preferably 40 pixels or less. The lower limit of the standard deviation of the number of pixels is not particularly limited. For example, the lower limit thereof is 0 pixel.
(Element 2)
The cured product of the resin composition of the present embodiment preferably satisfies the following requirement 2.
Element 2: when the number of each of the 6 regions of the filler was calculated (the 6 regions are randomly selected 6 regions of 37.8 μm in the transverse direction and 18.9 μm in the longitudinal direction in the cross section of the cured product of the resin composition), the standard deviation of the number of the obtained 6 fillers was 80 or less. Here, regarding the amount of filler, the cross section of the cured product of the resin composition was observed at a magnification of 1000 times by a scanning electron microscope, thereby obtaining the amount of filler.
The following describes the element 2 in detail.
In element 2, the standard deviation of the amount of filler in the cross section of the cured product of the resin composition is calculated. The smaller the value of the standard deviation, the higher the uniformity of the composition of the resin composition. That is, the standard deviation is related to the uniformity of the resin composition (5) above. Therefore, the smaller the standard deviation of element 2, the larger Δk th. The standard deviation of element 2 is preferably 60 or less, more preferably 55 or less. The lower limit of the standard deviation is not particularly limited. In many cases, the standard deviation is 0 or more. In more cases, the standard deviation is 5 or more.
Hereinafter, an example of a calculation method of the standard deviation of the amount of filler in the sub-region where the filler of element 2 is located will be described in detail.
In the calculation of the standard deviation of the element 2, a binarized observation image was obtained in the same procedure as that described in the element 1.
Then, the amount of filler in the region of 37.8 μm in the horizontal direction×18.9 μm in the vertical direction in the binarized observation image was calculated.
By the above-described processing, the amounts of the fillers in the 6 areas (the areas indicated as a to F in fig. 2) in the binarized observation image 20 shown in fig. 2 were calculated. The standard deviation was calculated using the values of the amounts of the 6 fillers obtained. When the obtained value is 80 or less, the requirement 2 is satisfied.
In the above, when the standard deviation is calculated, binarization processing is performed on an observation image larger than a region of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction. Among these, the region itself of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction selected from the regions A to F may be subjected to binarization treatment. The amount of filler in the selected region can then also be calculated by the above-described process. The standard deviation may be obtained by performing such processing on the different points 6.
The randomly selected 6 regions corresponding to the standard deviation obtained above mean 6 regions whose regions do not overlap each other.
The semiconductor device according to the present embodiment is a semiconductor device including a substrate, a semiconductor element, and a cured product, wherein the semiconductor element is a semiconductor element disposed on the substrate, and the cured product is a cured product of the resin composition according to the present embodiment sealing the semiconductor element.
The semiconductor element is not particularly limited. Examples of the semiconductor element include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a capacitor.
The method for manufacturing a semiconductor device according to the present embodiment includes: the resin composition according to the present embodiment fills a void between a substrate and a semiconductor element disposed on the substrate, and cures the resin composition.
For filling the resin composition, for example, the resin composition of the present embodiment is applied to one end of the semiconductor element while heating the substrate to 70 to 120 ℃. Then, the gap between the substrate and the semiconductor element is filled with the resin composition of the present embodiment by capillary phenomenon. In this case, the substrate may be tilted in order to shorten the time required for filling the resin composition of the present embodiment. Alternatively, a pressure difference may be generated between the inside and the outside of the gap.
For curing the resin composition, after the gap is filled with the resin composition of the present embodiment, the substrate is heated at a predetermined temperature for a predetermined time, for example, at 150 to 165 ℃ for 0.5 to 2 hours. Thereby, the gap is sealed by heat curing the resin composition.
Examples
Hereinafter, the present embodiment will be described in detail with reference to examples. However, the present embodiment is not limited to these examples.
(Examples 1 to 13, comparative examples 1 to 5)
The raw materials were kneaded using a roll mill (three-roll mill) in the compounding ratios shown in the following table. Resin compositions of examples 1 to 13 and comparative examples 1 to 5 were prepared. The pressure at the time of kneading by the roll mill (inter-roll pressure) was 3MPa, except for comparative example 5, which was 1MPa. In addition, the numerical values related to the respective compositions in the table represent parts by mass.
The components used in the preparation of the resin composition are as follows.
Component (A): epoxy resin
Epoxy resin A-1: liquid bisphenol F type epoxy resin, product name YDF8170, manufactured by Nitro chemical company, epoxy equivalent 158g/eqs
Epoxy resin A-2: liquid aminophenol type epoxy resin, product name jER630, manufactured by Mitsubishi chemical corporation, epoxy equivalent 98g/eq
Epoxy resin A-3: liquid naphthalene type epoxy resin, product name HP-4032D, manufactured by DIC Co., ltd., epoxy equivalent weight of 140g/eq
Epoxy resin A-4: liquid cyclohexane type epoxy resin, product name EP-4085S, manufactured by ADEKA Co., ltd., epoxy equivalent weight 145g/eq
Component (B): curing agent
Curing agent B-1: amine-based curing agent, 4 '-diamino-3, 3' -diethyldiphenylmethane, product name HDAA, active hydrogen equivalent 63.5g/eq, manufactured by Japanese chemical Co., ltd
Curing agent B-2: amine curing agent, diethyl toluenediamine, product name of Abelmoschus 100, active hydrogen equivalent 44.5g/eq, manufactured by Abelmoschus company
Curing agent B-3: amine curing agent, dithiotoluenediamine, product name of Abelmoschus 300, active hydrogen equivalent of 53.5g/eq, manufactured by Abelmoschus company
Curing agent B-4: anhydride-based curing agent, 3, 4-dimethyl-6- (2-methyl-1-propenyl) -4-cyclohexene-1, 2-dicarboxylic anhydride, product name YH307, active hydrogen equivalent 117g/eq, mitsubishi chemical industry Co., ltd
Component (C): packing material
Filler C-1: 3-glycidoxypropyl trimethoxysilane surface treated silica having an average particle diameter of 0.5 μm and a product name of SE2200-SEJ manufactured by Kyoto Inc
Filler C-2: silica having an average particle diameter of 0.5 μm and a product name of SO-E2, manufactured by Koku Kogyo Co., ltd
Filler C-3: 3-glycidoxypropyl trimethoxysilane surface treated silica having an average particle diameter of 1.5 μm and a product name of SE5050-SEJ manufactured by Etoque corporation
Filler C-4: 3-glycidoxypropyl trimethoxysilane surface treated silica, product name SE1050-SEO, average particle diameter 0.3 μm, manufactured by Kyoto corporation
Filler C-5: alumina, product name A9-SX-E2, average particle size 10 μm, manufactured by the doctor company
Component (D): core-shell rubber
Core-shell rubber D-1: product name MX-137 (core-shell butadiene rubber particle, manufactured by Apollo Co., ltd.)
Core-shell rubber D-2: product name MX-965 (core-shell silicone rubber particle, manufactured by Apollo Co., ltd.)
Component (E): curing accelerator
Curing accelerator E-1: 2-phenyl-4-methylimidazole, product name 2P4MZ, manufactured by four chemical industry Co., ltd
(Viscosity)
The viscosity (pa·s) of the evaluation sample immediately after preparation was measured at 25 ℃ and 50rpm using a brussel viscometer.
(Tg)
The storage elastic modulus and the loss elastic modulus of the cured products of the resin compositions of each example and each comparative example were measured using a dynamic viscoelasticity apparatus. The peak value of tan delta of the ratio of these elastic moduli was measured as Tg. The elastic modulus was measured based on JIS C6481, japanese Industrial Specification.
More specifically, first, spacers composed of overlapping heat-resistant tapes are disposed at two places on a teflon (registered trademark) sheet attached to the surface of a glass plate having a thickness of 3 mm. In this case, the thickness of the spacers was adjusted so that the thickness of a cured product of the resin composition to be described later became 2000.+ -.100. Mu.m. Then, the resin composition was coated on the teflon sheet between the spacers. The coated resin composition was held by another glass plate with a teflon (registered trademark) sheet attached to the surface, while taking care not to trap air bubbles. In this state, the resin composition was cured at 165℃for 2 hours. Finally, the cured product thus obtained was peeled off from the teflon (registered trademark) sheet. Then, the cured product was cut to a predetermined size (10 mm. Times.50 mm) by a cutter. Thus, a test piece was obtained. The cut-out of the cured product was smoothed by sandpaper. Tg of the test piece was measured by a double-support bending method using a dynamic thermo-mechanical measuring Device (DMA) (manufactured by Hitachi-Tek corporation) under conditions of a frequency of 1Hz and a temperature rising rate of 3 ℃/min at a temperature ranging from-20 ℃ to 260 ℃. Tg is determined by the peak temperature (. Degree.C.) of tan. Delta. Where tan. Delta. Is determined from E '/E'.
(ΔKth)
Δk th was obtained as follows.
Fatigue crack propagation test was performed to obtain a stress expansion coefficient amplitude Δk represented by the following formula.
ΔK＝f(a/W)σ(πa)1/2
W: width of the test piece; a: crack length; sigma: load stress; f: a constant determined by the ratio of a to W.
The resin compositions of each of the examples and comparative examples were cured at 165℃for 2 hours to prepare test pieces.
The dimensions of the test piece were 20mm (L). Times.2 mm (W). Times.0.5 mm (T). As illustrated in FIG. 1, a crack having a length of 0.3mm was provided in the test piece. A micro load tester (LMH 207-10 manufactured by Lu palace manufacturing) was used as a test device. For crack observation, a microscope (SZX-16), a moving image/still image (slow) long-time acquisition system, and the like are used. The load waveform of the micro load testing machine is sine wave. The frequency was 2Hz.
Then, as described above, the test was repeated while changing the value of X under the load condition of one cycle in which the load waveform is a sine wave, the frequency is 2Hz, the minimum stress is 0 (N), and the maximum stress is X (N). The minimum value of X was obtained when crack growth of 1 μm or more was confirmed in the test piece after 20000 cycles of loading under the same loading conditions. The test piece was repeatedly loaded with the obtained minimum value, and the obtained relationship between the crack propagation speed da/dN and the stress expansion coefficient amplitude Δk was plotted. The Δk at da/dn=1.0×10 -9 m/cycle obtained was defined as Δk th.
(Reliability test)
The resin compositions of each example and comparative example were applied to test pieces mounted on a substrate manufactured by Walts: walts-silicon chip on KIT FC150 01A 150P-10: walts-TEG FC150 JY. The coated resin composition was cured at 165℃for 2 hours.
Preconditioning test was performed under JEDEC Level3 conditions. Then, 1000 cycles THERMAL CYCLE were performed under Condition B. Then, as an evaluation of the fillet crack resistance, the fillet portion was observed by a microscope. The presence or absence of fillet cracks was observed. Further, as an evaluation of the bump crack resistance, the presence or absence of a broken daisy chain in the test piece was observed using a resistance value meter. The reliability test was performed 5 times using different test pieces.
In tables 1 to 3, "filler addition amount" indicates the content of filler (parts by mass) relative to 100 parts by mass of the resin composition.
In tables 1 to 3, the "rubber particle addition amount" represents the content (parts by mass) of the core-shell rubber relative to 100 parts by mass of the resin composition.
In tables 1 to 3, the "equivalent ratio" represents the ratio of the active hydrogen equivalent of the curing agent to the epoxy equivalent of the epoxy resin (active hydrogen equivalent/epoxy equivalent).
In tables 1 to 3, "fillet crack" represents the number of test pieces having fillet cracks observed in the above-described reliability test. For example, "0/5" means that no fillet crack was observed in any of the test pieces when the above-described reliability test was performed 5 times using different test pieces. "1/5" means that fillet cracks were observed in one test piece.
In tables 1 to 3, "conduction failure (open circuit)" indicates the number of test pieces showing a daisy chain break observed in the above-described reliability test. For example, "0/5" means that no broken line of the daisy chain was observed in any of the test pieces when the above-described reliability test was performed 5 times using different test pieces. "1/5" means that a broken line of the daisy chain was observed in one test piece.
In tables 1 to 3, "pressure between rolls (MPa)" means pressure between rolls (MPa) at the time of roll grinding.
TABLE 1
TABLE 2
TABLE 3
No occurrence of fillet cracks was confirmed in any of examples 1 to 13 showing Δk th of 0.55mpa·m 0.5 or more. The frequency of occurrence of disconnection is 1 time or less among 5 times. No disconnection was confirmed in any of examples 1 to 7 and examples 9 to 13 showing Tg of 105 ℃ or higher.
In example 2 and example 3, the filler blending ratio of example 1 was changed.
In example 4,2 different epoxy resins of component (A) were used.
In examples 5 and 6, the equivalent ratio of the epoxy resin (A) to the curing agent (B) in example 4 was changed.
In example 7, the epoxy resin A-2 was replaced, and the epoxy resin A-4 and the epoxy resin A-1 were used as the component (A), unlike in example 4.
In example 8, the equivalent ratio of the epoxy resin (a) to the curing agent (B) in example 7 was changed.
In example 9, 2 different epoxy resins of component (A) were used. The composition further contains a core-shell rubber as component (D).
In example 10, an epoxy resin different from example 1 was used as component (a). The composition further contains a core-shell rubber as component (D).
In example 11, 3 different epoxy resins (A) were used in combination. Further, 2 kinds of curing agents different from example 1 were used as the component (B).
In example 12, a curing agent different from that of example 1 was used as the component (B). Furthermore, 2 kinds of fillers different from example 1 were used as the component (C).
In example 13, a curing agent different from that of example 1 was used as the component (B). Moreover, a filler different from example 1 was used as the component (C).
Any of comparative examples 1 to 5 having Δk th of less than 0.55mpa·m 0.5 confirmed the occurrence of fillet cracks.
(Evaluation of element 1)
Using the resin compositions of example 3, example 10, example 12 and comparative example 5, the evaluation of the element 1 was performed according to the following procedure. Table 4 shows the results obtained.
In order to evaluate the requirement 1, first, the resin compositions of example 3, example 10, example 12 and comparative example 5 were subjected to curing treatment to obtain test pieces. Specifically, first, a glass plate was fixed on an organic substrate (FR-4 substrate) with a gap of 100 μm therebetween. The organic substrate having the above-mentioned fixed glass plate was placed on a hot plate set to 110 ℃. Then, the resin compositions of example 3, example 10, example 12 and comparative example 5 were injected into the gaps, respectively. The implantation width was 10mm. The injection length was 20mm. Then, as a curing treatment, the injected resin composition was heat-treated at 165℃for 2 hours.
The obtained test piece (cured product of the resin composition) was cut. Then, a cross section exposed at an injection distance site of 10mm was observed. For observation, a scanning electron microscope (Hitachi-pass electron Xuan micromirror array S-3400N) was used. The observation magnification was 1000 times. The size of the image when observed was 122.4. Mu.m, 93.4. Mu.m, in the horizontal direction. The resolution is 1280×960.
Then, the obtained observation image was subjected to image analysis using image analysis software windof 2018 (ver4.5.5, san francisco). The range of image analysis is a range of 113.4 μm in the horizontal direction and 37.8 μm in the vertical direction in the obtained observation image. The number of pixels is 1200×400. As a specific step of image analysis, the above software was used, and a cross-sectional view image of the cured product was subjected to a filter process using a median filter (5×5 pixels), thereby reducing noise. Further, observation is enhanced by a monochromatic imaging process, and then binarization process is performed. In the binarization processing, an image having a depth that does not reach a predetermined threshold is cut off. The image is processed by taking 1 as an image having a depth equal to or greater than the threshold value and taking 0 as an image having a depth less than the threshold value. Binarization was performed by the method of Otsu (discriminant analysis).
Then, the filler area (μm 2) in the region of 37.8 μm in the horizontal direction by 18.9 μm in the vertical direction in the binarized observation image was calculated.
The above processing is performed on 6 points (see fig. 2) in the observation image subjected to the binarization processing. The packing area of each zone was calculated therefrom. The standard deviation (standard deviation of area (. Mu.m 2)) was calculated using the obtained values of 6 filler areas.
The standard deviation (μm 2) of the area was calculated, and the standard deviation of the average value of the pixel numbers was also calculated.
(Evaluation of element 2)
Using the resin compositions of example 3, example 10, example 12 and comparative example 5, the evaluation of the element 2 was performed according to the procedure shown below.
In order to evaluate the element 2, first, a binarized observation image was obtained in the same manner as described above (evaluation of the element 1).
Then, the amount of filler in the region of 37.8 μm in the horizontal direction by 18.9 μm in the vertical direction in the binarized observation image was calculated. By the above-described processing, the respective numbers of the filler at 6 areas, which are 6 areas in the binarized observation image (refer to fig. 2), are calculated. The standard deviation (number) of the obtained 6 fillers) was calculated using the value of the number thereof.
In table 4, "pressure between rolls (MPa)" indicates pressure between rolls (MPa) at the time of roll grinding.
In table 4, "standard deviation of area (μm 2)" is the standard deviation of the filler area calculated as described above (evaluation of element 1).
In table 4, "standard deviation of area (number of pixels)" is the standard deviation of the average value of the number of pixels.
In table 4, "standard deviation of number" is the standard deviation of the amount of filler calculated as described above (evaluation of element 2).
TABLE 4
| TABLE 4 Table 4 | Example 3 | Example 10 | Example 12 | Comparative example 5 |
| Pressure between rollers (Mpa) | 3.0 | 3.0 | 3.0 | 1.0 |
| Standard deviation of area (mum 2) | 0.23 | 0.06 | 0.05 | 0.40 |
| Standard deviation of area (number of pixels) | 26.3 | 6.6 | 5.3 | 45.3 |
| Standard deviation of number (individual) | 47 | 22 | 37 | 112 |
As shown in table 4 above, the resin compositions of example 3, example 10 and example 12 satisfy the requirements 1 and 2. These compositions were confirmed to be excellent in uniformity of the resin composition. It is considered that a desired effect can be obtained by using a resin composition showing such characteristics.
Symbol description
10. Test piece
12. Cracking of
20. Binarized observation image
Claims (13)
1. A resin composition, wherein the resin composition comprises:
(A) An epoxy resin,
(B) A curing agent,
(C) The filler is used for filling the filler,
The cured product of the resin composition has a fatigue crack propagation lower limit stress expansion coefficient range DeltaK th of 0.55MPa m 0.5 or more.
2. The resin composition according to claim 1, wherein,
The glass transition temperature (Tg) of the cured product of the resin composition is 100 ℃ or higher.
3. The resin composition according to claim 1 or 2, wherein,
The epoxy resin (A) contains a liquid epoxy resin.
4. The resin composition according to claim 1 to 3, wherein,
The (A) epoxy resin contains at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin and cyclohexane type epoxy resin.
5. The resin composition according to claim 1 to 4, wherein,
The filler (C) is contained in an amount of 40 to 80 parts by mass based on 100 parts by mass of the total of all components of the resin composition.
6. The resin composition according to claim 1 to 5, wherein,
The average particle diameter of the filler (C) is 0.1-20.0 μm.
7. The resin composition according to claim 1 to 6, wherein,
The filler (C) is surface-treated with a silane coupling agent.
8. The resin composition according to any one of claim 1 to 7, wherein,
The resin composition further comprises (D) a core-shell rubber.
9. The resin composition according to any one of claim 1 to 8, wherein,
The cured product of the resin composition satisfies the following requirement 1,
Element 1: when the cross section of the cured product of the resin composition was observed by a scanning electron microscope at a magnification of 1000 times, and an operation of calculating the average area (μm 2) of the fillers in the region of 37.8 μm x 18.9 μm in the horizontal direction was performed at 6 selected randomly, the standard deviation of the areas of the 6 fillers obtained was 0.36 μm 2 or less.
10. The resin composition according to any one of claim 1 to 9, wherein,
The cured product of the resin composition satisfies the following requirement 2,
Element 2: when the cross section of the cured product of the resin composition was observed by a scanning electron microscope at a magnification of 1000 times, and an operation of calculating the number of fillers in the region of 37.8 μm in the horizontal direction and 18.9 μm in the vertical direction was performed at 6 selected randomly, the standard deviation of the number of the obtained 6 fillers was 80 or less.
11. A semiconductor device, wherein,
The semiconductor device comprises a substrate, a semiconductor element disposed on the substrate, and a cured product of the resin composition according to any one of claims 1 to 10 sealing the semiconductor element.
12. A method of manufacturing a semiconductor device, wherein,
The manufacturing method includes filling a void, which is a void between a substrate and a semiconductor element disposed on the substrate, with the resin composition according to any one of claims 1 to 10, and curing the resin composition.
13. A method for producing a resin composition according to any one of claim 1 to 10, wherein,
The production method includes producing a resin composition by mixing the (A) epoxy resin, the (B) curing agent and the (C) filler using a roll mill,
The pressure between rollers of the roller mill is more than 3.0 MPa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022037993 | 2022-03-11 | ||
| JP2022-037993 | 2022-03-11 | ||
| PCT/JP2022/040388 WO2023171028A1 (en) | 2022-03-11 | 2022-10-28 | Resin composition, semiconductor device, and methods for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN118451123A true CN118451123A (en) | 2024-08-06 |
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| CN202280086025.0A Pending CN118451123A (en) | 2022-03-11 | 2022-10-28 | Resin composition, semiconductor device, and method for producing same |
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| Country | Link |
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| CN (1) | CN118451123A (en) |
| TW (1) | TW202336148A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012162585A (en) * | 2011-02-03 | 2012-08-30 | Namics Corp | Resin sealng material for semiconductor |
| JP2015117361A (en) * | 2013-11-18 | 2015-06-25 | 四国化成工業株式会社 | Resin composition for semiconductor encapsulation |
| JP6335807B2 (en) * | 2015-01-27 | 2018-05-30 | 四国化成工業株式会社 | Novel glycolurils and their use |
| WO2020111244A1 (en) * | 2018-11-30 | 2020-06-04 | 日立化成株式会社 | Underfill material, semiconductor package and method for producing semiconductor package |
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- 2022-10-28 WO PCT/JP2022/040388 patent/WO2023171028A1/en active Application Filing
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| WO2023171028A1 (en) | 2023-09-14 |
| TW202336148A (en) | 2023-09-16 |
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