CN112752783B - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
- Publication number
- CN112752783B CN112752783B CN201980004492.2A CN201980004492A CN112752783B CN 112752783 B CN112752783 B CN 112752783B CN 201980004492 A CN201980004492 A CN 201980004492A CN 112752783 B CN112752783 B CN 112752783B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- component
- thiol
- resin composition
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 173
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 173
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000003566 sealing material Substances 0.000 claims abstract description 17
- -1 thiol compound Chemical class 0.000 claims description 116
- 239000004593 Epoxy Substances 0.000 claims description 36
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 32
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000003607 modifier Substances 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 15
- 230000001070 adhesive effect Effects 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 60
- 238000001723 curing Methods 0.000 description 50
- 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 26
- 150000003573 thiols Chemical class 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 20
- 239000000945 filler Substances 0.000 description 19
- 238000004132 cross linking Methods 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 229920006295 polythiol Polymers 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 4
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 101001057956 Homo sapiens 55 kDa erythrocyte membrane protein Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- VUTVSWPVTJZPFU-UHFFFAOYSA-N propylsulfanylmethanethiol Chemical compound CCCSCS VUTVSWPVTJZPFU-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- VRQFYSHDLYCPRC-UHFFFAOYSA-N (ethylsulfanyl)methanethiol Chemical compound CCSCS VRQFYSHDLYCPRC-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- IMLSAISZLJGWPP-UHFFFAOYSA-N 1,3-dithiolane Chemical compound C1CSCS1 IMLSAISZLJGWPP-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- MLHBQCMRBXCFLT-UHFFFAOYSA-N 2,2-bis(sulfanylmethylsulfanyl)ethanethiol Chemical compound SCSC(CS)SCS MLHBQCMRBXCFLT-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- WXDDGAZCUPULGL-UHFFFAOYSA-N 2,3-bis(sulfanylmethylsulfanyl)propylsulfanylmethanethiol Chemical compound SCSCC(SCS)CSCS WXDDGAZCUPULGL-UHFFFAOYSA-N 0.000 description 1
- NQFUSWIGRKFAHK-UHFFFAOYSA-N 2,3-epoxypinane Chemical compound CC12OC1CC1C(C)(C)C2C1 NQFUSWIGRKFAHK-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- DUILGEYLVHGSEE-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1CO1 DUILGEYLVHGSEE-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- GQTBMBMBWQJACJ-UHFFFAOYSA-N 2-[(4-butan-2-ylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)CC)=CC=C1OCC1OC1 GQTBMBMBWQJACJ-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- GXANCFOKAWEPIS-UHFFFAOYSA-N 2-[(4-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C1=CC=CC=C1 GXANCFOKAWEPIS-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- QTEWPHJCEXIMRJ-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCC(SCCS)CSCCS QTEWPHJCEXIMRJ-UHFFFAOYSA-N 0.000 description 1
- NKMOLEYVYVWWJC-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCN1C(=O)N(CCOC(=O)CC(C)S)C(=O)N(CCOC(=O)CC(C)S)C1=O NKMOLEYVYVWWJC-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- KIVDBXVDNQFFFL-UHFFFAOYSA-N 2-[3-(2-sulfanylethylsulfanyl)-2,2-bis(2-sulfanylethylsulfanylmethyl)propyl]sulfanylethanethiol Chemical compound SCCSCC(CSCCS)(CSCCS)CSCCS KIVDBXVDNQFFFL-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- HRSLYNJTMYIRHM-UHFFFAOYSA-N 2-[[4-[3,5-dimethyl-4-(oxiran-2-ylmethoxy)phenyl]-2,6-dimethylphenoxy]methyl]oxirane Chemical group CC1=CC(C=2C=C(C)C(OCC3OC3)=C(C)C=2)=CC(C)=C1OCC1CO1 HRSLYNJTMYIRHM-UHFFFAOYSA-N 0.000 description 1
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- DUYICINCNBSZMH-UHFFFAOYSA-N 3-[2,3-bis(3-sulfanylpropylsulfanyl)propylsulfanyl]propane-1-thiol Chemical compound SCCCSCC(SCCCS)CSCCCS DUYICINCNBSZMH-UHFFFAOYSA-N 0.000 description 1
- KLGUKVGNYAOWNX-UHFFFAOYSA-N 3-[3-(3-sulfanylpropylsulfanyl)-2,2-bis(3-sulfanylpropylsulfanylmethyl)propyl]sulfanylpropane-1-thiol Chemical compound SCCCSCC(CSCCCS)(CSCCCS)CSCCCS KLGUKVGNYAOWNX-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- DRPJWBIHQOHLND-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]oxybutyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)OCCCCOC(=O)C(C)=C DRPJWBIHQOHLND-UHFFFAOYSA-N 0.000 description 1
- CXXSQMDHHYTRKY-UHFFFAOYSA-N 4-amino-2,3,5-tris(oxiran-2-ylmethyl)phenol Chemical compound C1=C(O)C(CC2OC2)=C(CC2OC2)C(N)=C1CC1CO1 CXXSQMDHHYTRKY-UHFFFAOYSA-N 0.000 description 1
- JBBURRWEMSTGIX-UHFFFAOYSA-N 5-ethyl-5-methyl-1,3-bis(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound O=C1N(CC2OC2)C(=O)C(CC)(C)N1CC1CO1 JBBURRWEMSTGIX-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- PAPZLZMDZDWUGM-UHFFFAOYSA-N BBBBOB Chemical compound BBBBOB PAPZLZMDZDWUGM-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- PUZHXYSDMURDFB-UHFFFAOYSA-N O(CCOCCOCCOC)C(CCCOCCOCCOBOCCOCCOCCOCCOC)OCCOCCOCCOC Chemical compound O(CCOCCOCCOC)C(CCCOCCOCCOBOCCOCCOCCOCCOC)OCCOCCOCCOC PUZHXYSDMURDFB-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- XAAGVUQLDIOQGP-UHFFFAOYSA-N [3,3-bis[2,2-bis(sulfanylmethylsulfanyl)ethyl]-1,5,5-tris(sulfanylmethylsulfanyl)pentyl]sulfanylmethanethiol Chemical compound SCSC(SCS)CC(CC(SCS)SCS)(CC(SCS)SCS)CC(SCS)SCS XAAGVUQLDIOQGP-UHFFFAOYSA-N 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-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
- VLDJWLWRDVWISM-UHFFFAOYSA-N [3-(sulfanylmethylsulfanyl)-2,2-bis(sulfanylmethylsulfanylmethyl)propyl]sulfanylmethanethiol Chemical compound SCSCC(CSCS)(CSCS)CSCS VLDJWLWRDVWISM-UHFFFAOYSA-N 0.000 description 1
- FHKCCRRDKWJYCG-UHFFFAOYSA-N [3-[2,2-bis(sulfanylmethylsulfanyl)ethyl]-1,5,5-tris(sulfanylmethylsulfanyl)pentyl]sulfanylmethanethiol Chemical compound SCSC(SCS)CC(CC(SCS)SCS)CC(SCS)SCS FHKCCRRDKWJYCG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- NQFUSWIGRKFAHK-BDNRQGISSA-N alpha-Pinene epoxide Natural products C([C@@H]1O[C@@]11C)[C@@H]2C(C)(C)[C@H]1C2 NQFUSWIGRKFAHK-BDNRQGISSA-N 0.000 description 1
- 229930006723 alpha-pinene oxide Natural products 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BFNMYGGAHBQEHW-UHFFFAOYSA-N sulfanylmethylsulfanyl-[3-(sulfanylmethylsulfanyl)propylsulfanylmethylsulfanylmethylsulfanyl]methanethiol Chemical compound SCSC(SCSCSCCCSCS)S BFNMYGGAHBQEHW-UHFFFAOYSA-N 0.000 description 1
- OOZWJYRXTAYWTJ-UHFFFAOYSA-N sulfanylmethylsulfanyl-[3-[3-(sulfanylmethylsulfanyl)propylsulfanylmethylsulfanyl]propylsulfanylmethylsulfanylmethylsulfanyl]methanethiol Chemical compound SCSCCCSCSCCCSCSCSC(S)SCS OOZWJYRXTAYWTJ-UHFFFAOYSA-N 0.000 description 1
- QMHKMLUVKWZPCH-UHFFFAOYSA-N sulfanylmethylsulfanyl-[3-[3-(sulfanylmethylsulfanyl)propylsulfanylmethylsulfanylmethylsulfanylmethylsulfanyl]propylsulfanyl]methanethiol Chemical compound SCSCCCSCSCSCSCCCSC(S)SCS QMHKMLUVKWZPCH-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- IJJNTMLAAKKCML-UHFFFAOYSA-N tribenzyl borate Chemical compound C=1C=CC=CC=1COB(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 IJJNTMLAAKKCML-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- BOOITXALNJLNMB-UHFFFAOYSA-N tricyclohexyl borate Chemical compound C1CCCCC1OB(OC1CCCCC1)OC1CCCCC1 BOOITXALNJLNMB-UHFFFAOYSA-N 0.000 description 1
- HWJYGSDXNANCJM-UHFFFAOYSA-N tridodecyl borate Chemical compound CCCCCCCCCCCCOB(OCCCCCCCCCCCC)OCCCCCCCCCCCC HWJYGSDXNANCJM-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WZGVRXXJKGXOBR-UHFFFAOYSA-N trihexadecyl borate Chemical compound CCCCCCCCCCCCCCCCOB(OCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCC WZGVRXXJKGXOBR-UHFFFAOYSA-N 0.000 description 1
- KDQYHGMMZKMQAA-UHFFFAOYSA-N trihexyl borate Chemical compound CCCCCCOB(OCCCCCC)OCCCCCC KDQYHGMMZKMQAA-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- QYJYJTDXBIYRHH-UHFFFAOYSA-N trimethoxy-[8-(oxiran-2-ylmethoxy)octyl]silane Chemical compound C(C1CO1)OCCCCCCCC[Si](OC)(OC)OC QYJYJTDXBIYRHH-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- AZLXEMARTGQBEN-UHFFFAOYSA-N trinonyl borate Chemical compound CCCCCCCCCOB(OCCCCCCCCC)OCCCCCCCCC AZLXEMARTGQBEN-UHFFFAOYSA-N 0.000 description 1
- GZKLCETYSGSMRA-UHFFFAOYSA-N trioctadecyl borate Chemical compound CCCCCCCCCCCCCCCCCCOB(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC GZKLCETYSGSMRA-UHFFFAOYSA-N 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- JLPJTCGUKOBWRJ-UHFFFAOYSA-N tripentyl borate Chemical compound CCCCCOB(OCCCCC)OCCCCC JLPJTCGUKOBWRJ-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- DLVYHYUFIXLWKV-UHFFFAOYSA-N tris(2-ethylhexyl) borate Chemical compound CCCCC(CC)COB(OCC(CC)CCCC)OCC(CC)CCCC DLVYHYUFIXLWKV-UHFFFAOYSA-N 0.000 description 1
- RTMBXAOPKJNOGZ-UHFFFAOYSA-N tris(2-methylphenyl) borate Chemical compound CC1=CC=CC=C1OB(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RTMBXAOPKJNOGZ-UHFFFAOYSA-N 0.000 description 1
- RQNVJDSEWRGEQR-UHFFFAOYSA-N tris(prop-2-enyl) borate Chemical compound C=CCOB(OCC=C)OCC=C RQNVJDSEWRGEQR-UHFFFAOYSA-N 0.000 description 1
- WAXLMVCEFHKADZ-UHFFFAOYSA-N tris-decyl borate Chemical compound CCCCCCCCCCOB(OCCCCCCCCCC)OCCCCCCCCCC WAXLMVCEFHKADZ-UHFFFAOYSA-N 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
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Images
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
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
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- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
The present invention relates to: curing in a short time even under low temperature conditions, providing a glass transition temperature (T) g ) An epoxy resin composition which is a cured product having a low tensile strength; a sealing material comprising the epoxy resin composition; a cured product obtained by curing the epoxy resin composition; and an electronic component comprising the cured product. The epoxy resin composition of the present invention provides a cured T g A cured product having a low tensile strength and a high tensile strength is useful as an adhesive, a sealing material, a dam agent, or the like for a semiconductor device or an electronic component.
Description
Technical Field
The present invention relates to an epoxy resin composition, a sealing material containing the same, a cured product obtained by curing the same, and an electronic component containing the cured product.
Background
Conventionally, in the assembly and mounting of electronic components used in semiconductor devices, for example, semiconductor chips, adhesives, sealing materials, and the like containing curable resin compositions, particularly epoxy resin compositions, have been frequently used for the purpose of maintaining reliability and the like. In particular, in the case of a semiconductor device including a member which is deteriorated under high temperature conditions, the manufacturing process thereof needs to be performed under low temperature conditions. Therefore, adhesives and sealing materials used for manufacturing such devices are required to exhibit sufficient curability even under low temperature conditions. For them, curing in a short time is also required at the same time from the aspect of production cost.
The epoxy resin composition (hereinafter, sometimes simply referred to as "curable composition") used for an adhesive or a sealing material for electronic components generally contains an epoxy resin and a curing agent. The epoxy resin includes various polyfunctional epoxy resins (epoxy resins having 2 or more epoxy groups). The curing agent contains a compound having 2 or more functional groups that react with epoxy groups in the epoxy resin. It is known that the type of the curing agent using a thiol curing agent in such a curable composition can be cured in a short time even under a low temperature condition of 0 ℃ to-20 ℃. The thiol curing agent contains a polyfunctional thiol compound which is a compound having 2 or more thiol groups. As an example of such a curable composition, a curable composition disclosed in patent document 1 can be cited.
The epoxy resin composition provides a cured product having various characteristics depending on the composition thereof. In this connection, the glass transition temperature (T) depends on the purpose of use of the curable composition and the like g ) The higher is sometimes not preferred. For example, 2 members each made of a different material may be joined using the curable composition.
When the ambient temperature of an assembly in which 2 parts each made of a different material are bonded to each other by an adhesive is changed, the parts generate thermal stress according to the thermal expansion coefficients of the materials thereof, respectively. The thermal stress is not uniform due to the difference in thermal expansion coefficient and cannot be offset, resulting in deformation of the assembly. Stress associated with the deformation particularly acts on a joint portion of the members, that is, a cured product of the adhesive, and the cured product may be cracked. In particular, when the cured product is brittle and lacks flexibility, such cracks are likely to occur. Therefore, an adhesive for joining members made of different materials needs to have flexibility (low elastic modulus) to such an extent that it can follow deformation of an assembly due to thermal expansion of the members after curing. Therefore, T is required for a cured product g Suitably low.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2012/093510
Disclosure of Invention
[ problems to be solved by the invention ]
However, the present inventors found that: the epoxy resin composition described in the above patent document 1 is T g Sufficiently low and show excellenceThe resin composition has a problem of low tensile strength (Japanese プル strength), though it has a low-temperature curability. Electronic parts sometimes require drop impact resistance, and it is desirable to increase the tensile strength of the adhesive in order to improve the drop impact resistance.
The present invention has been made in view of the above problems, and an object of the present invention is to provide: curing in a short time even under low temperature conditions, providing a glass transition temperature (T) g ) An epoxy resin composition which is a cured product having a low tensile strength; a sealing material comprising the epoxy resin composition. Another object of the present invention is to provide a cured product obtained by curing the epoxy resin composition or the sealing material. Still another object of the present invention is to provide an electronic component comprising the cured product.
Means for solving the problems
Under such circumstances, the present inventors have developed a curing method for curing a curable resin composition in a short time even under low temperature conditions, and have provided a cured resin composition containing T g A curable composition of a cured product having a low tensile strength has been intensively studied. The results are unexpectedly found to be: the curable composition is prepared by using a thiol curing agent and an epoxy resin as components, and further using a crosslink density modifier containing an aromatic monofunctional epoxy resin to adjust the physical property value of a cured product provided from the curable composition to a predetermined range, whereby the resulting cured product has high tensile strength, i.e., excellent drop impact resistance. The present invention has been completed based on the above new findings.
That is, the present invention is not limited to the following, but includes the following inventions.
1. An epoxy resin composition comprising the following components (A) to (D):
component (A): a thiol-based curing agent comprising at least 1 multifunctional thiol compound having 3 or more thiol groups;
component (B): at least 1 multifunctional epoxy resin;
component (C): a crosslink density modifier comprising at least 1 aromatic monofunctional epoxy resin; and
component (D): a curing catalyst, which is used for curing the resin,
the epoxy resin composition provides: a cured product having a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a temperature at which the loss modulus (E') is maximum in a DMA measurement by a stretching method, which is in the range of 20 ℃ to 55 ℃.
2. The epoxy resin composition as described in the above item 1, wherein the molar ratio (B)/(A) of the component (B) to the component (A) is 1.15 or more and 1.45 or less.
3. The epoxy resin composition according to item 1 or 2 above, wherein the molar ratio (C)/(A) of the component (C) to the component (A) is 0.55 to 1.65.
4. The epoxy resin composition as described in any one of the preceding items 1 to 3, wherein the component (C) comprises an aromatic monofunctional epoxy resin.
5. A sealing material comprising the epoxy resin composition as described in any one of the above items 1 to 4.
6. A cured product obtained by curing the epoxy resin composition according to any one of the above items 1 to 4 or the sealing material according to the above item 5.
7. An electronic component comprising the cured product of item 6 above.
Drawings
Fig. 1 is a graph showing the relationship between the corrected tensile strength and the peak temperature (maximum value) of E ″.
Detailed Description
The present invention is described in detail below.
The epoxy resin composition (curable composition) of the present invention contains, as essential components, a thiol curing agent (component (a)), a polyfunctional epoxy resin (component (B)), a crosslinking density modifier (component (C)), and a curing catalyst (component (D)) as described above. These components (A) to (D) will be described below.
In the present specification, in accordance with the common practice in the field of epoxy resins, the name of the term "resin" which is generally used to refer to a polymer (particularly a synthetic polymer) is sometimes used for components constituting an epoxy resin composition before curing, even though the components are not polymers.
(1) Thiol curing agent (component (A))
The thiol curing agent (component (a)) used in the present invention contains at least 1 kind of polyfunctional thiol compound having 3 or more thiol groups that react with epoxy groups in the polyfunctional epoxy resin (component (B)) and the crosslinking density adjusting agent (component (C)) described later. Component (a) preferably comprises 3-functional and/or 4-functional thiol compounds. The mercaptan equivalent is preferably 90 to 150g/eq, more preferably 90 to 140g/eq, and still more preferably 90 to 130 g/eq. The 3-functional and 4-functional thiol compounds are thiol compounds having 3 thiol groups and 4 thiol groups, respectively.
In one embodiment of the present invention, the above-mentioned polyfunctional thiol compound is preferably used as the component (a) containing a non-hydrolyzable polyfunctional thiol compound having no hydrolyzable partial structure such as an ester bond, from the viewpoint of improving the moisture resistance of a cured product. The non-hydrolyzable polyfunctional thiol compound is not easily hydrolyzed even in a high-temperature and high-humidity environment.
In another embodiment of the present invention, the component (a) contains a thiol compound having an ester bond in a molecule and a thiol compound having no ester bond in a molecule. In addition, from low T g From the viewpoint of conversion, the component (a) preferably contains a thiol resin having no urea bond.
Examples of the hydrolyzable polyfunctional thiol compound include: trimethylolpropane tris (3-mercaptopropionate) (manufactured by SC organic Chemicals: TMMP), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate (manufactured by SC organic Chemicals: TEMPIC), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC organic Chemicals: PEMP), tetraethyleneglycol bis (3-mercaptopropionate) (manufactured by SC organic Chemicals: EGMP-4), dipentaerythritol hexa (3-mercaptopropionate) (manufactured by SC organic Chemicals: DPMP), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) PE1), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1, 3, 5-triazine-2, 4,6(1H,3H,5H) -trione (manufactured by Showa Denko K.K.: Karenz MT (registered trademark) NR1), and the like.
Preferred non-hydrolyzable polyfunctional thiol compounds usable in the present invention are compounds represented by the following formula (1):
[ solution 1]
(in the formula, wherein,
R 1 and R 2 Independently selected from hydrogen atom, C1-C12 alkyl or phenyl,
R 3 、R 4 、R 5 and R 6 Each independently selected from mercaptomethyl, mercaptoethyl, and mercaptopropyl).
Examples of the compound represented by the formula (1) include: 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Sizhou chemical industry Co., Ltd.), (1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril (trade name: C3 TS-G, manufactured by Sizhou chemical industry Co., Ltd.), 1,3,4, 6-tetrakis (mercaptomethyl) glycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a-methylglycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a,6 a-dimethylglycoluril, 1,3,4, 6-tetrakis (mercaptomethyl) -3 a,6 a-diphenylglycoluril, 1,3,4, 6-tetrakis (2-mercaptoethyl) -3 a,6 a-diphenylglycoluril, 1,3,4, 6-tetrakis (3-mercaptopropyl) -3 a,6 a-diphenylglycoluril, and the like. These may be used alone or in combination of two or more. Of these, 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril and 1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril are particularly preferable
Other preferred non-hydrolyzable polyfunctional thiol compounds that can be used in the present invention are compounds represented by the following formula (2):
(R 8 ) m －A－(R 7 －SH) n (2)
(in the formula, wherein,
a is a residue of a polyhydric alcohol having n + m hydroxyl groups, containing n + m oxygen atoms derived from the above hydroxyl groups,
each R is 7 Independently an alkylene group having 1 to 10 carbon atoms,
each R is 8 Independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
m is an integer of 0 or more,
n is an integer of 3 or more,
r is as defined above 7 And R 8 Bonded to the above A via the above oxygen atom, respectively).
Two or more compounds represented by formula (2) may be used in combination. Examples of the compound represented by the formula (2) include pentaerythritol tripropylmercaptan (trade name: PEPT, manufactured by SC organic Chemicals) and pentaerythritol tetrapropylmercaptan. Among these, pentaerythritol tripropylmercaptan is particularly preferable.
As the non-hydrolyzable polyfunctional thiol compound, a 3-or more-functional polythiol compound having 2 or more thioether bonds in the molecule may also be used. Examples of such thiol compounds include: 1,2, 3-tris (mercaptomethylthio) propane, 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, 4-mercaptomethyl-1, 8-dimercapto-3, 6-dimercaptoThio groupOctane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, 1,3, 3-tetrakis (mercaptomethylthio) propane, 1,2, 2-tetrakis (mercaptomethylthio) ethane, 1,5, 5-tetrakis (mercaptomethylthio) -3-thiopentane, 1,6, 6-tetrakis (mercaptomethylthio) -3, 4-dithiohexane, 2, 2-bis (mercaptomethylthio) ethanethiol, 3-mercaptomethylthio-1, 7-dimercapto-2, 6-dithioheptane, 3, 6-bis (mercaptomethylthio) -1, 9-dimercapto-2, 5, 8-trithiononane, 3-mercaptomethylthio-1, 6-dimercapto-2, 5-dithiohexane, 1,9, 9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thiopropyl) 3, 7-dithiononane, tris (2, 2-bis (mercaptomethylthio) ethyl) methane, tris (4, 4-bis (mercaptomethylthio) -2-thio) nonaneTetrabutyl) methane, tetrakis (2, 2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, 3,5,9, 11-tetrakis (mercaptomethylthio) -1, 13-dimercapto-2, 6,8, 12-tetrathiotridecane, 3,5,9,11,15, 17-hexakis (mercaptomethylthio) -1, 19-dimercapto-2, 6,8,12,14, 18-hexathiononadecane, 9- (2, 2-bis (mercaptomethylthio) ethyl) -3, 5,13, 15-tetrakis (methylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathioheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathioundecane, 3,4,8,9,13, 14-hexakis (methylthio) -1, 16-dimercapto-2, 5,7,10,12, 15-hexathiohexadecane, 8- [ bis (mercaptomethylthio) methyl]-3, 4,12, 13-tetrakis (mercaptomethylthio) -1, 15-dimercapto-2, 5,7,9,11, 14-hexathiopentadecane, 4, 6-bis [3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithioheptylthio]-1, 3-dithiane, 4- [3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithioheptylthio]-6-mercaptomethylthio-1, 3-dithiane, 1-bis [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-1, 3-bis (mercaptomethylthio) propane, 1- [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-3- [2, 2-bis (mercaptomethylthio) ethyl]-7, 9-bis (mercaptomethylthio) -2, 4,6, 10-tetrathiaundecane, 3- [ 2- (1, 3-dithiocyclobutyl)]Methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- [ 2- (1, 3-dithiocyclobutyl)]Methyl-3, 5,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathiaheptadecane, 3- [ 2- (1, 3-dithiocyclobutyl)]Aliphatic polythiol compounds such as methyl-7, 9,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 4,6,10,12, 16-hexathiaheptadecane; 4, 6-bis [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-6- [ 4- (6-mercaptomethylthio) -1, 3-dithianylthio]-1, 3-dithiane, 4- [3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecanyl]-5-mercaptomethylthio-1, 3-dithiolane, 4, 5-bis [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]-1, 3-dithiolane, 4- [3, 4-bis (mercapto)Methylthio) -6-mercapto-2, 5-dithiohexylthio]-5-mercaptomethylthio-1, 3-dithiolane, 4- [ 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl]-5-mercaptomethylthio-1, 3-dithiolane, 2- { bis [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]Methyl } -1, 3-dithiolane butane, 2- [3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio]Mercaptomethylthiomethyl-1, 3-dithiocyclobutane, 2- [3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio]Mercaptomethylthiomethyl-1, 3-dithiocyclobutane, 2- [ 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl]Mercaptomethylthiomethyl-1, 3-dithiolane, 4- { 1- [ 2- (1, 3-dithiolane butyl)]-3-mercapto-2-thiopropylthio } -5- [1, 2-bis (mercaptomethylthio) -4-mercapto-3-thiobutylthio]Polythiol compounds having a cyclic structure such as 1, 3-dithiolane.
(2) Epoxy resin (component (B))
The epoxy resin (component (B)) used in the present invention is not particularly limited as long as it contains at least 1 kind of polyfunctional epoxy resin. Therefore, conventionally used epoxy resins can be used as the component (B). As described above, the multifunctional epoxy resin means an epoxy resin having 2 or more epoxy groups. In one embodiment of the present invention, the component (B) contains a 2-functional epoxy resin.
The polyfunctional epoxy resin is roughly classified into an aliphatic polyfunctional epoxy resin and an aromatic polyfunctional epoxy resin.
Examples of the aliphatic polyfunctional epoxy resin include:
a diepoxy resin such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether;
-a triglycidyl resin such as trimethylolpropane triglycidyl ether, glycerol triglycidyl ether;
alicyclic epoxy resins such as vinyl (3, 4-cyclohexene) dioxide, 2- (3, 4-epoxycyclohexyl) -5, 1-spiro- (3, 4-epoxycyclohexyl) m-dioxane;
glycidyl amine type epoxy resins such as tetraglycidyl bis (aminomethyl) cyclohexane;
hydantoin type epoxy resins such as 1, 3-diglycidyl-5-methyl-5-ethylhydantoin; and
epoxy resins having a siloxane skeleton such as 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane, and the like, but are not limited thereto.
In the above examples, "cyclohexane type diglycidyl ether" refers to a compound having the following structure: 2 glycidyl groups are bonded to a 2-valent saturated hydrocarbon group having 1 cyclohexane ring as a parent structure via an ether bond. "Dicyclopentadiene-type diglycidyl ether" refers to a compound having the following structure: 2 glycidyl groups are bonded to a 2-valent saturated hydrocarbon group having a dicyclopentadiene skeleton as a parent structure via an ether bond. The aliphatic polyfunctional epoxy resin preferably has an epoxy equivalent of 90 to 450 g/eq. Further, as the cyclohexane type diglycidyl ether, cyclohexanedimethanol diglycidyl ether is particularly preferable.
In one embodiment of the present invention, the component (B) contains an aliphatic multifunctional epoxy resin. When an aliphatic polyfunctional epoxy resin is used as the component (B), the component (a) to be combined preferably contains a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton. The ratio of the epoxy functional group equivalent of the aliphatic polyfunctional epoxy resin to the thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton ([ epoxy functional group equivalent ]/[ thiol functional group equivalent ]) is preferably 0.40 to 0.85.
In a certain embodiment of the present invention, the component (a) contains a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton. When a 3-functional thiol compound or a 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton is used as the component (a), a cyclohexane-type diglycidyl ether or an epoxy resin having a silicone skeleton is preferably used as the component (B). Particular preference is given to using 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane.
In addition, in a certain embodiment of the present invention, the component (a) contains a 3-functional thiol compound or a 4-functional thiol compound having no glycoluril skeleton or isocyanuric acid skeleton (specifically, a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton). In order to set the temperature at which E ″ becomes maximum to a desired range, the total amount of the aliphatic polyfunctional epoxy resin and the 3-functional thiol compound or the 4-functional thiol compound having no glycoluril skeleton or isocyanuric acid skeleton in the epoxy resin composition is preferably 10% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and still more preferably 25% by mass or more and 50% by mass or less.
The aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having a structure containing an aromatic ring such as a benzene ring. The epoxy resins are frequently used in the past, such as bisphenol a type epoxy resins. Examples of the aromatic polyfunctional epoxy resin include:
-bisphenol a type epoxy resins;
a branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether;
-bisphenol F type epoxy resins;
-epoxy resins of the novolac type;
-tetrabromobisphenol a type epoxy resin;
-epoxy resins of the fluorene type;
-biphenyl aralkyl epoxy resins;
diepoxy resins such as 1, 4-phenyl dimethanol diglycidyl ether;
biphenyl type epoxy resins such as 3,3',5,5' -tetramethyl-4, 4' -diglycidyloxybiphenyl;
glycidyl amine type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl p-aminophenol, tetraglycidyl m-xylylenediamine; and
naphthalene ring-containing epoxy resins and the like, but are not limited thereto.
From the viewpoint of compatibility with the thiol compound, the component (B) preferably further contains an aromatic polyfunctional epoxy resin, as compared with the aliphatic polyfunctional epoxy resin. The aromatic polyfunctional epoxy resin is preferably a bisphenol F type epoxy resin, a bisphenol A type epoxy resin or a glycidylamine type epoxy resin, and among these, an epoxy resin having an epoxy equivalent of 90 to 200g/eq is particularly preferable, and an epoxy resin having an epoxy equivalent of 110 to 190g/eq is most preferable.
When an aromatic polyfunctional epoxy resin is used as the component (B), the component (a) to be combined is preferably a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton. The ratio of epoxy functional group equivalent of the aromatic polyfunctional epoxy resin to a thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton ([ epoxy functional group equivalent ]/[ thiol functional group equivalent ]) is preferably 0.30 to 1.10. When a 3-functional thiol compound or a 4-functional thiol compound having a polyether skeleton, a polythioether skeleton or a polyester skeleton is used as the component (a), it is preferable to use at least one of a bisphenol a-type epoxy resin, a bisphenol F-type epoxy resin and a naphthalene ring-containing epoxy resin as the component (B).
In order to set the temperature at which E ″ becomes maximum within a desired range, the total amount of the aromatic epoxy resin (monofunctional or polyfunctional aromatic epoxy resin) and the 3-functional thiol compound or 4-functional thiol compound having a glycoluril skeleton or an isocyanuric acid skeleton in the epoxy resin composition is preferably 45% by mass or more and 90% by mass or less, more preferably 50% by mass or more and 80% by mass or less, and still more preferably 50% by mass or more and 75% by mass or less.
(3) Crosslinking Density modifier (component (C))
The crosslinking density modifier (component (C)) used in the present invention is not particularly limited as long as it contains at least 1 aromatic monofunctional epoxy resin. Monofunctional epoxy resins are epoxy resins having 1 epoxy group, and have been used as reactive diluents for adjusting the viscosity of epoxy resin compositions. Monofunctional epoxy resins are roughly classified into aliphatic monofunctional epoxy resins and aromatic monofunctional epoxy resins. From the viewpoint of volatility, the epoxy equivalent of the component (C) is preferably 180 to 400 g/eq. In the present invention, the component (C) preferably contains an aromatic monofunctional epoxy resin from the viewpoint of viscosity and low volatility. Further, the component (C) is more preferably substantially an aromatic monofunctional epoxy resin.
Examples of the aromatic monofunctional epoxy resin contained in the component (C) include: phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidylphthalimide, etc., but are not limited thereto. Among these, p-tert-butylphenyl glycidyl ether and phenyl glycidyl ether are preferred, and p-tert-butylphenyl glycidyl ether is particularly preferred. Examples of aliphatic monofunctional epoxy resins include: n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α -pinene oxide, allyl glycidyl ether, 1-vinyl-3, 4-epoxycyclohexane, 1, 2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane, 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane, glycidyl neodecanoate, and the like, but are not limited thereto.
(4) Curing catalyst (component (D))
The curing catalyst (component (D)) used in the present invention is not particularly limited as long as it is a curing catalyst for an epoxy resin (component (B)) and a known one can be used. Component (D) is preferably a latent curing catalyst. Latent cure catalysts refer to: the compound which is in an inactive state at room temperature, is activated by heating, and functions as a curing catalyst includes, for example: an imidazole compound which is solid at normal temperature; solid dispersion type amine adduct-based latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct-based); a reaction product of an amine compound with an isocyanate compound or a urea compound (urea-type adduct system), and the like. By using the above-mentioned component (D), the epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.
As typical examples of commercially available products of latent curing catalysts, amine-epoxy adduct systems (amine adduct systems) include: "AMICURE PN-23" (Ajinomoto Fine-Techni Co., trade name), "AMICURE PN-40" (Ajinomoto Fine-Techni Co., trade name), "AMICURE PN-50" (Ajinomoto Fine-Techni Co., trade name), "Harden X-3661S" (ACR Co., trade name), "Harden X-3670S" (ACR Co., trade name), "NOVACURE HXE-3742" (Asahi Kasei Co., trade name), "NOVACURE HXE-3721" (Asahi Kasei Co., trade name), "NOVARE A9322 HP" (Asahi Kasei Co., trade name), "NOVACURE 3922 HP" (Asahi Ka, Su Ka) (Asahi Ka) (Asahi Ka) (Fuji Ka) (Fuji Ko Ka) (Fuji Ka) (Fuji Ka) (Fuji) 5932, Su Ka) (Asahi Ka) (Asahi Ka) (Asahi Ka) (Cui Ka) (Su Ka) (Cui Ka) (Cui Ka) (Su Ka, Ka) (Su Ka) (Su) Ka) (Su Ka, Ka) Ka) (Su) Ka) Ka) (Su) Ka) (Su, Ka, tradename), Ka) (Su) (Cui Ka) Ka, Ka) (Su) (Cui Ka, Ka) (Su Ka) K.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e.e., Trade name), "Fuji Cure FXR-1030" (T & K TOKA, trade name), and the like, but are not limited thereto. The component (D) may be used alone or in combination of two or more. The component (D) is preferably a solid dispersion type amine adduct type latent curing catalyst from the viewpoint of pot life and curability.
The component (D) includes a type provided in the form of a dispersion liquid dispersed in the polyfunctional epoxy resin. It is to be noted that, when the component (D) in this form is used, the amount of the polyfunctional epoxy resin in which the component (D) is dispersed is also included in the amount of the above-mentioned component (B) in the epoxy resin composition of the present invention.
Thiol functional group equivalents refer to: the total number of thiol groups of the thiol compound contained in the component or composition of interest is a quotient obtained by dividing the mass (g) of the thiol compound contained in the component or composition of interest by the thiol equivalent weight of the thiol compound (when a plurality of thiol compounds are contained, the total of the quotient of each thiol compound). The mercaptan equivalent weight can be determined by iodometric titration. This method is well known and is disclosed, for example, in paragraph 0079 of Japanese patent laid-open No. 2012-153794. When the thiol equivalent weight cannot be obtained by this method, it can be calculated as a quotient obtained by dividing the molecular weight of the thiol compound by the number of thiol groups in 1 molecule of the thiol compound.
On the other hand, the epoxy functional group equivalent means: the total number of epoxy groups in the epoxy resins (the above-mentioned components (B) and (C)) contained in the same component or composition is a quotient obtained by dividing the mass (g) of the epoxy resin contained in the component or composition of interest by the epoxy equivalent weight of the epoxy resin (when a plurality of epoxy resins are contained, the total of the quotient of the respective epoxy resins). The epoxy equivalent can be determined by the method described in JIS K7236. When the epoxy equivalent cannot be obtained by this method, the epoxy equivalent can be calculated as a quotient obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups in 1 molecule of the epoxy resin.
The epoxy resin composition having an excess of thiol-based curing agent relative to the epoxy resin provides an initial T g (T immediately after curing g ) Low content of cured product. However, when the thiol curing agent is excessive in amount relative to the epoxy resin, many thiol groups remain in the cured product in an unreacted state without reacting with the epoxy group. The inventors of the present invention found that: although patent document 1 discloses T after the heat resistance test g However, such a composition may be newly crosslinked by excessive thiol groups after a moisture resistance reliability test (particularly, 100 hours in an environment of 85 ℃ and 85%) is performed. As compared with epoxy resins, with respect to thiol-based curing agentsThe crosslinking proceeds more slowly than in the case of the amount, but brings about T g Is increased. In one embodiment of the present invention, therefore, the ratio of the sum of the epoxy functional group equivalents of the components (B) and (C) to the thiol functional group equivalent of the component (a) [ epoxy functional group equivalent ]/[ thiol functional group equivalent ] is preferably 0.70 or more and 1.10 or less, more preferably 0.75 or more and 1.10 or less, and particularly preferably 0.80 or more and 1.05 or less. In such a curable composition, since the epoxy group contained in the component (C) is present to reduce the unreacted thiol group, the unreacted thiol group is mostly eliminated as a result of the reaction between the epoxy group and the epoxy group. The polyfunctional epoxy resin contained in the component (B) has a function of extending polymer chains or forming crosslinks between polymer chains by linking 2 molecules of the polyfunctional thiol compound contained in the component (a). However, since the monofunctional epoxy resin contained in the component (C) does not have such a function, T which causes a cured product to be T can be suppressed by the reaction between the components (A) and (C) g Increased new cross-linking occurs. Therefore, the cured product provided by such a curable composition has a small content of functional groups capable of forming new crosslinks, and therefore, after curing, T associated with the formation of new crosslinks is hardly observed even after a long period of time g Is increased.
In one aspect of the present invention, when the ratio of the sum of the epoxy functional group equivalents of the components (B) and (C) to the thiol functional group equivalent of the component (a) [ epoxy functional group equivalent ]/[ thiol functional group equivalent ] is 0.70 or more and 1.10 or less, both of the epoxy group and the thiol group in the composition participate in the reaction between the epoxy group and the thiol group at a certain ratio or more, and therefore, the properties of the resulting cured product become suitable. When the above ratio is less than 0.70, the thiol group is excessive relative to the epoxy group, so that the number of thiol groups remaining in an unreacted state in the cured product increases, and it becomes difficult to suppress T of the cured product associated with the reaction between the thiol groups g Is increased. On the other hand, when the above ratio exceeds 1.10, the epoxy group is excessive relative to the thiol group, and therefore, in addition to the reaction between the epoxy group and the thiol group, there is also a possibility that the epoxy group and the thiol group may react with each otherA reaction (homopolymerization) between excess epoxy groups is performed. As a result, intermolecular crosslinking by these two reactions is formed in the resulting cured product, and the crosslinking density becomes excessively high, resulting in T g And (4) rising. Alternatively, curing at a low temperature of 80 ℃ for 1 hour or the like becomes difficult.
The curable composition of the present invention may contain any components other than the above-mentioned components (a) to (D), for example, the following components, as required.
Stabilizers
If desired, stabilizers may be added to the epoxy resin composition of the present invention. A stabilizer may be added to the epoxy resin composition of the present invention in order to improve the storage stability and prolong the pot life. Various stabilizers known as stabilizers for one-pack type adhesives mainly composed of epoxy resins can be used, and at least 1 selected from liquid borate compounds, aluminum chelates, and organic acids is preferable from the viewpoint of high effect of improving storage stability.
Examples of the liquid boric acid ester compound include: 2,2 '-oxybis (5, 5' -dimethyl-1, 3, 2-oxahexaborane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7, 10-tetraoxaundecyl) (1,4,7,10, 13-pentaoxatetradecyl) (1,4, 7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tricresyl borate, triethanolamine borate, and the like. The liquid boric acid ester compound is preferably used because it is liquid at room temperature (25 ℃ C.) and the viscosity of the composition is suppressed to a low level. As the aluminum chelate compound, for example, aluminum chelate compound A (available from Chuan Min Kogyo Co., Ltd.) can be used. As the organic acid, barbituric acid, for example, can be used.
When the stabilizer is added, the amount added is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total amount of the components (a) to (D).
Fillers
If desired, a filler may be added to the epoxy resin composition of the present invention. When the epoxy resin composition of the present invention is used as a one-pack adhesive, the moisture resistance and heat cycle resistance, particularly the heat cycle resistance, of the part to be bonded are improved by adding a filler thereto. The reason why the thermal cycle resistance is improved by adding the filler is that the linear expansion coefficient of the cured product is reduced, that is, expansion and contraction of the cured product due to thermal cycle are suppressed.
The filler is not particularly limited as long as it has an effect of reducing the linear expansion coefficient, and various fillers can be used. Specific examples of the filler include a silica filler, an alumina filler, a talc filler, a calcium carbonate filler, a Polytetrafluoroethylene (PTFE) filler, and the like. Among these, silica fillers are preferable because the loading amount can be increased.
When a filler is added, the content of the filler in the epoxy resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 65% by mass, and still more preferably 5 to 50% by mass of the entire epoxy resin composition.
Coupling agent
If desired, a coupling agent may be added to the epoxy resin composition of the present invention. From the viewpoint of improving the adhesive strength, it is preferable to add a coupling agent, particularly a silane coupling agent. As the coupling agent, various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, mercapto and the like can be used. Specific examples of the silane coupling agent include: 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. These silane coupling agents may be used alone or in combination of two or more.
In the epoxy resin composition of the present invention, the amount of the coupling agent to be added is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the components (a) to (D), from the viewpoint of improving the adhesive strength.
Other additives
If desired, other additives such as carbon black, titanium black, ion capturing agents, leveling agents, antioxidants, antifoaming agents, thixotropic agents, viscosity adjusting agents, flame retardants, colorants, solvents, and the like may be added to the epoxy resin composition of the present invention within a range that does not impair the gist of the present invention. The kind and amount of each additive are determined by a conventional method.
The epoxy resin composition of the present invention provides a cured product having a temperature at which the loss modulus (E') is maximized within a range of 20 ℃ to 55 ℃. The loss modulus is an imaginary part of a complex modulus representing a dynamic elastic modulus of an object in a complex number, and is a dissipation energy representing viscoelasticity in a dynamic behavior. In the present specification, unless otherwise specified, the loss modulus represents a value measured by dynamic viscoelasticity measurement (DMA) by a tensile method at a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a strain amplitude of 5.0 μm.
The amount of the components (a) to (D) constituting the epoxy resin composition of the present invention can be adjusted by those skilled in the art so that the cured product provided from the composition has a predetermined loss modulus. Further, a method of measuring the loss modulus is well known, and a person skilled in the art can easily measure the loss modulus by using a conventional dynamic viscoelasticity measuring apparatus.
As described above, the temperature at which such a loss modulus (E') is maximized in the cured product provided by the epoxy resin composition of the present invention is in the range of 20 ℃ to 55 ℃. In the case of an epoxy resin composition having a temperature outside the above range, the tensile strength of the cured product, that is, the drop impact resistance, is not sufficiently improved.
The epoxy resin composition of the present invention provides a cured product having a temperature at which the loss modulus is extremely high, preferably in the range of 20 ℃ to 50 ℃, more preferably 20 ℃ to 45 ℃.
From the viewpoint of the dynamic viscoelasticity of the cured product being as described above, the molar ratio (B)/(a) of the component (B) to the component (a) in the epoxy resin composition of the present invention is preferably 1.15 to 1.45.
For the same reason, in the epoxy resin composition of the present invention, the molar ratio (C)/(a) of the component (C) to the component (a) is 0.55 to 1.65.
The relationship between the molar ratio (B)/(a) of the component (B) and the component (a) means that the crosslinking point of the component (a) containing a thiol compound having 3 or more thiol groups is reduced, and for example, a 2-functional thiol compound or a 3-functional thiol compound is used as long as the thiol compound has 4 thiol groups. If the above ratio is less than 1.15, the amount of the polyfunctional epoxy resin as a crosslinking component is too small, and therefore, the resulting cured product may exhibit properties such as a thermoplastic resin that melts at a high temperature. On the other hand, if the above ratio exceeds 1.45, the polyfunctional epoxy resin as a crosslinking component becomes excessive, and therefore, intermolecular crosslinking due to the reaction of the components (a) and (B) may excessively form in the obtained cured product, and the crosslinking density may become too high, resulting in a decrease in tensile strength.
The relationship between the molar ratio (C)/(a) of the component (C) and the component (a) means that the thiol group of the component (a) is excessively added to the number (amount) of epoxy groups contained in the component (C). Satisfying this relationship is preferable because a cured product having an appropriate crosslink density formed by the reaction of the components (a) and (B) can be obtained.
By satisfying the relationship between the molar ratio (B)/(a) of the component (B) to the component (a) and the molar ratio (C)/(a) of the component (C) to the component (a), the thiol group of the component (a) which does not react with the component (B) reacts with the component (C), and the unreacted thiol group remaining in the cured product is reduced, so that the properties of the obtained cured product become suitable.
The cured product provided by the epoxy resin composition of the present invention exhibits excellent tensile strength particularly for an adherend selected from LCP (liquid crystal polymer), PC (polycarbonate), PBT (polybutylene terephthalate), SUS, alumina, and nickel (including those having a nickel-plated surface). These may be surface-treated by plasma or the like. In the present specification, "tensile strength" typically means the tensile strength when these adherends are made of these materials.
The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the epoxy resin composition of the present invention can be obtained by introducing the components (a) to (D) and, if desired, other additives into an appropriate mixer simultaneously or separately, and stirring and mixing them while melting them by heating if necessary to obtain a uniform composition. The mixer is not particularly limited, and a kneader provided with a stirring device and a heating device, a henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like can be used. These devices may be used in combination as appropriate.
The epoxy resin composition thus obtained is thermosetting, and is preferably cured at a temperature of 80 ℃ within 5 hours, more preferably within 1 hour. In addition, high-temperature and ultra-short-time curing at a temperature of 150 ℃ for several seconds can be realized. When the curable composition of the present invention is used for manufacturing an image sensor module including a component that deteriorates under high temperature conditions, the composition is preferably heat-cured at a temperature of 60 to 90 ℃ for 30 to 120 minutes, or at a temperature of 120 to 200 ℃ for 1 to 300 seconds.
The epoxy resin composition of the present invention cures in a short time even under low temperature conditions and provides T g Low content of cured product. T of cured product of epoxy resin composition of the present invention g Preferably 65 ℃ or lower, more preferably 60 ℃ or lower, and still more preferably 50 DEG CThe following. In addition, from the viewpoint of adhesion, T of cured product g Preferably 30 ℃ or higher, more preferably 32 ℃ or higher. In the present invention, T g The strain amplitude can be determined by a stretching method using a dynamic thermomechanical measuring Device (DMA) under the conditions of a temperature range of-20 ℃ to 110 ℃, a frequency of 1 Hz to 10Hz, a temperature rise rate of 1 ℃/min to 10 ℃/min, and a strain amplitude of 5.0 μm. The preferred frequency is 10Hz, and the preferred rate of temperature rise is 3 deg.C/min. T is g The loss tangent (tan δ) is determined from the peak temperature of the loss tangent (E ″)/storage modulus (E').
The epoxy resin composition of the present invention can be used as an adhesive, a sealing material, a dam agent or a raw material thereof for fixing, bonding or protecting, for example, a semiconductor device including various electronic components, components constituting the electronic components, or the like.
The present invention also provides a sealing material comprising the epoxy resin composition of the present invention. The sealing material of the present invention is suitable as a filling material for protecting and fixing, for example, a module, an electronic component, and the like.
The present invention also provides a cured product obtained by curing the epoxy resin composition or the sealing material of the present invention.
The present invention further provides an electronic component comprising the cured product of the present invention.
[ examples ]
The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and% are parts by mass and% by mass unless otherwise specified.
Examples 1 to 9 and comparative examples 1 to 3
Epoxy resin compositions were prepared by mixing predetermined amounts of the respective components using a three-roll mill in the proportions shown in tables 1 to 2. In tables 1 to 2, the amounts of the respective components are expressed in parts by mass (unit: g).
Thiol curing agent (component (A))
In examples and comparative examples, compounds used as the component (a) are shown below.
(A-1): 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril (trade name: TS-G, manufactured by Siguo Kasei Kogyo Co., Ltd., thiol equivalent: 100)
(A-2): trimethylolpropane tris (3-mercaptomercaptopropionate) (trade name: TMMP, manufactured by SC organic Chemicals, thiol equivalent: 133)
(A-3): pentaerythritol Tetrakis (3-mercaptopropionate) (trade name: PEMP, manufactured by SC organic Chemicals Co., Ltd., thiol equivalent: 122)
Epoxy resin (component (B))
In examples and comparative examples, compounds used as the component (B) are shown below.
(B-1): bisphenol F type epoxy resin (trade name: YDF-8170, made by Nissi iron Corp., epoxy equivalent: 159)
(B-2): bisphenol F epoxy resin-bisphenol A epoxy resin mixture (trade name: EXA-835 LV, manufactured by DIC Co., Ltd.; epoxy equivalent: 165)
(B-3): dicyclopentadiene type epoxy resin (trade name: EP4088L, manufactured by ADEKA Co., Ltd., epoxy equivalent 165)
(B-4): 1, 4-cyclohexanedimethanol diglycidyl ether (trade name: CDMDG, manufactured by Showa Denko K.K.: epoxy equivalent: 133)
(B-5): 1, 3-bis (3-glycidoxypropyl) -1, 1,3, 3-tetramethyldisiloxane (trade name: TSL9906, manufactured by Momentive Performance Materials Japan contract Co., Ltd., epoxy equivalent: 181)
Crosslinking Density adjuster (component (C))
In examples and comparative examples, compounds used as the component (C) are shown below.
(C-1): p-tert-butylphenyl glycidyl ether (trade name: ED509S, manufactured by ADEKA corporation; epoxy equivalent: 205)
(C-2): phenyl glycidyl ether (trade name: DENACOL EX141, manufactured by Nagase ChemteX, epoxy equivalent: 151)
(C-3): 2-ethylhexyl glycidyl ether (trade name: DENACOL EX121, manufactured by Nagase ChemteX, Ltd., epoxy equivalent: 187)
Curing catalyst (component (D))
In examples and comparative examples, compounds used as the component (D) are shown below.
(D-1) amine-epoxy adduct-based latent curing catalyst 1 (trade name: NOVACURE HXA9322HP, manufactured by Asahi Chemicals Co., Ltd.)
The latent curing catalyst (D-1) is provided in the form of: a dispersion liquid in which a fine particle latent curing catalyst was dispersed in an epoxy resin (a mixture of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin (epoxy equivalent: 170)) (latent curing catalyst/a mixture of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin: 33/67 (mass ratio)). (D-1) in tables 1 to 2 represents parts by mass of a dispersion containing a latent curing catalyst. The epoxy resin constituting the dispersion is treated as a substance that becomes a part of the component (B). Accordingly, the epoxy resin in (D-1) is contained in (B) of "(B)/(A) (molar ratio)" in tables 1 to 2.
Other component (E)
In examples and comparative examples, compounds used as the component (E) are shown below.
(E-1): silica Filler 1 (trade name: SE2300, average particle diameter 0.6 μm, manufactured by ADMATECHS Co., Ltd.)
(E-2): silica Filler 2 (trade name: SO-E5, average particle diameter 2.0 μm, manufactured by ADMATECHS Co., Ltd.)
In examples and comparative examples, the properties of cured products obtained by curing the epoxy resin compositions were measured in the following manner.
(preparation of cured product)
The resin compositions of examples 1 to 9 and comparative examples 1 to 3 were heated at 80 ℃ for 120 minutes to obtain cured products.
Loss modulus (E') of cured product
T according to JIS C6481 g The assay of (1). Specifically, a Teflon (registered trademark) sheet was first stuck to the surface of a glass plate having a thickness of 3mm, and 2 positions thereon were set so that the film thickness at the time of curing was 400. + -. 150. mu.mA spacer (formed by overlapping heat-resistant belts) is disposed in the form of m. Then, the resin composition was applied between the spacers, and sandwiched between separate glass plates having a teflon (registered trademark) sheet attached to the surface thereof to avoid inclusion of air bubbles, and the resultant was cured at 80 ℃ for 120 minutes to obtain a cured product. Finally, the cured product was peeled off from the glass plate to which a teflon (registered trademark) sheet was attached, and then cut into a predetermined size (10mm × 40mm) with a knife to obtain a test piece. Note that the cut was smoothed with sandpaper. The loss modulus (E) of the cured product was measured by a tensile method using a dynamic thermomechanical measuring Device (DMA) (manufactured by Seiko Instruments) under conditions of a temperature range of-20 ℃ to 110 ℃, a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a strain amplitude of 5.0 μm, and the temperature (. degree.C.) at which E' reaches the maximum was obtained. The results are shown in tables 1 to 2.
Measured and corrected tensile Strength of cured Material
Spacers (150 μm thick heat-resistant belts) were disposed at 2 positions on an alumina plate 20mm in length by 20mm in width by 1.6mm in thickness. Then, 1mg of the resin composition was applied between the spacers. A square plate (2.5g) having a thickness of 9mm square and subjected to a bright nickel plating treatment was placed on the spacer so as to contact the resin composition applied. Thereafter, the cured product was heated at 80 ℃ for 120 minutes to cure the cured product, thereby obtaining a test piece. The nut was bonded to the upper part of the thick plate of the test piece using a moisture-curable adhesive, and the thick plate and the nut were left to stand for 12 hours to sufficiently join each other in order to prevent peeling between the thick plate and the nut when the tensile strength was measured. Thereafter, the alumina plate was fixed to a precision load measuring instrument (model 1605HTP, manufactured by Aikoh Engineering) so that the adhesion surface became horizontal, and then a rope was passed through the ring of the nut, the rope was attached to a jig, and a pulling load was applied at a speed of 12 mm/min in the vertical direction at 23 ℃. The measured tensile strength was obtained by dividing the maximum load applied until the alumina plate and the thick plate were separated by the bonding area between the alumina plate and the thick plate (N6). Unit is N/mm 2 . Further, from the measured tensile strength, a corrected tensile strength was obtained using the following formula derived from the comparison of examples 1 and 2. Unit is N/mm 2 . The results are shown in tables 1 to 2.
Corrected tensile strength measured tensile strength/((100-content of component (E) (% by weight) × 1.2)/100)
The epoxy resin composition of the present invention can be used by adding the component (E) (filler) as needed, but as is clear from comparison of examples 1 and 2, the actual tensile strength of the cured product tends to decrease when the content of the component (E) (filler) increases. The corrected tensile strength is a tensile strength that cancels out the influence of the component (E).
As is clear from tables 1 to 2, in any of examples 1 to 9, the tensile strength after curing (particularly, the corrected tensile strength) was a satisfactory value.
In contrast, in comparative examples 1 to 2 in which the temperature at which the maximum E' of the cured product is reached is not within the predetermined range and comparative example 3 in which the component (C) is not contained, the tensile strength after curing is insufficient. As is clear from comparative example 3, in the epoxy resin composition having no predetermined composition, the tensile strength after curing is not sufficiently improved even when the temperature at which the maximum E ″ of the cured product is reached is within a predetermined range.
The relationship between the corrected tensile strength and the peak temperature (maximum value) of E' in tables 1-2 is shown in FIG. 1. In FIG. 1, it is seen from the linear relationship between I and II that the tensile strength is increased as the equivalent of the epoxy functional group of the component (C) is increased relative to the equivalent of the thiol functional group of the component (A).
Industrial applicability
The epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions to provide a cured product. The cured product shows a low T g Has appropriate flexibility and pliability. In addition, the cured product shows high tensile strength becauseThus, by using the epoxy resin composition of the present invention, an electronic component having excellent drop impact resistance can be easily produced. Therefore, the epoxy resin composition of the present invention is useful as an adhesive, a sealing material, a dam agent, and the like for a semiconductor device, an electronic component, and the like, in particular, in which a plurality of components made of different materials are joined and assembled.
Claims (6)
1. An epoxy resin composition comprising the following components A to D,
component A: a thiol-based curing agent comprising at least 1 multifunctional thiol compound having 3 or more thiol groups;
component B: at least 12 functional epoxy resin;
component C: a crosslink density modifier comprising at least 1 aromatic monofunctional epoxy resin; and
component D: a curing catalyst is used for curing the epoxy resin,
the molar ratio B/A of the component B to the component A is 1.15 to 1.45,
the molar ratio C/A of the component C to the component A is 0.55 to 1.65,
the epoxy resin composition provides: a cured product having a frequency of 10Hz, a temperature rise rate of 3 ℃/min, and a temperature at which the loss modulus E' is at a maximum in a DMA measurement by a stretching method, which is in the range of 20 ℃ to 55 ℃.
2. The epoxy resin composition according to claim 1, wherein,
component a comprises a thiol compound having 3 or 4 thiol groups.
3. The epoxy resin composition according to claim 1 or 2, wherein,
the ratio of the sum of the epoxy functional group equivalents of the component B and the component C to the thiol functional group equivalent of the component A, that is, the epoxy functional group equivalent/thiol functional group equivalent is 0.70 to 1.10,
the thiol functional group equivalent means the total number of thiol groups of the thiol compound contained in component a,
the epoxy functional group equivalent means the total number of epoxy groups of the epoxy resin contained in the component B and the component C.
4. A sealing material comprising the epoxy resin composition as claimed in any one of claims 1 to 3.
5. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 3 or the sealing material according to claim 4.
6. An electronic component comprising the cured product according to claim 5.
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| JP2019-151618 | 2019-08-21 | ||
| PCT/JP2019/032925 WO2021033329A1 (en) | 2019-08-21 | 2019-08-22 | Epoxy resin composition |
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| WO2024024881A1 (en) * | 2022-07-29 | 2024-02-01 | 株式会社スリーボンド | Epoxy resin composition |
| WO2024090259A1 (en) * | 2022-10-28 | 2024-05-02 | ナミックス株式会社 | Resin composition, adhesive, sealing material, cured product, semiconductor device, and electronic component |
| JP7217565B1 (en) | 2022-10-28 | 2023-02-03 | ナミックス株式会社 | Resin compositions, adhesives, sealing materials, cured products, semiconductor devices and electronic components |
| JP7217566B1 (en) | 2022-10-28 | 2023-02-03 | ナミックス株式会社 | Resin compositions, adhesives, sealing materials, cured products and semiconductor devices |
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| TWI826714B (en) | 2023-12-21 |
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