TWI835960B - Sealing composition and semiconductor device - Google Patents
Sealing composition and semiconductor device Download PDFInfo
- Publication number
- TWI835960B TWI835960B TW108147087A TW108147087A TWI835960B TW I835960 B TWI835960 B TW I835960B TW 108147087 A TW108147087 A TW 108147087A TW 108147087 A TW108147087 A TW 108147087A TW I835960 B TWI835960 B TW I835960B
- Authority
- TW
- Taiwan
- Prior art keywords
- sealing composition
- mass
- group
- inorganic filler
- hardener
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 238000007789 sealing Methods 0.000 title claims abstract description 108
- 239000004065 semiconductor Substances 0.000 title claims description 26
- -1 silane compound Chemical class 0.000 claims abstract description 84
- 239000011256 inorganic filler Substances 0.000 claims abstract description 61
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 61
- 229910000077 silane Inorganic materials 0.000 claims abstract description 47
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000004848 polyfunctional curative Substances 0.000 claims description 44
- 239000005011 phenolic resin Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000002430 hydrocarbons Chemical group 0.000 claims description 23
- 125000000524 functional group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 23
- 239000007822 coupling agent Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 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 11
- 150000001875 compounds Chemical class 0.000 description 11
- 150000002989 phenols Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 239000002516 radical scavenger Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
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- 239000000654 additive Substances 0.000 description 6
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- 238000011156 evaluation Methods 0.000 description 6
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- 239000003566 sealing material Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
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- 125000004429 atom Chemical group 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 125000001424 substituent group Chemical group 0.000 description 5
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- 239000003054 catalyst Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- 229910052698 phosphorus Inorganic materials 0.000 description 4
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- GAYWTJPBIQKDRC-UHFFFAOYSA-N 8-trimethoxysilyloctyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCOC(=O)C(C)=C GAYWTJPBIQKDRC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 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 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
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- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 2
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- UIXPTCZPFCVOQF-UHFFFAOYSA-N ubiquinone-0 Chemical compound COC1=C(OC)C(=O)C(C)=CC1=O UIXPTCZPFCVOQF-UHFFFAOYSA-N 0.000 description 2
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- XGINAUQXFXVBND-UHFFFAOYSA-N 1,2,6,7,8,8a-hexahydropyrrolo[1,2-a]pyrimidine Chemical compound N1CC=CN2CCCC21 XGINAUQXFXVBND-UHFFFAOYSA-N 0.000 description 1
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- 125000004104 aryloxy group Chemical group 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
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- 150000001638 boron Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 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 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VRINOTYEGADLMW-UHFFFAOYSA-N heptyl(trimethoxy)silane Chemical compound CCCCCCC[Si](OC)(OC)OC VRINOTYEGADLMW-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical compound C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical group C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- SAWDTKLQESXBDN-UHFFFAOYSA-N triethoxy(heptyl)silane Chemical compound CCCCCCC[Si](OCC)(OCC)OCC SAWDTKLQESXBDN-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- VRHBBGAASHNPHT-UHFFFAOYSA-N trimethoxy-[6-(oxiran-2-ylmethoxy)hexyl]silane Chemical compound CO[Si](OC)(OC)CCCCCCOCC1CO1 VRHBBGAASHNPHT-UHFFFAOYSA-N 0.000 description 1
- ITQVMIOKEJEYEZ-UHFFFAOYSA-N trimethoxy-[7-(oxiran-2-ylmethoxy)heptyl]silane Chemical compound CO[Si](OC)(OC)CCCCCCCOCC1CO1 ITQVMIOKEJEYEZ-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- 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
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本揭示是有關於一種密封組成物及半導體裝置。 The present disclosure relates to a sealing composition and a semiconductor device.
近年來,伴隨小型化及高積體化,擔心半導體封裝體內部的發熱。由於存在因發熱而產生具有半導體封裝體的電氣零件或電子零件的性能下降之虞,因此對半導體封裝體中所使用的構件要求高的導熱性。因此,要求對半導體封裝體的密封材進行高導熱化。 In recent years, with the trend of miniaturization and high integration, there are concerns about heat generation inside semiconductor packages. Since there is a risk of performance degradation of electrical or electronic components with semiconductor packages due to heat generation, high thermal conductivity is required for components used in semiconductor packages. Therefore, it is required that the sealing material of the semiconductor package has high thermal conductivity.
例如,藉由高填充無機填充材,密封材的高導熱化成為可能。 For example, high thermal conductivity of sealing materials is possible through high filling of inorganic fillers.
作為高填充有無機填充材的密封材的例子,已知有一種半導體密封用環氧樹脂組成物,其以(A)環氧樹脂、(B)硬化劑以及(D)含有球狀氧化鋁及球狀二氧化矽的無機填充材為必需成分,所述半導體密封用環氧樹脂組成物的特徵在於,所述球狀氧化鋁包含(d1)平均粒徑40μm以上且70μm以下的第一球狀氧化鋁及(d2)平均粒徑10μm以上且15μm以下的第二球狀氧化鋁,所述球狀二氧化矽包含(d3)平均粒徑4μm以上且8μm以 下的第一球狀二氧化矽、(d4)平均粒徑0.05μm以上~1.0μm以下的第二球狀二氧化矽,相對於全部無機填充材(d3)+(d4)的合計量為17%以上且23%以下,(d3)/(d4)的比率為(d3)/(d4)=1/8以上且5/4以下,無機填充劑量在全部樹脂組成物中為85質量%~95質量%(例如,參照專利文獻1)。 As an example of a sealing material highly filled with an inorganic filler, there is known an epoxy resin composition for semiconductor sealing, which has (A) an epoxy resin, (B) a hardener, and (D) an inorganic filler containing spherical alumina and spherical silica as essential components, wherein the spherical alumina comprises (d1) a first spherical alumina having an average particle size of 40 μm or more and 70 μm or less and (d2) a second spherical alumina having an average particle size of 10 μm or more and 15 μm or less, wherein the spherical alumina comprises (d2) a first spherical alumina having an average particle size of 10 μm or more and (d3) a second spherical alumina having an average particle size of 10 μm or more and (d4) a second spherical alumina having an average particle size of 15 μm or less. The silicon oxide includes (d3) a first spherical silicon dioxide having an average particle size of 4 μm or more and 8 μm or less, (d4) a second spherical silicon dioxide having an average particle size of 0.05 μm or more and 1.0 μm or less, the total amount of (d3) + (d4) relative to all inorganic fillers is 17% or more and 23% or less, the ratio of (d3) / (d4) is (d3) / (d4) = 1/8 or more and 5/4 or less, and the amount of the inorganic filler in the entire resin composition is 85% by mass to 95% by mass (for example, refer to Patent Document 1).
[現有技術文獻] [Prior art documents]
[專利文獻] [Patent Document]
[專利文獻1]日本專利特開2006-273920號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-273920
但是,在專利文獻1中記載的半導體密封用環氧樹脂組成物中,雖藉由高填充作為高導熱填料的氧化鋁,可獲得導熱性高的硬化物,但存在密封材的流動性下降的情況。因此,難題是流動性高的高導熱密封材的開發。 However, in the epoxy resin composition for semiconductor sealing described in Patent Document 1, a cured product with high thermal conductivity can be obtained by high filling of alumina as a highly thermally conductive filler, but there is a problem that the fluidity of the sealing material decreases. condition. Therefore, the difficult problem is the development of high thermal conductivity sealing materials with high fluidity.
根據本發明的一實施形態,提供一種可兼顧導熱性高的硬化物的獲得與流動性的提高的密封組成物以及使用了密封組成物的半導體裝置。 According to one embodiment of the present invention, there are provided a sealing composition that can achieve both the acquisition of a hardened material with high thermal conductivity and improvement in fluidity, and a semiconductor device using the sealing composition.
本發明包含以下的實施形態。 The present invention includes the following implementation forms.
<1> <1>
一種密封組成物,含有: 環氧樹脂;硬化劑;無機填充材,包含比表面積為100m2/g以上的二氧化矽粒子;以及矽烷化合物,具有碳數6以上的鏈狀烴基鍵結於矽原子的結構。 A sealing composition containing: epoxy resin; hardener; inorganic filler, including silica particles with a specific surface area of 100 m 2 /g or more; and a silane compound having a chain hydrocarbon group with a carbon number of 6 or more bonded to the silicon The structure of atoms.
<2> <2>
如<1>所述的密封組成物,其中將密封組成物在硬化溫度175℃及硬化時間90秒的條件下加熱硬化時所獲得的硬化物的蕭氏D所表示的熱時硬度為70以上。 The sealing composition as described in <1>, wherein the hot hardness of the cured product obtained by heat curing the sealing composition at a curing temperature of 175°C and a curing time of 90 seconds is 70 or more as indicated by Shaw's D.
<3> <3>
如<1>或<2>所述的密封組成物,其中相對於密封組成物整體,所述無機填充材的含有率為78體積%以上。 The sealing composition according to <1> or <2>, wherein the content of the inorganic filler is 78 volume % or more relative to the entire sealing composition.
<4> <4>
如<1>至<3>中任一項所述的密封組成物,其中所述硬化劑含有多官能酚樹脂硬化劑。 The sealing composition according to any one of <1> to <3>, wherein the hardener contains a polyfunctional phenol resin hardener.
<5> <5>
如<1>至<4>中任一項所述的密封組成物,其中所述硬化劑含有三苯基甲烷型酚樹脂。 A sealing composition as described in any one of <1> to <4>, wherein the hardener contains a triphenylmethane type phenol resin.
<6> <6>
如<1>至<5>中任一項所述的密封組成物,其中所述鏈狀烴基具有選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中 的至少一個官能基。 A sealing composition as described in any one of <1> to <5>, wherein the chain alkyl group has at least one functional group selected from the group consisting of (meth)acryl group, epoxy group and alkoxy group.
<7> <7>
如<1>至<6>中任一項所述的密封組成物,其中所述鏈狀烴基具有(甲基)丙烯醯基。 The sealing composition according to any one of <1> to <6>, wherein the chain hydrocarbon group has a (meth)acrylyl group.
<8> <8>
一種半導體裝置,包含半導體元件、以及將所述半導體元件密封的如<1>至<7>中任一項所述的密封組成物的硬化物。 A semiconductor device comprising a semiconductor element and a cured product of the sealing composition described in any one of <1> to <7> for sealing the semiconductor element.
根據本發明的一實施形態,提供一種可兼顧導熱性高的硬化物的獲得與流動性的提高的密封組成物以及使用了密封組成物的半導體裝置。 According to one embodiment of the present invention, a sealing composition that can achieve both the acquisition of a hardened material with high thermal conductivity and the improvement of fluidity and a semiconductor device using the sealing composition are provided.
以下,對用以實施本揭示的密封組成物及半導體裝置的形態進行詳細說明。其中,本發明並不限定於以下的實施形態。在以下的實施形態中,其構成要素(例如亦包括要素步驟等)除特別明示的情況以外,並非必需。關於數值及其範圍亦同樣,並不限制本發明。 Hereinafter, the sealing composition and the form of the semiconductor device used for implementing this disclosure will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (for example, including element steps) are not essential unless otherwise expressly stated. The same applies to numerical values and their ranges, which do not limit the present invention.
在本揭示中,使用「~」所表示的數值範圍中包含「~」 的前後所記載的數值分別作為最小值及最大值。 In this disclosure, the numerical range represented by "~" includes the numerical values recorded before and after "~" as the minimum value and the maximum value, respectively.
在本揭示中階段性記載的數值範圍中,一個數值範圍所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。而且,在本揭示中所記載的數值範圍中,該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 In the numerical range recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can also be replaced by the upper limit or lower limit of another numerical range recorded in stages. Moreover, in the numerical range recorded in this disclosure, the upper limit or lower limit of the numerical range can also be replaced by the value shown in the embodiment.
在本揭示中,各成分亦可包含多種相符的物質。當在組成物中存在多種與各成分相符的物質時,只要無特別說明,則各成分的含有率或含量是指組成物中所存在的該多種物質的合計含有率或含量。 In this disclosure, each component may also include a variety of consistent substances. When there are multiple substances corresponding to each component in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the multiple substances present in the composition.
在本揭示中,亦可包含多種與各成分相符的粒子。當在組成物中存在多種與各成分相符的粒子時,只要無特別說明,則各成分的粒徑是指關於組成物中所存在的該多種粒子的混合物的值。 In the present disclosure, multiple types of particles corresponding to each component may also be included. When multiple types of particles corresponding to each component exist in a composition, unless otherwise specified, the particle size of each component refers to the value of the mixture of the multiple types of particles present in the composition.
在本揭示中,「(甲基)丙烯醯基」是指丙烯醯基及甲基丙烯醯基中的至少一者,「(甲基)丙烯酸」是指丙烯酸及甲基丙烯酸中的至少一者,「(甲基)丙烯酸酯」是指丙烯酸酯及甲基丙烯酸酯中的至少一者。 In this disclosure, "(meth)acrylyl" refers to at least one of acrylic acid and methacrylic acid, and "(meth)acrylic acid" refers to at least one of acrylic acid and methacrylic acid. , "(meth)acrylate" refers to at least one of acrylate and methacrylate.
<密封組成物> <Sealing composition>
本揭示的密封組成物含有:環氧樹脂;硬化劑;無機填充材,包含比表面積為100m2/g以上的二氧化矽粒子;以及矽烷化合物,具有碳數6以上的鏈狀烴基鍵結於矽原子的結構。 The sealing composition disclosed herein comprises: epoxy resin; hardener; inorganic filler including silicon dioxide particles with a specific surface area of 100 m 2 /g or more; and silane compound having a structure in which a chain hydrocarbon group with 6 or more carbon atoms is bonded to silicon atoms.
以下,有時將比表面積為100m2/g以上的二氧化矽粒子稱為「特定二氧化矽粒子」,將具有碳數6以上的鏈狀烴基鍵結於矽原 子的結構的矽烷化合物稱為「特定矽烷化合物」。 Hereinafter, silica particles having a specific surface area of 100 m 2 /g or more may be referred to as "specific silica particles", and a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to silicon atoms may be referred to as "specific silane compound".
本揭示的密封組成物含有所述特定矽烷化合物,因此可兼顧導熱性高的硬化物的獲得與流動性的提高。 The sealing composition disclosed herein contains the specific silane compound, so that it can obtain a cured product with high thermal conductivity and improve fluidity.
一般而言,藉由高填充無機填充材,可獲得導熱性高的硬化物。但是,若不斷提高無機填充材的填充量,則除了流動性容易下降以外,亦存在即便進而提高無機填充材的填充量,硬化物的導熱性亦不易上升,而導熱性成為飽和狀態的情況。相對於此,本揭示的密封組成物中含有所述特定矽烷化合物,藉此相較於不含特定矽烷化合物的情況,流動性高,可藉由提高無機填充材的填充量來提高硬化物的導熱性。其原因雖不確定,但認為藉由含有特定矽烷化合物,密封組成物內的無機填充材的分散性提高,藉此密封組成物的流動性提高,並且容易發揮無機填充材提高導熱性的功能。根據以上的內容推測:本揭示的密封組成物可兼顧導熱性高的硬化物的獲得與流動性的提高。 Generally speaking, a hardened material with high thermal conductivity can be obtained by highly filling the inorganic filler. However, if the filling amount of the inorganic filler is continuously increased, the fluidity is likely to decrease. Even if the filling amount of the inorganic filler is further increased, the thermal conductivity of the cured product is not likely to increase, and the thermal conductivity may become saturated. On the other hand, since the sealing composition of the present disclosure contains the specific silane compound, it has higher fluidity than the case where the specific silane compound is not contained, and can increase the filling amount of the inorganic filler to improve the strength of the cured product. Thermal conductivity. Although the reason for this is not certain, it is believed that the inclusion of a specific silane compound improves the dispersibility of the inorganic filler in the sealing composition, thereby improving the fluidity of the sealing composition and making it easier for the inorganic filler to exert its function of improving thermal conductivity. Based on the above, it is speculated that the sealing composition of the present disclosure can achieve both the acquisition of a hardened material with high thermal conductivity and the improvement of fluidity.
以下,對構成密封組成物的各成分進行說明。本揭示的密封組成物含有環氧樹脂、硬化劑、以及無機填充材,視需要亦可含有其他成分。 Each component constituting the sealing composition will be described below. The sealing composition of the present disclosure contains epoxy resin, hardener, and inorganic filler, and may also contain other components if necessary.
-環氧樹脂- -Epoxy resin-
本揭示的密封組成物含有環氧樹脂。環氧樹脂的種類並無特別限定,可使用公知的環氧樹脂。 The sealing composition disclosed herein contains an epoxy resin. The type of epoxy resin is not particularly limited, and a known epoxy resin can be used.
作為環氧樹脂的具體例,可列舉:將使選自由苯酚化合物(苯酚、甲酚、二甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F等)以 及萘酚化合物(α-萘酚、β-萘酚、二羥基萘等)所組成的群組中的至少一種、與醛化合物(甲醛、乙醛、丙醛、苯甲醛、水楊醛等)在酸性觸媒下縮合或共縮合而獲得的酚醛清漆樹脂環氧化而得者(苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂等);選自由雙酚(雙酚A、雙酚AD、雙酚F、雙酚S等)及聯苯酚(經烷基取代或未經取代的聯苯酚等)所組成的群組中的至少一種二縮水甘油醚;苯酚.芳烷基樹脂的環氧化物;苯酚化合物與選自由二環戊二烯及萜烯化合物所組成的群組中的至少一種的加成物或聚合加成物的環氧化物;藉由多元酸(鄰苯二甲酸、二聚物酸等)與表氯醇的反應而獲得的縮水甘油酯型環氧樹脂;藉由多胺(二胺基二苯基甲烷、異三聚氰酸等)與表氯醇的反應而獲得的縮水甘油胺型環氧樹脂;利用過氧酸(過乙酸等)對烯烴鍵進行氧化而獲得的線狀脂肪族環氧樹脂;脂環族環氧樹脂等。環氧樹脂可單獨使用一種,亦可併用兩種以上。 Specific examples of the epoxy resin include those selected from phenol compounds (phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc.) and and at least one of the group consisting of naphthol compounds (α-naphthol, β-naphthol, dihydroxynaphthalene, etc.), and aldehyde compounds (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc.) Novolac resin obtained by epoxidation by condensation or co-condensation under an acidic catalyst (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.); selected from bisphenols (bisphenol A, At least one diglycidyl ether in the group consisting of bisphenol AD, bisphenol F, bisphenol S, etc.) and bisphenol (alkyl-substituted or unsubstituted bisphenol, etc.); phenol. Epoxides of aralkyl resins; epoxides of adducts or polymeric adducts of phenolic compounds and at least one selected from the group consisting of dicyclopentadiene and terpene compounds; by polybasic acids Glycidyl ester type epoxy resin obtained by the reaction of (phthalic acid, dimer acid, etc.) and epichlorohydrin; by reacting polyamine (diaminodiphenylmethane, isocyanuric acid, etc.) with Glycidyl amine type epoxy resin obtained by the reaction of epichlorohydrin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peroxyacid (peracetic acid, etc.); alicyclic epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.
就積體電路(Integrated Circuit,IC)等的元件上的鋁配線或銅配線的防腐蝕的觀點而言,環氧樹脂的純度以高為佳,水解性氯量以少為佳。就提高密封組成物的耐濕性的觀點而言,水解性氯量較佳為以質量基準計為500ppm以下。 From the viewpoint of anti-corrosion of aluminum wiring or copper wiring on components such as integrated circuits (ICs), the purity of the epoxy resin is preferably high, and the amount of hydrolyzable chlorine is preferably small. From the viewpoint of improving the moisture resistance of the sealing composition, the amount of hydrolyzable chlorine is preferably 500 ppm or less on a mass basis.
此處,水解性氯量是藉由將作為試樣的環氧樹脂1g溶解於二噁烷30mL中,添加1N-KOH甲醇溶液5mL回流(reflux)30分鐘後,藉由電位滴定求出的值。 Here, the amount of hydrolyzable chlorine is a value determined by potentiometric titration after dissolving 1 g of epoxy resin as a sample in 30 mL of dioxane, adding 5 mL of 1N-KOH methanol solution, and refluxing for 30 minutes. .
關於環氧樹脂的熔點或軟化點,就密封組成物的成形性 的觀點而言,較佳為50℃以上,就兼顧密封組成物的成形性與混煉性的觀點而言,較佳為50℃~150℃,更佳為60℃~130℃,進而佳為70℃~120℃。 Regarding the melting point or softening point of the epoxy resin, the formability of the sealing composition From the viewpoint of both the formability and kneadability of the sealing composition, it is preferably 50°C to 150°C, more preferably 60°C to 130°C, and still more preferably 70℃~120℃.
此處,環氧樹脂的熔點設為利用示差掃描熱量測定(DSC)所測定的值,環氧樹脂的軟化點設為利用依據日本工業標準(Japanese Industrial Standards,JIS)K 7234:1986的方法(環球法)所測定的值。 Here, the melting point of the epoxy resin is set to a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is set to a value measured by a method (global method) in accordance with Japanese Industrial Standards (JIS) K 7234:1986.
環氧樹脂的環氧基當量並無特別限定,較佳為不足300g/eq,就成形性的觀點而言,更佳為120g/eq~270g/eq,進而佳為150g/eq~240g/eq。 The epoxy group equivalent of the epoxy resin is not particularly limited, but is preferably less than 300 g/eq. From the perspective of formability, it is more preferably 120 g/eq to 270 g/eq, and further preferably 150 g/eq to 240 g/eq.
所述「環氧基當量」是藉由秤量成為測定對象的環氧樹脂使其溶解於甲基乙基酮等的溶劑中,並加入乙酸與溴化四乙基銨乙酸溶液後,利用過氯酸乙酸標準液進行電位滴定,而進行測定。該滴定中亦可使用指示劑。 The "epoxy equivalent" is measured by weighing the epoxy resin to be measured, dissolving it in a solvent such as methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide acetic acid solution, and then performing potentiometric titration with a perchloric acid acetic acid standard solution. An indicator can also be used in this titration.
環氧樹脂在分子內具有至少兩個以上的環氧基。環氧樹脂在一分子中所具有的環氧基的數量並無特別限定,可列舉2~8,較佳為2~6,更佳為2~3,特佳為2。 The epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups in one molecule of the epoxy resin is not particularly limited, and can be 2 to 8, preferably 2 to 6, more preferably 2 to 3, and particularly preferably 2.
另外,所述環氧基亦可作為選自由縮水甘油基、縮水甘油基氧基、縮水甘油基氧基羰基、環氧基環烷基(環氧基環戊基、環氧基環己基、環氧基環辛基等)所組成的群組中的至少一種的一部分而包含在第一環氧樹脂的分子中。 In addition, the epoxy group may be included in the molecule of the first epoxy resin as a part of at least one selected from the group consisting of glycidyl, glycidyloxy, glycidyloxycarbonyl, and epoxycycloalkyl (epoxycyclopentyl, epoxycyclohexyl, epoxycyclooctyl, etc.).
環氧樹脂較佳為在分子內除了兩個以上的環氧基以 外,亦具有下述通式(1)所表示的二價的連結基。 The epoxy resin preferably has a divalent linking group represented by the following general formula (1) in addition to two or more epoxy groups in the molecule.
另外,下述通式(1)中,*表示鍵結部,R1~R8分別獨立地表示氫原子、碳數1~12的烷基或碳數4~18的芳香族基。 In the following general formula (1), * represents a bonding portion, and R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms.
所述通式(1)中,R1~R4分別獨立地較佳為氫原子或碳數1~3的烷基,更佳為氫原子或甲基,進而佳為甲基。 In the general formula (1), R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group.
而且,所述通式(1)中,R5~R8分別獨立地較佳為氫原子或碳數1~3的烷基,更佳為氫原子或甲基,進而佳為氫原子。 Furthermore, in the general formula (1), R 5 to R 8 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
環氧樹脂在密封組成物中所占的含有率較佳為2.5質量%~6質量%,更佳為2.8質量%~5.5質量%,進而佳為3.0質量%~5.0質量%。 The content of epoxy resin in the sealing composition is preferably 2.5% to 6% by mass, more preferably 2.8% to 5.5% by mass, and even more preferably 3.0% to 5.0% by mass.
環氧樹脂在除去無機填充材的密封組成物中所占的含有率較佳為40質量%~70質量%,更佳為45質量%~64質量%,進而佳為48質量%~55質量%。 The content rate of the epoxy resin in the sealing composition excluding the inorganic filler is preferably 40 mass% to 70 mass%, more preferably 45 mass% to 64 mass%, further preferably 48 mass% to 55 mass% .
-硬化劑- -Hardener-
本揭示的密封組成物含有硬化劑。硬化劑的種類並無特別限定,可使用公知的硬化劑。 The sealing composition of the present disclosure contains a hardener. The type of hardener is not particularly limited, and a known hardener can be used.
作為硬化劑,可列舉:酚硬化劑、胺硬化劑、酸酐硬化劑、聚硫醇硬化劑、聚胺基醯胺硬化劑、異氰酸酯硬化劑、嵌段異氰酸酯硬化劑等。就獲得維持流動性且耐回流(reflow)性優異的密封組成物的觀點而言,硬化劑較佳為酚硬化劑、胺硬化劑及酸酐硬化劑,更佳為酚硬化劑。硬化劑可單獨使用一種,亦可併用兩種以上。 As hardeners, there can be listed: phenol hardeners, amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, blocked isocyanate hardeners, etc. From the perspective of obtaining a sealing composition that maintains fluidity and has excellent reflow resistance, the hardener is preferably a phenol hardener, an amine hardener, and an acid anhydride hardener, and more preferably a phenol hardener. The hardener may be used alone or in combination of two or more.
作為酚硬化劑,可列舉在一分子中具有兩個以上的酚性羥基的酚樹脂、多元酚化合物等。具體而言,作為酚硬化劑,可列舉:間苯二酚、兒茶酚、雙酚A、雙酚F、經取代或未經取代的雙酚等多元酚化合物;使選自由苯酚、甲酚、二甲苯酚、間苯二酚、兒茶酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組中的至少一種酚性化合物與甲醛、乙醛、丙醛等醛化合物在酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂;由所述酚性化合物與二甲氧基對二甲苯(p-xylene)、雙(甲氧基甲基)聯苯等合成的芳烷基型酚樹脂(苯酚芳烷基樹脂、萘酚芳烷基樹脂等);對伸二甲苯(p-xylylene)改質酚樹脂;間伸二甲苯(m-xylylene)改質酚樹脂;三聚氰胺改質酚樹脂;萜烯改質酚樹脂;藉由所述酚性化合物與二環戊二烯的共聚而合成的二環戊二烯型苯酚樹脂及二環戊二烯型萘酚樹脂;環戊二烯改質酚樹脂;多環芳香環改質酚樹脂; 聯苯型酚樹脂;使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物在酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂;將該些兩種以上共聚而獲得的酚樹脂等。該些酚樹脂及多元酚化合物可單獨使用一種,亦可組合兩種以上來使用。 Examples of the phenol curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, examples of the phenol hardener include polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted bisphenols; selected from the group consisting of phenol and cresol , xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenol compounds and α-naphthol, β-naphthol, dihydroxynaphthol and other naphthol compounds A novolac-type phenolic resin obtained by condensation or co-condensation of at least one phenolic compound in the group and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; the phenolic compound and dimethyl Aralkyl-type phenol resins (phenol aralkyl resin, naphthol aralkyl resin, etc.) synthesized from oxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; p-xylene ( p-xylylene) modified phenol resin; m-xylylene (m-xylylene) modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; by copolymerization of the phenolic compound and dicyclopentadiene The synthesized dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; Biphenyl-type phenol resin; triphenylmethane-type phenol resin obtained by condensing or co-condensing the phenolic compound with benzaldehyde, salicylaldehyde and other aromatic aldehyde compounds under an acidic catalyst; combining two or more of these Phenol resin obtained by copolymerization, etc. These phenol resins and polyhydric phenol compounds may be used individually by one type, or in combination of two or more types.
該些中,酚硬化劑較佳為多官能酚樹脂硬化劑,其中較佳為酚醛清漆型酚樹脂、芳烷基型酚樹脂及三苯基甲烷型酚樹脂,更佳為三苯基甲烷型酚樹脂。 Among these, the phenol hardener is preferably a multifunctional phenol resin hardener, among which the novolak type phenol resin, the aralkyl type phenol resin and the triphenylmethane type phenol resin are preferred, and the triphenylmethane type is more preferred. Phenolic resin.
此處,「多官能酚樹脂硬化劑」是作為在一分子中具有三個以上官能基(即,羥基)的酚樹脂的硬化劑。 Here, the "polyfunctional phenol resin hardener" is a hardener for a phenol resin having three or more functional groups (that is, hydroxyl groups) in one molecule.
作為三苯基甲烷型酚樹脂,可列舉下述通式(2)所表示的酚樹脂。 As triphenylmethane type phenol resins, phenol resins represented by the following general formula (2) can be cited.
所述通式(2)中,R11~R15分別獨立地表示碳數1~18的一價有機基,b1~b2分別獨立地表示0~4的整數,b3表示0~3的整數,b4~b5分別獨立地表示0~4的整數,n表示0~10。 In the general formula (2), R 11 to R 15 each independently represent a monovalent organic group having 1 to 18 carbon atoms, b1 to b2 each independently represent an integer of 0 to 4, b3 represents an integer of 0 to 3, b4 to b5 each independently represent an integer of 0 to 4, and n represents 0 to 10.
作為通式(2)中的R11~R15所表示的碳數1~18的一價有機基,可列舉經取代或未經取代的烷基、經取代或未經取代的烷氧基、經取代或未經取代的芳基、經取代或未經取代的芳烷基等。 Examples of the monovalent organic group having 1 to 18 carbon atoms represented by R 11 to R 15 in the general formula (2) include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, etc.
通式(2)中的b1~b5較佳為0~1的整數,更佳為0。 b1 to b5 in the general formula (2) are preferably integers from 0 to 1, more preferably 0.
通式(2)中的n較佳為1~7,更佳為2~5。 n in the general formula (2) is preferably 1 to 7, more preferably 2 to 5.
硬化劑的官能基當量並無特別限制,就成形性的觀點而言,較佳為70g/eq~500g/eq,更佳為70g/eq~300g/eq,進而佳為80g/eq~250g/eq。另外,官能基當量是指依據JIS K0070:1992而測定的值。 The functional group equivalent of the curing agent is not particularly limited. From the perspective of formability, it is preferably 70g/eq~500g/eq, more preferably 70g/eq~300g/eq, and even more preferably 80g/eq~250g/eq. In addition, the functional group equivalent refers to the value measured in accordance with JIS K0070:1992.
在硬化劑為固體的情況下,其軟化點或熔點並無特別限制。就成形性與耐回流性的觀點而言,硬化劑的軟化點或熔點較佳為40℃~180℃,就密封組成物的製造時的處理性的觀點而言,軟化點或熔點更佳為50℃~130℃,進而佳為55℃~100℃。 In the case where the hardener is solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, the softening point or melting point of the hardener is preferably 40°C to 180°C, and from the viewpoint of handleability during production of the sealing composition, the softening point or melting point is more preferably 40°C to 180°C. 50℃~130℃, preferably 55℃~100℃.
硬化劑的熔點或軟化點設為與環氧樹脂的熔點或軟化點同樣地測定的值。 The melting point or softening point of the hardener is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.
關於環氧樹脂與硬化劑的調配比,就將各自的未反應成分抑制得少的觀點而言,較佳為以相對於環氧樹脂的環氧基1當量,硬化劑的官能基(例如,在酚樹脂的情況下為酚性羥基)的當量成為0.5當量~1.5當量的方式調配硬化劑,特佳為以成為0.7當量~1.2當量的方式調配硬化劑。 The blending ratio of the epoxy resin and the hardener is preferably one equivalent of the functional group of the hardener (for example, In the case of a phenol resin, the hardener is prepared so that the equivalent of the phenolic hydroxyl group is 0.5 to 1.5 equivalents, and particularly preferably 0.7 to 1.2 equivalents.
-無機填充材- -Inorganic filler material-
本揭示的密封組成物至少包含特定二氧化矽粒子(即,比表面積為100m2/g以上的二氧化矽粒子)作為無機填充材,視需要亦可包含特定二氧化矽粒子以外的填充材(以下,亦稱為「其他填充材」)。 The sealing composition disclosed herein contains at least specific silica particles (i.e., silica particles having a specific surface area of 100 m 2 /g or more) as an inorganic filler, and may contain fillers other than the specific silica particles (hereinafter also referred to as "other fillers") as necessary.
藉由使密封組成物包含特定二氧化矽粒子,例如可抑制藉由轉移模塑法進行半導體元件的密封時毛邊的產生。 By including specific silicon dioxide particles in the sealing composition, it is possible to suppress the generation of burrs when sealing semiconductor components by transfer molding, for example.
密封組成物較佳為包含特定二氧化矽粒子與其他填充材作為無機填充材。 The sealing composition preferably contains specific silica particles and other fillers as inorganic fillers.
特定二氧化矽粒子的比表面積為100m2/g以上,就所述毛邊抑制的觀點而言,較佳為150m2/g~300m2/g,更佳為170m2/g~270m2/g,進而佳為190m2/g~230m2/g。 The specific surface area of the specific silica particles is 100 m 2 /g or more, preferably 150 m 2 /g to 300 m 2 /g, more preferably 170 m 2 /g to 270 m 2 /g, and even more preferably 190 m 2 /g to 230 m 2 /g from the viewpoint of burr suppression.
無機填充材的比表面積(即,布厄特(Brunauer-Emmett-Teller,BET)比表面積)可依據JIS Z 8830:2013並根據氮吸收能來進行測定。作為評價裝置,可使用康塔(QUANTACHROME)公司:自動吸附-1(AUTOSORB-1)(商品名)。在進行BET比表面積的測定時,由於認為吸附於試樣表面及結構中的水分會影響氣體吸附能,所以較佳為首先藉由加熱進行去除水分的前處理。 The specific surface area (ie, Brunauer-Emmett-Teller, BET) specific surface area of the inorganic filler can be measured based on nitrogen absorption energy in accordance with JIS Z 8830:2013. As an evaluation device, QUANTACHROME: AUTOSORB-1 (trade name) can be used. When measuring the BET specific surface area, since it is believed that moisture adsorbed on the surface and structure of the sample will affect the gas adsorption capacity, it is best to first perform a pretreatment to remove moisture by heating.
在前處理中,將投入有0.05g的測定試樣的測定用單元利用真空泵減壓至10Pa以下後,以110℃進行加熱,保持3小時以上,之後在保持著減壓的狀態下自然冷卻至常溫(25℃)。進行該前處理後,將評價溫度設為77K,將評價壓力範圍設為以相對壓(相 對於飽和蒸氣壓的平衡壓力)計不足1來進行測定。 In the pretreatment, the measuring unit with 0.05g of the measuring sample is depressurized to less than 10Pa by a vacuum pump, heated at 110℃, maintained for more than 3 hours, and then naturally cooled to room temperature (25℃) while maintaining the depressurization. After this pretreatment, the evaluation temperature is set to 77K, and the evaluation pressure range is set to be less than 1 for relative pressure (equilibrium pressure relative to saturated vapor pressure) for measurement.
就所述毛邊抑制及成形性的觀點而言,相對於密封組成物中所含的無機填充材整體,特定二氧化矽粒子的含有率較佳為0.15質量%~1.0質量%,更佳為0.3質量%~0.8質量%,進而佳為0.4質量%~0.7質量%。 From the viewpoint of burr suppression and formability, the content rate of specific silica particles relative to the entire inorganic filler contained in the sealing composition is preferably 0.15 mass % to 1.0 mass %, more preferably 0.3 mass% to 0.8 mass%, more preferably 0.4 mass% to 0.7 mass%.
其他填充材可單獨使用一種,亦可併用兩種以上。 Other fillers may be used alone or in combination of two or more.
作為併用兩種以上的其他填充材的情況,可列舉使用兩種以上的成分、平均粒徑、形狀等不同的無機填充材的情況。 As a case where two or more other fillers are used in combination, there can be cited the case where two or more inorganic fillers with different components, average particle sizes, shapes, etc. are used.
其他填充材的形狀並無特別限制,可列舉:粉狀、球狀、纖維狀等。就密封組成物的成形時的流動性及金屬模具磨損性的方面而言,其他填充材的形狀較佳為球狀。 The shape of other fillers is not particularly limited, and examples include: powdery, spherical, fibrous, etc. In terms of fluidity during molding of the sealing composition and abrasion resistance of the metal mold, the shape of other fillers is preferably spherical.
就高導熱性的觀點而言,其他填充材較佳為包含氧化鋁。其他填充材可全部為氧化鋁,亦可併用氧化鋁與氧化鋁以外的其他填充材。 From the perspective of high thermal conductivity, other fillers preferably include alumina. Other fillers may be all alumina, or alumina and other fillers other than alumina may be used in combination.
作為氧化鋁以外的其他填充材,可列舉:比表面積不足100m2/g的二氧化矽(球狀二氧化矽、結晶二氧化矽等)、鋯石、氧化鎂、矽酸鈣、碳酸鈣、鈦酸鉀、碳化矽、氮化矽、氮化硼、氧化鈹、氧化鋯等。進而,作為具有阻燃效果的無機填充材,可列舉氫氧化鋁、硼酸鋅等。 Examples of fillers other than alumina include silica with a specific surface area of less than 100 m 2 /g (spherical silica, crystalline silica, etc.), zircon, magnesium oxide, calcium silicate, calcium carbonate, Potassium titanate, silicon carbide, silicon nitride, boron nitride, beryllium oxide, zirconium oxide, etc. Furthermore, examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, zinc borate, and the like.
就吸濕性、線膨脹係數的降低、強度提高及焊料耐熱性的觀點而言,相對於密封組成物的整體,無機填充材的含有率(例如,在無機填充材包含特定二氧化矽粒子及其他填充材的情況 下,為包含特定二氧化矽粒子及其他填充材的無機填充材整體的含有率)較佳為60體積%以上,更佳為70體積%以上,進而佳為75體積%以上。 From the viewpoint of hygroscopicity, reduction in linear expansion coefficient, improvement in strength, and solder heat resistance, the content rate of the inorganic filler relative to the entire sealing composition (for example, when the inorganic filler contains specific silica particles and Other filling materials (below, the content rate of the entire inorganic filler including specific silica particles and other fillers) is preferably 60 volume % or more, more preferably 70 volume % or more, and still more preferably 75 volume % or more.
而且,就高導熱性的觀點而言,相對於密封組成物的整體,無機填充材的含有率較佳為78體積%以上,更佳為80體積%以上。就密封組成物的成形性的觀點而言,相對於密封組成物的整體,無機填充材的含有率較佳為95體積%以下,更佳為90體積%以下,進而佳為85體積%以下。就兼顧高導熱性與密封組成物的成形性的觀點而言,無機填充材的含有率較佳為78體積%~90體積%,更佳為78體積%~85體積%,進而佳為80體積%~85體積%。 Furthermore, from the viewpoint of high thermal conductivity, the content rate of the inorganic filler relative to the entire sealing composition is preferably 78 volume % or more, more preferably 80 volume % or more. From the viewpoint of the formability of the sealing composition, the content rate of the inorganic filler relative to the entire sealing composition is preferably 95 volume % or less, more preferably 90 volume % or less, and still more preferably 85 volume % or less. From the viewpoint of balancing high thermal conductivity and formability of the sealing composition, the content rate of the inorganic filler is preferably 78 volume % to 90 volume %, more preferably 78 volume % to 85 volume %, and further preferably 80 volume %. %~85% by volume.
無機填充材的平均粒徑(例如,在無機填充材包含特定二氧化矽粒子及其他填充材的情況下,為包含特定二氧化矽粒子及其他填充材的無機填充材整體的平均粒徑)較佳為4μm~100μm,更佳為7μm~70μm,進而佳為7μm~40μm。 The average particle size of the inorganic filler (for example, when the inorganic filler includes specific silica particles and other fillers, the average particle size of the entire inorganic filler including specific silica particles and other fillers) is preferably 4μm to 100μm, more preferably 7μm to 70μm, and even more preferably 7μm to 40μm.
密封組成物的硬化物的導熱率具有隨著無機填充材的平均粒徑變大而變高的傾向。 The thermal conductivity of the cured product of the sealing composition tends to become higher as the average particle diameter of the inorganic filler becomes larger.
無機填充材的平均粒徑可藉由以下的方法來測定。 The average particle size of the inorganic filler can be measured by the following method.
向溶媒(純水)中添加1質量%~5質量%的範圍內的作為測定對象的無機填充材、以及1質量%~8質量%的界面活性劑,利用110W的超音波清洗機振動30秒~5分鐘,將無機填充材分散。將分散液的約3mL左右注入至測定用單元中並在25℃ 下進行測定。測定裝置是使用雷射繞射式粒度分佈計(堀場製作所股份有限公司,LA920)來測定體積基準的粒度分佈。平均粒徑是在體積基準的粒度分佈中作為自小徑側的累積成為50%時的粒徑(D50%)而求出。另外,折射率是使用氧化鋁的折射率。在無機填充材為氧化鋁與其他無機填充材的混合物的情況下,折射率設為使用氧化鋁的折射率。 Add 1% to 5% by mass of the inorganic filler to be measured and 1% to 8% by mass of the surfactant to the solvent (pure water), and use a 110W ultrasonic cleaner to shake for 30 seconds to 5 minutes to disperse the inorganic filler. Pour about 3 mL of the dispersion into the measurement unit and measure at 25°C. The measurement device uses a laser diffraction particle size distribution meter (Horiba, Ltd., LA920) to measure the volume-based particle size distribution. The average particle size is calculated as the particle size (D50%) when the accumulation from the small diameter side in the volume-based particle size distribution becomes 50%. In addition, the refractive index is the refractive index of aluminum oxide. When the inorganic filler is a mixture of aluminum oxide and other inorganic fillers, the refractive index is set to the refractive index of aluminum oxide.
就流動性及成形性的觀點而言,無機填充材的比表面積(例如,在無機填充材包含特定二氧化矽粒子及其他填充材的情況下,為包含特定二氧化矽粒子及其他填充材的無機填充材整體的比表面積)較佳為0.7m2/g~4.0m2/g,更佳為0.9m2/g~3.0m2/g,進而佳為1.0m2/g~2.5m2/g。 From the viewpoint of fluidity and formability, the specific surface area of the inorganic filler (for example, when the inorganic filler contains specific silica particles and other fillers, is the specific surface area of the inorganic filler containing specific silica particles and other fillers). The specific surface area of the entire inorganic filler material is preferably 0.7m 2 /g~4.0m 2 /g, more preferably 0.9m 2 /g~3.0m 2 /g, and further preferably 1.0m 2 /g~2.5m 2 /g.
密封組成物的流動性具有隨著無機填充材的比表面積變小而變高的傾向。 The fluidity of the sealing composition tends to increase as the specific surface area of the inorganic filler decreases.
-特定矽烷化合物- -Specific silane compounds-
本揭示的密封組成物含有特定矽烷化合物(即,具有碳數6以上的鏈狀烴基鍵結於矽原子的結構的矽烷化合物)。 The sealing composition disclosed herein contains a specific silane compound (i.e., a silane compound having a structure in which a chain hydrocarbon group with 6 or more carbon atoms is bonded to a silicon atom).
特定矽烷化合物具有碳數6以上的鏈狀烴基(以下,亦將碳數6以上的鏈狀烴基簡稱為鏈狀烴基)鍵結於矽原子的結構。鏈狀烴基可分支亦可具有取代基。另外,在本揭示中,鏈狀烴基的碳數是指不包含分支或取代基的碳的碳數。鏈狀烴基可包含不飽和鍵,亦可不包含,較佳為不包含不飽和鍵。 The specific silane compound has a structure in which a chain alkyl group with more than 6 carbon atoms (hereinafter, a chain alkyl group with more than 6 carbon atoms is also referred to as a chain alkyl group) is bonded to a silicon atom. The chain alkyl group may be branched or may have a substituent. In addition, in the present disclosure, the carbon number of the chain alkyl group refers to the carbon number of the carbon not including the branch or the substituent. The chain alkyl group may contain an unsaturated bond or may not contain it, and preferably does not contain an unsaturated bond.
特定矽烷化合物被認為在密封組成物中作為無機填充材的偶 合劑來發揮功能。 Specific silane compounds are considered to be used as coupling materials for inorganic fillers in sealing compositions. mixture to function.
特定矽烷化合物中鍵結於矽原子的鏈狀烴基的數量為1~4即可,較佳為1~3,更佳為1或2,進而佳為1。 The number of chain hydrocarbon groups bonded to silicon atoms in the specific silane compound may be 1 to 4, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.
當特定矽烷化合物中鍵結於矽原子的鏈狀烴基的數量為1~3時,鍵結於矽原子的、鏈狀烴基以外的原子或原子團並無特別限制,可分別獨立地為氫原子、碳數1~5的烷基、烷氧基、芳基、芳基氧基等。其中,特定矽烷化合物中的矽原子較佳為除了鏈狀烴基以外亦鍵結有一個或多個烷氧基,更佳為一個鏈狀烴基與三個烷氧基鍵結於矽原子。 When the number of chain hydrocarbon groups bonded to silicon atoms in the specific silane compound is 1 to 3, the atoms or atomic groups other than the chain hydrocarbon groups bonded to the silicon atoms are not particularly limited, and can be independently hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, alkoxy groups, aryl groups, aryloxy groups, etc. Among them, the silicon atom in the specific silane compound is preferably bonded to one or more alkoxy groups in addition to the chain hydrocarbon group, and more preferably one chain hydrocarbon group and three alkoxy groups are bonded to the silicon atom.
特定矽烷化合物的鏈狀烴基的碳數為6以上,就抑制黏度的觀點而言,較佳為7以上,更佳為8以上。特定矽烷化合物的鏈狀烴基的碳數的上限並無特別限制,就在樹脂中的分散性、硬化物的物性平衡等觀點而言,較佳為12以下,更佳為11以下,進而佳為10以下。 The carbon number of the chain hydrocarbon group of the specific silane compound is 6 or more, preferably 7 or more, and more preferably 8 or more from the viewpoint of suppressing viscosity. The upper limit of the carbon number of the chain hydrocarbon group of the specific silane compound is not particularly limited, but from the viewpoint of dispersibility in the resin, physical property balance of the cured product, etc., it is preferably 12 or less, more preferably 11 or less, and further preferably 10 or less.
在鏈狀烴基具有取代基的情況下,取代基並無特別限定。取代基可存在於鏈狀烴基的末端,亦可存在於鏈狀烴基的側鏈。 When the chain hydrocarbon group has a substituent, the substituent is not particularly limited. The substituent may exist at the terminal end of the chain hydrocarbon group or on the side chain of the chain hydrocarbon group.
鏈狀烴基較佳為具有選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中的至少一個官能基(以下,亦稱為「特定官能基」),更佳為具有選自由(甲基)丙烯醯基及環氧基所組成的群組中的至少一個官能基,進而佳為具有(甲基)丙烯醯基。特定官能基可存在於鏈狀烴基的末端,亦可存在於鏈狀烴基的側鏈。就抑 制黏度的觀點而言,特定官能基較佳為存在於鏈狀烴基的末端。 The chain alkyl group preferably has at least one functional group selected from the group consisting of (meth)acryloyl, epoxy and alkoxy (hereinafter also referred to as "specific functional group"), more preferably at least one functional group selected from the group consisting of (meth)acryloyl and epoxy, and more preferably has a (meth)acryloyl group. The specific functional group may be present at the end of the chain alkyl group or at the side chain of the chain alkyl group. From the viewpoint of suppressing viscosity, the specific functional group is preferably present at the end of the chain alkyl group.
在鏈狀烴基具有(甲基)丙烯醯基的情況下,(甲基)丙烯醯基可直接鍵結於鏈狀烴基,亦可經由其他原子或原子團而鍵結。例如,鏈狀烴基亦可具有(甲基)丙烯醯氧基。其中,鏈狀烴基較佳為具有甲基丙烯醯氧基。 When the chain alkyl group has a (meth)acryloyl group, the (meth)acryloyl group may be directly bonded to the chain alkyl group or may be bonded via other atoms or atomic groups. For example, the chain alkyl group may also have a (meth)acryloyloxy group. Among them, the chain alkyl group preferably has a methacryloyloxy group.
在鏈狀烴基具有環氧基的情況下,環氧基可直接鍵結於鏈狀烴基,亦可經由其他原子或原子團而鍵結。例如,鏈狀烴基亦可具有縮水甘油基氧基、脂環式環氧基等。其中,鏈狀烴基較佳為具有縮水甘油基氧基。 When the chain alkyl group has an epoxide group, the epoxide group may be directly bonded to the chain alkyl group or may be bonded via other atoms or atomic groups. For example, the chain alkyl group may also have a glycidyloxy group, an alicyclic epoxide group, etc. Among them, the chain alkyl group preferably has a glycidyloxy group.
在鏈狀烴基具有烷氧基的情況下,烷氧基可直接鍵結於鏈狀烴基,亦可經由其他原子或原子團而鍵結,較佳為直接鍵結於鏈狀烴基。烷氧基並無特別限定,可為甲氧基、乙氧基、丙氧基、異丙氧基等。其中,就容易獲得性的觀點而言,鏈狀烴基較佳為具有甲氧基。 When the chain hydrocarbon group has an alkoxy group, the alkoxy group may be directly bonded to the chain hydrocarbon group or may be bonded via other atoms or atomic groups, preferably directly bonded to the chain hydrocarbon group. The alkoxy group is not particularly limited and may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, etc. Among them, from the perspective of easy availability, the chain hydrocarbon group preferably has a methoxy group.
特定矽烷化合物中選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中的至少一個官能基的當量(分子量/官能基數)並無特別限制。就密封組成物的低黏度化的觀點而言,較佳為200g/eq~420g/eq,更佳為210g/eq~405g/eq,進而佳為230g/eq~390g/eq。 The equivalent weight (molecular weight/number of functional groups) of at least one functional group selected from the group consisting of (meth)acrylyl group, epoxy group and alkoxy group in the specific silane compound is not particularly limited. From the viewpoint of reducing the viscosity of the sealing composition, 200g/eq~420g/eq is preferred, 210g/eq~405g/eq is more preferred, and 230g/eq~390g/eq is still more preferred.
作為特定矽烷化合物,可列舉:己基三甲氧基矽烷、庚基三甲氧基矽烷、辛基三甲氧基矽烷、己基三乙氧基矽烷、庚基三乙氧基矽烷、辛基三乙氧基矽烷、6-縮水甘油氧基己基三甲氧 基矽烷、7-縮水甘油氧基庚基三甲氧基矽烷、8-縮水甘油氧基辛基三甲氧基矽烷、6-(甲基)丙烯醯氧基己基三甲氧基矽烷、7-(甲基)丙烯醯氧基庚基三甲氧基矽烷、8-(甲基)丙烯醯氧基辛基三甲氧基矽烷、癸基三甲氧基矽烷等。其中,就密封組成物的低黏度化的觀點而言,特定矽烷化合物較佳為8-縮水甘油氧基辛基三甲氧基矽烷、及8-甲基丙烯醯氧基辛基三甲氧基矽烷。特定矽烷化合物可單獨使用一種,亦可組合兩種以上來使用。 Specific silane compounds include: hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, and octyltriethoxysilane , 6-glycidyloxyhexyltrimethoxy silane, 7-glycidyloxyheptyltrimethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(methyl ) Acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, decyltrimethoxysilane, etc. Among them, from the viewpoint of reducing the viscosity of the sealing composition, the specific silane compound is preferably 8-glycidoxyoctyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane. A specific silane compound may be used individually by 1 type, and may be used in combination of 2 or more types.
特定矽烷化合物可合成,亦可使用市售者。作為市售的特定矽烷化合物,可列舉:信越化學工業股份有限公司製造的KBM-3063(己基三甲氧基矽烷)、KBE-3063(己基三乙氧基矽烷)、KBE-3083(辛基三乙氧基矽烷)、KBM-4803(8-縮水甘油氧基辛基三甲氧基矽烷)、KBM-5803(8-甲基丙烯醯氧基辛基三甲氧基矽烷)、KBM-3103C(癸基三甲氧基矽烷)等。 The specific silane compound can be synthesized or commercially available. Examples of commercially available specific silane compounds include KBM-3063 (hexyltrimethoxysilane), KBE-3063 (hexyltriethoxysilane), KBE-3083 (octyltriethoxysilane), KBM-4803 (8-glycidyloxyoctyltrimethoxysilane), KBM-5803 (8-methacryloyloxyoctyltrimethoxysilane), and KBM-3103C (decyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
密封組成物中的特定矽烷化合物的含量並無特別限制。相對於無機填充材100質量份,特定矽烷化合物的含量可為0.01質量份以上,亦可為0.02質量份以上。而且,相對於無機填充材100質量份,特定矽烷化合物的含量較佳為5質量份以下,更佳為2.5質量份以下。若相對於無機填充材100質量份,特定矽烷化合物的含量為0.01質量份以上,則具有可獲得流動性高的組成物的傾向。若相對於無機填充材100質量份,特定矽烷化合物的含量為5質量份以下,則具有封裝體的成形性進一步提高的傾向。就兼顧流動性與封裝體的成形性的觀點而言,相對於無機填 充材100質量份,特定矽烷化合物的含量較佳為0.05質量份~2.0質量份,更佳為0.1質量份~1.5質量份,進而佳為0.2質量份~1.0質量份。 The content of the specific silane compound in the sealing composition is not particularly limited. The content of the specific silane compound can be 0.01 parts by mass or more, or 0.02 parts by mass or more relative to 100 parts by mass of the inorganic filler. Moreover, the content of the specific silane compound is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less relative to 100 parts by mass of the inorganic filler. If the content of the specific silane compound is 0.01 parts by mass or more relative to 100 parts by mass of the inorganic filler, a composition with high fluidity tends to be obtained. If the content of the specific silane compound is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, the formability of the package tends to be further improved. From the perspective of both fluidity and package formability, the content of the specific silane compound is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass, and even more preferably 0.2 to 1.0 parts by mass, relative to 100 parts by mass of the inorganic filler.
而且,相對於密封組成物整體,特定矽烷化合物的含有率較佳為3質量%以下,更佳為2質量%以下,進而佳為1質量%以下,就發揮其效果的觀點而言,較佳為0.1質量%以上,更佳為0.15質量%以上,進而佳為0.2質量%以上。 Furthermore, the content rate of the specific silane compound relative to the entire sealing composition is preferably 3 mass% or less, more preferably 2 mass% or less, and further preferably 1 mass% or less. From the perspective of exerting its effect, The content is 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more.
-其他成分- -Other ingredients-
(其他偶合劑) (Other coupling agents)
密封組成物除了所述特定矽烷化合物以外,亦可進而含有其他偶合劑。作為其他偶合劑,只要為使用了環氧樹脂的密封組成物中一般所使用者則並無特別限制。作為其他偶合劑,可列舉環氧基矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等矽烷系化合物(特定矽烷化合物除外)、鈦系化合物、鋁螯合物化合物、鋁/鋯系化合物等公知的偶合劑。其他偶合劑可單獨使用一種,亦可組合兩種以上來使用。 In addition to the specific silane compound, the sealing composition may further contain other coupling agents. There are no particular restrictions on other coupling agents as long as they are generally used in sealing compositions using epoxy resins. Examples of other coupling agents include silane-based compounds (excluding specific silane compounds) such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, titanium-based compounds, and aluminum chelate compounds. , aluminum/zirconium-based compounds and other well-known coupling agents. Other coupling agents may be used alone or in combination of two or more.
在密封組成物含有特定矽烷化合物以外的其他偶合劑的情況下,相對於無機填充材100質量份,特定矽烷化合物與其他偶合劑的合計含量可為0.01質量份以上,可為0.02質量份以上。而且,相對於無機填充材100質量份,特定矽烷化合物與其他偶合劑的合計含量較佳為5質量份以下,更佳為2.5質量份以下。若相對於無機填充材100質量份,特定矽烷化合物與其他偶 合劑的合計含量為0.01質量份以上,則具有可獲得流動性高的組成物的傾向。若相對於無機填充材100質量份,特定矽烷化合物與其他偶合劑的合計含量為5質量份以下,則具有封裝體的成形性進一步提高的傾向。就兼顧流動性與封裝體的成形性的觀點而言,相對於無機填充材100質量份,特定矽烷化合物與其他偶合劑的合計含量較佳為0.05質量份~2.0質量份,更佳為0.1質量份~1.5質量份,進而佳為0.2質量份~1.0質量份。 When the sealing composition contains a coupling agent other than the specific silane compound, the total content of the specific silane compound and the other coupling agent may be 0.01 parts by mass or more or 0.02 parts by mass or more relative to 100 parts by mass of the inorganic filler. Furthermore, the total content of the specific silane compound and other coupling agents is preferably 5 parts by mass or less, more preferably 2.5 parts by mass or less, based on 100 parts by mass of the inorganic filler. If the specific silane compound is mixed with other silica fillers relative to 100 parts by mass of the inorganic filler When the total content of the mixture is 0.01 parts by mass or more, a composition with high fluidity tends to be obtained. If the total content of the specific silane compound and other coupling agents is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the formability of the package tends to be further improved. From the viewpoint of balancing fluidity and formability of the package, the total content of the specific silane compound and other coupling agents is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 parts by mass, based on 100 parts by mass of the inorganic filler. parts to 1.5 parts by mass, and more preferably 0.2 parts to 1.0 parts by mass.
而且,相對於密封組成物整體,特定矽烷化合物與其他偶合劑的合計含有率較佳為3質量%以下,更佳為2質量%以下,進而佳為1質量%以下,就發揮其效果的觀點而言,較佳為0.1質量%以上,更佳為0.15質量%以上,進而佳為0.2質量%以上。 Moreover, the total content of the specific silane compound and other coupling agents relative to the entire sealing composition is preferably 3 mass % or less, more preferably 2 mass % or less, and further preferably 1 mass % or less. From the perspective of exerting its effect, it is preferably 0.1 mass % or more, more preferably 0.15 mass % or more, and further preferably 0.2 mass % or more.
在密封組成物含有特定矽烷化合物以外的其他偶合劑的情況下,就良好地發揮特定矽烷化合物的作用的觀點而言,相對於特定矽烷化合物與其他偶合劑的合計量,其他偶合劑的含有率較佳為90質量%以下,更佳為70質量%以下,進而佳為50質量%以下,特佳為40質量%以下,極佳為20質量%以下,最佳為10質量%以下。 When the sealing composition contains other coupling agents other than the specific silane compound, from the viewpoint of well exerting the effect of the specific silane compound, the content of the other coupling agent relative to the total amount of the specific silane compound and the other coupling agent is preferably 90 mass % or less, more preferably 70 mass % or less, further preferably 50 mass % or less, particularly preferably 40 mass % or less, extremely preferably 20 mass % or less, and most preferably 10 mass % or less.
(硬化促進劑) (hardening accelerator)
密封組成物亦可進而含有硬化促進劑。硬化促進劑的種類並無特別限制,可使用公知的硬化促進劑。 The sealing composition may further contain a hardening accelerator. The type of hardening accelerator is not particularly limited, and known hardening accelerators can be used.
作為硬化促進劑,具體而言,可列舉:1,8-二氮雜-雙環[5.4.0]十一烯-7、1,5-二氮雜-雙環[4.3.0]壬烯、5,6-二丁基胺基-1,8-二氮 雜-雙環[5.4.0]十一烯-7等環脒化合物;對環脒化合物加成馬來酸酐、1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯基甲烷、苯酚樹脂等具有π鍵的化合物而成的具有分子內極化的化合物;苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺化合物;三級胺化合物的衍生物;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑化合物;咪唑化合物的衍生物;三丁基膦、甲基二苯基膦、三苯基膦、三(4-甲基苯基)膦、二苯基膦、苯基膦等有機膦化合物;對有機膦化合物加成馬來酸酐、所述醌化合物、重氮苯基甲烷、苯酚樹脂等具有π鍵的化合物而成的具有分子內極化的磷化合物;四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽、2-乙基-4-甲基咪唑四苯基硼酸鹽、N-甲基嗎啉四苯基硼酸鹽等四苯基硼鹽;四苯基硼鹽的衍生物;三苯基鏻-三苯基硼烷、N-甲基嗎啉四苯基鏻-四苯基硼酸鹽等膦化合物與四苯基硼鹽的加成物等。硬化促進劑可單獨使用一種,亦可併用兩種以上。 Specifically, as hardening accelerators, there are: 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7 and other cyclic amidine compounds; p-cyclic amidine compounds with maleic anhydride added, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2, Compounds with intramolecular polarization formed by quinone compounds such as 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, compounds with π bonds such as diazonophenylmethane and phenol resins; benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. Tertiary amine compounds; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds with intramolecular polarization obtained by adding maleic anhydride, the quinone compound, diazonophenylmethane, phenol resin, and other compounds having π bonds to organic phosphine compounds; tetraphenylborates such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylporphyrinium tetraphenylborate; derivatives of tetraphenylborates; adducts of phosphine compounds such as triphenylphosphonium-triphenylborane and N-methylporphyrinium tetraphenylphosphonium-tetraphenylborate with tetraphenylborates, etc. One hardening accelerator may be used alone or two or more may be used in combination.
該些中,硬化促進劑較佳為磷系硬化促進劑,其中更佳為有機膦化合物、有機膦化合物的加成物、及膦化合物與四苯基硼鹽的加成物,進而佳為有機膦化合物及有機膦化合物的加成物,特佳為對有機膦化合物加成醌化合物而成的化合物。 Among these, the hardening accelerator is preferably a phosphorus-based hardening accelerator, and among them, an organic phosphine compound, an adduct of an organic phosphine compound, and an adduct of a phosphine compound and a tetraphenyl boron salt are more preferred, and an organic phosphine compound is more preferred. As an adduct of a phosphine compound and an organic phosphine compound, a compound obtained by adding a quinone compound to an organic phosphine compound is particularly preferred.
另外,「磷系硬化促進劑」是具有磷原子的硬化促進劑。 In addition, "phosphorus-based hardening accelerator" is a hardening accelerator containing a phosphorus atom.
相對於環氧樹脂與硬化劑的合計量,硬化促進劑的含有 率較佳為0.1質量%~8質量%。 The content of hardening accelerator relative to the total amount of epoxy resin and hardener The preferable rate is 0.1 mass% to 8 mass%.
(離子捕捉劑) (ion capture agent)
密封組成物亦可進而含有離子捕捉劑。 The sealing composition may further contain an ion trapping agent.
本揭示中可使用的離子捕捉劑只要為用於半導體裝置的製造用途中的密封材中一般所使用的離子捕捉劑,則並無特別限制。作為離子捕捉劑,可列舉下述通式(3)或下述通式(4)所表示的化合物等。 The ion scavenger that can be used in the present disclosure is not particularly limited as long as it is an ion scavenger generally used in sealing materials for the manufacture of semiconductor devices. Examples of the ion scavenger include compounds represented by the following general formula (3) or the following general formula (4).
Mg1-aAla(OH)2(CO3)a/2.uH2O (3) Mg 1-a Al a (OH) 2 (CO 3 ) a/2 . uH 2 O (3)
(通式(3)中,a為0<a≦0.5,u為正數) (In general formula (3), a is 0<a≦0.5, and u is a positive number)
BiOb(OH)c(NO3)d (4) BiO b (OH) c (NO 3 ) d (4)
(通式(4)中,b為0.9≦b≦1.1,c為0.6≦c≦0.8,d為0.2≦d≦0.4) (In general formula (4), b is 0.9≦b≦1.1, c is 0.6≦c≦0.8, and d is 0.2≦d≦0.4)
離子捕捉劑可作為市售品而獲取。作為通式(3)所表示的化合物,例如可作為市售品而獲取「DHT-4A」(協和化學工業股份有限公司,商品名)。而且,作為通式(4)所表示的化合物,例如可作為市售品而獲取「IXE500」(東亞合成股份有限公司,商品名)。 Ion scavengers can be obtained as commercial products. For example, the compound represented by general formula (3) can be obtained as a commercial product, such as "DHT-4A" (Kyowa Chemical Industry Co., Ltd., trade name). Moreover, for example, the compound represented by general formula (4) can be obtained as a commercial product, such as "IXE500" (Toagosei Co., Ltd., trade name).
而且,作為所述以外的離子捕捉劑,可列舉選自鎂、鋁、鈦、鋯、銻等中的元素的含水氧化物等。 Examples of ion trapping agents other than those mentioned above include hydrous oxides of elements selected from the group consisting of magnesium, aluminum, titanium, zirconium, antimony, and the like.
離子捕捉劑可單獨使用一種,亦可併用兩種以上。 Ion scavengers can be used alone or in combination of two or more.
在密封組成物含有離子捕捉劑的情況下,就實現充分的耐濕可靠性的觀點而言,相對於環氧樹脂100質量份,離子捕捉劑的含量較佳為1質量份以上。就充分發揮其他成分的效果的觀點而言,相對於環氧樹脂100質量份,離子捕捉劑的含量較佳為15質量份以下。 When the sealing composition contains an ion scavenger, the content of the ion scavenger is preferably 1 part by mass or more relative to 100 parts by mass of the epoxy resin from the perspective of achieving sufficient moisture resistance reliability. From the perspective of fully exerting the effects of other components, the content of the ion scavenger is preferably 15 parts by mass or less relative to 100 parts by mass of the epoxy resin.
而且,離子捕捉劑的平均粒徑較佳為0.1μm~3.0μm,最大粒徑較佳為10μm以下。離子捕捉劑的平均粒徑可與無機填充材的情況同樣地進行測定。 Furthermore, the average particle diameter of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle diameter is preferably 10 μm or less. The average particle diameter of the ion scavenger can be measured in the same manner as in the case of the inorganic filler.
(脫模劑) (release agent)
密封組成物亦可進而含有脫模劑。脫模劑的種類並無特別限制,可使用公知的脫模劑。具體而言,作為脫模劑,可列舉:高級脂肪酸、棕櫚蠟、褐煤蠟、聚乙烯系蠟等。脫模劑可單獨使用一種,亦可併用兩種以上。 The sealing composition may further contain a release agent. The type of release agent is not particularly limited, and a known release agent can be used. Specifically, examples of the release agent include higher fatty acids, palm wax, montan wax, polyethylene wax, and the like. One type of release agent may be used alone, or two or more types may be used in combination.
在密封組成物含有脫模劑的情況下,相對於環氧樹脂與硬化劑的合計量,脫模劑的含有率較佳為10質量%以下,就發揮其效果的觀點而言,較佳為0.5質量%以上。 When the sealing composition contains a release agent, the content rate of the release agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the hardener. From the viewpoint of exerting its effect, the content rate of the release agent is preferably 10% by mass or less. 0.5% by mass or more.
(著色劑及改質劑) (colorants and modifiers)
密封組成物亦可含有著色劑(碳黑等)。而且,密封組成物亦可含有改質劑(矽酮、矽酮橡膠等)。著色劑及改質劑可分別單獨使用一種,亦可併用兩種以上。 The sealing composition may also contain a colorant (carbon black, etc.). Furthermore, the sealing composition may also contain a modifier (silicone, silicone rubber, etc.). The colorant and modifier may be used alone or in combination of two or more.
在使用碳黑等導電性粒子作為著色劑的情況下,導電性 粒子較佳為粒徑10μm以上的粒子的含有率為1質量%以下。 When using conductive particles such as carbon black as a colorant, the conductivity The content of particles having a particle diameter of 10 μm or more is preferably 1 mass % or less.
在密封組成物含有導電性粒子的情況下,相對於環氧樹脂與硬化劑的合計量,導電性粒子的含有率較佳為3質量%以下。 When the sealing composition contains conductive particles, the content of the conductive particles is preferably 3% by mass or less relative to the total amount of the epoxy resin and the hardener.
(其他添加劑) (other additives)
密封組成物可視需要進而包含其他添加劑。 The sealing composition may further contain other additives as required.
作為其他添加劑,可列舉阻燃劑、陰離子交換體、塑化劑等。而且,密封組成物中亦可視需要添加該技術領域眾所周知的各種添加劑。 As other additives, flame retardants, anion exchangers, plasticizers, etc. can be listed. In addition, various additives well known in the technical field can also be added to the sealing composition as needed.
<密封組成物的製作方法> <How to prepare sealing composition>
密封組成物的製作方法並無特別限制,可藉由公知的方法進行。例如,可藉由利用混合機等將規定調配量的原材料的混合物充分混合後,利用熱輥、擠出機等加以混煉,並經過冷卻、粉碎等處理而製作密封組成物。密封組成物的狀態並無特別限制,可為粉末狀、固體狀、液體狀等。 There is no particular restriction on the method for preparing the sealing composition, and it can be carried out by a known method. For example, the sealing composition can be prepared by fully mixing a mixture of a specified amount of raw materials using a mixer, etc., kneading it using a hot roller, an extruder, etc., and then cooling, crushing, etc. The state of the sealing composition is not particularly limited, and it can be powder, solid, liquid, etc.
<密封組成物的特性> <Characteristics of sealing composition>
將密封組成物在硬化溫度175℃及硬化時間90秒的條件下加熱硬化時所獲得的硬化物的蕭氏D所表示的熱時硬度較佳為70以上,更佳為74以上,進而佳為76以上。 When the sealing composition is heated and cured at a curing temperature of 175°C and a curing time of 90 seconds, the hot hardness of the cured product represented by Shaw's D is preferably 70 or more, more preferably 74 or more, and even more preferably 76 or more.
藉由使所述熱時硬度為所述範圍,藉由轉移模塑法進行半導體元件的密封時的連續成形性變良好。 By setting the hot hardness to the above range, the continuous molding property when sealing the semiconductor element by transfer molding becomes good.
<半導體裝置> <Semiconductor devices>
本揭示的半導體裝置包含半導體元件、以及將所述半導體元 件密封的本揭示的密封組成物的硬化物。 The semiconductor device of the present disclosure includes a semiconductor element, and the semiconductor element The hardened product of the disclosed sealing composition of the component seal.
使用密封組成物來密封半導體元件的方法並無特別限定,可應用公知的方法。一般為轉移模塑法等,但亦可使用壓縮模塑法、噴射成形法、壓縮成形法等。 The method of using the sealing composition to seal the semiconductor element is not particularly limited, and known methods can be applied. Generally, it is a transfer molding method, but compression molding, injection molding, compression molding, etc. can also be used.
本揭示的半導體裝置作為積體電路(Integrated Circuit,IC)、大規模積體電路(Large-Scale Integration,LSI)等而較佳。 The semiconductor device of the present disclosure is preferably an integrated circuit (IC), a large-scale integrated circuit (Large-Scale Integration, LSI), or the like.
[實施例] [Implementation example]
以下,參照以下的實施例對本發明的一實施形態進行說明,但本發明並不限定於該些。而且,表中的數值只要無特別說明,則是指「質量份」。 Hereinafter, one embodiment of the present invention will be described with reference to the following embodiments, but the present invention is not limited to these. Moreover, the numerical values in the table refer to "weight parts" unless otherwise specified.
<實施例1~實施例5及比較例1~比較例5> <Example 1 to Example 5 and Comparative Example 1 to Comparative Example 5>
將下述所示的成分按照表1及表2中所示的調配比例(質量份)預先混合(乾式摻雜)後,利用雙軸捏合機進行混煉,並進行冷卻粉碎而製造粉末狀的密封組成物。 The following components are pre-mixed (dry blended) according to the blending ratios (mass parts) shown in Tables 1 and 2, kneaded using a double-screw kneader, and then cooled and crushed to produce a powdered sealing composition.
另外,表1及表2中所示的成分的詳細情況如下。 In addition, the details of the components shown in Table 1 and Table 2 are as follows.
(A)環氧樹脂 (A)Epoxy resin
環氧樹脂A1:三菱化學股份有限公司,商品名「YX4000H」,環氧基當量「192g/eq」,軟化點「107℃」,聯苯型環氧樹脂,具有所述通式(1)所表示的二價的連結基的環氧樹脂 Epoxy resin A1: Mitsubishi Chemical Co., Ltd., trade name "YX4000H", epoxy equivalent "192g/eq", softening point "107°C", biphenyl type epoxy resin, epoxy resin having a divalent linking group represented by the general formula (1)
(B)硬化劑 (B) Hardener
硬化劑B1:三苯基甲烷型酚樹脂,愛沃特(AirWater)股份有限公司,商品名「HE910-09」,羥基當量「104g/eq」,軟化點「80 ℃」,所述通式(2)所表示的酚樹脂 Hardener B1: triphenylmethane type phenol resin, AirWater Co., Ltd., trade name "HE910-09", hydroxyl equivalent "104g/eq", softening point "80 ℃", the phenol resin represented by the general formula (2)
(C)硬化促進劑 (C) Hardening accelerator
硬化促進劑C1:磷系硬化促進劑(三丁基膦與苯醌的加成物) Hardening accelerator C1: Phosphorus-based hardening accelerator (addition product of tributylphosphine and benzoquinone)
(D)偶合劑 (D)Coupling agent
偶合劑D1:3-甲基丙烯醯氧基丙基三甲氧基矽烷,信越化學工業股份有限公司,商品名「KBM-503」,具有碳數為3的烴基的矽烷化合物 Coupling agent D1: 3-methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-503", a silane compound having a hydrocarbon group with 3 carbon atoms
偶合劑D2:8-甲基丙烯醯氧基辛基三甲氧基矽烷,信越化學工業股份有限公司,商品名「KBM-5803」,具有碳數為8的鏈狀烴基的矽烷化合物 Coupling agent D2: 8-methacryloxyoctyltrimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd., trade name "KBM-5803", a silane compound having a chain hydrocarbon group with 8 carbon atoms
(E)脫模劑 (E) Release agent
脫模劑E1:褐煤蠟,科萊恩(Clariant)公司,商品名「HW-E」 Release agent E1: montan wax, Clariant company, trade name "HW-E"
(F)著色劑 (F)Coloring agent
顏料F1:碳黑,三菱化學股份有限公司,商品名「MA600」 Pigment F1: Carbon black, Mitsubishi Chemical Co., Ltd., trade name "MA600"
(G)添加劑 (G)Additives
添加劑G1:三苯基氧化膦 Additive G1: triphenylphosphine oxide
(H)改質劑 (H) Modifier
改質劑H1:矽酮,東麗道康寧(Toray Dow Corning)股份有限公司,商品名「BY16-876」 Modifier H1: Silicone, Toray Dow Corning Co., Ltd., trade name "BY16-876"
(I)無機填充材 (I) Inorganic fillers
填料I1:二氧化矽粒子,球狀,比表面積「190m2/g~210m2/g」,特定二氧化矽粒子 Filler I1: Silica particles, spherical, specific surface area "190m 2 /g ~ 210m 2 /g", specific silica particles
填料I2:氧化鋁粒子,球狀,平均粒徑「0.7μm」 Filler I2: Alumina particles, spherical, average particle size "0.7μm"
填料I3:氧化鋁粒子,球狀,平均粒徑「10μm」 Filler I3: Alumina particles, spherical, average particle size "10μm"
-評價- -Evaluation-
藉由以下的特性試驗對實施例及比較例中製作的密封組成物的特性進行評價。將評價結果示於下述表1及表2。 The properties of the sealing compositions prepared in the embodiments and comparative examples were evaluated by the following property tests. The evaluation results are shown in Tables 1 and 2 below.
(熱時硬度) (Hot hardness)
使用上述所獲得的密封組成物,藉由轉注成形機,在金屬模具溫度175℃、成形壓力6.9MPa、硬化時間90秒的條件下進行成形,製作直徑50mm×厚度3mm的圓板形狀的試驗片。成形後立即使用蕭氏D型硬度計(高分子計量器股份有限公司,阿斯卡(ASKER),類型D硬度計(type D durometer))測定熱時硬度。 The sealing composition obtained above was used to form a circular plate-shaped test piece with a diameter of 50 mm and a thickness of 3 mm by using a transfer molding machine at a metal mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Immediately after forming, the hot hardness was measured using a Shaw type D durometer (ASKER, Polymer Measuring Instrument Co., Ltd., type D durometer).
(凝膠時間(gel time)) (gel time)
硬化性是基於使用凝膠化試驗機如下測定的凝膠時間來進行評價。 The hardening property is evaluated based on the gelation time measured as follows using a gelation tester.
將上述所獲得的密封組成物0.5g載置於加熱為175℃的熱板上,使用夾具以20轉/分~25轉/分的旋轉速度,將試樣均勻地擴展為2.0cm~2.5cm的圓狀。測量將試樣載置於熱板後,至試樣的黏性消失,成為凝膠狀態而可自熱板剝離為止的時間,將其作為凝膠時間(sec)來測定。 Place 0.5 g of the sealing composition obtained above on a hot plate heated to 175°C, and use a clamp to evenly expand the sample to 2.0 cm to 2.5 cm at a rotation speed of 20 rpm to 25 rpm. of round shape. After the sample is placed on the hot plate, the time until the viscosity of the sample disappears and the sample becomes a gel state and can be peeled off from the hot plate is measured, and this is measured as gel time (sec).
將結果示於表1及表2。在相對於環氧基100質量份,使用了相同的觸媒量的情況下,凝膠時間越短,硬化性越優異。 The results are shown in Tables 1 and 2. When the same amount of catalyst is used relative to 100 parts by mass of epoxy, the shorter the gelation time, the better the curing property.
(圓盤狀流動(disk flow,DF)) (disk flow (DF))
使上述所獲得的密封組成物通過二段篩(上段:2.38mm、下段:0.5mm),將下段殘留的試樣秤量7g。將所述密封組成物放置於加熱為180℃的平滑的金屬模具之上,將同樣地加熱為180℃的8kg的平滑的金屬模具放置於試樣之上放置60秒。其後,求出所獲得的圓板狀成形品的長徑(mm)與短徑(mm)的平均值(mm),將所述平均值(mm)設為圓盤狀流動(DF)。 The sealing composition obtained above is passed through a two-stage sieve (upper stage: 2.38mm, lower stage: 0.5mm), and the sample remaining in the lower stage is weighed 7g. The sealing composition is placed on a smooth metal mold heated to 180°C, and an 8kg smooth metal mold heated to 180°C is placed on the sample for 60 seconds. Thereafter, the average value (mm) of the long diameter (mm) and short diameter (mm) of the obtained disk-shaped molded product is calculated, and the average value (mm) is set as the disc flow (DF).
將結果示於表1及表2。圓盤狀流動越長,流動性越優異。 The results are shown in Tables 1 and 2. The longer the disc-shaped flow is, the better the fluidity is.
(毛邊) (Rough edges)
將上述所獲得的密封組成物15g載置於壓制熱板上的180℃的金屬模具上,以硬化時間90秒進行成形。成形後,使用遊標卡尺測定金屬模具中所製作的50μm、30μm、20μm、10μm、5μm及2μm的狹縫中密封組成物流動最長的部分的長度,將該測定值設為毛邊長度。 15 g of the sealing composition obtained above was placed on a 180° C. metal mold on a pressing hot plate, and molded with a hardening time of 90 seconds. After molding, a vernier caliper was used to measure the length of the portion where the sealing composition flows longest among the slits of 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm produced in the metal mold, and the measured value was regarded as the burr length.
結果,可知:在實施例1~實施例5的任一者中,毛邊長度均為10mm以下,毛邊的產生得到了抑制。 As a result, it can be seen that in any of Examples 1 to 5, the length of the burrs is less than 10 mm, and the generation of burrs is suppressed.
(導熱率) (thermal conductivity)
使用上述所獲得的密封組成物,藉由轉注成形機,在金屬模具溫度175℃~180℃、成形壓力7MPa、硬化時間300秒的條件下,製作導熱率評價用的試驗片。繼而,針對成形的試驗片,測定厚度方向的熱擴散率。熱擴散率的測定是藉由雷射閃光(Laser Flash)法(裝置:LFA467奈米閃光(LFA467 nanoflash),耐馳(NETZSCH)公司)來進行。脈衝光照射是在脈衝寬度0.31(ms)、 施加電壓247V的條件下來進行。測定是在環境溫度25℃±1℃下進行。而且,所述試驗片的密度是使用電子比重計(AUX220,島津製作所股份有限公司)來進行測定。比熱是使用藉由各材料的比熱的文獻值與調配比率而算出的密封組成物的理論比熱。 Using the sealing composition obtained above, a test piece for thermal conductivity evaluation was produced using a transfer molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a hardening time of 300 seconds. Next, the thermal diffusivity in the thickness direction of the formed test piece was measured. The thermal diffusivity was measured by the laser flash method (device: LFA467 nanoflash, NETZSCH company). Pulse light irradiation is performed at a pulse width of 0.31 (ms), It is carried out under the condition of applying voltage 247V. The measurement is carried out at an ambient temperature of 25°C±1°C. Furthermore, the density of the test piece was measured using an electronic hydrometer (AUX220, Shimadzu Corporation). The specific heat is the theoretical specific heat of the sealing composition calculated using the literature value of the specific heat of each material and the blending ratio.
繼而,使用式(5)將比熱及密度乘以熱擴散率,藉此獲得導熱率的值。 Next, use equation (5) to multiply the specific heat and density by the heat diffusion rate to obtain the value of thermal conductivity.
λ=α×Cp×ρ…式(5) λ=α×Cp×ρ…Equation (5)
(式(5)中,λ表示導熱率(W/(m.K)),α表示熱擴散率(m2/s)、Cp表示比熱(J/(kg.K)),ρ表示密度(kg/m3)) (In formula (5), λ represents thermal conductivity (W/(m.K)), α represents thermal diffusivity (m 2 /s), Cp represents specific heat (J/(kg.K)), and ρ represents density ( kg/m 3 ))
將結果示於表1及表2。 The results are shown in Table 1 and Table 2.
表1及表2中,「填料的平均粒徑」是指所使用的無機填充材整體中的體積基準的平均粒徑,「填料含有率」是指所使用的無機填充材整體相對於密封組成物整體的含有率。 In Tables 1 and 2, the "average particle size of the filler" refers to the volume-based average particle size of the entire inorganic filler used, and the "filler content rate" refers to the total inorganic filler used relative to the sealing composition. The overall content of the substance.
根據表1及表2的評價結果可明確:含有特定矽烷化合物的實施例1~實施例5的密封組成物相較於不含特定矽烷化合物的 比較例1~比較例5的密封組成物,獲得了流動性高,而且導熱率高的硬化物。而且,可知:在比較例1~比較例5的密封組成物中,相對於填料含有率的增加而言,導熱性的上升率低,導熱性成為飽和狀態,相對於此,在實施例1~實施例3的密封組成物中,伴隨著填料含有率的增加,導熱率變高。 From the evaluation results in Table 1 and Table 2, it is clear that the sealing compositions of Examples 1 to 5 containing the specific silane compound are better than those containing the specific silane compound. For the sealing compositions of Comparative Examples 1 to 5, cured products with high fluidity and high thermal conductivity were obtained. Furthermore, it is found that in the sealing compositions of Comparative Examples 1 to 5, the increase rate of thermal conductivity is low with respect to the increase in filler content, and the thermal conductivity becomes a saturated state. In contrast, in Examples 1 to 5, the thermal conductivity is in a saturated state. In the sealing composition of Example 3, as the filler content rate increases, the thermal conductivity becomes higher.
2018年12月21日申請的日本專利申請案2018-239254號的揭示的整體藉由參照而併入至本說明書中。 The entire disclosure of Japanese Patent Application No. 2018-239254 filed on December 21, 2018 is incorporated into this specification by reference.
關於本說明書中所記載的所有文獻、專利申請案、及技術規格,與具體且各個地記載有藉由參照而併入各個文獻、專利申請案、及技術規格的情況同等程度地,併入至本說明書中。 All documents, patent applications, and technical specifications described in this specification are hereby incorporated by reference to the same extent as if each individual document, patent application, or technical specification was specifically and individually stated to be incorporated by reference. in this manual.
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---|---|---|---|---|
JP2018188667A (en) * | 2011-04-01 | 2018-11-29 | 日立化成株式会社 | Solid sealing resin composition for compression molding and semiconductor device |
CN106833470A (en) * | 2017-02-24 | 2017-06-13 | 厦门安耐伟业新材料有限公司 | Fluid sealant and preparation method thereof, application method |
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