JP2008063564A - Semiconductor-sealing epoxy resin composition and semiconductor device - Google Patents
Semiconductor-sealing epoxy resin composition and semiconductor device Download PDFInfo
- Publication number
- JP2008063564A JP2008063564A JP2007195372A JP2007195372A JP2008063564A JP 2008063564 A JP2008063564 A JP 2008063564A JP 2007195372 A JP2007195372 A JP 2007195372A JP 2007195372 A JP2007195372 A JP 2007195372A JP 2008063564 A JP2008063564 A JP 2008063564A
- Authority
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- Prior art keywords
- epoxy resin
- resin composition
- tolylene diisocyanate
- semiconductor encapsulation
- modified oxidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 130
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 129
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 238000007789 sealing Methods 0.000 title claims abstract description 18
- 239000004065 semiconductor Substances 0.000 title claims description 73
- 125000005628 tolylene group Chemical group 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000011256 inorganic filler Substances 0.000 claims abstract description 25
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 25
- 239000005011 phenolic resin Substances 0.000 claims abstract description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract 2
- 229920001568 phenolic resin Polymers 0.000 claims abstract 2
- 239000001993 wax Substances 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 36
- 238000005538 encapsulation Methods 0.000 claims description 34
- -1 polypropylene Polymers 0.000 claims description 21
- 150000001768 cations Chemical group 0.000 claims description 20
- 125000000962 organic group Chemical group 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 57
- 239000011347 resin Substances 0.000 abstract description 57
- 238000000465 moulding Methods 0.000 abstract description 17
- 125000002091 cationic group Chemical group 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 238000000034 method Methods 0.000 description 23
- 229910000679 solder Inorganic materials 0.000 description 23
- 238000002156 mixing Methods 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 11
- 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 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000005204 segregation Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
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- 238000012546 transfer Methods 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-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
- 229930185605 Bisphenol Natural products 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
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- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-O phenylphosphanium Chemical compound [PH3+]C1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 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
- 235000012239 silicon dioxide Nutrition 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/13—Discrete devices, e.g. 3 terminal devices
- H01L2924/1301—Thyristor
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、半導体封止用エポキシ樹脂組成物、及びこれを用いた半導体装置に関するものである。 The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same.
ＩＣ、ＬＳＩ等の半導体素子の封止方法として、半導体封止用エポキシ樹脂組成物のトランスファー成形が低コスト、大量生産に適しており、採用されて久しく、信頼性の点でもエポキシ樹脂や硬化剤であるフェノール樹脂系硬化剤の改良により特性の向上が図られてきた。しかし、近年の電子機器の小型化、軽量化、高性能化の市場動向において、半導体の高集積化も年々進み、また半導体装置の表面実装化が促進されるなかで、半導体封止用エポキシ樹脂組成物への要求は益々厳しいものとなってきている。このため、従来からの半導体封止用エポキシ樹脂組成物では解決出来ない問題点も出てきている。
その最大の問題点は、表面実装の採用により半導体装置が半田浸漬或いは半田リフロー工程で急激に２００℃以上の高温にさらされ、吸湿した水分が爆発的に気化する際の応力により、半導体装置内、特に半導体素子、リードフレーム、インナーリード上の金メッキや銀メッキ等の各種メッキされた各接合部分とエポキシ樹脂組成物の硬化物の界面で剥離が生じたりして、信頼性が著しく低下する現象である。また、環境問題に端を発した有鉛半田から無鉛半田への移行に伴い、半田処理時の温度が高くなり、半導体装置中に含まれる水分の気化によって発生する爆発的な応力による耐半田性が、従来以上に大きな問題となってきている。
As a sealing method for semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition for semiconductor sealing is suitable for low-cost and mass production, and it has been used for a long time. The improvement of the characteristic has been aimed at by the improvement of the phenol resin hardening | curing agent which is. However, due to the recent trend toward smaller, lighter, and higher performance electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition for semiconductor sealing has also come out.
The biggest problem is that by adopting surface mounting, the semiconductor device is suddenly exposed to a high temperature of 200 ° C. or higher in the solder dipping or solder reflow process, and the moisture when moisture absorbed explosively evaporates. In particular, a phenomenon in which reliability is remarkably reduced due to peeling at the interface between various plated joints such as gold plating and silver plating on semiconductor elements, lead frames, and inner leads and the cured product of the epoxy resin composition. It is. In addition, with the shift from leaded solder to lead-free solder, which originated from environmental problems, the temperature during the soldering process increased, and the solder resistance due to explosive stress generated by the evaporation of moisture contained in the semiconductor device However, it has become a bigger problem than before.
半田処理による信頼性低下を改善するために、エポキシ樹脂組成物中の無機質充填材の充填量を増加させることでエポキシ樹脂組成物の硬化物の低吸湿化、高強度化、低熱膨張化を達成し、半導体装置の耐半田性を向上させ、かつ低溶融粘度の樹脂を使用することでエポキシ樹脂組成物の成形時に低粘度性と高流動性とを維持させる手法がある（例えば、特許文献１参照。）。この手法を用いることによりエポキシ樹脂組成物の硬化物の耐半田性はかなり改良されるが、無機充填材の充填割合の増加と共に、エポキシ樹脂組成物の成形時の流動性が犠牲になり、エポキシ樹脂組成物がパッケージ内に十分に充填されず、空隙が生じやすくなる欠点があった。
また、生産性向上への取り組みとしては、離型効果の高い離型剤の適用が提案されている（例えば、特許文献２参照。）が、無機充填材の増加に伴う樹脂成分の減少により、離型剤成分の分散性不足と思われる離型性不良、金型への樹脂トラレや樹脂硬化物の外観不良が問題となっており、特に離型効果の高い離型剤は必然的に樹脂硬化物の表面に浮き出しやすく、連続生産すると樹脂硬化物の外観を著しく汚してしまう欠点があった。このようなことから、無機充填材の配合量を高めても成形時の流動性及び充填性を損なわず、連続成形性、樹脂硬化物の外観、金型汚れといった課題にも対応し、かつ半導体装置の信頼性を満足させる更なる技術が求められていた。
In order to improve reliability reduction due to solder processing, the amount of inorganic filler in the epoxy resin composition is increased to achieve low moisture absorption, high strength, and low thermal expansion of the cured product of the epoxy resin composition. In addition, there is a technique for improving the solder resistance of a semiconductor device and maintaining low viscosity and high fluidity at the time of molding an epoxy resin composition by using a low melt viscosity resin (for example, Patent Document 1). reference.). By using this method, the solder resistance of the cured product of the epoxy resin composition is considerably improved. However, as the filling ratio of the inorganic filler increases, the fluidity at the time of molding the epoxy resin composition is sacrificed, and the epoxy resin composition is cured. There was a drawback that the resin composition was not sufficiently filled in the package and voids were likely to occur.
In addition, as an effort to improve productivity, application of a release agent having a high release effect has been proposed (see, for example, Patent Document 2), but due to a decrease in resin components accompanying an increase in inorganic filler, There are problems with poor mold releasability, which is thought to be due to insufficient dispersibility of the mold release agent component, and poor appearance of resin trays and cured resin products, especially mold release agents with a high mold release effect. There was a defect that the surface of the cured product was easily raised, and the appearance of the cured resin product was significantly soiled when continuously produced. For this reason, even if the amount of the inorganic filler is increased, the fluidity and filling property during molding are not impaired, and the problems such as continuous moldability, appearance of the cured resin product, and mold contamination are dealt with. There has been a demand for further technology that satisfies the reliability of the apparatus.
本発明は、無機充填材の配合量を高めた場合でも、封止成形時において良好な流動性、硬化性、離型性、連続成形性を有し、かつ樹脂硬化物の外観汚れや金型汚れが発生し難い半導体封止用エポキシ樹脂組成物を提供するものである。 The present invention has good fluidity, curability, releasability, and continuous moldability at the time of sealing molding even when the amount of inorganic filler is increased, and appearance stains and molds of resin cured products It is an object of the present invention to provide an epoxy resin composition for encapsulating a semiconductor that is less likely to cause dirt.
［１］ （Ａ）エポキシ樹脂、（Ｂ）フェノール樹脂系硬化剤、（Ｃ）無機充填材、（Ｄ）硬化促進剤、及び（Ｅ）トリレンジイソシアネート変性酸化ワックスを含み、前記硬化促進剤（Ｄ）がカチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）を含み、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の全エポキシ樹脂組成物中における配合割合が０．０１重量％以上、１重量％以下の割合であることを特徴とする半導体封止用エポキシ樹脂組成物、
［２］ 第［１］項に記載の半導体封止用エポキシ樹脂組成物において、前記カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）のカチオン部が燐カチオンを含むものであることを特徴とする半導体封止用エポキシ樹脂組成物、
[1] (A) epoxy resin, (B) phenol resin curing agent, (C) inorganic filler, (D) curing accelerator, and (E) tolylene diisocyanate-modified oxidized wax, D) includes a curing accelerator (d1) having a cation part and a silicate anion part, and the blending ratio of the tolylene diisocyanate-modified oxidized wax (E) in the total epoxy resin composition is 0.01% by weight or more, 1 An epoxy resin composition for encapsulating a semiconductor, characterized in that the proportion is equal to or less than wt%,
[2] The epoxy resin composition for semiconductor encapsulation according to item [1], wherein the cation part of the curing accelerator (d1) having a cation part and a silicate anion part contains a phosphorus cation. An epoxy resin composition for semiconductor encapsulation,
［３］ 第［１］項又は第［２］項に記載の半導体封止用エポキシ樹脂組成物において、前記カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）が下記一般式（１）で表される化合物であることを特徴とする半導体封止用エポキシ樹脂組成物、
［４］ 第［１］項ないし第［３］項のいずれかに記載の半導体封止用エポキシ樹脂組成物において、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の軟化点が７０℃以上、１２０℃以下であることを特徴とする半導体封止用エポキシ樹脂組成物、
［５］ 第［１］項ないし第［４］項のいずれかに記載の半導体封止用エポキシ樹脂組成物において、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の平均粒径が２０μｍ以上、７０μｍ以下であり、全トリレンジイソシアネート変性酸化ワックス（Ｅ）中における粒径１５０μｍ以上の粒子の含有割合が０．１重量％以下であることを特徴とする半導体封止用エポキシ樹脂組成物、
［６］ 第［１］項ないし第［５］項のいずれかに記載の半導体封止用エポキシ樹脂組成物において、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の酸価が１０ｍｇＫＯＨ／ｇ以上、５０ｍｇＫＯＨ／ｇ以下であることを特徴とする半導体封止用エポキシ樹脂組成物、
［７］ 第［１］項ないし第［６］項のいずれかに記載の半導体封止用エポキシ樹脂組成物において、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の数平均分子量が５００以上、５０００以下であることを特徴とする半導体封止用エポキシ樹脂組成物、
［８］ 第［１］項ないし第［７］項のいずれかに記載の半導体封止用エポキシ樹脂組成物において、前記トリレンジイソシアネート変性酸化ワックス（Ｅ）がトリレンジイソシアネート変性酸化ポリプロピレンワックス、トリレンジイソシアネート変性酸化ポリエチレンワックス及びトリレンジイソシアネート変性酸化パラフィンワックスから選ばれる少なくとも一つであることを特徴とする半導体封止用エポキシ樹脂組成物、
［９］ 第［１］項ないし第［８］項のいずれかに記載の半導体封止用エポキシ樹脂組成物の硬化物により半導体素子が封止されてなることを特徴とする半導体装置、
である。
[4] The epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [3], wherein the tolylene diisocyanate-modified oxidized wax (E) has a softening point of 70 ° C. or higher and 120 ° C. An epoxy resin composition for semiconductor encapsulation, characterized by:
[5] The epoxy resin composition for semiconductor encapsulation according to any one of [1] to [4], wherein the tolylene diisocyanate-modified oxidized wax (E) has an average particle size of 20 μm or more and 70 μm or less. An epoxy resin composition for encapsulating a semiconductor, wherein the content ratio of particles having a particle size of 150 μm or more in the all-tolylene diisocyanate-modified oxidized wax (E) is 0.1% by weight or less,
[6] The epoxy resin composition for semiconductor encapsulation according to any one of [1] to [5], wherein the acid value of the tolylene diisocyanate-modified oxidized wax (E) is 10 mgKOH / g or more and 50 mgKOH. Epoxy resin composition for semiconductor encapsulation, characterized by being / g or less,
[7] The epoxy resin composition for semiconductor encapsulation according to any one of [1] to [6], wherein the number-average molecular weight of the tolylene diisocyanate-modified oxidized wax (E) is 500 or more and 5000 or less. An epoxy resin composition for semiconductor encapsulation, characterized in that
[8] In the epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [7], the tolylene diisocyanate-modified oxidized wax (E) is tolylene diisocyanate-modified polypropylene wax, An epoxy resin composition for semiconductor encapsulation, which is at least one selected from a range isocyanate-modified polyethylene oxide wax and a tolylene diisocyanate-modified oxidation paraffin wax;
[9] A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin composition for sealing a semiconductor according to any one of [1] to [8],
It is.
本発明に従うと、無機充填材の配合量を高めた場合でも、半導体素子等の封止成形時において良好な流動性、硬化性、離型性、連続成形性を有し、かつ樹脂硬化物の外観汚れや金型汚れが発生し難い半導体封止用エポキシ樹脂組成物が得られるものである。 According to the present invention, even when the blending amount of the inorganic filler is increased, it has good fluidity, curability, releasability, and continuous moldability at the time of sealing molding of a semiconductor element, etc. An epoxy resin composition for encapsulating semiconductors that hardly causes appearance stains and mold stains is obtained.
本発明は、エポキシ樹脂、フェノール樹脂系硬化剤、無機充填材、カチオン部とシリケートアニオン部とを有する硬化促進剤、及びトリレンジイソシアネート変性酸化ワックスを含むことにより、成形封止する時の流動性、硬化性、離型性、連続成形性に優れた半導体封止用エポキシ樹脂組成物が得られるものである。
以下、本発明について詳細に説明する。
The present invention includes an epoxy resin, a phenol resin-based curing agent, an inorganic filler, a curing accelerator having a cation portion and a silicate anion portion, and fluidity at the time of molding and sealing by including a tolylene diisocyanate-modified oxidized wax. Thus, an epoxy resin composition for semiconductor encapsulation excellent in curability, mold release property and continuous moldability can be obtained.
Hereinafter, the present invention will be described in detail.
本発明に用いるエポキシ樹脂（Ａ）は、１分子内にエポキシ基を２個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定するものではないが、例えば、ビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェニレン骨格、ビフェニレン骨格等を有するフェノールアラルキル型エポキシ樹脂、硫黄原子含有型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレン骨格、ビフェニレン骨格等を有するナフトールアラルキル型エポキシ樹脂等が挙げられ、これらは１種類を単独で用いても２種類以上を併用しても差し支えない。これらの内で特に耐半田性が求められる場合には、常温では結晶性の固体であるが、融点以上では極めて低粘度の液状となり、無機質充填材を高充填化できるビフェニル型エポキシ樹脂、ビスフェノール型エポキシ樹脂、スチルベン型エポキシ樹脂等の結晶性エポキシ樹脂が好ましい。また、無機質充填材の高充填化という観点からは、その他のエポキシ樹脂の場合も極力粘度の低いものを使用することが望ましい。また、耐半田性、可撓性、低吸湿化が求められる場合には、エポキシ基が結合した芳香環の間にエポキシ基を有さず、疎水性を示すフェニレン骨格やビフェニレン骨格等を有することで、低吸湿性や実装高温域での低弾性を示すフェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂等のアラルキル型エポキシ樹脂が好ましい。しかしながら、上記のような低粘度や可撓性を有するエポキシ樹脂を用いた場合には、樹脂硬化物の架橋密度が低くなるため、樹脂硬化物の金型からの離型性が低下するという問題点もあり、後述するトリレンジイソシアネート変性酸化ワックス（Ｅ）を用いることにより離型性を改善する必要がある場合もある。 The epoxy resin (A) used in the present invention is a monomer, oligomer, or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified Phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene skeleton, biphenylene skeleton, etc., sulfur atom containing type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, phenylene skeleton, Naphthol aralkyl type epoxy resins. Having Eniren skeleton like, which may be used in combination of two or more be used one kind alone. Among these, when solder resistance is particularly required, it is a crystalline solid at room temperature, but it becomes a liquid with a very low viscosity above the melting point, and can be highly filled with inorganic fillers. Biphenyl type epoxy resin, bisphenol type Crystalline epoxy resins such as epoxy resins and stilbene type epoxy resins are preferred. From the viewpoint of increasing the filling of the inorganic filler, it is desirable to use other epoxy resins having a viscosity as low as possible. In addition, when solder resistance, flexibility, and low moisture absorption are required, there should be no phenylene skeleton or biphenylene skeleton or the like having an epoxy group between the aromatic rings to which the epoxy group is bonded. Thus, aralkyl type epoxy resins such as phenol aralkyl type epoxy resins and naphthol aralkyl type epoxy resins exhibiting low hygroscopicity and low elasticity in a high temperature range for mounting are preferable. However, when an epoxy resin having low viscosity or flexibility as described above is used, the crosslink density of the cured resin becomes low, so that the releasability of the cured resin from the mold is lowered. There are also points, and it may be necessary to improve the releasability by using the tolylene diisocyanate-modified oxidized wax (E) described later.
本発明に用いられるエポキシ樹脂（Ａ）全体の配合割合は、特に限定されないが、全エポキシ樹脂組成物中に、２重量％以上、１０重量％以下であることが好ましく、４重量％以上、８重量％以下であることがより好ましい。エポキシ樹脂（Ａ）全体の配合割合が上記範囲内であると、耐半田性の低下、流動性の低下等を引き起こす恐れが少ない。 The blending ratio of the entire epoxy resin (A) used in the present invention is not particularly limited, but is preferably 2% by weight or more and 10% by weight or less in the total epoxy resin composition, and is 4% by weight or more, 8 More preferably, it is less than or equal to weight percent. When the blending ratio of the entire epoxy resin (A) is within the above range, there is little risk of causing a decrease in solder resistance, a decrease in fluidity, and the like.
本発明に用いるフェノール樹脂系硬化剤（Ｂ）は、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造を特に限定するものではないが、例えばフェノールノボラック樹脂、クレゾールノボラック樹脂、ジシクロペンタジエン変性フェノール樹脂、テルペン変性フェノール樹脂、トリフェノールメタン型樹脂、フェニレン骨格、ビフェニレン骨格等を有するフェノールアラルキル樹脂、硫黄原子含有型フェノール樹脂、ナフトールノボラック樹脂、フェニレン骨格、ビフェニレン骨格等を有するナフトールアラルキル樹脂等が挙げられ、これらは１種類を単独で用いても２種類以上を併用しても差し支えない。これらの内で特に耐半田性が求められる場合には、エポキシ樹脂と同様に、低粘度の樹脂が無機質充填材の高充填化できるという点で好ましく、更に可撓性、低吸湿性が求められる場合には、フェニレン骨格、ビフェニレン骨格を有するフェノールアラルキル樹脂の使用が好ましい。しかしながら、低粘度や可撓性を有するフェノール樹脂系硬化剤を用いた場合には、樹脂硬化物の架橋密度が低くなるため、樹脂硬化物の金型からの離型性が低下するという問題点もあり、後述するトリレンジイソシアネート変性酸化ワックス（Ｅ）を用いることにより離型性を改善する必要がある場合もある。 The phenol resin-based curing agent (B) used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Phenol novolac resin, cresol novolak resin, dicyclopentadiene modified phenol resin, terpene modified phenol resin, triphenolmethane type resin, phenol aralkyl resin having phenylene skeleton, biphenylene skeleton, etc., sulfur atom-containing phenol resin, naphthol novolak resin, phenylene Examples thereof include naphthol aralkyl resins having a skeleton, a biphenylene skeleton, and the like, and these may be used alone or in combination of two or more. Among these, when solder resistance is particularly required, a low-viscosity resin is preferable in terms of being able to increase the filling of the inorganic filler, as well as the epoxy resin, and further, flexibility and low hygroscopicity are required. In this case, it is preferable to use a phenol aralkyl resin having a phenylene skeleton or a biphenylene skeleton. However, when a phenol resin-based curing agent having low viscosity or flexibility is used, the crosslink density of the cured resin becomes low, so that the releasability of the cured resin from the mold is lowered. In some cases, it is necessary to improve the releasability by using the tolylene diisocyanate-modified oxidized wax (E) described later.
本発明に用いられるフェノール樹脂系硬化剤（Ｂ）の配合割合は、特に限定されないが、全エポキシ樹脂組成物中に、２重量％以上、８重量％以下であることが好ましく、３重量％以上、６重量％以下であることがより好ましい。フェノール樹脂系硬化剤（Ｂ）全体の配合割合が上記範囲内であると、耐半田性の低下、流動性の低下等を引き起こす恐れが少ない。 The blending ratio of the phenol resin-based curing agent (B) used in the present invention is not particularly limited, but is preferably 2% by weight or more and 8% by weight or less in the total epoxy resin composition, and 3% by weight or more. 6% by weight or less is more preferable. When the blending ratio of the entire phenol resin-based curing agent (B) is within the above range, there is little risk of causing a decrease in solder resistance, a decrease in fluidity, and the like.
本発明に用いるエポキシ樹脂（Ａ）とフェノール樹脂系硬化剤（Ｂ）の配合比率としては、全エポキシ樹脂のエポキシ基数（ＥＰ）と全フェノール樹脂系硬化剤のフェノール性水酸基数（ＯＨ）の比（ＥＰ／ＯＨ）が、０．７以上、１．３以下であることが好ましい。この範囲であると、エポキシ樹脂組成物の硬化性の低下、或いは樹脂硬化物のガラス転移温度の低下、耐湿信頼性の低下等を抑えることができる。 As a compounding ratio of the epoxy resin (A) and the phenol resin curing agent (B) used in the present invention, the ratio of the number of epoxy groups (EP) of all epoxy resins and the number of phenolic hydroxyl groups (OH) of all phenol resin curing agents. (EP / OH) is preferably 0.7 or more and 1.3 or less. Within this range, it is possible to suppress a decrease in curability of the epoxy resin composition, a decrease in the glass transition temperature of the cured resin, a decrease in moisture resistance reliability, and the like.
本発明に用いる無機充填材（Ｃ）としては、一般に半導体封止用エポキシ樹脂組成物に使用されているものを用いることができ、特に限定されるものではないが、例えば、溶融シリカ、結晶シリカ、タルク、アルミナ、窒化珪素等が挙げられ、最も好適に使用されるものとしては、球状の溶融シリカである。これらの無機充填材は、１種類を単独で用いても２種類以上を併用しても差し支えない。無機充填材（Ｃ）の最大粒径については、特に限定されないが、無機充填材の粗大粒子が狭くなったワイヤー間に挟まることによって生じるワイヤー流れ等の不具合の防止を考慮すると、１０５μｍ以下であることが好ましく、７５μｍ以下であることがより好ましい。 As an inorganic filler (C) used for this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used, Although it does not specifically limit, For example, fused silica, crystalline silica , Talc, alumina, silicon nitride, and the like, and most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination of two or more. The maximum particle size of the inorganic filler (C) is not particularly limited, but is 105 μm or less in consideration of prevention of defects such as wire flow caused by the coarse particles of the inorganic filler being sandwiched between the narrowed wires. It is preferable that it is 75 μm or less.
本発明で用いられる無機充填材（Ｃ）の含有量は、特に限定されないが、全エポキシ樹脂組成物中に８０重量％以上、９４重量％以下であることが好ましく、８４重量％以上、９２重量％以下であることがより好ましい。この範囲であると、耐半田性の低下、流動性の低下等を抑えることができる。 Although content of the inorganic filler (C) used by this invention is not specifically limited, It is preferable that they are 80 weight% or more and 94 weight% or less in all the epoxy resin compositions, and 84 weight% or more and 92 weight%. % Or less is more preferable. Within this range, a decrease in solder resistance, a decrease in fluidity, and the like can be suppressed.
本発明で用いられる硬化促進剤（Ｄ）は、エポキシ樹脂の硬化反応を促進し得るカチオン部と前記硬化反応を促進するカチオン部の触媒活性を抑制するシリケートアニオン部とを有する硬化促進剤（ｄ１）（以下、単に「硬化促進剤（ｄ１）」ともいう。）を含むことが必須である。硬化促進剤（ｄ１）は、エポキシ樹脂（Ａ）とフェノール樹脂系硬化剤（Ｂ）の成形温度よりも低温域においては、容易には硬化反応を開始、促進させないため、流動性や保存安定性に優れた特性を付与することができるものである。また、硬化促進剤（ｄ１）は、成形温度域においては、容易にカチオン部が遊離して、硬化反応を促進するため、上記特性に加え、優れた硬化性をも同時に付与することができるものである。カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）としては、カチオン部が燐カチオンを含むものが好ましく、下記一般式（１）で表される化合物がさらに好ましい。
前記一般式（１）において、Ｒ１、Ｒ２、Ｒ３及びＲ４としては、例えば、フェニル基、メチルフェニル基、メトキシフェニル基、ヒドロキシフェニル基、ナフチル基、ヒドロキシナフチル基、ベンジル基、メチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基及びシクロヘキシル基等が挙げられ、これらの中でも、フェニル基、メチルフェニル基、メトキシフェニル基、ヒドロキシフェニル基、ヒドロキシナフチル基などの芳香族基がより好ましい。
In the general formula (1), examples of R1, R2, R3, and R4 include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, and an ethyl group. , N-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, aromatic groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, and hydroxynaphthyl group are more preferable.
また、前記一般式（１）において、基Ｘ１は、基Ｙ１及びＹ２と結合する有機基である。同様に、基Ｘ２は、基Ｙ３及びＹ４と結合する有機基である。基Ｙ１及びＹ２はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の基Ｙ１、及びＹ２が珪素原子と結合してキレート構造を形成するものである。同様に基Ｙ３、及びＹ４はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の基Ｙ３及びＹ４が珪素原子と結合してキレート構造を形成するものである。基Ｘ１、及びＸ２は互いに同一であっても異なっていてもよく、基Ｙ１、Ｙ２、Ｙ３、及びＹ４は互いに同一であっても異なっていてもよい。このような一般式（１）中のＹ１Ｘ１Ｙ２、及びＹ３Ｘ２Ｙ４で示される基は、プロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、プロトン供与体としては、例えば、カテコール、ピロガロール、１，２−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，２’−ビフェノール、２，２’−ビナフトール、サリチル酸、１−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、クロラニル酸、タンニン酸、２−ヒドロキシベンジルアルコール、１，２−シクロヘキサンジオール、１，２−プロパンジオール及びグリセリン等が挙げられるが、これらの中でも、カテコール、１，２−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレンがより好ましい。 In the general formula (1), the group X1 is an organic group bonded to the groups Y1 and Y2. Similarly, the group X2 is an organic group bonded to the groups Y3 and Y4. The groups Y1 and Y2 are groups formed by proton-donating substituents releasing protons, and the groups Y1 and Y2 in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, the groups Y3 and Y4 are groups formed by proton-donating substituents releasing protons, and the groups Y3 and Y4 in the same molecule are bonded to a silicon atom to form a chelate structure. The groups X1 and X2 may be the same or different, and the groups Y1, Y2, Y3, and Y4 may be the same or different. Such a group represented by Y1X1Y2 and Y3X2Y4 in the general formula (1) is composed of a group in which a proton donor releases two protons. Examples of the proton donor include: Catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2'-biphenol, 2,2'-binaphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphtho Acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, etc., among these, catechol, 1,2-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene is more preferred.
また、一般式（１）中のＺ１は、芳香環または複素環を有する有機基または脂肪族基を表し、これらの具体的な例としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基およびオクチル基等の脂肪族炭化水素基や、フェニル基、ベンジル基、ナフチル基およびビフェニル基等の芳香族炭化水素基、グリシジルオキシプロピル基、メルカプトプロピル基、アミノプロピル基およびビニル基等の反応性置換基などが挙げられるが、これらの中でも、メチル基、エチル基、フェニル基、ナフチル基およびビフェニル基が熱安定性の面から、より好ましい。 Z1 in the general formula (1) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions of aliphatic hydrocarbon groups such as octyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.
本発明で用いられるカチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）の配合量は、特に限定されないが、全エポキシ樹脂組成物中に０．１重量％以上、１．５重量％以下であることが好ましく、より好ましくは０.２重量％以上、１重量％以下である。上記範囲内であると、エポキシ樹脂組成物の成形時の低粘度化、高流動化、及び貯蔵時の保存安定性の向上を図ることができる。 Although the compounding quantity of the hardening accelerator (d1) which has a cation part and a silicate anion part used by this invention is not specifically limited, 0.1 weight% or more and 1.5 weight% or less in all the epoxy resin compositions More preferably, it is 0.2 wt% or more and 1 wt% or less. Within the above range, the viscosity of the epoxy resin composition can be lowered, the fluidity can be increased, and the storage stability during storage can be improved.
本発明では、カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）を用いることによる効果を損なわない範囲であれば、該硬化促進剤（ｄ１）以外の硬化促進剤も、エポキシ基とフェノール性水酸基の反応を促進するものであれば特に限定なく併用できるが、カチオン部シリケートアニオン部とを有する硬化促進剤（ｄ１）の配合割合は、全硬化促進剤（Ｄ）に対して５０重量％以上であることが好ましい。併用可能な硬化促進剤としては、例えば、ホスフィン化合物とキノン化合物との付加物；１，８−ジアザビシクロ（５，４，０）ウンデセン−７等のジアザビシクロアルケン及びその誘導体；トリブチルアミン、ベンジルジメチルアミン等のアミン系化合物；２−メチルイミダゾール等のイミダゾール化合物；トリフェニルホスフィン、メチルジフェニルホスフィン等の有機ホスフィン類；テトラフェニルホスホニウム・テトラフェニルボレート、テトラフェニルホスホニウム・テトラキス（ベンゾイルオキシ）ボレート、テトラフェニルホスホニウム・テトラキス（ナフトイルオキシ）ボレート等のテトラ置換ホスホニウム・テトラ置換ボレート等が挙げられ、これらは１種類を単独で用いても２種類以上を併用してもよい。 In the present invention, as long as the effect of using the curing accelerator (d1) having a cation part and a silicate anion part is not impaired, a curing accelerator other than the curing accelerator (d1) may be an epoxy group and a phenol. As long as it promotes the reaction of the reactive hydroxyl group, it can be used in combination without any particular limitation, but the blending ratio of the curing accelerator (d1) having a cation silicate anion moiety is 50% by weight with respect to the total curing accelerator (D). The above is preferable. Examples of curing accelerators that can be used in combination include adducts of phosphine compounds and quinone compounds; diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; tributylamine, benzyl Amine compounds such as dimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis (benzoyloxy) borate, tetra Examples thereof include tetra-substituted phosphonium / tetra-substituted borates such as phenylphosphonium / tetrakis (naphthoyloxy) borate, and these may be used alone or in combination of two or more.
本発明で用いられるトリレンジイソシアネート変性酸化ワックス（Ｅ）は、酸化ワックスをトリレンジイソシアネート変性することにより得られ、離型性が非常に優れている。本発明で用いられるトリレンジイソシアネート変性酸化ワックス（Ｅ）としては、特に限定するものではないが、例えば、トリレンジイソシアネート変性酸化ポリプロピレンワックス、トリレンジイソシアネート変性酸化ポリエチレンワックス、トリレンジイソシアネート変性酸化パラフィンワックスが挙げられる。中でもトリレンジイソシアネート変性酸化ポリエチレンワックスが、離型性と樹脂硬化物の外観の観点から、好ましい。 The tolylene diisocyanate-modified oxidized wax (E) used in the present invention is obtained by modifying an oxidized wax with tolylene diisocyanate, and has excellent releasability. The tolylene diisocyanate modified oxidized wax (E) used in the present invention is not particularly limited, and examples thereof include tolylene diisocyanate modified oxidized polypropylene wax, tolylene diisocyanate modified oxidized polyethylene wax, tolylene diisocyanate modified oxidized paraffin wax. Is mentioned. Among these, tolylene diisocyanate-modified polyethylene oxide wax is preferable from the viewpoint of releasability and appearance of the cured resin.
本発明で用いられるトリレンジイソシアネート変性酸化ワックス（Ｅ）の軟化点は、７０℃以上、１２０℃以下であることが好ましく、より好ましくは８０℃以上、１１０℃以下である。軟化点は、ＪＩＳ Ｋ２２０７−６．４に準拠した方法（環球法）により測定することができる。具体的には、規定の環に試料を充填し、水浴又はグリセリン浴中に水平に支え、試料の中央に規定の球を置き、浴温を毎分５℃の速さで上昇させ、球を包み込んだ試料が環台の底板に触れたときの温度として測定される。以下の例においても、同様の方法により測定することができる。軟化点が上記範囲内であると、トリレンジイソシアネート変性酸化ワックス（Ｅ）は熱安定性に優れ、成形時にトリレンジイソシアネート変性酸化ワックス（Ｅ）が焼き付きにくい。そのため、金型からの樹脂硬化物の離型性に優れるとともに、連続成形性にも優れる。さらに、上記範囲内であると、エポキシ樹脂組成物を硬化させる際、トリレンジイソシアネート変性酸化ワックス（Ｅ）が十分に溶融する。これにより、樹脂硬化物中にトリレンジイソシアネート変性酸化ワックス（Ｅ）が略均一に分散する。そのため、樹脂硬化物表面におけるトリレンジイソシアネート変性酸化ワックス（Ｅ）の偏析が抑制され、金型の汚れや樹脂硬化物の外観の悪化を低減することができる。 The softening point of the tolylene diisocyanate-modified oxidized wax (E) used in the present invention is preferably 70 ° C. or higher and 120 ° C. or lower, more preferably 80 ° C. or higher and 110 ° C. or lower. The softening point can be measured by a method (ring and ball method) based on JIS K2207-6.4. Specifically, a specified ring is filled with a sample, supported horizontally in a water bath or glycerin bath, a specified ball is placed in the center of the sample, the bath temperature is increased at a rate of 5 ° C. per minute, It is measured as the temperature when the wrapped sample touches the bottom plate of the platform. In the following examples, it can be measured by the same method. When the softening point is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is excellent in thermal stability, and the tolylene diisocyanate-modified oxidized wax (E) is hardly seized at the time of molding. Therefore, it is excellent in the mold release property of the resin cured material from a metal mold | die, and is excellent also in continuous moldability. Furthermore, when it is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is sufficiently melted when the epoxy resin composition is cured. Thereby, the tolylene diisocyanate-modified oxidized wax (E) is dispersed substantially uniformly in the cured resin. Therefore, segregation of the tolylene diisocyanate-modified oxide wax (E) on the surface of the cured resin product is suppressed, and deterioration of the appearance of the mold and the cured resin product can be reduced.
トリレンジイソシアネート変性酸化ワックス（Ｅ）の酸価は１０ｍｇＫＯＨ／ｇ以上、５０ｍｇＫＯＨ／ｇ以下であることが好ましく、より好ましくは１５ｍｇＫＯＨ／ｇ以上、４０ｍｇＫＯＨ／ｇ以下である。酸価は樹脂硬化物との相溶性に影響を及ぼす。酸価は、ＪＩＳ Ｋ ３５０４、ＡＳＴＭ Ｄ １３８６に準拠した方法により測定することができる。具体的には、ワックス類１ｇ中に含有する遊離脂肪酸を中和するのに要する水酸化カリウムのミリグラム数として測定される。以下の例においても、同様の方法により測定することができる。酸価が上記範囲内にあると、トリレンジイソシアネート変性酸化ワックス（Ｅ）は、樹脂硬化物中において、エポキシ樹脂マトリックスと好ましい相溶状態となる。これにより、トリレンジイソシアネート変性酸化ワックス（Ｅ）と、エポキシ樹脂マトリックスとが、相分離を起こすことがない。そのため、樹脂硬化物表面におけるトリレンジイソシアネート変性酸化ワックス（Ｅ）の偏析が抑制され、金型の汚れや樹脂硬化物の外観の悪化を低減することができる。さらに、トリレンジイソシアネート変性酸化ワックス（Ｅ）が樹脂硬化物表面に存在するため、樹脂硬化物は金型からの離型性に優れる。一方、エポキシ樹脂マトリックスとの相溶性が高すぎると、トリレンジイソシアネート変性酸化ワックス（Ｅ）が硬化物表面に染み出すことができず、十分な離型性を確保することができない場合がある。 The acid value of tolylene diisocyanate-modified oxidized wax (E) is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value affects the compatibility with the cured resin. The acid value can be measured by a method based on JIS K 3504 and ASTM D 1386. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of waxes. In the following examples, it can be measured by the same method. When the acid value is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the phase separation of tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix does not occur. Therefore, segregation of the tolylene diisocyanate-modified oxide wax (E) on the surface of the cured resin product is suppressed, and deterioration of the appearance of the mold and the cured resin product can be reduced. Furthermore, since the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, the cured resin is excellent in releasability from the mold. On the other hand, if the compatibility with the epoxy resin matrix is too high, the tolylene diisocyanate-modified oxidized wax (E) cannot ooze out on the surface of the cured product, and sufficient releasability may not be ensured.
トリレンジイソシアネート変性酸化ワックス（Ｅ）のケン化価は４０ｍｇＫＯＨ／ｇ以上、１２０ｍｇＫＯＨ／ｇ以下であることが好ましく、より好ましくは７０ｍｇＫＯＨ／ｇ以上、１００ｍｇＫＯＨ／ｇ以下である。ケン化価は樹脂硬化物との相溶性に影響を及ぼす。ケン化価は、基準油脂分析試験法、ＪＩＳ Ｋ ００７０、ＡＳＴＭ Ｄ １３８７に準拠した方法により測定することができる。具体的には、ワックス類１ｇを完全ケン化するのに要する水酸化カリウムのミリグラム数として測定される。以下の例においても、同様の方法により測定することができる。ケン化価が上記範囲内にあると、トリレンジイソシアネート変性酸化ワックス（Ｅ）は、樹脂硬化物中において、エポキシ樹脂マトリックスと好ましい相溶状態となる。これにより、トリレンジイソシアネート変性酸化ワックス（Ｅ）と、エポキシ樹脂マトリックスとが、相分離を起こすことがない。そのため、樹脂硬化物表面におけるトリレンジイソシアネート変性酸化ワックス（Ｅ）の偏析が抑制され、金型の汚れや樹脂硬化物の外観の悪化を低減することができる。さらに、トリレンジイソシアネート変性酸化ワックス（Ｅ）が樹脂硬化物表面に存在するため、樹脂硬化物は金型からの離型性に優れる。一方、エポキシ樹脂マトリックスとの相溶性が高すぎると、トリレンジイソシアネート変性酸化ワックス（Ｅ）が硬化物表面に染み出すことができず、十分な離型性を確保することができない場合がある。 The saponification value of the tolylene diisocyanate-modified oxidized wax (E) is preferably 40 mgKOH / g or more and 120 mgKOH / g or less, more preferably 70 mgKOH / g or more and 100 mgKOH / g or less. The saponification value affects the compatibility with the cured resin. The saponification value can be measured by a method according to the standard oil and fat analysis test method, JIS K 0070, and ASTM D 1387. Specifically, it is measured as the number of milligrams of potassium hydroxide required to completely saponify 1 g of waxes. In the following examples, it can be measured by the same method. When the saponification value is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the phase separation of tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix does not occur. Therefore, segregation of the tolylene diisocyanate-modified oxide wax (E) on the surface of the cured resin product is suppressed, and deterioration of the appearance of the mold and the cured resin product can be reduced. Furthermore, since the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, the cured resin is excellent in releasability from the mold. On the other hand, if the compatibility with the epoxy resin matrix is too high, the tolylene diisocyanate-modified oxidized wax (E) cannot ooze out on the surface of the cured product, and sufficient releasability may not be ensured.
トリレンジイソシアネート変性酸化ワックス（Ｅ）の数平均分子量は５００以上、５０００以下であることが好ましく、より好ましくは１０００以上、４０００以下である。数平均分子量は、例えば東ソー（株）製のＨＬＣ−８１２０などのＧＰＣ装置を用いて、ポリスチレン換算により算出することができる。以下の例においても、同様の方法により測定することができる。数平均分子量が上記範囲内にあると、トリレンジイソシアネート変性酸化ワックス（Ｅ）は、樹脂硬化物中において、エポキシ樹脂マトリックスと好ましい相溶状態となる。これにより、トリレンジイソシアネート変性酸化ワックス（Ｅ）と、エポキシ樹脂マトリックスとが、相分離を起こすことがない。そのため、樹脂硬化物表面におけるトリレンジイソシアネート変性酸化ワックス（Ｅ）の偏析が抑制され、金型の汚れや樹脂硬化物の外観の悪化を引き起こす恐れが少ない。また、トリレンジイソシアネート変性酸化ワックス（Ｅ）が樹脂硬化物表面に存在するため、樹脂硬化物は金型からの離型性に優れる。 The number average molecular weight of the tolylene diisocyanate-modified oxidized wax (E) is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less. The number average molecular weight can be calculated by polystyrene conversion using a GPC apparatus such as HLC-8120 manufactured by Tosoh Corporation. In the following examples, it can be measured by the same method. When the number average molecular weight is within the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a preferable compatible state with the epoxy resin matrix in the resin cured product. Thereby, the phase separation of tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix does not occur. Therefore, segregation of tolylene diisocyanate-modified oxidized wax (E) on the surface of the cured resin is suppressed, and there is little possibility of causing mold contamination and deterioration of the appearance of the cured resin. Moreover, since the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, the cured resin is excellent in releasability from the mold.
トリレンジイソシアネート変性酸化ワックス（Ｅ）の平均粒径は、２０μｍ以上、７０μｍ以下であることが好ましく、より好ましくは３０μｍ以上、６０μｍ以下である。平均粒径は、例えば（株）島津製作所製のＳＡＬＤ−７０００などのレーザー回折式粒度分布測定装置を用いて、溶媒を水として、重量基準の５０％粒子径を平均粒径として測定することができる。以下の例においても、同様の方法により測定することができる。平均粒径が上記範囲内にあると、トリレンジイソシアネート変性酸化ワックス（Ｅ）は、樹脂硬化物中において、エポキシ樹脂マトリックスと好ましい相溶状態となる。これにより、トリレンジイソシアネート変性酸化ワックス（Ｅ）が樹脂硬化物表面に存在し、金型からの樹脂硬化物の離型性に優れる。一方、エポキシ樹脂マトリックスとの相溶性が高すぎると、樹脂硬化物表面に染み出すことができず、十分な離型性を確保することができない。さらに、トリレンジイソシアネート変性酸化ワックス（Ｅ）と、エポキシ樹脂マトリックスとが好ましい相溶状態にあるため、樹脂硬化物表面におけるトリレンジイソシアネート変性酸化ワックス（Ｅ）の偏析が抑制され、金型の汚れや樹脂硬化物の外観の悪化を低減することができる。またさらに、上記範囲にあると、エポキシ樹脂組成物を硬化させる際、トリレンジイソシアネート変性酸化ワックス（Ｅ）が十分に溶融する。そのため、エポキシ樹脂組成物は流動性に優れる。 The average particle size of the tolylene diisocyanate-modified oxidized wax (E) is preferably 20 μm or more and 70 μm or less, more preferably 30 μm or more and 60 μm or less. The average particle diameter can be measured by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as a solvent and water, and a weight-based 50% particle diameter as an average particle diameter. it can. In the following examples, it can be measured by the same method. When the average particle size is in the above range, the tolylene diisocyanate-modified oxidized wax (E) is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the tolylene diisocyanate-modified oxidized wax (E) is present on the surface of the cured resin, and is excellent in releasability of the cured resin from the mold. On the other hand, if the compatibility with the epoxy resin matrix is too high, it cannot be oozed out on the surface of the cured resin and sufficient releasability cannot be ensured. Furthermore, since the tolylene diisocyanate-modified oxidized wax (E) and the epoxy resin matrix are in a preferable compatible state, segregation of the tolylene diisocyanate-modified oxidized wax (E) on the surface of the cured resin is suppressed, and the mold is stained. And deterioration of the appearance of the cured resin can be reduced. Furthermore, when it exists in the said range, when hardening an epoxy resin composition, tolylene diisocyanate modified | denatured oxidation wax (E) fully fuse | melts. Therefore, the epoxy resin composition is excellent in fluidity.
また、全トリレンジイソシアネート変性酸化ワックス（Ｅ）中における粒径１５０μｍ以上の粒子の含有割合は０．１重量％以下であることが好ましい。粒径１５０μｍ以上の粒子の含有割合は、ＪＩＳ Ｚ ８８０１の目開き１５０μｍの標準篩を用いて測定することができる。以下の例においても、同様の方法により測定することができる。上記の含有割合であれば、トリレンジイソシアネート変性酸化ワックス（Ｅ）がエポキシ樹脂組成物中に略均一に分散し、金型の汚れや樹脂硬化物の外観の悪化を抑制することができる。また、エポキシ樹脂組成物を硬化させる際、トリレンジイソシアネート変性酸化ワックス（Ｅ）が十分に溶融するため、流動性に優れる。 Moreover, it is preferable that the content rate of the particle | grains with a particle size of 150 micrometers or more in all the tolylene diisocyanate modified | denatured oxidation wax (E) is 0.1 weight% or less. The content ratio of particles having a particle size of 150 μm or more can be measured using a standard sieve having an opening of 150 μm according to JIS Z8801. In the following examples, it can be measured by the same method. If it is said content rate, tolylene diisocyanate modified | denatured oxidation wax (E) disperse | distributes substantially uniformly in an epoxy resin composition, and it can suppress the deterioration of the external appearance of a mold | die stain | pollution | contamination and a resin cured material. Further, when the epoxy resin composition is cured, the tolylene diisocyanate-modified oxidized wax (E) is sufficiently melted, and thus has excellent fluidity.
トリレンジイソシアネート変性酸化ワックス（Ｅ）の配合量はエポキシ樹脂組成物中に、０．０１重量％以上、１重量％以下であることが好ましく、より好ましくは０．０３重量％以上０．５重量％以下である。配合量が上記範囲内であると、金型からの樹脂硬化物の離型性に優れる。さらに、リードフレーム部材との密着性に優れるため、半田処理時において、リードフレーム部材と樹脂硬化物との剥離を抑制することができる。また、金型の汚れや樹脂硬化物の外観の悪化を抑制することもできる。 The blending amount of the tolylene diisocyanate-modified oxidized wax (E) is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.03% by weight or more and 0.5% by weight in the epoxy resin composition. % Or less. When the blending amount is within the above range, the mold releasability of the cured resin from the mold is excellent. Furthermore, since the adhesiveness with the lead frame member is excellent, peeling between the lead frame member and the cured resin can be suppressed during the soldering process. In addition, it is possible to suppress deterioration of the mold and the appearance of the cured resin.
本発明で用いられるトリレンジイソシアネート変性酸化ワックス（Ｅ）の製法については、特に限定するものではないが、例えば、原料化合物としてポリプロピレンワックス、ポリエチレンワックス、パラフィンワックスを用い、公知の方法に従って酸化反応させた後、公知の方法に従ってトリレンジイソシアネート変性反応させる方法などにより得ることができる。また、本発明で用いられるトリレンジイソシアネート変性酸化ワックス（Ｅ）は、市販のものを入手し、必要に応じて回転円板型ミル（ピンミル）、スクリーンミル（ハンマーミル）、遠心分離型ミル（ターボミル）、ジェットミル等の粉砕機を用い、粉砕し粒度調整して使用することができる。
本発明で用いられるトリレンジイソシアネート変性酸化ワックスを用いることによる効果を損なわない範囲で他の離型剤を併用することもできる。併用できる離型剤としては、例えばカルナバワックス等の天然ワックス、ステアリン酸亜鉛等の高級脂肪酸の金属塩類等が挙げられる。
The production method of tolylene diisocyanate-modified oxidized wax (E) used in the present invention is not particularly limited. For example, polypropylene wax, polyethylene wax, paraffin wax is used as a raw material compound, and an oxidation reaction is performed according to a known method. Then, it can be obtained by a method of modifying the tolylene diisocyanate according to a known method. The tolylene diisocyanate-modified oxide wax (E) used in the present invention is commercially available, and if necessary, a rotating disk mill (pin mill), a screen mill (hammer mill), a centrifugal mill ( It can be used after pulverization and particle size adjustment using a pulverizer such as a turbo mill or a jet mill.
Other release agents can be used in combination as long as the effects of using the tolylene diisocyanate-modified oxidized wax used in the present invention are not impaired. Examples of release agents that can be used in combination include natural waxes such as carnauba wax, and metal salts of higher fatty acids such as zinc stearate.
本発明は、エポキシ樹脂の硬化反応を促進し得るカチオン部と前記硬化反応を促進するカチオン部の触媒活性を抑制するシリケートアニオン部とを有する硬化促進剤（ｄ１）と、トリレンジイソシアネート変性酸化ワックス（Ｅ）と、を併用することによってその相乗効果を発現するものである。この２種を併用することにより、無機充填材を増量しても、離型剤の分散性を損なうことなく、理想的な離型挙動を示すものとなる。 The present invention relates to a curing accelerator (d1) having a cation moiety that can accelerate the curing reaction of an epoxy resin and a silicate anion moiety that suppresses the catalytic activity of the cation moiety that accelerates the curing reaction, and a tolylene diisocyanate-modified oxidized wax. The synergistic effect is expressed by using (E) together. By using these two types in combination, even when the amount of the inorganic filler is increased, an ideal release behavior is exhibited without impairing the dispersibility of the release agent.
本発明の半導体封止用エポキシ樹脂組成物は、エポキシ樹脂、フェノール樹脂、無機充填材、カチオン部とシリケートアニオン部とを有する硬化促進剤を含む硬化促進剤、及びトリレンジイソシアネート変性酸化ワックスを含むものであるが、更に必要に応じて、アミノシラン、エポキシシラン、メルカプトシラン、アルキルシラン、ウレイドシラン、アクリルシラン等のカップリング剤；ハイドロタルサイト類やマグネシウム、アルミニウム、ビスマス、チタン、ジルコニウムから選ばれる元素の含水酸化物等のイオントラップ剤；シリコーンオイル、ゴム等の低応力添加剤；チアゾリン、トリアゾール、トリアジン、ピリミジン等の密着付与剤；臭素化エポキシ樹脂や三酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、ほう酸亜鉛、モリブデン酸亜鉛、フォスファゼン等の難燃剤等の添加剤を適宜配合しても差し支えない。 The epoxy resin composition for semiconductor encapsulation of the present invention comprises an epoxy resin, a phenol resin, an inorganic filler, a curing accelerator including a curing accelerator having a cation part and a silicate anion part, and a tolylene diisocyanate-modified oxidized wax. However, if necessary, coupling agents such as amino silane, epoxy silane, mercapto silane, alkyl silane, ureido silane, and acrylic silane; hydrotalcite and elements selected from magnesium, aluminum, bismuth, titanium, zirconium Ion trapping agents such as hydrous oxides; Low stress additives such as silicone oils and rubbers; Tightening agents such as thiazolines, triazoles, triazines, pyrimidines; Brominated epoxy resins, antimony trioxide, aluminum hydroxide, magnesium hydroxide, Way Zinc, zinc molybdate, be suitably blended additives such as flame retardants such as phosphazene no problem.
また、本発明の半導体封止用エポキシ樹脂組成物は、例えば、ミキサー等を用いて原料を充分に均一に混合したもの、更にその後、熱ロール、ニーダー、押出機等の混練機で溶融混練し、冷却後粉砕したものなど、必要に応じて適宜分散度や流動性等を調整したものを用いることができる。 The epoxy resin composition for semiconductor encapsulation of the present invention is, for example, a material in which raw materials are sufficiently uniformly mixed using a mixer or the like, and then melt-kneaded with a kneader such as a hot roll, a kneader or an extruder. Those that have been appropriately adjusted in dispersity, fluidity, and the like can be used as needed, such as those pulverized after cooling.
本発明の半導体封止用エポキシ樹脂組成物を用いて、半導体素子等の各種の電子部品を封止し、半導体装置を製造するには、トランスファーモールド、コンプレッションモールド、インジェクションモールド等の従来からの成形方法で硬化成形すればよい。 Conventional molding such as transfer molding, compression molding, injection molding, etc., is used to manufacture semiconductor devices by sealing various electronic components such as semiconductor elements using the epoxy resin composition for semiconductor sealing of the present invention. It may be cured by the method.
本発明で封止を行う半導体素子としては、特に限定されるものではなく、例えば、集積回路、大規模集積回路、トランジスタ、サイリスタ、ダイオード、固体撮像素子等が挙げられる。
本発明の半導体装置の形態としては、特に限定されないが、例えば、デュアル・インライン・パッケージ（ＤＩＰ）、プラスチック・リード付きチップ・キャリヤ（ＰＬＣＣ）、クワッド・フラット・パッケージ（ＱＦＰ）、スモール・アウトライン・パッケージ（ＳＯＰ）、スモール・アウトライン・Ｊリード・パッケージ（ＳＯＪ）、薄型スモール・アウトライン・パッケージ（ＴＳＯＰ）、薄型クワッド・フラット・パッケージ（ＴＱＦＰ）、テープ・キャリア・パッケージ（ＴＣＰ）、ボール・グリッド・アレイ（ＢＧＡ）、チップ・サイズ・パッケージ（ＣＳＰ）等が挙げられる。
上記トランスファーモールドなどの成形方法で封止された半導体装置は、そのまま、或いは８０℃から２００℃程度の温度で、１０分から１０時間程度の時間をかけて完全硬化させた後、電子機器等に搭載される。
The semiconductor element that performs sealing in the present invention is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.
The form of the semiconductor device of the present invention is not particularly limited. For example, the dual in-line package (DIP), the plastic lead chip carrier (PLCC), the quad flat package (QFP), the small outline, and the like. Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Examples include an array (BGA), a chip size package (CSP), and the like.
A semiconductor device sealed by a molding method such as the above transfer mold is mounted on an electronic device or the like as it is or after being completely cured at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. Is done.
図１は、本発明に係るエポキシ樹脂組成物を用いた半導体装置の一例について、断面構造を示した図である。ダイパッド３上に、ダイボンド材硬化体２を介して半導体素子１が固定されている。半導体素子１の電極パッドとリードフレーム５との間は金線４によって接続されている。半導体素子１は、封止用樹脂組成物の硬化体６によって封止されている。
FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition according to the present invention. The semiconductor element 1 is fixed on the
以下に本発明の実施例を示すが、本発明はこれらに限定されるものではない。配合割合は重量部とする。
なお、実施例、比較例で用いた硬化促進剤と離型剤の内容について以下に示す。
Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
In addition, it shows below about the content of the hardening accelerator and mold release agent which were used by the Example and the comparative example.
硬化促進剤１：下記化学式（２）で表される化合物
硬化促進剤２：下記化学式（３）で表される化合物
硬化促進剤３：下記化学式（４）で表される化合物
硬化促進剤４：下記化学式（５）で表される化合物
硬化促進剤５：下記化学式（６）で表される化合物
硬化促進剤６：下記化学式（７）で表される化合物
硬化促進剤７：下記化学式（８）で表される化合物
離型剤１：トリレンジイソシアネート変性酸化ポリエチレンワックス（軟化点９０℃、酸価３０ｍｇＫＯＨ／ｇ、ケン化価８２ｍｇＫＯＨ／ｇ、数平均分子量１８００、平均粒径３５μｍ、粒径１５０μｍ以上の粒子０．０重量％） Release agent 1: Tolylene diisocyanate-modified polyethylene oxide wax (softening point 90 ° C., acid value 30 mg KOH / g, saponification value 82 mg KOH / g, number average molecular weight 1800, average particle size 35 μm, particle size 0.0 μm or more particles 0.0 weight%)
離型剤２：トリレンジイソシアネート変性酸化パラフィンワックス（軟化点８５℃、酸価２０ｍｇＫＯＨ／ｇ、ケン化価５０ｍｇＫＯＨ／ｇ、数平均分子量２５００、平均粒径３８μｍ、粒径１５０μｍ以上の粒子０．０重量％） Release agent 2: Tolylene diisocyanate-modified oxidized paraffin wax (softening point 85 ° C., acid value 20 mg KOH / g, saponification value 50 mg KOH / g, number average molecular weight 2500, average particle size 38 μm, particle size 0.0 μm or more particles 0.0 weight%)
離型剤３：トリレンジイソシアネート変性酸化ポリプロピレンワックス（軟化点７７℃、酸価１２ｍｇＫＯＨ／ｇ、ケン化価６５ｍｇＫＯＨ／ｇ、数平均分子量２３００、平均粒径４０μｍ、粒径１５０μｍ以上の粒子０．０重量％） Release agent 3: Tolylene diisocyanate modified polypropylene oxide wax (softening point 77 ° C., acid value 12 mg KOH / g, saponification value 65 mg KOH / g, number average molecular weight 2300, average particle size 40 μm, particle size 0.0 μm or more particles 0.0 weight%)
離型剤４：パラフィンワックス（日本精蝋（株）製、商品名ＨＮＰ−１０、軟化点７５℃、酸価０ｍｇＫＯＨ／ｇ、ケン化価０ｍｇＫＯＨ／ｇ、数平均分子量６００、平均粒径４５μｍ、粒径１５０μｍ以上の粒子０．０重量％） Release agent 4: Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name HNP-10, softening point 75 ° C., acid value 0 mg KOH / g, saponification value 0 mg KOH / g, number average molecular weight 600, average particle size 45 μm, 0.0% by weight of particles with a particle size of 150 μm or more)
離型剤５：カルナバワックス（日興ファインプロダクツ（株）製、商品名ニッコウカルナバ、軟化点８３℃、酸価５ｍｇＫＯＨ／ｇ、ケン化価８２ｍｇＫＯＨ／ｇ、数平均分子量６５０、平均粒径３８μｍ、粒径１５０μｍ以上の粒子０．０重量％） Release agent 5: Carnauba wax (manufactured by Nikko Fine Products Co., Ltd., trade name Nikko Carnauba, softening point 83 ° C., acid value 5 mgKOH / g, saponification value 82 mgKOH / g, number average molecular weight 650, average particle size 38 μm, grain 0.0% by weight of particles with a diameter of 150 μm or more)
ここで一例として硬化促進剤１の合成方法について示すが、これにより本発明が限定されるものではない。
メタノール１８００ｇを入れたフラスコに、フェニルトリメトキシシラン２４９．５ｇ、２，３−ジヒドロキシナフタレン３８４．０ｇを加えて溶かし、次に室温攪拌下２８％ナトリウムメトキシド−メタノール溶液２３１．５ｇを滴下した。さらにそこへ予め用意したテトラフェニルホスホニウムブロマイド５０３．０ｇをメタノール６００ｇに溶かした溶液を室温攪拌下滴下すると結晶が析出した。析出した結晶を濾過、水洗、真空乾燥し、桃白色結晶の硬化促進剤１を得た。
Here, as an example, a method for synthesizing the curing accelerator 1 will be described, but the present invention is not limited thereto.
In a flask containing 1800 g of methanol, 249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added and dissolved, and then 231.5 g of 28% sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide prepared in advance in 600 g of methanol was added dropwise with stirring at room temperature, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a pinky white crystal curing accelerator 1.
実施例１
エポキシ樹脂１：下記式（９）で表されるビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂（日本化薬（株）製、商品名ＮＣ３０００Ｐ、軟化点５８℃、エポキシ当量２７３。下記式（９）におけるｎの平均値１．８。） ６．１９重量部
Epoxy resin 1: phenol aralkyl epoxy resin having a biphenylene skeleton represented by the following formula (9) (manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000P, softening point: 58 ° C., epoxy equivalent: 273, in the following formula (9) The average value of n is 1.8.) 6.19 parts by weight
フェノール樹脂系硬化剤１：下記式（１０）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点６７℃、水酸基当量２０４。下記式（１０）におけるｎの平均値１．５。）
４．６１重量部
4.61 parts by weight
溶融球状シリカ１：（平均粒径２０μｍ、最大粒径７５μｍ、比表面積３．６ｍ２／ｇ） ７８．００重量部
溶融球状シリカ２：（平均粒径０．５μｍ、最大粒径１０μｍ、比表面積５．９ｍ２／ｇ） １０．００重量部
硬化促進剤１ ０．５０重量部
離型剤１ ０．１０重量部
カップリング剤１：γ−グリシドキシプロピルトリメトキシシラン（信越化学（株）製、商品名ＫＢＭ−４０３） ０．３０重量部
カーボンブラック：（三菱化学（株）製、商品名ＭＡ−６００） ０．３０重量部
をミキサーにて混合した後、熱ロールを用いて９５℃で８分間混練し、更に冷却後粉砕してエポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表１に示す。
Fused spherical silica 1: (average particle size 20 μm, maximum particle size 75 μm, specific surface area 3.6 m 2 / g) 78.00 parts by weight Fused spherical silica 2: (average particle size 0.5 μm, maximum particle size 10 μm, specific surface area) 5.9 m 2 / g) 10.00 parts by weight Curing accelerator 1 0.50 parts by weight Release agent 1 0.10 parts by weight Coupling agent 1: γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Product name KBM-403) 0.30 parts by weight Carbon black: (Mitsubishi Chemical Co., Ltd., product name MA-600) After mixing 0.30 parts by weight with a mixer, 95 ° C using a hot roll. Kneaded for 8 minutes, and further cooled and ground to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.
評価方法
スパイラルフロー：低圧トランスファー成形機（コータキ精機株式会社製、ＫＴＳ−１５）を用いて、ＥＭＭＩ−１−６６に準じたスパイラルフロー測定用金型に、金型温度１７５℃、注入圧力６．９ＭＰa、保圧時間１２０秒の条件で、エポキシ樹脂組成物を注入し、流動長を測定した。単位はｃｍ。スパイラルフローは、流動性のパラメータであり、数値が大きい方が良好な流動性を示す。
Evaluation method: Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement according to EMMI-1-66, a mold temperature of 175 ° C. and an injection pressure of 6. The epoxy resin composition was injected under the conditions of 9 MPa and holding pressure time of 120 seconds, and the flow length was measured. The unit is cm. Spiral flow is a parameter of fluidity, and a larger value indicates better fluidity.
金線流れ率：低圧トランスファー自動成形機（第一精工製、ＧＰ−ＥＬＦ）を用いて、金型温度１７５℃、注入圧力９．８ＭＰａＭＰａ、硬化時間７０秒の条件で、エポキシ樹脂組成物によりシリコンチップ等を封止成形して、１６０ピンＬＱＦＰ（プリプレーティングフレーム：ニッケル／パラジウム合金に金メッキしたもの、パッケージ外寸：２４ｍｍ×２４ｍｍ×１．４ｍｍ厚、パッドサイズ：８．５ｍｍ×８．５ｍｍ、チップサイズ７．４ｍｍ×７．４ｍｍ×３５０μｍ厚）を得た。得られた１６０ピンＬＱＦＰパッケージを軟Ｘ線透視装置（ソフテックス（株）製、ＰＲＯ−ＴＥＳＴ１００）で観察し、金線の流れ率を（流れ量）／（金線長）の比率を求めた。判定基準は５％未満を○、５％以上を×とした。 Metal wire flow rate: Using a low-pressure transfer automatic molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa MPa, and a curing time of 70 seconds, Chips and the like are sealed and molded, and 160-pin LQFP (preprating frame: nickel / palladium alloy gold-plated, package outer dimensions: 24 mm × 24 mm × 1.4 mm thickness, pad size: 8.5 mm × 8.5 mm, A chip size of 7.4 mm × 7.4 mm × 350 μm thickness) was obtained. The obtained 160-pin LQFP package was observed with a soft X-ray fluoroscope (PRO-TEST100, manufactured by Softex Corporation), and the flow rate of the gold wire was determined as the ratio of (flow rate) / (gold wire length). . The criterion was ○ for less than 5% and x for 5% or more.
硬化性（硬化トルク比）：キュラストメータ（（株）オリエンテック・製、ＪＳＲキュラストメータＩＶＰＳ型）を用いて、ダイスの直径３５ｍｍ、振幅角１°、金型温度１７５℃の条件で、装置内に投入した樹脂組成物の硬化挙動をトルクの変化により測定した。測定開始６０秒後と３００秒後のトルク値から、硬化トルク比：（６０秒後のトルク）／（３００秒後のトルク）を計算した。キュラストメータにおける硬化トルク比は硬化性を表すパラメータであり、硬化トルク比の大きい方が硬化性が良好である。判定基準は０．７以上を○、０．７未満を×とした。 Curability (curing torque ratio): Using a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type), under the conditions of a die diameter of 35 mm, an amplitude angle of 1 °, and a mold temperature of 175 ° C. The curing behavior of the resin composition charged into the apparatus was measured by the change in torque. From the torque values 60 seconds and 300 seconds after the start of measurement, the curing torque ratio: (torque after 60 seconds) / (torque after 300 seconds) was calculated. The curing torque ratio in the curast meter is a parameter representing curability, and the larger the curing torque ratio, the better the curability. Judgment criteria set 0.7 or more as ◯ and less than 0.7 as x.
連続成形性：低圧トランスファー自動成形機（第一精工製、ＧＰ−ＥＬＦ）を用いて、金型温度１７５℃、注入圧力９．８ＭＰａ、硬化時間７０秒の条件で、エポキシ樹脂組成物によりシリコンチップ等を封止して８０ピンＱＦＰ（プリプレーティングフレーム：ニッケル／パラジウム合金に金メッキしたもの、パッケージ外寸：１４ｍｍ×２０ｍｍ×２ｍｍ厚、パッドサイズ：６．５ｍｍ×６．５ｍｍ、チップサイズ６．０ｍｍ×６．０ｍｍ×３５０μｍ厚）を得る成形を、連続で８００ショットまで行なった。判定基準は未充填、離型不良等の問題が全く発生せずに８００ショットまで連続成形できたものを◎、５００ショットまで連続成形できたものを○、それ以外を×とした。 Continuous moldability: Silicon chip using epoxy resin composition under conditions of mold temperature of 175 ° C., injection pressure of 9.8 MPa, curing time of 70 seconds using low pressure transfer automatic molding machine (Daiichi Seiko, GP-ELF) 80 pin QFP (Pre-plating frame: nickel / palladium alloy gold-plated, package outer dimensions: 14 mm x 20 mm x 2 mm thickness, pad size: 6.5 mm x 6.5 mm, chip size 6.0 mm Molding to obtain (× 6.0 mm × 350 μm thickness) was continuously performed up to 800 shots. Judgment criteria were ◎ for those that could be continuously molded up to 800 shots without any problems such as unfilling or mold release failure, ◯ for those that could be continuously molded up to 500 shots, and × otherwise.
パッケージ外観及び金型汚れ性：上記連続成形性の評価において、５００ショット経過後のパッケージ及び金型について、目視で汚れを評価した。パッケージ外観及び金型汚れ性の判定基準は、５００ショットまでに汚れが発生したものを×、５００ショットまで汚れていないものを○、８００ショットまで汚れていないものを◎で表す。また、上記連続成形性において、８００ショットまで問題なく成形できなかったものについては、連続成形を断念した時点でのパッケージ外観及び金型汚れ状況で判断した。 Package appearance and mold stain resistance: In the evaluation of the above-mentioned continuous moldability, the package and the mold after 500 shots were visually evaluated for stain. Judgment criteria for package appearance and mold dirtiness are indicated by x for those in which dirt has occurred up to 500 shots, ◯ for those in which dirt has not been stained up to 500 shots, and ◎ for those not dirty up to 800 shots. Further, in the above-mentioned continuous formability, those that could not be formed without any problem up to 800 shots were judged based on the package appearance and mold contamination status when the continuous forming was abandoned.
耐半田性：上記連続成形性の評価において成形したパッケージを１７５℃、８時間で後硬化し、得られたパッケージを８５℃、相対湿度６０％で１６８時間加湿処理後、２６０℃のＩＲリフロー処理をした。パッケージ２０個について、半導体素子とエポキシ樹脂組成物の硬化物との界面の密着状態を超音波探傷装置により観察し、剥離発生率［（剥離発生パッケージ数）／（全パッケージ数）×１００］を算出した。単位は％。耐半田性の判断基準は、剥離が発生しなかったものは○、剥離発生率が２０％未満のものは△、剥離発生率が２０％以上のものは×とした。 Solder resistance: The package formed in the above-described evaluation of continuous formability is post-cured at 175 ° C. for 8 hours, and the resulting package is humidified at 85 ° C. and 60% relative humidity for 168 hours, followed by IR reflow treatment at 260 ° C. Did. For 20 packages, the adhesion state of the interface between the semiconductor element and the cured product of the epoxy resin composition was observed with an ultrasonic flaw detector, and the peeling occurrence rate [(number of peeling occurrence packages) / (total number of packages) × 100] Calculated. Units%. The criteria for determining solder resistance were ◯ when no peeling occurred, Δ when the peeling rate was less than 20%, and x when the peeling rate was 20% or more.
実施例２〜１２、比較例１〜７
表１、表２、表３の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得て、実施例１と同様にして評価した。結果を表１、表２、表３に示す。
実施例１以外で用いた原材料を以下に示す。
エポキシ樹脂２：下記式（１１）で表されるビフェニル型エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名ＹＸ−４０００、エポキシ当量１９０、融点１０５℃）
According to the composition of Table 1, Table 2, and Table 3, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1, Table 2, and Table 3.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: Biphenyl type epoxy resin represented by the following formula (11) (manufactured by Japan Epoxy Resin Co., Ltd., trade name YX-4000, epoxy equivalent 190, melting point 105 ° C.)
フェノール樹脂系硬化剤２：下記式（１２）で表されるフェノールアラルキル樹脂（三井化学（株）製、商品名ＸＬＣ−ＬＬ、水酸基当量１６５、軟化点７９℃）
実施例１〜１２は、無機充填材の配合量が樹脂組成物全体の８８重量％、９０重量％と高いにもかかわらず、いずれも良好な流動性、金線流れ率、硬化性、離型性、連続成形性、パッケージ外観、金型汚れ性が得られ、かつ良好な耐半田性を有する半導体装置が得られる結果となった。
一方、トリレンジイソシアネート変性酸化ワックス（Ｅ）を用いていない比較例１、２、６では、連続成形性が悪化し、パッケージ外観、金型汚れ性、耐半田性も劣る結果となった。また、カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）を用いていない比較例３、４、５、７では、樹脂組成物の流動性が低下することにより、金線流れ率が悪化し、連続成形性、パッケージ外観、金型汚れ性、耐半田性も劣る結果となった。また、樹脂と硬化促進剤の組合せによっては、硬化性が低下するものもあった。
以上より、本発明の半導体封止用エポキシ樹脂組成物は、無機充填材の配合量が樹脂組成物全体の８８重量％、９０重量％と高いにもかかわらず、成形時の流動性、硬化性、離型性、連続成形性、パッケージ外観、金型汚れ性及び耐半田性のバランスに優れ、信頼性に優れた半導体装置パッケージを提供することができることが判った。
In Examples 1 to 12, although the blending amount of the inorganic filler is as high as 88% by weight and 90% by weight of the entire resin composition, all have good fluidity, gold wire flow rate, curability, mold release As a result, it was possible to obtain a semiconductor device having good solderability, good moldability, continuous formability, package appearance, and mold contamination.
On the other hand, in Comparative Examples 1, 2, and 6 in which the tolylene diisocyanate-modified oxidized wax (E) was not used, the continuous moldability deteriorated, and the package appearance, mold stain resistance, and solder resistance were inferior. Further, in Comparative Examples 3, 4, 5, and 7 in which the curing accelerator (d1) having a cation portion and a silicate anion portion is not used, the flow rate of the gold wire is deteriorated due to a decrease in the fluidity of the resin composition. In addition, continuous formability, package appearance, mold stain resistance, and solder resistance were poor. Some combinations of resins and curing accelerators have reduced curability.
From the above, the epoxy resin composition for semiconductor encapsulation of the present invention has fluidity and curability at the time of molding even though the blending amount of the inorganic filler is as high as 88% by weight and 90% by weight of the whole resin composition. It has been found that a semiconductor device package having an excellent balance of releasability, continuous formability, package appearance, mold contamination and solder resistance can be provided.
本発明の半導体封止用エポキシ樹脂組成物は、無機充填材の配合量を高めた場合でも、成形時において良好な流動性、硬化性、離型性、連続成形性を有し、かつ樹脂硬化物の外観汚れや金型汚れが発生し難いエポキシ樹脂組成物が得られるものである。従って、低粘度や可撓性を有するエポキシ樹脂及び／又はフェノール樹脂系硬化剤と組合せて用いることで無機充填材の配合量を高めることができ、それによって無鉛半田に対応する高温の半田処理によってもクラックが発生しない良好な耐半田性を有する半導体封止用エポキシ樹脂組成物を得ることができるため、無鉛半田を用いて表面実装を行う半導体装置に好適に用いることができるものである。 The epoxy resin composition for semiconductor encapsulation of the present invention has good fluidity, curability, releasability, and continuous moldability at the time of molding even when the blending amount of the inorganic filler is increased, and the resin is cured. It is possible to obtain an epoxy resin composition that hardly causes appearance stains or mold stains on the product. Therefore, the amount of the inorganic filler can be increased by using it in combination with an epoxy resin and / or a phenol resin curing agent having low viscosity and flexibility, thereby enabling high-temperature solder processing corresponding to lead-free solder. In addition, since an epoxy resin composition for semiconductor encapsulation having good solder resistance that does not generate cracks can be obtained, it can be suitably used for a semiconductor device that performs surface mounting using lead-free solder.
１ 半導体素子
２ ダイボンド材硬化体
３ ダイパッド
４ 金線
５ リードフレーム
６ 封止用樹脂組成物の硬化体
DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding
Claims (9)
（Ｂ）フェノール樹脂系硬化剤、
（Ｃ）無機充填材、
（Ｄ）硬化促進剤、
及び（Ｅ）トリレンジイソシアネート変性酸化ワックスを含み、
前記硬化促進剤（Ｄ）がカチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）を含むことを特徴とする半導体封止用エポキシ樹脂組成物。 (A) epoxy resin,
(B) a phenolic resin-based curing agent,
(C) inorganic filler,
(D) a curing accelerator,
And (E) tolylene diisocyanate modified oxidized wax,
The epoxy resin composition for semiconductor encapsulation, wherein the curing accelerator (D) contains a curing accelerator (d1) having a cation part and a silicate anion part.
前記カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）のカチオン部が燐カチオンを含むものであることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to claim 1,
An epoxy resin composition for semiconductor encapsulation, wherein the cation part of the curing accelerator (d1) having a cation part and a silicate anion part contains a phosphorus cation.
前記カチオン部とシリケートアニオン部とを有する硬化促進剤（ｄ１）が下記一般式（１）で表される化合物であることを特徴とする半導体封止用エポキシ樹脂組成物。
An epoxy resin composition for semiconductor encapsulation, wherein the curing accelerator (d1) having a cation part and a silicate anion part is a compound represented by the following general formula (1).
前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の軟化点が７０℃以上、１２０℃以下であることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 3,
A softening point of the tolylene diisocyanate-modified oxidized wax (E) is 70 ° C. or higher and 120 ° C. or lower, and an epoxy resin composition for semiconductor encapsulation.
前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の平均粒径が２０μｍ以上、７０μｍ以下であり、全トリレンジイソシアネート変性酸化ワックス（Ｅ）中における粒径１５０μｍ以上の粒子の含有割合が０．１重量％以下であることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 4,
The average particle size of the tolylene diisocyanate-modified oxidized wax (E) is 20 μm or more and 70 μm or less, and the content ratio of particles having a particle size of 150 μm or more in the total tolylene diisocyanate-modified oxidized wax (E) is 0.1% by weight. An epoxy resin composition for semiconductor encapsulation, characterized by:
前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の酸価が１０ｍｇＫＯＨ／ｇ以上、５０ｍｇＫＯＨ／ｇ以下であることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 5,
An epoxy resin composition for semiconductor encapsulation, wherein the acid value of the tolylene diisocyanate-modified oxidized wax (E) is 10 mgKOH / g or more and 50 mgKOH / g or less.
前記トリレンジイソシアネート変性酸化ワックス（Ｅ）の数平均分子量が５００以上、５０００以下であることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 6,
The tolylene diisocyanate-modified oxidized wax (E) has a number average molecular weight of 500 or more and 5000 or less, which is an epoxy resin composition for semiconductor encapsulation.
前記トリレンジイソシアネート変性酸化ワックス（Ｅ）がトリレンジイソシアネート変性酸化ポリプロピレンワックス、トリレンジイソシアネート変性酸化ポリエチレンワックス及びトリレンジイソシアネート変性酸化パラフィンワックスから選ばれる少なくとも一つであることを特徴とする半導体封止用エポキシ樹脂組成物。 In the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 7,
The tolylene diisocyanate modified oxidized wax (E) is at least one selected from tolylene diisocyanate modified oxidized polypropylene wax, tolylene diisocyanate modified oxidized polyethylene wax and tolylene diisocyanate modified oxidized paraffin wax. Epoxy resin composition.
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| JP2006124643A (en) * | 2004-09-30 | 2006-05-18 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
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