JPH0232134A - Filler for semiconductor sealing resin - Google Patents
Filler for semiconductor sealing resinInfo
- Publication number
- JPH0232134A JPH0232134A JP18026088A JP18026088A JPH0232134A JP H0232134 A JPH0232134 A JP H0232134A JP 18026088 A JP18026088 A JP 18026088A JP 18026088 A JP18026088 A JP 18026088A JP H0232134 A JPH0232134 A JP H0232134A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- filler
- less
- resin
- solid
- 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.)
- Pending
Links
- 239000000945 filler Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims description 15
- 239000011347 resin Substances 0.000 title claims description 15
- 239000004065 semiconductor Substances 0.000 title claims description 7
- 238000007789 sealing Methods 0.000 title description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 42
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000005538 encapsulation Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007654 immersion Methods 0.000 abstract description 5
- 238000011282 treatment Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 229910052582 BN Inorganic materials 0.000 abstract description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005350 fused silica glass Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000005283 ground state Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 16
- 239000011342 resin composition Substances 0.000 description 16
- 230000035939 shock Effects 0.000 description 16
- -1 silicon imide Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 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 11
- 239000000463 material Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 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 3
- 239000004593 Epoxy Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- XYXBMCIMPXOBLB-UHFFFAOYSA-N 3,4,5-tris(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC(O)=C(C)C(N(C)C)=C1N(C)C XYXBMCIMPXOBLB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 101100272588 Escherichia coli (strain K12) bisC gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 101100099970 Haemophilus influenzae (strain ATCC 51907 / DSM 11121 / KW20 / Rd) torZ gene Proteins 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GOAJGXULHASQGJ-UHFFFAOYSA-N ethene;prop-2-enenitrile Chemical group C=C.C=CC#N GOAJGXULHASQGJ-UHFFFAOYSA-N 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Chemical class 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-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
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- LSZKGNJKKQYFLR-UHFFFAOYSA-J tri(butanoyloxy)stannyl butanoate Chemical compound [Sn+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O LSZKGNJKKQYFLR-UHFFFAOYSA-J 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、封止用樹脂組成物に用いた際に優れた耐熱衝
撃性、熱伝導性及び耐湿信頼性を付与することのできる
半導体封止樹脂用充填材に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a semiconductor encapsulation that can provide excellent thermal shock resistance, thermal conductivity, and moisture resistance reliability when used in a encapsulation resin composition. Related to filler for resin stopper.
従来、シリカ質充填材とエポキシ樹脂とからなる樹脂組
成物は、電気特性、機械的強度、耐熱性耐湿信頼性及び
成形性に優れるため、信頼性の高い電気絶縁材料として
、ＩＣ％ＬＳＩ 、 ＶＬＳＩ 、ダイオード、トリオ
ード、サイリスタ、トランジスタートランスデユーサ−
コイル、コンデンサー抵抗器等の電子部品の封止、含浸
、接着などく幅広く利用されている。Conventionally, resin compositions consisting of siliceous fillers and epoxy resins have excellent electrical properties, mechanical strength, heat resistance, moisture resistance reliability, and moldability, so they have been used as highly reliable electrical insulating materials for IC%LSI, VLSI , diode, triode, thyristor, transistor transducer
It is widely used for sealing, impregnating, and adhering electronic components such as coils and capacitor resistors.
近年、半導体素子自体は高密度化、大型チップ化される
とともく成形品のパッケージ構造も薄型化、小型化され
てきておシ、耐熱衝撃性及び熱伝導性に優れた封止材が
望まれている。一方、高密度実装及び実装工程の合理化
のため、半田浸漬もしくは半田リフロー法で半田付けす
る比率が高まっておシ、半田浸漬後の耐湿信頼性の確保
が重要になっている。したがって、半導体封止材用樹脂
組成物の耐熱衝撃性、高熱伝導性及び耐湿信頼性のいず
れをも向上させることが重要になってきている。In recent years, semiconductor devices themselves have become denser and larger chips, and the package structures of molded products have also become thinner and smaller, creating a demand for encapsulants with excellent thermal shock resistance and thermal conductivity. It is rare. On the other hand, in order to achieve high-density mounting and rationalize the mounting process, the proportion of soldering using solder immersion or solder reflow methods has increased, and ensuring moisture resistance reliability after solder immersion has become important. Therefore, it has become important to improve all of the thermal shock resistance, high thermal conductivity, and moisture resistance reliability of resin compositions for semiconductor encapsulants.
樹脂組成物に高熱伝導性と良好な耐熱衝撃性を付与する
ことができる充填材として窒化珪素が提案されている（
特開昭６１−２８５２４７号公報、特開昭＜５１−２２
１２２０号公報）が、このものでは半田浸漬後の耐湿信
頼性が不足するので近年の高密度実装化の要求を満たす
ことができない。Silicon nitride has been proposed as a filler that can impart high thermal conductivity and good thermal shock resistance to resin compositions (
JP-A No. 61-285247, JP-A No. 51-22
No. 1220), however, this type lacks moisture resistance reliability after immersion in solder, and cannot meet recent demands for high-density packaging.
本発明は、以上述べた窒化珪素充填材の欠点を解決する
ことを目的とするものであって、耐熱衝撃性、高熱伝導
性及び耐湿イ８頼性を付与することのできる半導体封止
樹脂用充填材を提供するものである。The present invention aims to solve the above-mentioned drawbacks of the silicon nitride filler, and is a material for semiconductor encapsulation resin that can provide thermal shock resistance, high thermal conductivity, moisture resistance, and reliability. It provides a filling material.
本発明は、湿式処理後固液分離をして得られた酸素含有
率７％以下の窒化珪素粉末を必須成分としてなることを
特徴とする半導体封止樹脂用充填材である。The present invention is a filler for semiconductor encapsulation resin, which is characterized in that it contains as an essential component silicon nitride powder with an oxygen content of 7% or less obtained by solid-liquid separation after wet processing.
以下さらに詳しく本発明について説明する。The present invention will be explained in more detail below.
窒化珪素の代置的製造法としては、（１）ハロデシ相
化珪素化合物とアンモニアから直接気粗合成もしくはシ
リコンイミド、シリコンアミドを経由して展進する方法
、（２）シリカを還元窒化する方法、（３１金属シリコ
ンを直接窒化する方法等が挙げられるが、本発明ではい
ずれの方法によって得られたものでも使用される。Alternative manufacturing methods for silicon nitride include (1) direct crude synthesis from a halide-phase silicon compound and ammonia or propagation via silicon imide or silicon amide, and (2) method of reducing and nitriding silica. (31) Although methods such as direct nitriding of metal silicon can be mentioned, materials obtained by any of these methods can be used in the present invention.
また、窒化珪素は、非晶質、α−型、β−型の３種類の
結晶形を有する。非晶質である窒イヒ珪素は、（１）の
方法によ１３００℃未満の温度で得られるが、粒度分布
がシャープで、かつ平均粒径が１１１ｍ以下であるため
、樹脂組成物中に高充填しずらかったシネ細物としてハ
ロゲンを多量に含有したシして、α−型、β−型に比較
して熱伝導率が低いのであまシ好ましくない。これに対
し、α−型とβ−型の窒化珪素はほぼ同等の耐熱衝撃性
及び高熱伝導性を樹脂組成物に付与することができるの
で、α−型、β−型のいずれか又は両方の混合物が望ま
しい、これらのα−型及びβ−型型化化珪素（１）〜（
３１のいずれの方法においても１３００℃以上の高温で
熱処理もしくは窒化することにより得ることができる。Furthermore, silicon nitride has three types of crystal forms: amorphous, α-type, and β-type. Silicon nitride, which is amorphous, can be obtained by the method (1) at a temperature below 1300°C, but because it has a sharp particle size distribution and an average particle size of 111 m or less, it is not included in the resin composition. It is difficult to fill the cine material, which contains a large amount of halogen, and has a lower thermal conductivity than the α-type and β-type, so it is not preferable. On the other hand, α-type and β-type silicon nitride can impart almost the same thermal shock resistance and high thermal conductivity to the resin composition, so either α-type, β-type silicon nitride, or both A mixture of these α-type and β-type silicones (1) to (
In any method of No. 31, it can be obtained by heat treatment or nitriding at a high temperature of 1300° C. or higher.
換言すれば、耐熱衝撃性及び高熱伝導性に優れた窒化珪
素を得るには還元雰囲気下で１６００°Ｃ以上で熱処理
をしなければならず、炉材の材質等に制限を受ける。さ
らに、１６００°Ｃ以上に度熱することにより炉材に含
まれていたナトリウムやカリウム等のアルカリ金楓が窒
化珪素に飛散付着し、そのため窒化珪素を含有する封止
材の耐湿信頼性を損ねる要因となっていた。In other words, in order to obtain silicon nitride with excellent thermal shock resistance and high thermal conductivity, heat treatment must be performed at 1600° C. or higher in a reducing atmosphere, and there are restrictions on the material of the furnace material, etc. Furthermore, by heating to 1600°C or more, alkali metals such as sodium and potassium contained in the furnace material scatter and adhere to silicon nitride, which impairs the moisture resistance reliability of the sealing material containing silicon nitride. This was a contributing factor.
そこで本発明者らは、窒化珪素に含有されるアルカリ金
属、特にナトリウムを低減させる方法を鋭意検討した結
果、窒化珪素を湿式処理し、その後固液分離を行なうこ
とによシ抽出ナトリウムを大幅に低減させることができ
、さらに意外にも窒化珪素そのものの加水分解安定性も
高められ、その結果、封止材用の充填材として使用した
場合、耐熱衝撃性、高熱伝導性及び耐湿信頼性のいずれ
においても優れた充填材となシ得ることを見出したので
ある。The inventors of the present invention have therefore conducted intensive studies on methods for reducing the alkali metals, particularly sodium, contained in silicon nitride.The inventors have found that by wet-processing silicon nitride and then performing solid-liquid separation, the extracted sodium can be significantly reduced. Moreover, surprisingly, the hydrolytic stability of silicon nitride itself is also increased, and as a result, when used as a filler for encapsulants, it has excellent thermal shock resistance, high thermal conductivity, and moisture resistance reliability. They discovered that it can also be used as an excellent filler.
本発明において、窒化珪素を湿式処理する場合、使用す
る溶媒としては、ナトリウム化合物を効果的に抽出除去
するために、水の含有率５０重量％以上好ましくは８０
重量％以上のものが望ましいつ水板外の溶媒としては、
アセトン、メタノール、エタノール、イソプロぎルアル
コール、テトラヒ「ロフラン等が挙げられる。また、抽
出効率を高めるために蟻酸、酢酸、アンモニア、アミン
等で一調節することは望ましい。使用する水としては、
イオン交換水もしくは蒸留水が好ましいが、目標とする
耐湿信頼性のレベルに応じて工業用水を使〜５００重量
部好ましくは０．８〜２００重量部特に好ましくは１〜
１００重量部である。、溶媒量が０．５重量部未満の場
合、スラリーのハンドリングが難しくなったシ湿式処理
回数が著しく多く必要となる。一方、５００重量部を超
えると、固液分離の際に設備への負荷量が増大する。In the present invention, when wet-processing silicon nitride, the solvent used should have a water content of 50% by weight or more, preferably 80% by weight, in order to effectively extract and remove sodium compounds.
As a solvent outside the water repellent plate, it is desirable to have a content of at least % by weight.
Examples include acetone, methanol, ethanol, isoprogyl alcohol, and tetrahedralofuran.Also, in order to increase extraction efficiency, it is desirable to adjust the extraction with formic acid, acetic acid, ammonia, amine, etc.The water used is:
Ion-exchanged water or distilled water is preferred, but industrial water is used depending on the target level of moisture resistance reliability, preferably 500 parts by weight, preferably 0.8 to 200 parts by weight, particularly preferably 1 to 200 parts by weight.
It is 100 parts by weight. If the amount of solvent is less than 0.5 part by weight, handling of the slurry becomes difficult and a significantly increased number of wet treatments are required. On the other hand, if it exceeds 500 parts by weight, the load on equipment increases during solid-liquid separation.
前述の（１）〜（３）の方法によって得られた窒化珪素
の粉末もしくは塊をそのまま湿式処理してもよいが、抽
出効率が良くなるという点で、窒化珪素を粉砕後湿式処
理するのが好ましいう
本発明において湿式処理とは、窒化珪素の粉末もしくは
塊を溶媒中に浸漬もしくは分散、又は湿式粉砕すること
を意味し、湿式処理を行なう際の温度としては、特に制
限がないが、加圧容器等を使用しなくてもよいという点
で、溶媒の沸点未満の温度が好ましい、湿式処理の時間
は、温度が高くなるほど短かくできるが、通常１分以上
好ましくは３分以上である。Although the silicon nitride powder or lump obtained by the above-mentioned methods (1) to (3) may be wet-processed as is, it is preferable to wet-process the silicon nitride after pulverizing it in order to improve the extraction efficiency. Preferably, in the present invention, wet processing means immersing or dispersing silicon nitride powder or lumps in a solvent, or wet pulverizing, and there is no particular restriction on the temperature at which the wet processing is performed. A temperature below the boiling point of the solvent is preferable in that it does not require the use of a pressure vessel, etc. The time for the wet treatment can be shortened as the temperature increases, but it is usually 1 minute or more, preferably 3 minutes or more.
窒化珪素粉末を分散させるための攪拌装置としては、ス
ラリーを急速に振盪できるものであれば何でもよいが、
サンドミル、ボールミル、コロイドミル、アトライター
高速攪拌機等が好ましい。Any stirring device for dispersing the silicon nitride powder may be used as long as it can rapidly shake the slurry.
Sand mills, ball mills, colloid mills, attritor high-speed stirrers, etc. are preferred.
本発明において、湿式処理後、固液分離することが重要
であシ、湿式処理後そのまま乾燥するだけではナトリウ
ムを十分に低減させることができず、封止材の耐湿信頼
性を大幅に改善することができない。本発明における固
液分離の操作としては、沈降分級、ラメラ分級、セント
ル、液体サイクロン、デカンタ−ろ過等の操作が挙げら
れるが、分級を兼ねたい場合には、沈降分級、ラメラ分
級、液体サイクロン、デカンタ−等が好ましく一方、ス
ラリーからの回収率を高めたい場合には、セントル、ろ
過等が好ましい。In the present invention, it is important to perform solid-liquid separation after wet processing, and simply drying after wet processing cannot sufficiently reduce sodium, which greatly improves the moisture resistance reliability of the sealing material. I can't. Examples of solid-liquid separation operations in the present invention include operations such as sedimentation classification, lamellar classification, center, liquid cyclone, and decanter filtration; A decanter or the like is preferred, while a centrifuge, filtration or the like is preferred if a higher recovery rate from the slurry is desired.
固液分離後の濃縮スラリー ケーキ、含水塊は、必要な
らば新しい溶媒を添加し湿式処理を繰シ返すことができ
る。抽出ナトリウムを低減できた濃縮スラリー、ケーキ
、含氷塊は、送風乾燥、パドルドライヤー乾燥、真空乾
燥、振動乾燥、スプレードライヤー乾燥、フラッシュ乾
燥、火炎中へのフィード、電気炉、キルン炉による乾燥
等で乾燥するが、スプレードライヤー乾燥の際、イツト
リア、アルミナ、シリカ、フォルステライト、珪酸エス
テル等を添加しておくことによシ、乾燥と同時に球状化
することもできる。乾燥中、好ましくない凝集塊が発生
した場合には、乾燥物を解砕する。After solid-liquid separation, the concentrated slurry cake and water-containing mass can be subjected to repeated wet processing by adding new solvent if necessary. Concentrated slurries, cakes, and ice-containing blocks with reduced extracted sodium can be dried by blow drying, paddle dryer drying, vacuum drying, vibration drying, spray dryer drying, flash drying, feeding into a flame, electric furnace, kiln furnace, etc. It dries, but it can be spheroidized at the same time as drying by adding yttoria, alumina, silica, forsterite, silicate ester, etc. during drying with a spray dryer. If undesirable agglomerates are generated during drying, the dried material is crushed.
乾燥温度としては、室温以上、好ましくは５０℃以上、
特に８０℃以上が乾燥所要時間を短くするうえで好まし
い。また乾燥温度の上限は特に制限はないが、乾燥温度
が著しく高温であると乾燥中に窒化珪素が酸化されやす
くなシ、過度の酸化は熱伝導性と耐熱衝撃性を損わせる
ので、１０００℃を超える温度で乾燥する場合には、乾
燥時間を１０時間以下、好ましくは５時間以下、特に好
ましくは３時間以下とする。The drying temperature is room temperature or higher, preferably 50°C or higher,
In particular, a temperature of 80° C. or higher is preferable in order to shorten the drying time. There is no particular upper limit to the drying temperature, but if the drying temperature is extremely high, silicon nitride will be easily oxidized during drying, and excessive oxidation will impair thermal conductivity and thermal shock resistance. When drying is carried out at a temperature exceeding .degree. C., the drying time is 10 hours or less, preferably 5 hours or less, particularly preferably 3 hours or less.
以上のようくして得られた窒化珪素粉末の酸素含有率は
７チ以下、好ましくは５％以下特に好ましくは４％以下
である。酸素含有率が７％を越えると熱伝導率は小さく
なる。なお、窒化珪素粉末の酸素含有率の測定は、例え
ば浴用金属として、ニッケル５０重量％及び錫５０重量
％からなる混合浴を用い、インパルス加熱炉、非分散赤
外線吸に好ましくは１０００°Ｃ以下特に６００℃以下
の温度で乾燥することが望ましく、それによシ、窒化珪
素の抽出水の電気伝導度（ＥＣ）を大幅に低下させるこ
とができる。つま［、Ｎａ＋の低減だけでなく驚くべき
ことに窒化珪素の加水分解安定性も同時に改良すること
ができる。その結果、樹脂組成物の熱伝導性や耐熱衝撃
性を損うことなく耐湿信頼性を改良することができたの
である。The oxygen content of the silicon nitride powder obtained as described above is 7% or less, preferably 5% or less, particularly preferably 4% or less. When the oxygen content exceeds 7%, the thermal conductivity decreases. The oxygen content of the silicon nitride powder is measured using, for example, a mixed bath consisting of 50% by weight of nickel and 50% by weight of tin as the bath metal, in an impulse heating furnace, preferably at a temperature of 1000°C or below, preferably at a temperature of 1000° C. or lower for non-dispersive infrared absorption. It is desirable to dry at a temperature of 600° C. or lower, thereby making it possible to significantly reduce the electrical conductivity (EC) of the silicon nitride extraction water. In addition to reducing Na+, surprisingly, the hydrolytic stability of silicon nitride can also be improved at the same time. As a result, it was possible to improve the moisture resistance reliability of the resin composition without impairing its thermal conductivity or thermal shock resistance.
本発明の窒化珪素粉末に含まれる抽出不純物としては、
Ｎａ” ２０ ｐｐｍ以下、（Ｊ−２０ｐｐｍ以下、Ｆ
ｅ” ５０００ ｐｐｍ以下であシ、好ましくはＮａ”
１０ ｐｐｍ以下、ｌ：ｊ−１０ｐｌ）ｍ以下、Ｆｅ”
４０００ｐｐｍ以下であシ、特に好ましくはＮａ”
８ ｐｐｍ以下、Ｃｊ−７ｐｐｍ以下、Ｆｅ” ５００
０１）１）ｍ以下である。The extracted impurities contained in the silicon nitride powder of the present invention include:
Na” 20 ppm or less, (J-20 ppm or less, F
e" 5000 ppm or less, preferably Na"
10 ppm or less, l:j-10pl)m or less, Fe”
4000 ppm or less, particularly preferably Na”
8 ppm or less, Cj-7 ppm or less, Fe” 500
01) 1) m or less.
Ｎａ＋やニーが２０ ｐｐｍを超えると耐湿信頼性が劣
った。ｊ）Ｆｅ”＋が５０００ ｐｐｍを超えると電気
絶縁性不良や高周波予熱時にスパークを発生する欠点が
あられれる。When Na+ or knee exceeds 20 ppm, moisture resistance reliability is poor. j) If Fe''+ exceeds 5000 ppm, defects may occur such as poor electrical insulation and generation of sparks during high frequency preheating.
本発明の必須成分である窒化珪素の平均粒径としては、
０．３〜７０μｍ好ましくは０．５〜５０μｍ特に好ま
しくは１〜４０μｍである。平均粒径が０．３μｍ未満
であると、樹脂組成物の成形性が損われる丸め、高充て
んし難く熱伝導性や耐熱衝撃性が損われる。また、平均
粒径が７０μｍを超えると、金型摩耗やポンディングワ
イヤの変形や切断が発生しやすくなる。The average particle size of silicon nitride, which is an essential component of the present invention, is as follows:
The thickness is preferably 0.3 to 70 μm, preferably 0.5 to 50 μm, particularly preferably 1 to 40 μm. If the average particle size is less than 0.3 μm, the moldability of the resin composition will be impaired, rounding will be difficult, and high filling will be difficult, resulting in impaired thermal conductivity and thermal shock resistance. Moreover, if the average particle size exceeds 70 μm, mold wear and deformation or breakage of the bonding wire are likely to occur.
本発明の窒化珪素粉末は、１０倍重量以下好ましくＦｉ
５倍重量以下特に好ましくは１倍重量以下（いずれも０
を含む）の形状が破砕状、球状、ウィスカー状、繊維状
又は鱗片状である溶融シリカ、生シリカ、シリカチタニ
アガラス、クリストバライト化シリカ、珪酸アルミニウ
ム、アルミナ、窒化チタン、窒化ホウ素等の他の充填材
を併用してもよい。１０倍重量を超えると放熱性、耐熱
衝撃性、耐湿信頼性の少くとも１つの特性が損われる。The silicon nitride powder of the present invention preferably has a Fi
5 times the weight or less, particularly preferably 1 time the weight or less (both 0
other fillings such as fused silica, raw silica, silica-titania glass, cristobalitized silica, aluminum silicate, alumina, titanium nitride, boron nitride, etc., which are in the form of crushed, spherical, whisker-like, fibrous or flake-like Materials may also be used together. If it exceeds 10 times the weight, at least one of the characteristics of heat dissipation, thermal shock resistance, and moisture resistance reliability will be impaired.
なお、他の充填材を併用する場合は、要求される封止材
の特性に応じて充填材を使いわけることが大切である。In addition, when using other fillers together, it is important to use the fillers properly depending on the required characteristics of the sealant.
すなわち、耐熱衝撃性及び耐湿信頼性を重視する場合は
溶融シリカやシリカチタニアガラスを選び、熱伝導性を
重視する場合は窒化チタン、窒化ホウ素、アルミナを選
び、金型等の摩耗抑制とほどほどの熱伝導性及びコスト
低減のためには生シリカ、クリストバライト化シリカ、
珪酸アルミニウム等を選ぶ。In other words, if thermal shock resistance and moisture resistance reliability are important, choose fused silica or silica titania glass, and if thermal conductivity is important, choose titanium nitride, boron nitride, or alumina. Raw silica, cristobalitized silica,
Choose aluminum silicate, etc.
本発明の充填材の最大粒径としては、小さいほど成型時
における素子表面の配線、パッシベーション膜、ボンデ
ィングワイヤ等に傷をつけたシ破損をさせたプすること
が少なくなるが、トランスファー成形時のデート詰シを
考慮した最大粒径は、５００μｍ以下好ましくは１４９
μｍ以下特く好ましくは７４μｍ以下である。なお、ダ
イボンディング接着用や鋼箔接着用に、は、４４μｍ以
下さらに必要により２０μｍ以下とすることによシ、平
滑性と接着性を向上させた樹脂組成物とすることができ
る。The smaller the maximum particle size of the filler of the present invention, the less likely it is to cause damage to wiring, passivation films, bonding wires, etc. on the element surface during molding, but it is less likely to cause damage during transfer molding. The maximum particle size considering date packing is 500 μm or less, preferably 149
It is preferably 74 μm or less, particularly preferably 74 μm or less. In addition, for die bonding adhesion and steel foil adhesion, by setting the thickness to 44 μm or less, and further 20 μm or less if necessary, a resin composition with improved smoothness and adhesiveness can be obtained.
本発明の充填材の樹脂組成物中の含有率は、２０〜９７
重量％好ましくは３０〜９５重量−特に好ましくは４０
〜９０重量％である。充填材の含有率が２０重量％未満
であると、樹脂組成物の成形性は優れるが、熱応力が大
きく耐熱衝熱性や耐湿信頼性が低下する。一方、９７重
量％を超えると、樹脂組成物の成形性が損われ、未充填
部やボイドが多発し、電気絶縁性や信頼性が損われる。The content of the filler of the present invention in the resin composition is 20 to 97
% by weight preferably 30-95% by weight - particularly preferably 40
~90% by weight. When the content of the filler is less than 20% by weight, the moldability of the resin composition is excellent, but thermal stress is large and heat shock resistance and moisture resistance reliability are reduced. On the other hand, if it exceeds 97% by weight, the moldability of the resin composition will be impaired, unfilled areas and voids will occur frequently, and electrical insulation and reliability will be impaired.
本発明の充填材が使用される樹脂としては、ビスフェノ
ール型エポキシ樹脂、フェノールノボラック型エポキシ
樹脂、脂環型エポキシ樹脂、複素環型エポキシ樹脂、グ
リシジルエステル型エポキシ樹脂、グリシジルアミン型
エポキシ樹脂、ハロゲン化エポキシ樹脂などのエポキシ
樹脂、ポリベンズイミダゾール、ポリベンズオキサゾー
ル、ポリベンズチアゾール、ポリオキサジアゾール、ポ
リピラゾール、ポリキノキサリン、ポリキナゾリンジオ
ン、ポリベンズオキサジノン、ポリインドロン、ポリ中
ナシロン、ポリインドキシル、シリコン樹脂、シリコン
−エポキシ樹脂、フェノール樹脂、メラミン樹脂、エリ
ア樹脂、不飽和ポリエステル、ポリアミノビスマレイミ
ド、ジアリルフタレート樹脂、フッ素樹脂、ＴＰＸ樹脂
（メチルペンテンポリマー「三層石油化学社製商品名」
）、ポリイミド、ポリアミドイミド、ポリエーテルイミ
ド、６ローナイロン及びＭＸＤ−ナイロン、アモルファ
スナイロン等のポリアミド、ポリエチレンテレフタレー
ト及びポリエチレンテレフタレート等のポリエステル、
ポリフェニレンスルフィド、変性ポリフェニレンエーテ
ル、ポリアリレート、全芳香族ポリエステル、ポリスル
ホン、液晶ボリサルプム・スチレン） 樹脂、Ａｌ３ｊ
８ （アクリロニトリル−エチレン自プロピレン・ジエ
ンデムースチレン）樹脂等が挙げられるが、封止材、電
気絶縁−４−Ｘ ）等には、通常、エポキシ樹脂やシリ
コン−エポキシ樹脂、よシ高温下での金属との接着強度
や曲げ強度等の保持のためには、ケルイミド（三層石油
化学社製−商品名）、ＢＴ樹脂（三菱瓦斯化学社製商品
名）等のポリアミノビスマレイミド系樹脂、デートやラ
ンナーを再利用できる封止用樹脂としては、ポリフェニ
レンスルフィド、ポリフェニレンスルフィドと液晶ポリ
マー及び／又はエポキシ基含有ポリマーとのアロイ等が
好ましい。Resins for which the filler of the present invention can be used include bisphenol-type epoxy resins, phenol novolak-type epoxy resins, alicyclic-type epoxy resins, heterocyclic-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, and halogenated epoxy resins. Epoxy resins such as epoxy resins, polybenzimidazole, polybenzoxazole, polybenzthiazole, polyoxadiazole, polypyrazole, polyquinoxaline, polyquinazolinedione, polybenzoxazinone, polyindolone, polyamide, polyindoxyl, silicone Resin, silicone-epoxy resin, phenolic resin, melamine resin, area resin, unsaturated polyester, polyamino bismaleimide, diallyl phthalate resin, fluororesin, TPX resin (methylpentene polymer "Product name manufactured by Sankai Petrochemical Co., Ltd.")
), polyimide, polyamideimide, polyetherimide, polyamide such as 6-row nylon and MXD-nylon, amorphous nylon, polyester such as polyethylene terephthalate and polyethylene terephthalate,
Polyphenylene sulfide, modified polyphenylene ether, polyarylate, fully aromatic polyester, polysulfone, liquid crystal borisalpum styrene) resin, Al3j
8 (acrylonitrile-ethylene self-propylene/diene demousstyrene) resin, etc., but for sealing materials, electrical insulation-4-X), etc., epoxy resins and silicone-epoxy resins are usually used. In order to maintain adhesion strength and bending strength with metal, polyamino bismaleimide resins such as Kelimide (manufactured by Sankai Petrochemical Co., Ltd. - trade name), BT resin (trade name made by Mitsubishi Gas Chemical Co., Ltd.), etc. As the sealing resin whose runner can be reused, polyphenylene sulfide, an alloy of polyphenylene sulfide and a liquid crystal polymer and/or an epoxy group-containing polymer, etc. are preferable.
本発明の充填材を使用した樹脂組成物には、耐熱衝撃性
を高めるために、ブチルゴム、アクリルがム、エチレン
プロピレンビム、シリコーンゴム、ポリエステルエラス
トマー ポリブタジェン等のデム成分をこれら樹脂中に
含有させることもできる。さらに必要に応じて、ベンゾ
グアナミン、２゜４−ジヒドラジン−６−メチルアミノ
−Ｓ−１リアジン、２−メチルイミダゾール、２−エチ
ル−４−メチルイミダゾール、１−シアノエチル−２−
エチル−４−メチルイミダゾール等のイミダゾ−ル誘導
体、弗化ホウ素の各種アミン錯体、トリスジメチルアミ
ノメチルフェノール、１．８−ジアゾ・ビシクロ（５，
４，０）−ウンデセン−７゜ベンジルジメチルアミン等
の第３級アミン化合物、ジシアンジアミド、ビスフェノ
ール型エポキシ樹脂もしくはクレゾールノボラック型エ
ポキシ樹脂とアンモニアとの反応により得られるアミノ
アルコール化合物、アジピン酸ヒドラジｒ等の含窒素硬
化（促進）剤、フェノールノボラック、クレゾールノボ
ラック等の７エノール系硬化剤、無水テトラヒドロフタ
ル酸、無水へキサヒドロフタ、ル酸、無水メチルへキサ
ヒドロフタル酸等の酸無水物系硬化剤、トリフェニルホ
スフィン、トリシクロヘキシルホスフィン、メチルジフ
ェニルホスフィン、トリトリルホスフィン、１．２−ビ
ス（ジフェニルホスフィノ）エタン、ビスＣジフェニル
ホスフィノ）メタン等の有機ホスフィン系硬化（促進）
剤、ビス−（トリブチル錫）オキシド、ゾオクテン酸錫
、オクタン酸アンチモン、酪酸錫、−酸化鉛、硫化鉛、
炭酸鉛等の硬化触媒、白金化合物等の重合触媒、ベンゾ
イルペルオキシド、ジクミルペルオキシド等の加硫剤、
カルナバワックス、モンタンワックス、ポリエステルオ
リゴマー シリコン油、低分子量ポリエチレン、パラフ
ィン、直鎖脂肪酸の金属塩、酸アミド、エステル等の滑
剤・離型剤、２．６−ジーｔ−ブチル−４−メチルフェ
ノール、１，３．５−）リス（２−メチル−４−ヒドロ
キシ−５−３−ブチルフェノール）ブタン、ジステアリ
ルチオシクロビオネート、トリノニルフェニルホスファ
イト、トリデシルホスファイト等の安定剤、２．２’−
’ジヒドロキシー４−メトキシベンゾフェノン、２（２
’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾ
ール、４−ｔ−１”？ルフェニルサリチレート、エチル
−２−シアノ−３，３−ジフェニルアクリレート等の光
安定剤、ベンガラ、カーボンプラック等の着色剤、三酸
化アンチモン、五酸化アンチモン、トリフェニルスチビ
ン、水利アルミナ、フェロセン、ホスファゼン、ヘキサ
ブロモベンゼン、テトラプロモアタル酸無水物、トリク
レジルホスフェート、テトラブロモビスフェノールＡ、
臭素化エポキシ誘導体等の難燃剤、ビニルトリメト中ジ
シラン、γ−グリシドキシゾロビルトリメトキシシラン
、ｒ−ウレイドｆｃ１ｔルトリエトキシシラン、Ｎ−β
−（アミノエチル）−ｒ−アミノゾロｔルト、リメトキ
シシラン、β−（３，４−エボキシシクｑヘキシル）エ
チルトリメトキシシラン等のシラン系カップリング剤、
イソゾロビルトリインステアロイルチタネート、ジクミ
ルフェニルオキシアセテートチタネート、ビス（ジオク
チルパイロホスフェート）オキシアセテートチタネート
、イソゾロぎルトリデシルベンゼンスルホニルチタネー
ト等のチタン系カップリング剤、アセトアルコキシアル
ミニウムジイソゾロビレート等のアルミ系カップリング
剤等を配合することができる。In the resin composition using the filler of the present invention, a dem component such as butyl rubber, acrylic gum, ethylene propylene bim, silicone rubber, polyester elastomer, polybutadiene, etc. may be included in the resin to improve thermal shock resistance. You can also do it. Furthermore, as necessary, benzoguanamine, 2゜4-dihydrazine-6-methylamino-S-1 riazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-
Imidazole derivatives such as ethyl-4-methylimidazole, various amine complexes of boron fluoride, trisdimethylaminomethylphenol, 1,8-diazo bicyclo(5,
Tertiary amine compounds such as 4,0)-undecene-7゜benzyldimethylamine, dicyandiamide, amino alcohol compounds obtained by reaction of bisphenol type epoxy resin or cresol novolak type epoxy resin with ammonia, adipic acid hydrazir, etc. Nitrogen-containing curing (accelerator) agents, 7-enol curing agents such as phenol novolak and cresol novolak, acid anhydride curing agents such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, fluoric acid, and methyl hexahydrophthalic anhydride, Organic phosphine curing (acceleration) such as phenylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, tritolylphosphine, 1,2-bis(diphenylphosphino)ethane, bisC diphenylphosphino)methane, etc.
agent, bis-(tributyltin) oxide, tin zooctenate, antimony octoate, tin butyrate, -lead oxide, lead sulfide,
Curing catalysts such as lead carbonate, polymerization catalysts such as platinum compounds, vulcanizing agents such as benzoyl peroxide and dicumyl peroxide,
Carnauba wax, montan wax, polyester oligomer, silicone oil, low molecular weight polyethylene, paraffin, metal salts of straight chain fatty acids, lubricants and mold release agents such as acid amides and esters, 2,6-di-t-butyl-4-methylphenol, Stabilizers such as 1,3.5-)lis(2-methyl-4-hydroxy-5-3-butylphenol)butane, distearylthiocyclobionate, trinonylphenyl phosphite, tridecyl phosphite, 2.2 '−
'Dihydroxy-4-methoxybenzophenone, 2(2
Light stabilizers such as '-hydroxy-5-methylphenyl)benzotriazole, 4-t-1''?ruphenyl salicylate, ethyl-2-cyano-3,3-diphenylacrylate, coloring such as red iron oxide, carbon plaque, etc. agent, antimony trioxide, antimony pentoxide, triphenylstibine, hydric alumina, ferrocene, phosphazene, hexabromobenzene, tetrapromoalic anhydride, tricresyl phosphate, tetrabromobisphenol A,
Flame retardants such as brominated epoxy derivatives, disilane in vinyltrimethane, γ-glycidoxyzolobyltrimethoxysilane, r-ureido fc1trutriethoxysilane, N-β
Silane coupling agents such as -(aminoethyl)-r-aminozolotol, trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
Titanium-based coupling agents such as isozolobyl triine stearoyl titanate, dicumylphenyloxyacetate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, isozologyltridecylbenzenesulfonyl titanate, aluminum such as acetalkoxyaluminum diisozolobyrate, etc. A system coupling agent etc. can be blended.
本発明の充填材を含有する樹脂組成物は、前記に示した
各成分の所定量をヘンシェルミキサー等により充分混合
後、ロール、バンバリーミキサ−ニーダ−らいかい機、
アジホモミキサー ２軸押出機、１軸押出機等の公知の
混線手段によシ加熱混練して製造することができる。The resin composition containing the filler of the present invention can be prepared by thoroughly mixing predetermined amounts of each of the above-mentioned components using a Henschel mixer or the like, and then using a roll, a Banbury mixer, a kneader, a sieve machine, etc.
Ajihomo mixer It can be produced by heating and kneading using a known mixing means such as a twin-screw extruder or a single-screw extruder.
本発明を実施例により具体的に説明するが、本発明は以
下の実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples.
実施例および比較例において「部」、「チ」とあるのは
、「重量部」、「重量％」を意味する。In Examples and Comparative Examples, "parts" and "chi" mean "parts by weight" and "% by weight".
窒化珪素−粉末の製造
金属Ｓ１粉末（最大粒径１４９μｍ１平均粒径ｌＱμｍ
、純度９９．８１ ） １００部、ポリビニ７’ｔ。Production of silicon nitride powder Metal S1 powder (maximum particle size 149 μm 1 average particle size lQ μm
, purity 99.81) 100 parts, polyvinyl 7't.
アルコール５％水溶液１０部をＶデレンダーにて２０分
間混合し、金型プレス成形、乾燥、脱脂後室素気流中で
１０００℃まで２００℃／ｈｒで昇温し％１０００〜１
４５０℃の間を１０℃／ｈｒで昇温し、１４５０℃でさ
らにｌ Ｑ ｈｒ反応をさせて反応塊を得意。この反応
塊を粗砕後、ボールミルで５ ｈｒ微粉砕し目開き１４
９μｍｏｌｌ網で粗粒を除去し、平均粒径が２４．８μ
ｍの窒化珪素粉末Ａ−１を得た。Ｘ線回折の結果α化率
８８．９ ％であつ九。なおα化率は次式で算出した。10 parts of a 5% alcohol aqueous solution was mixed for 20 minutes in a V delander, mold press-molded, dried, and degreased, then heated to 1000°C at a rate of 200°C/hr in a room gas stream to give a mixture of %1000 to 1.
The temperature is raised between 450℃ and 10℃/hr, and the reaction is further carried out at 1450℃ for 1 Q hr to produce a reaction mass. After coarsely crushing this reaction mass, it was finely crushed in a ball mill for 5 hours with a mesh size of 14
Coarse particles were removed using a 9μmol screen, and the average particle size was 24.8μ.
m silicon nitride powder A-1 was obtained. As a result of X-ray diffraction, the gelatinization rate was 88.9%. Note that the gelatinization rate was calculated using the following formula.
ｈα（１０２） ； α−窒化珪素の（１０２）面の高
さｈα（２１０） ； α−窒化珪素の（２１０）面の
高さｈβ（１０１）； β−窒化珪素の（１０１）面の
高さｈβ（２１０） ； β−窒化珪素の（２１０）面
の高さ窒化珪素粉末Ａ−１の湿式処理・固液分離・乾燥
窒化珪素粉末Ａ−１２０部及び５０℃のイオン交換水８
０部を高速攪拌機で１分間攪拌後さらｔｌｃ５０分間低
速攪拌を続けた後セントルで固液分離を行ない、濃縮ケ
ーキを得た。この濃縮ケーキの一部を１５０℃で２４時
間送風乾燥し、粉末Ａ−２を得た。残りのケーキを固形
分濃度が２０％になるようにイオン交換水を加え、１分
間高速攪拌、３０分間低速攪拌後、セントルで再び濃縮
ケ窒化珪素反応塊の湿式粉砕・固液分離・乾燥前述の窒
化珪素の反応塊５０部、イオン交換水４５部及びエタノ
ール５部をボールミルに入れ、３時間、室温で湿式粉砕
後１４９μｍの篩網で粗粒を除去し、一部を１５０℃で
２４時間送風乾燥して粉末Ａ−６を得た。残シのスラリ
ーを加圧ろ過し、濃縮ケーキを得た。この濃縮ケーキを
電気炉で８００°ＣＸ６時間、１２００°０Ｘ１６時間
、１２００°ＣＸＳ時間、１２００℃×４時間、１２０
０’ｃｘ２時間乾燥し、それぞれ粉末Ａ−７、Ａ−８、
Ａ−９、Ａ−１０、Ａ−１１を得た。hα(102); height of the (102) plane of α-silicon nitride hα(210); height of the (210) plane of α-silicon nitride hβ(101); height of the (101) plane of β-silicon nitride hβ(210) ; height of the (210) plane of β-silicon nitride Wet treatment of silicon nitride powder A-1, solid-liquid separation, and drying 120 parts of silicon nitride powder A-1 and 8 parts of ion-exchanged water at 50°C
After stirring 0 part with a high speed stirrer for 1 minute, low speed stirring was continued for 50 minutes using a tlc, and solid-liquid separation was performed using a centrifuge to obtain a concentrated cake. A part of this concentrated cake was air-dried at 150° C. for 24 hours to obtain powder A-2. Add ion-exchanged water to the remaining cake so that the solid content concentration is 20%, stir at high speed for 1 minute, stir at low speed for 30 minutes, and then concentrate again in the center.The silicon nitride reaction mass is wet-pulverized, solid-liquid separated, and dried as described above. 50 parts of the silicon nitride reaction mass, 45 parts of ion-exchanged water, and 5 parts of ethanol were placed in a ball mill, wet-pulverized at room temperature for 3 hours, coarse particles were removed with a 149 μm sieve, and a portion was heated at 150°C for 24 hours. It was dried with air to obtain powder A-6. The residual slurry was filtered under pressure to obtain a concentrated cake. This concentrated cake was heated in an electric furnace at 800°C for 6 hours, 1200°C for 16 hours, 1200°C for 4 hours, and 120°C for 4 hours.
Dry for 0'cx2 hours to obtain powders A-7, A-8, and
A-9, A-10, and A-11 were obtained.
クレゾールノボラックエポキシ樹脂Ｃエポキシ当量２１
５）１５０部、臭素化クレゾールノボラックエポキシ樹
脂（エポキシ当量３５０）４５部、の操作を繰シ返し粉
末Ａ−４、さらに繰シ返して粉末Ａ−５を得た。Cresol novolak epoxy resin C epoxy equivalent weight 21
5) 150 parts of brominated cresol novolac epoxy resin (epoxy equivalent: 350) 45 parts were repeated to obtain powder A-4 and further to obtain powder A-5.
三酸化アンチモン５．６部、カーボンブラック３部、カ
ルナバワックス４．４部および硬化促進剤として２−ウ
ンデシルイミダゾール２．５部、ｒ−グリシドキシゾロ
ピルトリメトキシシラン５部をミキシングロールで混線
後粉砕してエポキシ樹脂組成物を調整した。これらの樹
脂組成物を次に示す評価試験を実施した。その結果を表
−１に示す。5.6 parts of antimony trioxide, 3 parts of carbon black, 4.4 parts of carnauba wax, 2.5 parts of 2-undecylimidazole as a curing accelerator, and 5 parts of r-glycidoxyzolopyltrimethoxysilane were mixed on a mixing roll. After mixing, the mixture was pulverized to prepare an epoxy resin composition. These resin compositions were subjected to the following evaluation tests. The results are shown in Table-1.
表−１において記載した測定値は次の方法によった。The measured values listed in Table 1 were determined by the following method.
（１） 平均粒径
レーデ−回折式法による粒度測定（シーラス社製ｏｒａ
ｎｕｘｏｍｅｔｅｒモデル７１５型）を行なった。(1) Average particle size Particle size measurement by Lehde diffraction method (Ora manufactured by Cirrus Co., Ltd.
nuxometer model 715).
（２１Ｎａ＋及びＥＣ
褪
充填材１０部及び蒸留水４ｏ部を試験容器に仕込み、９
０℃で２４時間浸漬抽出したつ冷却後抽出水を２つに分
け、１つの液でＮａ＋を原子吸光法で定量し、別の液で
電気伝導度（ＥＣ）測定を行なりた。(Pour 10 parts of 21Na+ and EC filler and 4 parts of distilled water into a test container,
After immersion extraction at 0° C. for 24 hours and cooling, the extracted water was divided into two parts, Na + was determined by atomic absorption spectrometry in one part, and electrical conductivity (EC) was measured in another part.
（３１酸素含有率
相場製作所製セラミックス用酸素・窒素同時分析装置ｗ
ｏＡ−２８００を使用し、ｎ ＝ ５の測定の平均値で
代表させた。(31 Oxygen content simultaneous oxygen and nitrogen analyzer for ceramics made by Aiba Seisakusho)
oA-2800 was used and represented by the average value of n = 5 measurements.
（４） 耐熱衝撃性（耐Ｔ／８性）
アイランドサイズ４Ｘ７．５１１１１の１６ピンリード
フレームを各組成物によシトランスファー成形し、その
１６ピンＤＩＰ型成形体を一１９６°Ｃの液体と２６０
°Ｃの液体に６０秒ずつ浸漬を２００回繰シ返して成形
体表面のクラックの発生率を試料数５０個から求めた。(4) Thermal shock resistance (T/8 resistance) A 16-pin lead frame with an island size of 4 x 7.51111 was transfer-molded with each composition, and the 16-pin DIP molded body was heated with a liquid at 196°C and 260°C.
The molded product was immersed in a liquid for 60 seconds 200 times, and the crack occurrence rate on the surface of the molded product was determined from 50 samples.
（５）熱伝導率
熱伝導率測定装置（アグネ社ｍ ｒ ＡＲｃ−Ｔｅ−１
型」）を用い、室温において温度傾斜法で測定した。(5) Thermal conductivity Thermal conductivity measuring device (Agne Corporation m r ARc-Te-1
The measurement was carried out by the temperature gradient method at room temperature.
（６）耐湿信頼性
アルミニウム配線を有する１６ピンモニターＩＣをトラ
ンスファー成形し硬化後２６０℃のハンダ浴に１０秒間
浸漬したのち１２０℃、２気圧Ｆ）水Ｍ気中で１０Ｖ印
加してアルミニウム配線のオープン不良率（断線率）と
リーク不良率（アルミニウム線間の漏れ電流値が１、Ｑ
ｎＡ以上になった率）との和が５０％以上になるまで
の時間を求めた。試料数は２０個である。(6) Moisture-resistant reliability A 16-pin monitor IC with aluminum wiring was transfer-molded, and after curing, it was immersed in a solder bath at 260°C for 10 seconds, and then 10V was applied at 120°C and 2 atm (F) in a water atmosphere to form aluminum wiring. Open defect rate (disconnection rate) and leak defect rate (leakage current value between aluminum wires is 1, Q
The time required for the sum to reach 50% or more was determined. The number of samples was 20.
撃性、熱伝導性及び耐湿信頼性に優れた樹脂組成物を得
ることができる。A resin composition with excellent impact resistance, thermal conductivity, and moisture resistance reliability can be obtained.
Claims (1)
以下の窒化珪素粉末を必須成分としてなることを特徴と
する耐湿信頼性に優れた半導体封止樹脂用充填材。1. Oxygen content 7% obtained by solid-liquid separation after wet processing
A filler for semiconductor encapsulation resin with excellent moisture resistance and reliability, characterized by containing the following silicon nitride powder as an essential component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18026088A JPH0232134A (en) | 1988-07-21 | 1988-07-21 | Filler for semiconductor sealing resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18026088A JPH0232134A (en) | 1988-07-21 | 1988-07-21 | Filler for semiconductor sealing resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0232134A true JPH0232134A (en) | 1990-02-01 |
Family
ID=16080145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18026088A Pending JPH0232134A (en) | 1988-07-21 | 1988-07-21 | Filler for semiconductor sealing resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0232134A (en) |
-
1988
- 1988-07-21 JP JP18026088A patent/JPH0232134A/en active Pending
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