JP6185719B2 - Epoxy resin molding material for sealing and electronic component device - Google Patents
Epoxy resin molding material for sealing and electronic component device Download PDFInfo
- Publication number
- JP6185719B2 JP6185719B2 JP2012509467A JP2012509467A JP6185719B2 JP 6185719 B2 JP6185719 B2 JP 6185719B2 JP 2012509467 A JP2012509467 A JP 2012509467A JP 2012509467 A JP2012509467 A JP 2012509467A JP 6185719 B2 JP6185719 B2 JP 6185719B2
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- Prior art keywords
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- epoxy resin
- general formula
- substituted
- molding material
- Prior art date
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- 229920000647 polyepoxide Polymers 0.000 title claims description 170
- 239000003822 epoxy resin Substances 0.000 title claims description 166
- 239000012778 molding material Substances 0.000 title claims description 64
- 238000007789 sealing Methods 0.000 title claims description 56
- -1 silane compound Chemical class 0.000 claims description 116
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 49
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 150000002430 hydrocarbons Chemical group 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229920005989 resin Polymers 0.000 description 45
- 239000011347 resin Substances 0.000 description 45
- 125000000547 substituted alkyl group Chemical group 0.000 description 33
- 125000003710 aryl alkyl group Chemical group 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
- 239000005011 phenolic resin Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 27
- 238000002156 mixing Methods 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 19
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 18
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 17
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 17
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 17
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 16
- 125000003545 alkoxy group Chemical group 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- 150000002989 phenols Chemical class 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 10
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 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 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 9
- 239000013065 commercial product Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
- 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 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 125000000732 arylene group Chemical group 0.000 description 7
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 7
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 7
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 125000004103 aminoalkyl group Chemical group 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 125000006267 biphenyl group Chemical group 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 description 5
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000004780 naphthols Chemical class 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 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 5
- 230000009467 reduction Effects 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 4
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 125000003944 tolyl group Chemical group 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
- 125000006725 C1-C10 alkenyl group Chemical group 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000005628 tolylene group Chemical group 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 125000006839 xylylene group Chemical group 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- NADHCXOXVRHBHC-UHFFFAOYSA-N 2,3-dimethoxycyclohexa-2,5-diene-1,4-dione Chemical compound COC1=C(OC)C(=O)C=CC1=O NADHCXOXVRHBHC-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 241000257303 Hymenoptera Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- GDKAFTKCUOBEDW-UHFFFAOYSA-N tris(2-tert-butylphenyl)phosphane Chemical compound CC(C)(C)C1=CC=CC=C1P(C=1C(=CC=CC=1)C(C)(C)C)C1=CC=CC=C1C(C)(C)C GDKAFTKCUOBEDW-UHFFFAOYSA-N 0.000 description 1
- RYXYUARTMQUYKV-UHFFFAOYSA-N tris(4-butylphenyl)phosphane Chemical compound C1=CC(CCCC)=CC=C1P(C=1C=CC(CCCC)=CC=1)C1=CC=C(CCCC)C=C1 RYXYUARTMQUYKV-UHFFFAOYSA-N 0.000 description 1
- LQEKTSMTEYLBLJ-UHFFFAOYSA-N tris(4-ethoxyphenyl)phosphane Chemical compound C1=CC(OCC)=CC=C1P(C=1C=CC(OCC)=CC=1)C1=CC=C(OCC)C=C1 LQEKTSMTEYLBLJ-UHFFFAOYSA-N 0.000 description 1
- PCCAGZSOGFNURV-UHFFFAOYSA-N tris(4-ethylphenyl)phosphane Chemical compound C1=CC(CC)=CC=C1P(C=1C=CC(CC)=CC=1)C1=CC=C(CC)C=C1 PCCAGZSOGFNURV-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- JTOQWGJGVSYTTN-UHFFFAOYSA-N tris(4-propylphenyl)phosphane Chemical compound C1=CC(CCC)=CC=C1P(C=1C=CC(CCC)=CC=1)C1=CC=C(CCC)C=C1 JTOQWGJGVSYTTN-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 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
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Description
本発明は、封止用エポキシ樹脂成形材料、及びこの成形材料で封止した素子を備えた電子部品装置に関する。 The present invention relates to an epoxy resin molding material for sealing and an electronic component device including an element sealed with the molding material.
近年の電子機器の小型化、軽量化、高性能化に伴い、実装の高密度化が進み、電子部品装置は従来のピン挿入型から、表面実装型のパッケージがなされるようになってきている。表面実装型のIC、LSI等は、実装密度を高くし、実装高さを低くするために薄型、小型のパッケージになっており、素子のパッケージに対する占有面積が大きくなり、パッケージの肉厚は非常に薄くなってきた。さらにこれらのパッケージは従来のピン挿入型のものと実装方法が異なっている。すなわち、配線板に取り付ける場合、従来のピン挿入型パッケージはピンを配線板に挿入した後、配線板裏面から半田付けを行うため、パッケージが直接高温にさらされることはなかった。しかし、表面実装型パッケージでは半導体装置全体が半田バスやリフロー装置などで処理されるため、直接半田付け温度(リフロー温度)にさらされる。この結果、パッケージが吸湿した場合、半田付け時に吸湿水分が急激に膨張し、発生した蒸気圧が剥離応力として働き、素子、リードフレーム等のインサートと封止材との間で剥離が発生し、パッケージクラックの発生や電気的特性不良の原因となる。このため、半田耐熱性(耐リフロー性)に優れた封止材料の開発が望まれている。
これらの要求に対応するために、これまで、主材となるエポキシ樹脂側から様々な検討がされているが、エポキシ樹脂側の改良だけでは、低吸湿下に伴う耐熱性の低下、密着性の向上に伴う硬化性の低下等が生じ、物性のバランスをとることが困難であった。従って、上記背景から種々のエポキシ樹脂改質剤が検討されており、その中の1例として素子、リードフレーム等のインサートとの密着力向上に注目した硫黄原子含有化合物(例えば特許文献1、2参照)及び硫黄原子含有シランカップリング剤(例えば特許文献3参照)や、インデン・スチレン・フェノール共重合オリゴマー(例えば特許文献4参照)がある。As electronic devices have become smaller, lighter, and higher performance in recent years, mounting density has been increasing, and electronic component devices have come to be made surface mount packages from conventional pin insertion types. . Surface-mount ICs, LSIs, etc. are thin and small packages to increase the mounting density and reduce the mounting height, increasing the area occupied by the device package, and the package thickness is extremely high It has become thinner. Furthermore, these packages are different in mounting method from the conventional pin insertion type. That is, when attaching to a wiring board, since the conventional pin insertion type package is soldered from the back surface of the wiring board after inserting the pins into the wiring board, the package was not directly exposed to high temperature. However, in the surface mount type package, the entire semiconductor device is processed by a solder bus, a reflow device, or the like, and thus is directly exposed to a soldering temperature (reflow temperature). As a result, when the package absorbs moisture, moisture absorption moisture rapidly expands during soldering, and the generated vapor pressure works as a peeling stress, and peeling occurs between the insert such as the element and the lead frame and the sealing material, It may cause package cracks and poor electrical characteristics. For this reason, development of the sealing material excellent in solder heat resistance (reflow resistance) is desired.
In order to meet these demands, various studies have been made from the epoxy resin side which is the main material so far, but the improvement on the epoxy resin side alone has caused a decrease in heat resistance and adhesion due to low moisture absorption. A decrease in curability associated with the improvement occurred, and it was difficult to balance physical properties. Therefore, various epoxy resin modifiers have been studied from the above background. As an example, sulfur atom-containing compounds focused on improving adhesion to inserts such as elements and lead frames (for example, Patent Documents 1 and 2). And sulfur atom-containing silane coupling agents (see, for example, Patent Document 3) and indene / styrene / phenol copolymer oligomers (see, for example, Patent Document 4).
しかしながら、上記特許文献3に記載の硫黄原子含有シランカップリング剤を用いた場合はAgやAuのような貴金属との接着性向上効果が乏しく、また特許文献1、2に記載の硫黄原子含有化合物を用いて、文献開示の量を添加しても貴金属との接着性が充分に向上せず、場合によっては化合物中の硫黄に起因すると考えられる電気特性の悪化を引き起こす場合がある。特許文献4に記載のインデン・スチレン・フェノール共重合オリゴマーを用いた場合は他の特性の悪化はないが耐リフロー性の向上効果に乏しい。 However, when the sulfur atom-containing silane coupling agent described in Patent Document 3 is used, the effect of improving adhesion with noble metals such as Ag and Au is poor, and the sulfur atom-containing compound described in Patent Documents 1 and 2 Even if the amount disclosed in the literature is added, the adhesion with the noble metal is not sufficiently improved, and in some cases, the electrical characteristics that may be caused by sulfur in the compound may be deteriorated. When the indene / styrene / phenol copolymer oligomer described in Patent Document 4 is used, other properties are not deteriorated, but the effect of improving the reflow resistance is poor.
上述したように、従来においては、耐リフロー性を満足するものは得られておらず、本発明はかかる状況に鑑みなされたもので、成形性や難燃性を低下させることなく耐リフロー性に優れる封止用エポキシ樹脂成形材料、及びこれにより封止した素子を備えた電子部品装置を提供しようとするものである。 As described above, in the past, those satisfying the reflow resistance have not been obtained, and the present invention has been made in view of such a situation, and the reflow resistance is not reduced without lowering the moldability and flame retardancy. An object of the present invention is to provide an excellent epoxy resin molding material for sealing, and an electronic component device including an element sealed thereby.
本発明は、特定のケイ素含有化合物を含有する封止用エポキシ樹脂成形材料及びこの封止用エポキシ樹脂成形材料により封止された素子を備える電子部品装置に関する。より具体的には、以下の通りである。 The present invention relates to an epoxy resin molding material for sealing containing a specific silicon-containing compound and an electronic component device including an element sealed with the epoxy resin molding material for sealing. More specifically, it is as follows.
(1)本発明は、(A)エポキシ樹脂、(B)硬化剤、(C)硬化促進剤、(D)無機充てん剤、及び(E)ケイ素含有重合物を含有し、(E)ケイ素含有重合物は、下記一般式(I)、下記一般式(II)、下記一般式(III)で示す構造のうちのいずれか2つまたは全ての構造を有し、(E)ケイ素含有重合物の重量平均分子量が、1500以上7000以下である封止用エポキシ樹脂成形材料に関する。 (1) The present invention contains (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) a silicon-containing polymer. The polymer has any two or all of the structures represented by the following general formula (I), the following general formula (II), and the following general formula (III). The present invention relates to a sealing epoxy resin molding material having a weight average molecular weight of 1500 or more and 7000 or less.
(2)本発明は、(E)ケイ素含有重合物の含有量が、封止用エポキシ樹脂成形材料中の(A)エポキシ樹脂に対して、2.5質量%以上40質量%以下である(1)に記載の封止用エポキシ樹脂成形材料に関する。 (2) In the present invention, the content of the (E) silicon-containing polymer is 2.5% by mass or more and 40% by mass or less with respect to the (A) epoxy resin in the sealing epoxy resin molding material ( It is related with the epoxy resin molding material for sealing as described in 1).
(3)本発明は、封止用エポキシ樹脂成形材料中の(E)ケイ素含有重合物中の全R1における置換または非置換のフェニル基の割合が40モル%以上100モル%以下である(1)または(2)に記載の封止用エポキシ樹脂成形材料に関する。(3) In the present invention, the ratio of substituted or unsubstituted phenyl groups in all R 1 in the (E) silicon-containing polymer in the epoxy resin molding material for sealing is 40 mol% or more and 100 mol% or less ( The present invention relates to an epoxy resin molding material for sealing as described in 1) or (2).
(4)本発明は、インデンオリゴマーをさらに含有する(1)〜(3)のいずれかに記載の封止用エポキシ樹脂成形材料に関する。 (4) This invention relates to the epoxy resin molding material for sealing in any one of (1)-(3) which further contains an indene oligomer.
(5)本発明は、下記一般式(IV)で示すシラン化合物(a)をさらに含有する(1)〜(4)のいずれかに記載の封止用エポキシ樹脂成形材料に関する。 (5) This invention relates to the epoxy resin molding material for sealing in any one of (1)-(4) which further contains the silane compound (a) shown by the following general formula (IV).
(6)本発明は(1)〜(5)のいずれかに記載の封止用エポキシ樹脂成形材料により封止された素子を備える電子部品装置に関する。 (6) This invention relates to an electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of (1)-(5).
本発明によって得られる封止用エポキシ樹脂成形材料は、成形性や難燃性を低下させることなく耐リフロー性に優れる信頼性の高い電子部品装置を得ることができ、その工業的価値は大である。 The epoxy resin molding material for sealing obtained by the present invention can provide a highly reliable electronic component device having excellent reflow resistance without reducing moldability and flame retardancy, and its industrial value is great. is there.
本発明は、(A)エポキシ樹脂、(B)硬化剤、(C)硬化促進剤、(D)無機充てん剤及び(E)ケイ素含有重合物を含有する封止用エポキシ樹脂成形材料である。本発明の詳細について、以下に記載する。 The present invention is an epoxy resin molding material for sealing containing (A) an epoxy resin, (B) a curing agent, (C) a curing accelerator, (D) an inorganic filler, and (E) a silicon-containing polymer. Details of the present invention are described below.
[(E)ケイ素含有化合物]
本発明で用いられる(E)ケイ素含有重合物は、下記一般式(I)、一般式(II)、一般式(III)で示す構造のうちいずれか2つまたは全ての構造を有するケイ素含有重合物であることが必要である。このような重合物としては、分岐状ポリシロキサン、シリコーンレジン又はシリコーンレジン変性用中間体などの三次元架橋をもつケイ素含有重合物であり、直鎖状のポリシロキサンは含まれない。[(E) silicon-containing compound]
The silicon-containing polymer (E) used in the present invention is a silicon-containing polymer having any two or all of the structures represented by the following general formula (I), general formula (II), and general formula (III). It is necessary to be a thing. Such a polymer is a silicon-containing polymer having a three-dimensional crosslinking such as a branched polysiloxane, a silicone resin, or an intermediate for modifying a silicone resin, and does not include a linear polysiloxane.
本発明に係るケイ素含有重合物は、上記一般式(I)、一般式(II)、一般式(III)で示す構造のうちいずれか2つまたは全ての構造を有するが、いずれか2つの場合においては、難燃性の観点から、一般式(I)及び一般式(II)が好ましい。 The silicon-containing polymer according to the present invention has any two or all of the structures represented by the general formula (I), the general formula (II), and the general formula (III). In general, general formula (I) and general formula (II) are preferable from the viewpoint of flame retardancy.
上記一般式(I)及び(II)中のR1としてはメチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、t−ブチル基、ペンチル基、ヘキシル基等のアルキル基、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基、フェニル基等が挙げられ、なかでも入手の容易性からメチル基、プロピル基、フェニル基が好ましく、流動性及び難燃性の観点からフェニル基がさらに好ましい。R 1 in the above general formulas (I) and (II) includes methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and other alkyl groups, vinyl Group, allyl group, butenyl group, pentenyl group, hexenyl group and other alkenyl groups, phenyl group and the like. Among them, methyl group, propyl group, and phenyl group are preferable because of easy availability, and fluidity and flame retardancy. From the viewpoint, a phenyl group is more preferable.
シリコーンオイル等に代表される直鎖状ポリシロキサンでは、入手可能な化合物の多くが液状で、ハンドリング性に劣るとともに、耐リフロー性に関して充分な効果が得られず、硬化物表面への染みだし性、難燃性も悪化する。また分岐状ポリシロキサンであっても、本発明と異なる構造を有する場合、例えばエポキシ基含有分岐状ポリシロキサン等では、弾性率低減効果が充分でなく耐リフロー性に関して充分な効果が得られない。 In linear polysiloxanes represented by silicone oils, many of the available compounds are liquid, inferior in handling properties, and are not effective in terms of reflow resistance. In addition, flame retardancy also deteriorates. Even if it is a branched polysiloxane, when it has a structure different from that of the present invention, for example, an epoxy group-containing branched polysiloxane does not have a sufficient elastic modulus reduction effect and a sufficient effect on reflow resistance cannot be obtained.
また、(E)ケイ素含有重合物の重量平均分子量(Mw)は、1500以上7000以下であることが必要である。さらに、2000以上5500以下が好ましく、より好ましくは2000以上3500以下である。重量平均分子量(Mw)が1500未満では、ケイ素含有重合物が常温で液状又は半液状となり、ハンドリング性に劣るとともに、低分子成分に起因した揮発分の増加により、耐リフロー性が充分に向上せず、さらに難燃性も充分に得られない。一方、重量平均分子量(Mw)が7000を超えて大きいと、高温領域での弾性率低減効果が充分ではなく、耐リフロー性が充分に向上しない傾向にある。また、流動性の観点からは2000以上3500以下が好ましく、更にこの範囲の中でも分子量が低い程、流動性及び難燃性の点で優れる傾向にある。ここで、Mwはゲルパーミエーションクロマトグラフィー法(GPC)により標準ポリスチレンによる検量線を用いて測定することで得られ、上記Mwは、GPCとしてポンプ(株式会社日立製作所製L−6200型)、カラム(TSKgel−G5000HXL+TSKgel−G2000HXL、いずれも東ソー株式会社製商品名)、検出器(株式会社日立製作所製L−3300RI型)を用い、テトラヒドロフランを溶離液として温度30℃、流量1.0ml/minの条件で測定した結果を参照した。 Moreover, the weight average molecular weight (Mw) of (E) silicon-containing polymer needs to be 1500 or more and 7000 or less. Furthermore, 2000 or more and 5500 or less are preferable, More preferably, it is 2000 or more and 3500 or less. When the weight average molecular weight (Mw) is less than 1500, the silicon-containing polymer becomes liquid or semi-liquid at room temperature, and the handling property is inferior, and the reflow resistance is sufficiently improved due to the increase in the volatile content attributed to the low molecular component. Furthermore, sufficient flame retardancy cannot be obtained. On the other hand, if the weight average molecular weight (Mw) is larger than 7000, the effect of reducing the elastic modulus in the high temperature region is not sufficient, and the reflow resistance tends not to be sufficiently improved. Further, from the viewpoint of fluidity, it is preferably 2000 or more and 3500 or less. Further, in this range, the lower the molecular weight, the more excellent in fluidity and flame retardancy. Here, Mw is obtained by measurement using a standard polystyrene calibration curve by gel permeation chromatography (GPC), and the above Mw is GPC as a pump (L-6200 manufactured by Hitachi, Ltd.), column (TSKgel-G5000HXL + TSKgel-G2000HXL, both trade names manufactured by Tosoh Corporation), detector (L-3300RI type manufactured by Hitachi, Ltd.), tetrahydrofuran as an eluent, temperature 30 ° C., flow rate 1.0 ml / min Reference was made to the results measured in.
さらに、成形性、耐リフロー性及び難燃性の観点から、(E)ケイ素含有重合物中の全R1における置換または非置換のフェニル基の割合(Ph基の割合)が40モル%以上100モル%以下であることが好ましく、より好ましくは50モル%以上90モル%以下である。40モル%以上とすることで、エポキシ樹脂や硬化剤との相溶性が良く、硬化物表面に染み出しにくくなり、外観不良を起こしにくくなる。また、室温領域及び高温領域での弾性率低減効果が充分に得られやすくなり、耐リフロー性が充分に向上する。更に、難燃性も向上する傾向もある。特に耐リフロー性及び難燃性の観点からは50モル%以上がより好ましい。また、ケイ素含有重合物の製造の容易性、ケイ素含有重合物の入手のしやすさの観点から、90モル%以下とすることが好ましい。更にこの範囲の中でもPh基の割合が高いほど、難燃性の点で優れる傾向にある。
ここで、Ph基の割合は、ケイ素含有重合物の1H NMR測定から算出することができ、Si−O−Si結合のO原子を除く、Si原子上の各置換基(フェニル基、アルキル基、水酸基等)に対するフェニル基のモル比を算出し、Ph基の割合とする。Furthermore, from the viewpoint of moldability, reflow resistance and flame retardancy, (E) the ratio of substituted or unsubstituted phenyl groups (ratio of Ph groups) in all R 1 in the silicon-containing polymer is 40 mol% or more and 100 It is preferable that it is mol% or less, More preferably, it is 50 mol% or more and 90 mol% or less. By setting it as 40 mol% or more, compatibility with an epoxy resin and a hardening | curing agent is good, it becomes difficult to ooze out to the hardened | cured material surface, and it becomes difficult to raise | generate an external appearance defect. In addition, the effect of reducing the elastic modulus in the room temperature region and the high temperature region can be sufficiently obtained, and the reflow resistance is sufficiently improved. Furthermore, the flame retardancy also tends to improve. In particular, 50 mol% or more is more preferable from the viewpoint of reflow resistance and flame retardancy. Moreover, it is preferable to set it as 90 mol% or less from a viewpoint of the ease of manufacture of a silicon containing polymer, and the availability of a silicon containing polymer. Furthermore, it exists in the tendency which is excellent in the flame retardance point, so that the ratio of Ph group is high also in this range.
Here, the ratio of the Ph group can be calculated from 1H NMR measurement of the silicon-containing polymer, and each substituent on the Si atom (a phenyl group, an alkyl group, an O atom of the Si—O—Si bond) is excluded. The molar ratio of the phenyl group to the hydroxyl group or the like is calculated and set as the ratio of the Ph group.
さらに、本発明において、上記の(E)ケイ素含有重合物中の全R1における置換または非置換のフェニル基の割合(Ph基の割合)を分子量(Mw)で除した値(Ph/Mw)に注目すると、Ph/Mwは簡易的にケイ素含有重合物全体に対するフェニル基の割合と考えられる。Ph/Mwが高いほど、流動性に優れ、高温領域での弾性率低減効果に優れ耐リフロー性の点で優れる傾向にある。Furthermore, in the present invention, the value (Ph / Mw) obtained by dividing the ratio of substituted or unsubstituted phenyl groups (ratio of Ph groups) in all R 1 in the above (E) silicon-containing polymer by molecular weight (Mw) Paying attention to Ph / Mw, the ratio of phenyl groups to the entire silicon-containing polymer is simply considered. The higher the Ph / Mw, the better the fluidity, the better the elastic modulus reduction effect in the high temperature region, and the better the reflow resistance.
このような(E)ケイ素含有重合物としては、以下に示す製造方法で得ることができるが、市販品としては、東レ・ダウコーング(株)製シリコーンレジン又はシリコーンレジン変性用中間体として、SH−6018、217FLAKE、220FLAKE、233FLAKE等が市販品として入手可能である。 Such (E) silicon-containing polymer can be obtained by the following production method, but as a commercial product, as a silicone resin or an intermediate for silicone resin modification manufactured by Toray Dow Corning, SH- 6018, 217 FLAKE, 220 FLAKE, 233 FLAKE and the like are commercially available.
(E)ケイ素含有重合物の製造方法は、特に制限なく公知の方法で製造することができる。例えば、加水分解縮合反応により上記一般式(I)、一般式(II)、一般式(III)で示す単位を形成し得るオルガノクロロシラン、オルガノアルコキシシラン、シロキサン、あるいはそれらの部分加水分解縮合物を原料及び反応生成物を溶解可能な有機溶剤と原料のすべての加水分解性基を加水分解可能な量の水との混合溶液中に混合し、加水分解縮合反応させて得ることができる。この際、封止用エポキシ樹脂成形材料中に不純物として含有される塩素量を低減させるためにオルガノアルコキシシラン及び/又はシロキサンを原料とすることが好ましい。この場合、反応を促進する触媒として、酸、塩基、有機金属化合物を添加することが好ましい。また、ケイ素含有重合物の分子量(Mw)及びフェニル基の割合は、製造に用いる原料、有機溶剤、水、反応触媒等の仕込み比や反応温度、反応時間等の変更で調整可能である。分子量は主に有機溶剤中の原料濃度や仕込み比に、フェニル基の割合は主に原料の仕込み比に影響されやすい。 (E) The manufacturing method of a silicon containing polymer can be manufactured by a well-known method without a restriction | limiting in particular. For example, organochlorosilane, organoalkoxysilane, siloxane, or a partially hydrolyzed condensate thereof, which can form units represented by the above general formula (I), general formula (II), and general formula (III) by hydrolysis condensation reaction. It can be obtained by mixing a raw material and a reaction product in an organic solvent capable of dissolving the raw material and all hydrolyzable groups of the raw material in a mixed solution of a hydrolyzable amount of water and subjecting it to a hydrolytic condensation reaction. At this time, in order to reduce the amount of chlorine contained as an impurity in the epoxy resin molding material for sealing, it is preferable to use organoalkoxysilane and / or siloxane as a raw material. In this case, it is preferable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction. The molecular weight (Mw) of the silicon-containing polymer and the proportion of the phenyl group can be adjusted by changing the charging ratio of raw materials, organic solvent, water, reaction catalyst, etc. used in the production, reaction temperature, reaction time, and the like. The molecular weight is mainly affected by the raw material concentration and the charging ratio in the organic solvent, and the proportion of the phenyl group is mainly influenced by the charging ratio of the raw material.
(E)ケイ素含有重合物の原料となるオルガノアルコキシシラン及び/又はシロキサンとしては、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメチルジメトキシシラン、メチルフェニルジメトキシシラン、メチルビニルジメトキシシラン、フェニルビニルジメトキシシラン、ジフェニルジメトキシシラン、メチルフェニルジエトキシシラン、メチルビニルジエトキシシラン、フェニルビニルジエトキシシラン、ジフェニルジエトキシシラン、ジメチルジエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、ジメトキシジエトキシシラン、およびこれらの加水分解縮合物等が挙げられる。 (E) The organoalkoxysilane and / or siloxane used as a raw material for the silicon-containing polymer is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, phenylvinyldimethoxysilane, diphenyldimethoxysilane, methylphenyldiethoxysilane, methylvinyldiethoxysilane, phenylvinyldiethoxy Silane, diphenyldiethoxysilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane And like these hydrolytic condensation products thereof.
上記(E)ケイ素含有重合物の含有量は、本発明を達成できる範囲であれば特に制限は無いが、含有量の増加に伴い、室温領域の弾性率、高温領域の弾性率が低減し、耐リフロー性が向上し、難燃性も向上する傾向があり、配合量を減少させると、熱時硬度が向上する傾向がある。これらを鑑みて封止用エポキシ樹脂成形材料中の(A)エポキシ樹脂に対して、2.5質量%以上40質量%以下が好ましく、5質量%以上30質量%以下がより好ましく10質量%以上20質量%以下が更に好ましい。 The content of the above-mentioned (E) silicon-containing polymer is not particularly limited as long as the present invention can be achieved, but as the content increases, the elastic modulus in the room temperature region, the elastic modulus in the high temperature region decreases, The reflow resistance is improved and the flame retardancy tends to be improved. When the blending amount is decreased, the hot hardness tends to be improved. In view of these, 2.5 mass% or more and 40 mass% or less are preferable with respect to (A) epoxy resin in the epoxy resin molding material for sealing, 5 mass% or more and 30 mass% or less are more preferable, and 10 mass% or more are more preferable. 20 mass% or less is still more preferable.
[(A)エポキシ樹脂]
本発明において用いられる(A)エポキシ樹脂は、1分子中にエポキシ基を2個以上含有するものであれば特に制限ないが、たとえばフェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、トリフェニルメタン骨格を有するエポキシ樹脂をはじめとするフェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールA、ビスフェノールF等のフェノール類及び/又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したもの、アルキル置換、芳香環置換又は非置換のビスフェノールA、ビスフェノールF、ビスフェノールS、ビフェノール、チオジフェノール等のジグリシジルエーテル、スチルベン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、フタル酸、ダイマー酸等の多塩基酸とエピクロルヒドリンの反応により得られるグリシジルエステル型エポキシ樹脂、ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂、ジシクロペンタジエンとフェノール類の共縮合樹脂のエポキシ化物、ナフタレン環を有するエポキシ樹脂、フェノール類及び/又はナフトール類とジメトキシパラキシレン又はビス(メトキシメチル)ビフェニルから合成されるフェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等のアラルキル型フェノール樹脂のエポキシ化物、トリメチロールプロパン型エポキシ樹脂、テルペン変性エポキシ樹脂、オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂、脂環族エポキシ樹脂などが挙げられ、これらの1種を単独で用いても2種以上を組み合わせて用いてもよい。[(A) Epoxy resin]
The (A) epoxy resin used in the present invention is not particularly limited as long as it contains two or more epoxy groups in one molecule. For example, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, triphenylmethane Phenols such as epoxy resins having a skeleton, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde, acetaldehyde, Epoxidized novolac resin obtained by condensation or cocondensation with a compound having an aldehyde group such as propionaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst. A polybasic acid such as aromatic ring-substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol, thiodiphenol, stilbene type epoxy resin, hydroquinone type epoxy resin, phthalic acid, dimer acid, and epichlorohydrin Glycidyl ester type epoxy resin obtained by reaction, diaminodiphenylmethane, isocyanuric acid and other polyamines and epichlorohydrin obtained by reaction of epichlorohydrin, epoxidized product of dicyclopentadiene and phenol co-condensation resin, epoxy having naphthalene ring Phenol aralkyl resin, naphthol alla synthesized from resins, phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxides of aralkyl type phenol resins such as kill resins, trimethylolpropane type epoxy resins, terpene modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, alicyclic epoxies Resin etc. are mentioned, These 1 type may be used independently or may be used in combination of 2 or more type.
なかでも、流動性と硬化性の両立の観点からはアルキル置換、芳香環置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂を含有していることが好ましく、硬化性の観点からはノボラック型エポキシ樹脂を含有していることが好ましく、低吸湿性の観点からはジシクロペンタジエン型エポキシ樹脂を含有していることが好ましく、耐熱性及び低反り性の観点からはナフタレン型エポキシ樹脂を含有していることが好ましく、流動性と難燃性の両立の観点からはアルキル置換、芳香環置換又は非置換のビスフェノールFのジグリシジルエーテルであるビスフェノールF型エポキシ樹脂を含有していることが好ましく、流動性とリフロー性の両立の観点からはアルキル置換、芳香環置換又は非置換のチオジフェノールのジグリシジルエーテルであるチオジフェノール型エポキシ樹脂を含有していることが好ましく、硬化性と難燃性の両立の観点からはアルキル置換、芳香環置換又は非置換のフェノールとジメトキシパラキシレン又はビス(メトキシメチル)ビフェニルから合成されるフェノール・アラルキル樹脂のエポキシ化物を含有していることが好ましく、保存安定性と難燃性の両立の観点からはアルキル置換、芳香環置換又は非置換のナフトール類とジメトキシパラキシレンから合成されるナフトール・アラルキル樹脂のエポキシ化物を含有していることが好ましい。 Among them, from the viewpoint of compatibility between fluidity and curability, it is preferable to contain a biphenyl type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted biphenol, and from the viewpoint of curability. It preferably contains a novolac-type epoxy resin, preferably contains a dicyclopentadiene-type epoxy resin from the viewpoint of low hygroscopicity, and naphthalene-type epoxy resin from the viewpoint of heat resistance and low warpage Preferably, it contains bisphenol F type epoxy resin which is diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol F from the viewpoint of compatibility between fluidity and flame retardancy. Preferably, from the viewpoint of compatibility between fluidity and reflowability, alkyl-substituted, aromatic ring-substituted or unsubstituted thiodiphe It is preferable to contain a thiodiphenol type epoxy resin which is a diglycidyl ether of alcohol, and from the viewpoint of achieving both curability and flame retardancy, alkyl-substituted, aromatic ring-substituted or unsubstituted phenol and dimethoxyparaxylene Alternatively, it preferably contains an epoxidized product of a phenol / aralkyl resin synthesized from bis (methoxymethyl) biphenyl, and is alkyl-substituted, aromatic-ring-substituted or unsubstituted from the viewpoint of both storage stability and flame retardancy. It preferably contains an epoxidized naphthol-aralkyl resin synthesized from naphthols and dimethoxyparaxylene.
ビフェニル型エポキシ樹脂としては、たとえば下記一般式(V)で示されるエポキシ樹脂等が挙げられる。 Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (V).
上記一般式(V)で示されるビフェニル型エポキシ樹脂は、ビフェノール化合物にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(V)中のR1〜R8としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、tert−ブチル基等の炭素数1〜10のアルキル基、ビニル基、アリル基、ブテニル基等の炭素数1〜10のアルケニル基などが挙げられ、なかでも水素原子又はメチル基が好ましい。このようなエポキシ樹脂としては、たとえば、4,4´−ビス(2,3−エポキシプロポキシ)ビフェニル又は4,4´−ビス(2,3−エポキシプロポキシ)−3,3´,5,5´−テトラメチルビフェニルを主成分とするエポキシ樹脂、エピクロルヒドリンと4,4´−ビフェノール又は4,4´−(3,3´,5,5´−テトラメチル)ビフェノールとを反応させて得られるエポキシ樹脂等が挙げられる。なかでも4,4´−ビス(2,3−エポキシプロポキシ)−3,3´,5,5´−テトラメチルビフェニルを主成分とするエポキシ樹脂が好ましい。そのようなエポキシ樹脂としては市販品としてジャパンエポキシレジン株式会社製商品名YX−4000、YL−6121Hとして入手可能である。上記ビフェニル型エポキシ樹脂の配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。The biphenyl type epoxy resin represented by the general formula (V) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method. As R < 1 > -R < 8 > in general formula (V), C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert- butyl group etc., for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5 ′. -Epoxy resin mainly composed of tetramethylbiphenyl, epoxy resin obtained by reacting epichlorohydrin with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol Etc. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable. Such epoxy resins are commercially available as trade names YX-4000 and YL-6121H manufactured by Japan Epoxy Resin Co., Ltd. The blending amount of the biphenyl type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.
チオジフェノール型エポキシ樹脂としては、たとえば下記一般式(VI)で示されるエポキシ樹脂等が挙げられる。 Examples of the thiodiphenol type epoxy resin include an epoxy resin represented by the following general formula (VI).
上記一般式(VI)で示されるチオジフェノール型エポキシ樹脂は、チオジフェノール化合物にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(VI)中のR1〜R8としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、tert−ブチル基等の炭素数1〜10のアルキル基、ビニル基、アリル基、ブテニル基等の炭素数1〜10のアルケニル基などが挙げられ、なかでも水素原子、メチル基又はtert−ブチル基が好ましい。このようなエポキシ樹脂としては、たとえば、4,4´−ジヒドロキシジフェニルスルフィドのジグリシジルエーテルを主成分とするエポキシ樹脂、2,2´,5,5´−テトラメチル−4,4´−ジヒドロキシジフェニルスルフィドのジグリシジルエーテルを主成分とするエポキシ樹脂、2,2´−ジメチル−4,4´−ジヒドロキシ−5,5´−ジ−tert−ブチルジフェニルスルフィドのジグリシジルエーテルを主成分とするエポキシ樹脂等が挙げられ、なかでも2,2´−ジメチル−4,4´−ジヒドロキシ−5,5´−ジ−tert−ブチルジフェニルスルフィドのジグリシジルエーテルを主成分とするエポキシ樹脂を主成分とするエポキシ樹脂が好ましい。そのようなエポキシ樹脂としては市販品として新日鐵化学株式会社製商品名YSLV−120TEとして入手可能である。上記チオジフェノール型エポキシ樹脂の配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。The thiodiphenol type epoxy resin represented by the general formula (VI) can be obtained by reacting a thiodiphenol compound with epichlorohydrin by a known method. Examples of R 1 to R 8 in the general formula (VI) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, and a tert-butyl group. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom, a methyl group, or a tert- butyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-dihydroxydiphenyl sulfide diglycidyl ether, and 2,2 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl. Epoxy resin based on diglycidyl ether of sulfide, epoxy resin based on diglycidyl ether of 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di-tert-butyldiphenyl sulfide Among them, an epoxy mainly composed of an epoxy resin mainly composed of 2,2′-dimethyl-4,4′-dihydroxy-5,5′-di-tert-butyldiphenyl sulfide diglycidyl ether Resins are preferred. Such an epoxy resin is commercially available as a trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd. The blending amount of the thiodiphenol type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.
ビスフェノールF型エポキシ樹脂としては、たとえば下記一般式(VII)で示されるエポキシ樹脂等が挙げられる。 Examples of the bisphenol F type epoxy resin include an epoxy resin represented by the following general formula (VII).
上記一般式(VII)で示されるビスフェノールF型エポキシ樹脂は、ビスフェノールF化合物にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(VII)中のR1〜R8としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、tert−ブチル基等の炭素数1〜10のアルキル基、ビニル基、アリル基、ブテニル基等の炭素数1〜10のアルケニル基などが挙げられ、なかでも水素原子又はメチル基が好ましい。このようなエポキシ樹脂としては、たとえば、4,4´−メチレンビス(2,6−ジメチルフェノール)のジグリシジルエーテルを主成分とするエポキシ樹脂、4,4´−メチレンビス(2,3,6−トリメチルフェノール)のジグリシジルエーテルを主成分とするエポキシ樹脂、4,4´−メチレンビスフェノールのジグリシジルエーテルを主成分とするエポキシ樹脂等が挙げられ、なかでも4,4´−メチレンビス(2,6−ジメチルフェノール)のジグリシジルエーテルを主成分とするエポキシ樹脂が好ましい。そのようなエポキシ樹脂としては市販品として新日鐵化学株式会社製商品名YSLV−80XYとして入手可能である。上記ビスフェノールF型エポキシ樹脂の配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。The bisphenol F type epoxy resin represented by the general formula (VII) can be obtained by reacting a bisphenol F compound with epichlorohydrin by a known method. As R < 1 > -R < 8 > in general formula (VII), it is C1-C10, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a tert- butyl group, for example. C1-C10 alkenyl groups, such as an alkyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, Especially, a hydrogen atom or a methyl group is preferable. Examples of such an epoxy resin include an epoxy resin mainly composed of 4,4′-methylenebis (2,6-dimethylphenol) diglycidyl ether, and 4,4′-methylenebis (2,3,6-trimethyl). (Epoxy) epoxy resin mainly composed of diglycidyl ether, epoxy resin mainly composed of 4,4′-methylenebisphenol diglycidyl ether, etc., among others, 4,4′-methylene bis (2,6- An epoxy resin mainly composed of diglycidyl ether of (dimethylphenol) is preferred. Such an epoxy resin is commercially available as a trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. The blending amount of the bisphenol F-type epoxy resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the epoxy resin in order to exhibit its performance.
ノボラック型エポキシ樹脂としては、たとえば下記一般式(VIII)で示されるエポキシ樹脂等が挙げられる。 Examples of the novolac type epoxy resin include an epoxy resin represented by the following general formula (VIII).
上記一般式(VIII)で示されるノボラック型エポキシ樹脂は、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させることによって容易に得られる。なかでも、上記一般式(V)中のRとしては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基等の炭素数1〜10のアルキル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の炭素数1〜10のアルコキシル基が好ましく、水素原子又はメチル基がより好ましい。nは0〜3の整数が好ましい。上記一般式(VIII)で示されるノボラック型エポキシ樹脂のなかでも、オルソクレゾールノボラック型エポキシ樹脂が好ましい。このようなエポキシ樹脂としては、住友化学工業株式会社製商品名:ESCN−190が市販品として入手可能である。ノボラック型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましい。 The novolak type epoxy resin represented by the general formula (VIII) can be easily obtained by reacting a novolak type phenol resin with epichlorohydrin. Among them, R in the general formula (V) is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group, a methoxy group, an ethoxy group, or a propoxy group. C1-C10 alkoxyl groups, such as a group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable. n is preferably an integer of 0 to 3. Among the novolak type epoxy resins represented by the general formula (VIII), orthocresol novolak type epoxy resins are preferable. As such an epoxy resin, Sumitomo Chemical Co., Ltd. trade name: ESCN-190 is available as a commercial product. In the case of using a novolac type epoxy resin, the blending amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.
ジシクロペンタジエン型エポキシ樹脂としては、たとえば下記一般式(IX)で示されるエポキシ樹脂等が挙げられる。 Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (IX).
上記一般式(IX)中のR1としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数1〜10の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、メチル基及び水素原子がより好ましい。R2としては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数1〜10の置換又は非置換の一価の炭化水素基が挙げられ、なかでも水素原子が好ましい。ジシクロペンタジエン型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましい。Examples of R 1 in the general formula (IX) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, a vinyl group, an allyl group, and a butenyl group. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as alkenyl groups, halogenated alkyl groups, amino group-substituted alkyl groups, mercapto group-substituted alkyl groups, etc., among which methyl group, ethyl An alkyl group such as a group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable. Examples of R 2 include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, and an alkyl halide. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms such as a group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group, and among them, a hydrogen atom is preferable. When a dicyclopentadiene type epoxy resin is used, its blending amount is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.
ナフタレン型エポキシ樹脂としてはたとえば下記一般式(X)で示されるエポキシ樹脂等が挙げられる。 Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (X).
上記一般式(X)で示されるナフタレン型エポキシ樹脂としては、m個の構成単位及びn個の構成単位をランダムに含むランダム共重合体、交互に含む交互共重合体、規則的に含む共重合体、ブロック状に含むブロック共重合体が挙げられ、これらのいずれか1種を単独で用いても、2種以上を組み合わせて用いてもよい。このようなエポキシ樹脂としては、日本化薬株式会社製商品名:NC−7300が市販品として入手可能である。これらナフタレン型エポキシ樹脂を使用する場合、その配合量は、その性能を発揮するためにエポキシ樹脂全量中、合わせて20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上とすることがさらに好ましい。 The naphthalene type epoxy resin represented by the general formula (X) includes a random copolymer containing m structural units and n structural units at random, an alternating copolymer containing alternating units, and a copolymer containing regularly. Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination. As such an epoxy resin, Nippon Kayaku Co., Ltd. brand name: NC-7300 is available as a commercial product. When these naphthalene type epoxy resins are used, the blending amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 50% by mass in the total amount of the epoxy resin in order to exhibit the performance. More preferably, the above is used.
フェノール・アラルキル樹脂のエポキシ化物としては、たとえば下記一般式(XI)又は(XII)で示されるエポキシ樹脂等が挙げられる。 Examples of the epoxidized phenol / aralkyl resin include epoxy resins represented by the following general formula (XI) or (XII).
上記一般式(XI)で示されるビフェニレン骨格含有フェノール・アラルキル樹脂のエポキシ化物は、アルキル置換、芳香環置換又は非置換のフェノールとビス(メトキシメチル)ビフェニルから合成されるフェノール・アラルキル樹脂にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(XI)中のR1〜R9としては、たとえば、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、アミノアルキル基、ジメチルアミノアルキル基、ジエチルアミノアルキル基等のアミノ基置換アルキル基、水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、tert−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、tert−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましい。また一般式(XI)中のnとしては平均で6以下がより好ましく、そのようなエポキシ樹脂としては、市販品として日本化薬株式会社製商品名NC−3000Sとして入手可能である。The epoxidized product of the biphenylene skeleton-containing phenol / aralkyl resin represented by the general formula (XI) is obtained by adding epichlorohydrin to a phenol / aralkyl resin synthesized from alkyl-substituted, aromatic ring-substituted or unsubstituted phenol and bis (methoxymethyl) biphenyl. It can be obtained by reacting by a known method. Examples of R 1 to R 9 in the general formula (XI) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, and aryl group-substituted alkyl groups such as benzyl group and phenethyl group , Alkoxy groups substituted alkyl groups such as methoxy group substituted alkyl groups, ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as aminoalkyl groups, dimethylaminoalkyl groups, diethylaminoalkyl groups, hydroxyl group substituted alkyl groups , Phenyl group, naphthyl group, biphenyl group, etc. Alkyl group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert- Examples include alkoxy group-substituted aryl groups such as butoxyphenyl group and methoxynaphthyl group, amino group-substituted aryl groups such as dimethylamino group and diethylamino group, and hydroxyl group-substituted aryl groups. Among them, a hydrogen atom or a methyl group is preferable. Moreover, as an n in general formula (XI), 6 or less is more preferable on the average, and as such an epoxy resin, it can obtain as a commercial item by Nippon Kayaku Co., Ltd. brand name NC-3000S.
また、難燃性と耐リフロー性、流動性の両立の観点からは上記一般式(V)で示されるエポキシ樹脂と併用することが好ましく、なかでも上記一般式(XI)のR1〜R8が水素原子で上記一般式(V)のR1〜R8が水素原子でn=0であることがより好ましい。
また、特にその配合質量比は、(V)/(XI)=50/50〜5/95であることが好ましく、40/60〜10/90であるものがより好ましく、30/70〜15/85であるものがさらに好ましい。このような配合質量比を満足する化合物としては、CER−3000L(日本化薬株式会社製商品名)等が市販品として入手可能である。Further, R 1 to R 8 of the flame retardancy and reflow resistance, it is preferably used in combination with an epoxy resin represented by the general formula (V) from the viewpoint of compatibility between fluidity, among others the general formula (XI) Is more preferably a hydrogen atom and R 1 to R 8 in the general formula (V) are hydrogen atoms and n = 0.
In particular, the blending mass ratio is preferably (V) / (XI) = 50/50 to 5/95, more preferably 40/60 to 10/90, and 30/70 to 15 /. More preferred is 85. As a compound satisfying such a blending mass ratio, CER-3000L (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.
上記一般式(XII)で示されるフェノール・アラルキル樹脂のエポキシ化物は、アルキル置換、芳香環置換又は非置換のフェノールとジメトキシパラキシレンから合成されるフェノール・アラルキル樹脂にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(XII)中のR1〜R5としては、たとえば、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、アミノアルキル基、ジメチルアミノアルキル基、ジエチルアミノアルキル基等のアミノ基置換アルキル基、水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、tert−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、tert−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましい。また一般式(XII)中のnとしては平均で6以下がより好ましく、そのようなエポキシ樹脂としては、市販品として日本化薬株式会社製商品名NC−2000Lとして入手可能である。In the epoxidized phenol / aralkyl resin represented by the general formula (XII), epichlorohydrin is reacted with a phenol / aralkyl resin synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted phenol and dimethoxyparaxylene by a known method. Can be obtained. Examples of R 1 to R 5 in the general formula (XII) include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Chain alkyl groups such as octyl group, decyl group and dodecyl group, cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group and cyclohexenyl group, and aryl group-substituted alkyl groups such as benzyl group and phenethyl group , Alkoxy groups substituted alkyl groups such as methoxy group substituted alkyl groups, ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as aminoalkyl groups, dimethylaminoalkyl groups, diethylaminoalkyl groups, hydroxyl group substituted alkyl groups Unsubstituted phenyl group, naphthyl group, biphenyl group, etc. Reel group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, alkyl-substituted aryl group such as dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxy Examples include an alkoxy group-substituted aryl group such as a phenyl group and a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable. Moreover, as an n in general formula (XII), 6 or less is more preferable on average, and such an epoxy resin is commercially available as a product name NC-2000L manufactured by Nippon Kayaku Co., Ltd.
ナフトール・アラルキル樹脂のエポキシ化物としては、たとえば下記一般式(XIII)で示されるエポキシ樹脂等が挙げられる。 Examples of the epoxidized naphthol / aralkyl resin include an epoxy resin represented by the following general formula (XIII).
Xは、たとえばフェニレン基、ビフェニレン基、ナフチレン基等のアリーレン基、トリレン基等のアルキル基置換アリーレン基、アルコキシル基置換アリーレン基、アラルキル基置換アリーレン基、ベンジル基、フェネチル基等のアラルキル基から得られる二価の基、キシリレン基等のアリーレン基を含む二価の基などが挙げられ、なかでも、難燃性及び保存安定性の両立の観点からはフェニレン基、ビフェニレン基が好ましい。 X is obtained from an aralkyl group such as an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, an aralkyl group-substituted arylene group, a benzyl group or a phenethyl group. And a divalent group containing an arylene group such as a xylylene group. Among them, a phenylene group and a biphenylene group are preferable from the viewpoint of both flame retardancy and storage stability.
上記一般式(XIII)で示されるナフトール・アラルキル樹脂のエポキシ化物は、アルキル置換、芳香環置換又は非置換のナフトールとジメトキシパラキシレン又はビス(メトキシメチル)ビフェニルから合成されるナフトール・アラルキル樹脂にエピクロルヒドリンを公知の方法で反応させることによって得られる。一般式(XIII)中のRとしてはたとえば、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、アミノアルキル基、ジメチルアミノアルキル基、ジエチルアミノアルキル基等のアミノ基置換アルキル基水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、tert−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、tert−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましく、たとえば下記一般式(XIV)又は(XV)で示されるナフトール・アラルキル樹脂のエポキシ化物が挙げられる。nは0又は1〜10の整数を示し、平均で6以下がより好ましい。下記一般式(XIV)で示されるエポキシ樹脂としては市販品として新日鐵化学株式会社製商品名ESN−375が挙げられ、下記一般式(XV)で示されるエポキシ樹脂としては市販品として新日鐵化学株式会社製商品名ESN−175が挙げられる。上記ナフトール・アラルキル樹脂のエポキシ化物の配合量は、その性能を発揮するためにエポキシ樹脂全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。 The epoxidized product of the naphthol / aralkyl resin represented by the general formula (XIII) is obtained by adding epichlorohydrin to a naphthol / aralkyl resin synthesized from alkyl-substituted, aromatic ring-substituted or unsubstituted naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl. Can be obtained by a known method. R in the general formula (XIII) is, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group. Chain alkyl groups such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group substituted alkyl Groups, alkoxy groups substituted alkyl groups such as ethoxy group substituted alkyl groups, butoxy group substituted alkyl groups, amino group substituted alkyl groups such as aminoalkyl groups, dimethylaminoalkyl groups, diethylaminoalkyl groups, hydroxyl group substituted alkyl groups, phenyl groups, naphthyl groups An unsubstituted aryl group such as a biphenyl group, Alkyl group-substituted aryl groups such as ryl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxyphenyl group, Examples include an alkoxy group-substituted aryl group such as a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable. For example, the following general formula (XIV And epoxidized naphthol / aralkyl resin represented by (XV). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average. As an epoxy resin represented by the following general formula (XIV), a product name ESN-375 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned as a commercial product. As an epoxy resin represented by the following general formula (XV), a commercial product may be manufactured by Nippon Steel. A trade name ESN-175 manufactured by Sakai Chemical Co., Ltd. may be mentioned. The blended amount of the epoxidized naphthol / aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.
また(A)エポキシ樹脂として下記構造式(XVI)のエポキシ樹脂も使用することができる。 Moreover, the epoxy resin of following structural formula (XVI) can also be used as (A) epoxy resin.
上記一般式(XVI)で示されるエポキシ樹脂としては、たとえば下記一般式(XVII)〜(XXXV)で示されるエポキシ樹脂等が挙げられる。 Examples of the epoxy resin represented by the general formula (XVI) include epoxy resins represented by the following general formulas (XVII) to (XXXV).
上記エポキシ樹脂を各々の観点で性能を発揮するためには、その配合量は、エポキシ樹脂全量に対して30質量%以上とすることが好ましく、50質量%以上がより好ましく、60質量%以上とすることがさらに好ましい。 In order to exhibit the performance of the epoxy resin from each viewpoint, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more with respect to the total amount of the epoxy resin. More preferably.
本発明において用いられる(B)硬化剤は、封止用エポキシ樹脂成形材料に一般に使用されているもので特に制限はないが、たとえば、フェノール、クレゾール、レゾルシン、カテコール、ビスフェノールA、ビスフェノールF、フェニルフェノール、チオジフェノール、アミノフェノール等のフェノール類及び/又はα−ナフトール、β−ナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック型フェノール樹脂、フェノール類及び/又はナフトール類とジメトキシパラキシレン又はビス(メトキシメチル)ビフェニルから合成されるフェノール・アラルキル樹脂、ナフトール・アラルキル樹脂等のアラルキル型フェノール樹脂、フェノール・ノボラック構造とフェノール・アラルキル構造がランダム、ブロック又は交互に繰り返された共重合型フェノール・アラルキル樹脂、パラキシリレン及び/又はメタキシリレン変性フェノール樹脂、メラミン変性フェノール樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、シクロペンタジエン変性フェノール樹脂、多環芳香環変性フェノール樹脂などが挙げられ、これらを単独で用いても2種以上を組合わせて用いてもよい。 The (B) curing agent used in the present invention is generally used for an epoxy resin molding material for sealing and is not particularly limited. For example, phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenyl Phenols such as phenol, thiodiphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, benzaldehyde and salicylaldehyde are condensed in an acidic catalyst. Alternatively, a novolak-type phenolic resin obtained by co-condensation, a phenol / aralkyl resin synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol / aral Aralkyl-type phenol resins such as kill resins, phenol / aralkyl structures having a phenol / novolak structure and phenol / aralkyl structures randomly, block or alternately repeated, paraxylylene and / or metaxylylene-modified phenol resins, melamine-modified phenol resins, Examples include terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, cyclopentadiene-modified phenol resins, and polycyclic aromatic ring-modified phenol resins. These may be used alone or in combination of two or more.
なかでも、流動性、難燃性及び耐リフロー性の観点からはフェノール・アラルキル樹脂及びナフトール・アラルキル樹脂が好ましく、低吸湿性の観点からはジシクロペンタジエン型フェノール樹脂が好ましく、硬化性の観点からはノボラック型フェノール樹脂が好ましく、これらのフェノール樹脂の少なくとも1種を含有していることが好ましい。 Of these, phenol / aralkyl resins and naphthol / aralkyl resins are preferred from the viewpoints of fluidity, flame retardancy and reflow resistance, and dicyclopentadiene type phenol resins are preferred from the viewpoint of low hygroscopicity, from the viewpoint of curability. Is preferably a novolac type phenolic resin, and preferably contains at least one of these phenolic resins.
フェノール・アラルキル樹脂としては、たとえば下記一般式(XXXVI)で示される樹脂が挙げられる。 Examples of the phenol / aralkyl resin include resins represented by the following general formula (XXXVI).
上記一般式(XXXVI)中のRとしては、たとえば、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、アミノアルキル基、ジメチルアミノアルキル基、ジエチルアミノアルキル基等のアミノ基置換アルキル基水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、tert−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、tert−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましい。 As R in the general formula (XXXVI), for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Decyl group, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, amino group substituted alkyl group such as diethylaminoalkyl group, hydroxyl group substituted alkyl group, phenyl group, Unsubstituted ants such as naphthyl group and biphenyl group Group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxy Examples include an alkoxy group-substituted aryl group such as a phenyl group and a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable.
また、Xは芳香環を含む基を示し、たとえばフェニレン基、ビフェニレン基、ナフチレン基等のアリーレン基、トリレン基等のアルキル基置換アリーレン基、アルコキシル基置換アリーレン基、ベンジル基、フェネチル基等のアラルキル基から得られる二価の基、アラルキル基置換アリーレン基、キシリレン基等のアリーレン基を含む二価の基などが挙げられる。なかでも、難燃性と耐リフロー性の両立の観点からは置換又は非置換のビフェニレン基が好ましく、例えば、下記一般式(XXXVII)で示されるフェノール・アラルキル樹脂が挙げられ、難燃性、流動性と硬化性の両立の観点からは置換又は非置換のフェニレン基が好ましく、例えば下記一般式(XXXVIII)で示されるフェノール・アラルキル樹脂が挙げられる。nは0又は1〜10の整数を示し、平均で6以下がより好ましい。 X represents a group containing an aromatic ring, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, a benzyl group or a phenethyl group. And a divalent group containing an arylene group such as a divalent group obtained from a group, an aralkyl group-substituted arylene group, and a xylylene group. Among them, a substituted or unsubstituted biphenylene group is preferable from the viewpoint of achieving both flame retardancy and reflow resistance, and examples thereof include a phenol / aralkyl resin represented by the following general formula (XXXVII). From the standpoint of achieving both compatibility and curability, a substituted or unsubstituted phenylene group is preferable, and examples thereof include a phenol / aralkyl resin represented by the following general formula (XXXVIII). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average.
上記一般式(XXXVII)で示されるビフェニレン骨格含有フェノール・アラルキル樹脂としては、市販品として明和化成株式会社製商品名MEH−7851が挙げられ、一般式(XXXVIII)で示されるフェノール・アラルキル樹脂としては、市販品として三井化学株式会社製商品名XLCが挙げられる。上記フェノール・アラルキル樹脂の配合量は、その性能を発揮するために硬化剤全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。 As a biphenylene skeleton containing phenol aralkyl resin represented by the above general formula (XXXVII), MEH-7851 manufactured by Meiwa Kasei Co., Ltd. may be mentioned as a commercially available product, and as a phenol aralkyl resin represented by the general formula (XXXVIII) As a commercial product, trade name XLC manufactured by Mitsui Chemicals, Inc. may be mentioned. The blending amount of the phenol-aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the curing agent in order to exhibit its performance.
ナフトール・アラルキル樹脂としては、たとえば下記一般式(XXXIX)で示される樹脂が挙げられる。 Examples of the naphthol / aralkyl resin include resins represented by the following general formula (XXXIX).
上記一般式(XXXIX)中のRとしては、たとえば、メチル基、エチル基、プロピル基、イソプロピル基、n−ブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の鎖状アルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロペンテニル基、シクロヘキセニル基等の環状アルキル基、ベンジル基、フェネチル基等のアリール基置換アルキル基、メトキシ基置換アルキル基、エトキシ基置換アルキル基、ブトキシ基置換アルキル基等のアルコキシ基置換アルキル基、アミノアルキル基、ジメチルアミノアルキル基、ジエチルアミノアルキル基等のアミノ基置換アルキル基水酸基置換アルキル基、フェニル基、ナフチル基、ビフェニル基等の無置換アリール基、トリル基、ジメチルフェニル基、エチルフェニル基、ブチルフェニル基、tert−ブチルフェニル基、ジメチルナフチル基等のアルキル基置換アリール基、メトキシフェニル基、エトキシフェニル基、ブトキシフェニル基、tert−ブトキシフェニル基、メトキシナフチル基等のアルコキシ基置換アリール基、ジメチルアミノ基、ジエチルアミノ基等のアミノ基置換アリール基、水酸基置換アリール基などが挙げられ、なかでも水素原子又はメチル基が好ましい。 As R in the general formula (XXXIX), for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, Decyl group, chain alkyl group such as dodecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups, benzyl group, phenethyl group and other aryl group substituted alkyl groups, methoxy group Substituted alkyl group, ethoxy group substituted alkyl group, alkoxy group substituted alkyl group such as butoxy group substituted alkyl group, aminoalkyl group, dimethylaminoalkyl group, amino group substituted alkyl group such as diethylaminoalkyl group, hydroxyl group substituted alkyl group, phenyl group, Unsubstituted ants such as naphthyl group and biphenyl group Group, tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and other alkyl group-substituted aryl groups, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tert-butoxy Examples include an alkoxy group-substituted aryl group such as a phenyl group and a methoxynaphthyl group, an amino group-substituted aryl group such as a dimethylamino group and a diethylamino group, and a hydroxyl group-substituted aryl group. Among them, a hydrogen atom or a methyl group is preferable.
また、Xは芳香環を含む二価の有機基を示し、たとえばフェニレン基、ビフェニレン基、ナフチレン基等のアリーレン基、トリレン基等のアルキル基置換アリーレン基、アルコキシル基置換アリーレン基、アラルキル基置換アリーレン基、ベンジル基、フェネチル基等のアラルキル基から得られる二価の基、キシリレン基等のアリーレン基を含む二価の基などが挙げられ、なかでも、保存安定性と難燃性の観点からは置換又は非置換のフェニレン基及びビフェニレン基が好ましく、フェニレン基がより好ましく、たとえば下記一般式(XXXX)及び(XXXXI)で示されるナフトール・アラルキル樹脂が挙げられる。nは0又は1〜10の整数を示し、平均で6以下がより好ましい。 X represents a divalent organic group containing an aromatic ring, for example, an arylene group such as a phenylene group, a biphenylene group or a naphthylene group, an alkyl group-substituted arylene group such as a tolylene group, an alkoxyl group-substituted arylene group, an aralkyl group-substituted arylene. Groups, divalent groups obtained from aralkyl groups such as benzyl groups, phenethyl groups, and the like, and divalent groups including arylene groups such as xylylene groups, among others, from the viewpoint of storage stability and flame retardancy A substituted or unsubstituted phenylene group and a biphenylene group are preferable, and a phenylene group is more preferable, and examples thereof include naphthol-aralkyl resins represented by the following general formulas (XXXX) and (XXXXI). n shows 0 or the integer of 1-10, and 6 or less is more preferable on average.
上記一般式(XXXX)で示されるナフトール・アラルキル樹脂としては、市販品として新日鐵化学株式会社製商品名SN−475が挙げられ、上記一般式(XXXXI)で示されるナフトール・アラルキル樹脂としては、市販品として新日鐵化学株式会社製商品名SN−170が挙げられる。上記ナフトール・アラルキル樹脂の配合量は、その性能を発揮するために硬化剤全量中20質量%以上とすることが好ましく、30質量%以上がより好ましく、50質量%以上がさらに好ましい。 As a naphthol aralkyl resin represented by the above general formula (XXXX), a commercial product SN-475 manufactured by Nippon Steel Chemical Co., Ltd. may be mentioned, and as a naphthol aralkyl resin represented by the above general formula (XXXXI), Moreover, Nippon Steel Chemical Co., Ltd. brand name SN-170 is mentioned as a commercial item. The blending amount of the naphthol / aralkyl resin is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more in the total amount of the curing agent in order to exhibit its performance.
上記一般式(XXXVI)で示されるフェノール・アラルキル樹脂、一般式(XXXIX)で示されるナフトール・アラルキル樹脂は、難燃性の観点からその一部又は全部がアセナフチレンと予備混合されていることが好ましい。アセナフチレンはアセナフテンを脱水素して得ることができるが、市販品を用いてもよい。また、アセナフチレンの代わりにアセナフチレンの重合物又はアセナフチレンと他の芳香族オレフィンとの重合物として用いることもできる。アセナフチレンの重合物又はアセナフチレンと他の芳香族オレフィンとの重合物を得る方法としては、ラジカル重合、カチオン重合、アニオン重合等が挙げられる。また、重合に際しては従来公知の触媒を用いることができるが、触媒を使用せずに熱だけで行うこともできる。この際、重合温度は80〜160℃が好ましく、90〜150℃がより好ましい。得られるアセナフチレンの重合物又はアセナフチレンと他の芳香族オレフィンとの重合物の軟化点は、60〜150℃が好ましく、70〜130℃がより好ましい。
60℃より低いと成形時の染み出しにより成形性が低下する傾向にあり、150℃より高いと樹脂との相溶性が低下する傾向にある。アセナフチレンと共重合させる他の芳香族オレフィンとしては、スチレン、α−メチルスチレン、インデン、ベンゾチオフェン、ベンゾフラン、ビニルナフタレン、ビニルビフェニル又はそれらのアルキル置換体等が挙げられる。また、上記した芳香族オレフィン以外に本発明の効果に支障の無い範囲で脂肪族オレフィンを併用することもできる。脂肪族オレフィンとしては、(メタ)アクリル酸及びそれらのエステル、無水マレイン酸、無水イタコン酸、フマル酸及びそれらのエステル等が挙げられる。これら脂肪族オレフィンの使用量は重合モノマー全量中20質量%以下が好ましく、9質量%以下がより好ましい。The phenol / aralkyl resin represented by the general formula (XXXVI) and the naphthol / aralkyl resin represented by the general formula (XXXIX) are preferably partially or preliminarily mixed with acenaphthylene from the viewpoint of flame retardancy. . Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Moreover, it can also be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins instead of acenaphthylene. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. At this time, the polymerization temperature is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. 60-150 degreeC is preferable and, as for the softening point of the polymer of the polymer of acenaphthylene obtained or acenaphthylene and another aromatic olefin, 70-130 degreeC is more preferable.
When the temperature is lower than 60 ° C., the moldability tends to decrease due to oozing during molding, and when the temperature is higher than 150 ° C., the compatibility with the resin tends to decrease. Examples of other aromatic olefins to be copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid and esters thereof. The use amount of these aliphatic olefins is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomers.
硬化剤の一部又は全部とアセナフチレンとの予備混合の方法としては、硬化剤及びアセナフチレンをそれぞれ微細に粉砕し固体状態のままミキサー等で混合する方法、両成分を溶解する溶媒に均一に溶解させた後、溶媒を除去する方法、硬化剤及び/又はアセナフチレンの軟化点以上の温度で両者を溶融混合する方法等で行うことができるが、均一な混合物が得られて不純物の混入が少ない溶融混合法が好ましい。前記の方法により予備混合物(アセナフチレン変性硬化剤)が、製造される。溶融混合は、硬化剤及び/又はアセナフチレンの軟化点以上の温度であれば制限はないが、100〜250℃が好ましく、120〜200℃がより好ましい。また、溶融混合は両者が均一に混合すれば混合時間に制限はないが、1〜20時間が好ましく、2〜15時間がより好ましい。硬化剤とアセナフチレンを予備混合する場合、混合中にアセナフチレンが重合もしくは硬化剤と反応しても構わない。 As a method of premixing part or all of the curing agent with acenaphthylene, the curing agent and acenaphthylene are finely pulverized and mixed in a solid state with a mixer or the like, or both components are uniformly dissolved in a solvent that dissolves them. Then, a method of removing the solvent, a method of melting and mixing the curing agent and / or acenaphthylene at a temperature equal to or higher than the softening point of the acenaphthylene, etc. can be performed. The method is preferred. A premix (acenaphthylene-modified curing agent) is produced by the above method. Although melt mixing will not have a restriction | limiting, if it is the temperature more than the softening point of a hardening | curing agent and / or acenaphthylene, 100-250 degreeC is preferable and 120-200 degreeC is more preferable. Moreover, although melt mixing will not have a restriction | limiting in mixing time if both are mixed uniformly, 1 to 20 hours are preferable and 2 to 15 hours are more preferable. When the curing agent and acenaphthylene are premixed, the acenaphthylene may polymerize or react with the curing agent during mixing.
ジシクロペンタジエン型フェノール樹脂としては、たとえば下記一般式(XXXXII)で示されるフェノール樹脂等が挙げられる。 Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XXXXII).
R1及びR2が水素原子である上記化合物としてはDPP(新日本石油化学株式会社製商品名)等が市販品として入手可能である。
As said compound whose R < 1 > and R < 2 > is a hydrogen atom, DPP (New Nippon Petrochemical Co., Ltd. brand name) etc. are available as a commercial item.
ノボラック型フェノール樹脂としては、たとえば下記一般式(XXXXIII)で示されるフェノール樹脂等のノボラック型フェノール樹脂、クレゾールノボラック樹脂等が挙げられ、なかでも下記一般式(XXXXIII)で示されるノボラック型フェノール樹脂が好ましい。 Examples of the novolak-type phenol resin include novolak-type phenol resins such as a phenol resin represented by the following general formula (XXXXIII), cresol novolak resins, and the like. Among these, novolak-type phenol resins represented by the following general formula (XXXXIII) preferable.
上記一般式(XXXXIII)中のRとしては、たとえば、水素原子、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert−ブチル基等のアルキル基、ビニル基、アリル基、ブテニル基等のアルケニル基、ハロゲン化アルキル基、アミノ基置換アルキル基、メルカプト基置換アルキル基などの炭素数1〜10の置換又は非置換の一価の炭化水素基が挙げられ、なかでもメチル基、エチル基等のアルキル基及び水素原子が好ましく、水素原子がより好ましく、nの平均値が0〜8であることが好ましい。上記一般式(XXXXIII)で示されるノボラック型フェノール樹脂としては、明和化成株式会社製商品名:H−4が市販品として入手可能である。
ノボラック型フェノール樹脂を用いる場合、その配合量はその性能を発揮するために硬化剤全量中30質量%以上とすることが好ましく、50質量%以上がより好ましい。Examples of R in the general formula (XXXXIII) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a tert-butyl group, a vinyl group, an allyl group, a butenyl group, and the like. C1-C10 substituted or unsubstituted monovalent hydrocarbon group such as alkenyl group, halogenated alkyl group, amino group-substituted alkyl group, mercapto group-substituted alkyl group, etc., among which methyl group, ethyl group Alkyl groups and hydrogen atoms such as hydrogen atoms, hydrogen atoms are more preferable, and the average value of n is preferably 0 to 8. As a novolak-type phenol resin represented by the above general formula (XXXXIII), a product name: H-4 manufactured by Meiwa Kasei Co., Ltd. is available as a commercial product.
When using a novolac type phenol resin, the blending amount is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.
上記の硬化剤は、いずれか1種を単独で用いても2種以上を組み合わせて用いてもよいが、2種以上を組み合わせて用いる場合の配合量は、フェノール樹脂全量中合わせて50質量%以上とすることが好ましく、60質量%以上がより好ましく、80質量%以上がさらに好ましい。 The above curing agents may be used alone or in combination of two or more, but the blending amount when using two or more in combination is 50% by mass in the total amount of phenol resin. It is preferable to set it as the above, 60 mass% or more is more preferable, 80 mass% or more is further more preferable.
本発明において、(A)エポキシ樹脂と(B)硬化剤との当量比、すなわちエポキシ基に対する硬化剤中の水酸基数の比(硬化剤中の水酸基数/エポキシ樹脂中のエポキシ基数)は、特に制限はないが、それぞれの未反応分を少なく抑えるために0.5〜2の範囲に設定されることが好ましく、0.6〜1.3がより好ましい。成形性、耐半田リフロー性に優れる封止用エポキシ樹脂成形材料を得るためには0.8〜1.2の範囲に設定されることがさらに好ましい。 In the present invention, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the epoxy group (number of hydroxyl groups in the curing agent / number of epoxy groups in the epoxy resin) is particularly Although there is no restriction | limiting, in order to suppress each unreacted part few, it is preferable to set to the range of 0.5-2, and 0.6-1.3 are more preferable. In order to obtain a sealing epoxy resin molding material excellent in moldability and solder reflow resistance, it is more preferably set in the range of 0.8 to 1.2.
[(C)硬化促進剤]
本発明で用いられる(C)硬化促進剤としては、封止用エポキシ樹脂成形材料で一般に使用されているもので特に限定はない。たとえば、1,8−ジアザビシクロ[5.4.0]ウンデセン−7、1,5−ジアザビシクロ[4.3.0]ノネン−5、5,6−ジブチルアミノ−1,8−ジアザビシクロ[5.4.0]ウンデセン−7等のシクロアミジン化合物及びこれらの化合物に無水マレイン酸、1,4−ベンゾキノン、2,5−トルキノン、1,4−ナフトキノン、2,3−ジメチルベンゾキノン、2,6−ジメチルベンゾキノン、2,3−ジメトキシ−5−メチル−1,4ベンゾキノン、2,3−ジメトキシ−1,4−ベンゾキノン、フェニル−1,4−ベンゾキノン等のキノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有する化合物、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の三級アミン類及びこれらの誘導体、2−メチルイミダゾール、2−フェニルイミダゾール、2―フェニル−4−メチルイミダゾール、2−ヘプタデシルイミダゾール等のイミダゾール類及びこれらの誘導体、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス(4−メチルフェニル)ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン類及びこれらのホスフィン類に無水マレイン酸、上記キノン化合物、ジアゾフェニルメタン、フェノール樹脂等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物、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エチルトリフェニルボレート、テトラブチルホスホニウムテトラブチル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、2−エチル−4−メチルイミダゾール・テトラフェニルボレート、N−メチルモルホリン・テトラフェニルボレート等のテトラフェニルボロン塩及びこれらの誘導体などが挙げられ、これらの1種を単独で用いても2種以上組み合わせて用いてもよい。[(C) Curing accelerator]
The (C) curing accelerator used in the present invention is not particularly limited as it is generally used in an epoxy resin molding material for sealing. For example, 1,8-diazabicyclo [5.4.0] undecene-7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4 .0] cycloamidine compounds such as undecene-7 and these compounds to maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethyl Quinones such as benzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, π such as diazophenylmethane, phenol resin, etc. Compound with intramolecular polarization formed by adding a compound with bond, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amines such as ethanol and tris (dimethylaminomethyl) phenol and their derivatives, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and the like Derivatives, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine and the like, and maleic anhydride, the above quinone compounds, diazophenylmethane Phosphorus compounds with intramolecular polarization formed by adding a compound having a π bond such as phenol resin, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltrif Tetra-substituted phosphonium and tetra-substituted borates such as nylborate and tetrabutylphosphonium tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, N-methylmorpholine and tetraphenylborate, and derivatives thereof These may be used alone or in combination of two or more.
なかでも、硬化性及び流動性の観点からは第三ホスフィンとキノン化合物との付加物が好ましく、トリフェニルホスフィンとベンゾキノンとの付加物又はトリブチルホスフィンとベンゾキノンとの付加物がより好ましい。保存安定性の観点からはシクロアミジン化合物とフェノール樹脂との付加物が好ましく、ジアザビシクロウンデセンのノボラック型フェノール樹脂塩がより好ましい。
これらの硬化促進剤の配合量は硬化促進剤全量中合わせて60質量%以上が好ましく、80質量%以上がより好ましい。Among these, from the viewpoint of curability and fluidity, an adduct of a tertiary phosphine and a quinone compound is preferable, and an adduct of triphenylphosphine and benzoquinone or an adduct of tributylphosphine and benzoquinone is more preferable. From the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable.
The blending amount of these curing accelerators is preferably 60% by mass or more, and more preferably 80% by mass or more in the total amount of the curing accelerator.
第三ホスフィンとキノン化合物との付加物に用いられる第三ホスフィンとしては特に制限はないが、たとえば、トリブチルホスフィン、ジブチルフェニルホスフィン、ブチルジフェニルホスフィン、エチルジフェニルホスフィン、トリフェニルホスフィン、トリス(4−メチルフェニル)ホスフィン、トリス(4−エチルフェニル)ホスフィン、トリス(4−プロピルフェニル)ホスフィン、トリス(4−ブチルフェニル)ホスフィン、トリス(イソプロピルフェニル)ホスフィン、トリス(tert−ブチルフェニル)ホスフィン、トリス(2,4−ジメチルフェニル)ホスフィン、トリス(2,6−ジメチルフェニル)ホスフィン、トリス(2,4,6−トリメチルフェニル)ホスフィン、トリス(2,6−ジメチル−4−エトキシフェニル)ホスフィン、トリス(4−メトキシフェニル)ホスフィン、トリス(4−エトキシフェニル)ホスフィン等のアリール基を有する第三ホスフィンが挙げられ、成形性の点からはトリフェニルホスフィン及びトリブチルホスフィンが好ましい。 The tertiary phosphine used in the adduct of the tertiary phosphine and the quinone compound is not particularly limited. For example, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methyl Phenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris (4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-butylphenyl) phosphine, tris (2 , 4-Dimethylphenyl) phosphine, Tris (2,6-dimethylphenyl) phosphine, Tris (2,4,6-trimethylphenyl) phosphine, Tris (2,6-dimethyl-4-ethoxyphene) Le) phosphine, tris (4-methoxyphenyl) phosphine, tertiary phosphine having an aryl group such as tris (4-ethoxyphenyl) phosphine and the like, triphenylphosphine and tributylphosphine are preferable from the viewpoint of moldability.
また、第三ホスフィンとキノン化合物との付加物に用いられるキノン化合物としては特に制限はないが、たとえば、o−ベンゾキノン、p−ベンゾキノン、ジフェノキノン、1,4−ナフトキノン、アントラキノン等が挙げられ、耐湿性又は保存安定性の観点からはp−ベンゾキノンが好ましい。 Further, the quinone compound used for the adduct of the tertiary phosphine and the quinone compound is not particularly limited, and examples thereof include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like. P-benzoquinone is preferable from the viewpoint of stability or storage stability.
硬化促進剤の配合量は、硬化促進効果が達成される量であれば特に限定されるものではないが、(A)エポキシ樹脂と(B)硬化剤の合計量100質量部に対して0.1〜10質量部が好ましく、0.3〜5質量部がより好ましい。0.1質量部未満では短時間で硬化させることが困難となり、10質量部を超えると硬化速度が早すぎて良好な成形品が得られない傾向がある。 Although the compounding quantity of a hardening accelerator will not be specifically limited if the hardening acceleration effect is achieved, it is 0.00 with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent. 1-10 mass parts is preferable and 0.3-5 mass parts is more preferable. If it is less than 0.1 parts by mass, it is difficult to cure in a short time, and if it exceeds 10 parts by mass, the curing rate tends to be too fast and a good molded product tends not to be obtained.
[(D)無機充てん剤]
本発明で用いられる(D)無機充てん剤は、吸湿性、線膨張係数低減、熱伝導性向上及び強度向上のために成形材料に配合されるものであり、封止用エポキシ樹脂成形材料に一般に使用されているものであれば特に制限されるものではないが、例えば、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア等の粉体、又はこれらを球形化したビーズ、ガラス繊維などが挙げられ、これらを単独で用いても2種以上を組み合わせて用いてもよい。なかでも、線膨張係数低減の観点からは溶融シリカが、高熱伝導性の観点からはアルミナが好ましく、充てん剤形状は成形時の流動性及び金型摩耗性の点から球形が好ましい。特にコストと性能のバランスの観点からは球状溶融シリカが好ましい。[(D) Inorganic filler]
The (D) inorganic filler used in the present invention is blended into a molding material for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is generally used as an epoxy resin molding material for sealing. There is no particular limitation as long as it is used, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride. , Beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, etc., or spherical beads, glass fibers, etc. May be used. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the filler shape is preferably spherical from the viewpoint of fluidity during molding and mold wear. In particular, spherical fused silica is preferable from the viewpoint of a balance between cost and performance.
無機充てん剤の配合量は、本発明が達成される範囲であれば特に制限は無いが、難燃性、成形性、吸湿性、線膨張係数低減及び強度向上の観点から、封止用エポキシ樹脂成形材料中70〜95質量%が好ましく、吸湿性、線膨張係数低減の観点から85〜95質量%がより好ましい。70質量%未満では、難燃性及び耐リフロー性が低下する傾向があり、95質量%を超えると流動性が不足する傾向がある。 The amount of the inorganic filler is not particularly limited as long as the present invention is achieved, but from the viewpoints of flame retardancy, moldability, hygroscopicity, linear expansion coefficient reduction and strength improvement, an epoxy resin for sealing. 70-95 mass% is preferable in a molding material, and 85-95 mass% is more preferable from a viewpoint of hygroscopicity and a linear expansion coefficient reduction. If it is less than 70% by mass, the flame retardancy and reflow resistance tend to decrease, and if it exceeds 95% by mass, the fluidity tends to be insufficient.
本発明の成形材料は、耐リフロー性の向上の観点から、インデンオリゴマーを含むことが好ましい。インデンオリゴマーはインデン、アルキルインデン等のインデン類とスチレン、アルキルスチレン等のスチレン類とフェノ−ル類の共重合樹脂である。製造方法としては、これらのモノマーをルイス酸、ブレンステッド酸、固体酸を触媒として、カチオン重合して得られる。インデン類の割合は共重合樹脂成分全体に対して60質量%以上であることが好ましく、他の構成モノマーとして、クマロン等の芳香族オレフィンを含有しても良い。インデン系オリゴマーとしては特に限定はないが、数平均分子量が300〜1000、軟化点が50〜160℃のものが特に好ましい。これらの具体例としては、東都化成株式会社製商品名I−100等が挙げられる。インデン系オリゴマーの配合量は特に限定はないが、(A)成分のエポキシ樹脂100質量部に対して1〜20質量部であることが好ましい。 The molding material of the present invention preferably contains an indene oligomer from the viewpoint of improving the reflow resistance. The indene oligomer is a copolymer resin of indenes such as indene and alkylindene, and styrenes and phenols such as styrene and alkylstyrene. As a production method, these monomers are obtained by cationic polymerization using a Lewis acid, Bronsted acid or solid acid as a catalyst. The proportion of indene is preferably 60% by mass or more based on the entire copolymer resin component, and may contain an aromatic olefin such as coumarone as another constituent monomer. The indene oligomer is not particularly limited, but those having a number average molecular weight of 300 to 1000 and a softening point of 50 to 160 ° C. are particularly preferable. Specific examples thereof include trade name I-100 manufactured by Tohto Kasei Co., Ltd. Although the compounding quantity of an indene type oligomer does not have limitation in particular, it is preferable that it is 1-20 mass parts with respect to 100 mass parts of epoxy resin of (A) component.
[一般式(IV)で示すシラン化合物(a)]
本発明の成形材料は、耐リフロー性向上の観点から、下記一般式(IV)で示すシラン化合物(a)を含むことが好ましい。下記一般式(I)で示される化合物であれば特に制限は無く、いずれか1種を単独で用いても、2種以上を組み合わせて用いてもよい。[Silane Compound (a) represented by Formula (IV)]
The molding material of the present invention preferably contains a silane compound (a) represented by the following general formula (IV) from the viewpoint of improving reflow resistance. If it is a compound shown by the following general formula (I), there will be no restriction | limiting in particular, Any 1 type may be used independently or 2 or more types may be used in combination.
前記一般式(IV)中のR1としては、例えば、シクロペンチル基、シクロヘキシル基、シクロへプチル基、シクロオクチル基、シクロヘキセニル基、シクロペンテニル基等が挙げられ、シクロペンチル基及びシクロヘキシル基が好ましい。R2としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、ter−ブチル基、フェニル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基、シクロオクチル基、シクロヘキセニル基、シクロペンテニル基等が挙げられ、メチル基、エチル基、シクロペンチル基及びシクロヘキシル基が好ましい。R3としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、イソブチル基、ter−ブチル基、フェニル基、シクロペンチル基、シクロヘキシル基等が挙げられ、メチル基及びエチル基が好ましい。また、これらの基は置換されていてもよい。Examples of R 1 in the general formula (IV) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclohexenyl group, and a cyclopentenyl group, and a cyclopentyl group and a cyclohexyl group are preferable. R 2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, ter-butyl, phenyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl. Group, cyclohexenyl group, cyclopentenyl group and the like, and a methyl group, an ethyl group, a cyclopentyl group and a cyclohexyl group are preferable. Examples of R 3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a ter-butyl group, a phenyl group, a cyclopentyl group, and a cyclohexyl group. Groups are preferred. Moreover, these groups may be substituted.
上記一般式(IV)で示されるシラン化合物の好ましい構造の具体例としては、下記で示される化合物が挙げられる。 Specific examples of the preferred structure of the silane compound represented by the general formula (IV) include the compounds shown below.
中でも流動性と成形性及び耐リフロー性のバランスに優れ、入手が容易である点から上記一般式(XXXXVIII)及び(XXXXXX)で示される化合物が特に好ましい。
一般式(XXXXVIII)で示される化合物としては、東レ・ダウコーニング株式会社製商品名:Z6187が市販品として入手可能で、一般式(XXXXXX)で示される化合物としては、東レ・ダウコーニング株式会社製商品名:Z6228が市販品として入手可能である。Of these, the compounds represented by the above general formulas (XXXXVIII) and (XXXXXXX) are particularly preferable because they are excellent in balance between fluidity, moldability and reflow resistance and are easily available.
As a compound represented by the general formula (XXXXVIII), a product name: Z6187 manufactured by Toray Dow Corning Co., Ltd. is commercially available, and as a compound represented by the general formula (XXXXXXX), manufactured by Toray Dow Corning Co., Ltd. Trade name: Z6228 is available as a commercial product.
また一般的にアルコキシシリル基又はフェノキシシリル基等の加水分解性基を有するシラン化合物は空気中の水分等で加水分解してシラノール基を生成し、シラノール基同士の脱水縮合物を生じることが知られている。従って本発明で用いられる上記一般式(IV)で示されるシラン化合物(a)は、シラン化合物が加水分解して生成したシラノール基及び脱水縮合物を含んでもいても良い。 In general, silane compounds having a hydrolyzable group such as an alkoxysilyl group or a phenoxysilyl group are hydrolyzed with moisture in the air to form a silanol group, resulting in a dehydration condensate between the silanol groups. It has been. Therefore, the silane compound (a) represented by the general formula (IV) used in the present invention may contain a silanol group and a dehydration condensate generated by hydrolysis of the silane compound.
上記一般式(IV)で示されるシラン化合物(a)の全配合量は、本発明の効果が達成される範囲であれば特に制限は無いが、流動性、成形性及び耐リフロー性の観点から封止用エポキシ樹脂成形材料中0.03〜0.80質量%が好ましく、0.04〜0.75質量%がより好ましく、0.05〜0.7質量%がさらに好ましい。0.03質量%未満では発明の効果が小さくなる傾向にあり、0.8質量%を超える場合には流動性は向上するが成形性及び耐リフロー性が大幅に低下する傾向がある。 The total amount of the silane compound (a) represented by the general formula (IV) is not particularly limited as long as the effects of the present invention are achieved, but from the viewpoint of fluidity, moldability, and reflow resistance. 0.03-0.80 mass% is preferable in the epoxy resin molding material for sealing, 0.04-0.75 mass% is more preferable, 0.05-0.7 mass% is further more preferable. If it is less than 0.03% by mass, the effect of the invention tends to be small, and if it exceeds 0.8% by mass, the fluidity is improved but the moldability and reflow resistance tend to be greatly reduced.
本発明の成形材料は、成形材料中の樹脂成分と無機成分との接着性の向上等の観点から、必要に応じてシラン化合物(b)を含有することが好ましい。シラン化合物(b)とは、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等の各種シラン系化合物であり、なお、シラン化合物(b)は、前記シラン化合物(a)と重複するシラン系化合物を除くものとする。
これらを例示すると、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(β−メトキシエトキシ)シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルジメチルメトキシシラン、γ−メタクリロキシプロピルジメチルエトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルジメチルメトキシシラン、γ−グリシドキシプロピルジメチルエトキシシラン、ビニルトリアセトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−[ビス(β−ヒドロキシエチル)]アミノプロピルトリエトキシシラン、N−β−(アミノエチル)−γ−アミノプロピルトリエトキシシラン、N−(トリメトキシシリルプロピル)エチレンジアミン、イソシアネートプロピルトリメトキシシラン、イソシアネートプロピルトリエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ジフェニルシランジオール、トリフェニルメトキシシラン、トリフェニルエトキシシラン、トリフェニルシラノール、N−β−(N−ビニルベンジルアミノエチル)−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、ヘキサメチルジシラン、γ−アニリノプロピルトリメトキシシラン、γ−アニリノプロピルトリエトキシシラン、2−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン、3−トリエトキシシリル−N−(1,3−ジメチル−ブチリデン)プロピルアミン、N−(3−トリエトキシシリルプロピル)フェニルイミン、3−(3−(トリエトキシシリル)プロピルアミノ)−N,N−ジメチルプロピオンアミド、N−トリエトキシシリルプロピル−β−アラニンメチルエステル、3−(トリエトキシシリルプロピル)ジヒドロ−3,5−フランジオン、ビス(トリメトキシシリル)ベンゼン等のシラン系化合物、1H−イミダゾール、2−アルキルイミダゾール、2,4−ジアルキルイミダゾール、4−ビニルイミダゾール等のイミダゾール化合物とγ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等のγ−グリシドキシプロピルアルコキシシランの反応物であるイミダゾール系シラン化合物が挙げられる。これらの1種を単独で用いても2種以上を組み合わせて用いてもよい。The molding material of the present invention preferably contains a silane compound (b) as necessary from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. The silane compound (b) is various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and the silane compound (b) overlaps with the silane compound (a). Excluding silane compounds.
Examples of these are vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy. Propylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltri Ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, isocyanatepropyltrimethoxysilane, isocyanate group Pyrtriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenylmethoxy Silane, triphenylethoxysilane, triphenylsilanol, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyltri Methoxysilane, γ-anilinopropyltriethoxysilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl- -(1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, N-dimethylpropionamide, N- Silane compounds such as triethoxysilylpropyl-β-alanine methyl ester, 3- (triethoxysilylpropyl) dihydro-3,5-furandion, bis (trimethoxysilyl) benzene, 1H-imidazole, 2-alkylimidazole, It is a reaction product of imidazole compounds such as 2,4-dialkylimidazole and 4-vinylimidazole and γ-glycidoxypropylalkoxysilane such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. Imidazole-based silane compounds It is. One of these may be used alone, or two or more may be used in combination.
シラン化合物(b)を配合する場合、その全配合量は成形性及び接着性の観点から封止用エポキシ樹脂成形材料中0.06〜2質量%が好ましく、0.1〜0.75質量%がより好ましく、0.2〜0.7質量%がさらに好ましい。0.06質量%未満では接着性向上効果が現れにくく、2質量%を超える場合にはボイド等の成形不良が発生しやすい傾向がある。 When mix | blending a silane compound (b), 0.06-2 mass% is preferable in the epoxy resin molding material for sealing from the viewpoint of a moldability and adhesiveness, and the whole compounding quantity is 0.1-0.75 mass%. Is more preferable, and 0.2-0.7 mass% is further more preferable. If the amount is less than 0.06% by mass, the effect of improving adhesiveness is difficult to appear, and if it exceeds 2% by mass, molding defects such as voids tend to occur.
本発明の封止用エポキシ樹脂成形材料には、成形材料中の樹脂成分と無機成分との接着性を向上等の観点から、上記シラン化合物(b)以外の従来公知のカップリング剤を配合してもよい。たとえば、イソプロピルトリイソステアロイルチタネート、イソプロピルトリス(ジオクチルパイロホスフェート)チタネート、イソプロピルトリ(N−アミノエチル−アミノエチル)チタネート、テトラオクチルビス(ジトリデシルホスファイト)チタネート、テトラ(2,2−ジアリルオキシメチル−1−ブチル)ビス(ジトリデシル)ホスファイトチタネート、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、ビス(ジオクチルパイロホスフェート)エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ(ジオクチルホスフェート)チタネート、イソプロピルトリクミルフェニルチタネート、テトライソプロピルビス(ジオクチルホスファイト)チタネート等のチタネート系カップリング剤、アルミニウムキレート類、アルミニウム/ジルコニウム系化合物等が挙げられ、これらの1種を単独で用いても2種以上を組み合わせて用いてもよい。またこれらカップリング剤を配合する場合、その全配合量は成形性及び接着性の観点から封止用エポキシ樹脂成形材料中0.06〜2質量%が好ましく、0.1〜0.75質量%がより好ましく、0.2〜0.7質量%がさらに好ましい。0.06質量%未満では各種パッケージ部材との接着性が低下する傾向にあり、2質量%を超える場合にはボイド等の成形不良が発生しやすい傾向がある。 In the sealing epoxy resin molding material of the present invention, a conventionally known coupling agent other than the silane compound (b) is blended from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. May be. For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) -1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyldiacrylic Titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumi Examples include titanate coupling agents such as phenyl titanate and tetraisopropyl bis (dioctyl phosphite) titanate, aluminum chelates, aluminum / zirconium compounds, etc. Even if one of these is used alone, two or more are combined. It may be used. Moreover, when mix | blending these coupling agents, 0.06-2 mass% is preferable in the epoxy resin molding material for sealing from the viewpoint of a moldability and adhesiveness, and the total compounding quantity is 0.1-0.75 mass%. Is more preferable, and 0.2-0.7 mass% is further more preferable. If it is less than 0.06% by mass, the adhesion to various package members tends to be reduced, and if it exceeds 2% by mass, molding defects such as voids tend to occur.
また、本発明の封止用エポキシ樹脂成形材料には、ICの耐湿性、高温放置特性を向上させる目的で陰イオン交換体を必要に応じて配合することができる。陰イオン交換体としては特に制限はなく、従来公知のものを用いることができるが、たとえば、ハイドロタルサイト類や、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマスから選ばれる元素の含水酸化物等が挙げられ、これらを単独で用いても2種類以上を組み合わせて用いてもよい。なかでも、下記組成式(XXXXXXIV)で示されるハイドロタルサイトが好ましい。 Moreover, an anion exchanger can be blended with the epoxy resin molding material for sealing of the present invention, if necessary, for the purpose of improving the moisture resistance and high temperature storage characteristics of the IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, and bismuth. These may be used alone or in combination of two or more. Especially, the hydrotalcite shown by the following compositional formula (XXXXXXXIV) is preferable.
陰イオン交換体の配合量は、ハロゲンイオンなどの陰イオンを捕捉できる充分量であれば特に限定されるものではないが、(A)エポキシ樹脂100質量部に対して、0.1〜30質量部が好ましく、1〜5質量部がより好ましい。 The amount of the anion exchanger is not particularly limited as long as it is a sufficient amount capable of capturing anions such as halogen ions, but (A) 0.1 to 30 masses per 100 mass parts of the epoxy resin. Part is preferable, and 1 to 5 parts by mass is more preferable.
本発明の封止用エポキシ樹脂成形材料には、接着性をより向上させるために、必要に応じて接着促進剤を用いることができる。接着促進剤としては、たとえば、イミダゾール、トリアゾール、テトラゾール、トリアジン等の誘導体、アントラニル酸、没食子酸、マロン酸、リンゴ酸、マレイン酸、アミノフェノール、キノリン等及びこれらの誘導体、脂肪族酸アミド化合物、ジチオカルバミン酸塩、チアジアゾール誘導体などが挙げられ、これらの1種を単独で用いても2種類以上を組み合わせて用いてもよい。 In the sealing epoxy resin molding material of the present invention, an adhesion promoter can be used as necessary in order to further improve the adhesion. Examples of the adhesion promoter include derivatives such as imidazole, triazole, tetrazole and triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline and the like, and derivatives thereof, aliphatic acid amide compounds, Examples thereof include dithiocarbamate and thiadiazole derivatives. One of these may be used alone, or two or more may be used in combination.
本発明の封止用エポキシ樹脂成形材料には、必要に応じて離型剤を用いてもよい。離型剤としては、酸化型又は非酸化型のポリオレフィンを(A)エポキシ樹脂100質量部に対して0.01〜10質量部用いることが好ましく、0.1〜5質量部用いることがより好ましい。0.01質量部未満では離型性が不充分となる傾向があり、10質量部を超えると接着性が低下する傾向がある。酸化型又は非酸化型のポリオレフィンとしては、ヘキスト株式会社製商品名H4やPE、PEDシリーズ等の数平均分子量が500〜10000程度の低分子量ポリエチレンなどが挙げられる。また、これ以外の離型剤としては、たとえばカルナバワックス、モンタン酸エステル、モンタン酸、ステアリン酸等が挙げられ、これらの1種を単独で用いても2種以上組み合わせて用いてもよい。酸化型又は非酸化型のポリオレフィンに加えてこれら他の離型剤を併用する場合、その配合量は合わせて(A)エポキシ樹脂100質量部に対して0.l〜10質量部が好ましく、0.5〜3質量部がより好ましい。 A release agent may be used in the sealing epoxy resin molding material of the present invention as necessary. As a mold release agent, it is preferable to use 0.01-10 mass parts with respect to 100 mass parts of (A) epoxy resins, and it is more preferable to use 0.1-5 mass parts as a mold release agent. . If it is less than 0.01 parts by mass, the releasability tends to be insufficient, and if it exceeds 10 parts by mass, the adhesiveness tends to decrease. Examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name H4 manufactured by Hoechst Corporation, PE, and PED series. Other examples of the release agent include carnauba wax, montanic acid ester, montanic acid, stearic acid, and the like. These may be used alone or in combination of two or more. When these other release agents are used in combination with the oxidized or non-oxidized polyolefin, the blending amount thereof is set to 0.000 parts per 100 parts by mass of the (A) epoxy resin. 1-10 mass parts is preferable, and 0.5-3 mass parts is more preferable.
本発明の封止用エポキシ樹脂成形材料には、成形材料の難燃性向上のために、従来公知の難燃剤を必要に応じて配合することができる。たとえば、ブロム化エポキシ樹脂、三酸化アンチモン、赤リン、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛等の無機物及び/又はフェノール樹脂等の熱硬化性樹脂等で被覆された赤リン、リン酸エステル等のリン化合物、メラミン、メラミン誘導体、メラミン変性フェノール樹脂、トリアジン環を有する化合物、シアヌル酸誘導体、イソシアヌル酸誘導体等の窒素含有化合物、シクロホスファゼン等のリン及び窒素含有化合物、水酸化アルミニウム、水酸化マグネシウム及び下記組成式(XXXXXXV)で示される複合金属水酸化物などが挙げられる。 In the epoxy resin molding material for sealing of the present invention, a conventionally known flame retardant can be blended as necessary in order to improve the flame retardancy of the molding material. For example, red phosphorus coated with inorganic substances such as brominated epoxy resin, antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, zinc oxide and / or thermosetting resins such as phenol resin, phosphoric acid ester, etc. Phosphorus compounds, melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, aluminum hydroxide, magnesium hydroxide And a composite metal hydroxide represented by the following composition formula (XXXXXXXV).
上記組成式(XXXXXXV)中のM1、M2及びM3は互いに異なる金属元素であれば特に制限はないが、難燃性の観点からは、M1が第3周期の金属元素、IIA族のアルカリ土類金属元素、IVB族、IIB族、VIII族、IB族、IIIA族及びIVA族に属する金属元素から選ばれ、M2がIIIB〜IIB族の遷移金属元素から選ばれることが好ましく、M1がマグネシウム、カルシウム、アルミニウム、スズ、チタン、鉄、コバルト、ニッケル、銅及び亜鉛から選ばれ、M2が鉄、コバルト、ニッケル、銅及び亜鉛から選ばれることがより好ましい。流動性の観点からは、M1がマグネシウム、M2が亜鉛又はニッケルで、r=0のものが好ましい。p、q及びrのモル比は特に制限はないが、r=0で、p/qが1/99〜1/1であることが好ましい。なお、金属元素の分類は、典型元素をA亜族、遷移元素をB亜族とする長周期型の周期律表(出典:共立出版株式会社発行「化学大辞典4」1987年2月15日縮刷版第30刷)に基づいて行った。また、酸化亜鉛、錫酸亜鉛、硼酸亜鉛、酸化鉄、酸化モリブデン、モリブデン酸亜鉛、ジシクロペンタジエニル鉄等の金属元素を含む化合物などが挙げられ、これらの1種を単独で用いても2種以上を組み合わせて用いてもよい。難燃剤の配合量は特に制限はないが、(A)エポキシ樹脂100質量部に対して1〜30質量部が好ましく、2〜15質量部がより好ましい。M 1 , M 2 and M 3 in the composition formula (XXXXXXXV) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M 1 is a metal element of the third period, group IIA Preferably selected from metal elements belonging to the alkaline earth metal elements, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA, and M 2 is selected from transition metal elements of groups IIIB to IIB, More preferably, M 1 is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M 2 is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of fluidity, it is preferable that M 1 is magnesium, M 2 is zinc or nickel, and r = 0. The molar ratio of p, q and r is not particularly limited, but preferably r = 0 and p / q is 1/99 to 1/1. The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing). Further, compounds containing metal elements such as zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, etc. may be mentioned, and one of these may be used alone. Two or more kinds may be used in combination. Although the compounding quantity of a flame retardant does not have a restriction | limiting in particular, 1-30 mass parts is preferable with respect to 100 mass parts of (A) epoxy resins, and 2-15 mass parts is more preferable.
また、本発明の封止用エポキシ樹脂成形材料には、カーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の着色剤を用いても良い。さらに、その他の添加剤として、シリコーンオイルやシリコーンゴム粉末等の応力緩和剤等を必要に応じて配合することができる。 Moreover, you may use coloring agents, such as carbon black, an organic dye, an organic pigment, a titanium oxide, a red lead, a bengara, for the epoxy resin molding material for sealing of this invention. Furthermore, as other additives, stress relaxation agents such as silicone oil and silicone rubber powder can be blended as required.
本発明の封止用エポキシ樹脂成形材料は、各種成分を均一に分散混合できるのであれば、いかなる手法を用いても調製できるが、一般的な手法として、所定の配合量の成分をミキサー等によって充分混合した後、ミキシングロール、押出機等によって溶融混練した後、冷却、粉砕する方法を挙げることができる。たとえば、上述した成分の所定量を均一に撹拌、混合し、予め70〜140℃に加熱してあるニーダー、ロール、エクストルーダーなどで混練、冷却し、粉砕するなどの方法で得ることができる。成形条件に合うような寸法及び質量でタブレット化すると使いやすい。 The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various components can be uniformly dispersed and mixed, but as a general method, components of a predetermined blending amount are mixed by a mixer or the like. An example is a method in which the mixture is sufficiently mixed, melted and kneaded by a mixing roll, an extruder, or the like, and then cooled and pulverized. For example, a predetermined amount of the above-described components can be uniformly stirred and mixed, and can be obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 to 140 ° C. in advance. It is easy to use if it is tableted with dimensions and mass that match the molding conditions.
本発明で得られる封止用エポキシ樹脂成形材料により封止した素子を備えた電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ等の支持部材に、半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子等の素子を搭載し、必要な部分を本発明の封止用エポキシ樹脂成形材料で封止した、電子部品装置などが挙げられる。このような電子部品装置としては、たとえば、リードフレーム上に半導体素子を固定し、ボンディングパッド等の素子の端子部とリード部をワイヤボンディングやバンプで接続した後、本発明の封止用エポキシ樹脂成形材料を用いてトランスファ成形等により封止してなる、DIP(Dual Inline Package)、PLCC(Plastic Leaded Chip Carrier)、QFP(Quad Flat Package)、SOP(Small Outline Package)、SOJ(Small Outline J−lead package)、TSOP(Thin Small Outline Package)、TQFP(Thin Quad Flat Package)等の一般的な樹脂封止型IC、テープキャリアにバンプで接続した半導体チップを、本発明の封止用エポキシ樹脂成形材料で封止したTCP(Tape Carrier Package)、配線板やガラス上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子及び/又はコンデンサ、抵抗体、コイル等の受動素子を、本発明の封止用エポキシ樹脂成形材料で封止したCOB(Chip On Board)モジュール、ハイブリッドIC、マルチチップモジュール、裏面に配線板接続用の端子を形成した有機基板の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と有機基板に形成された配線を接続した後、本発明の封止用エポキシ樹脂成形材料で素子を封止したBGA(Ball Grid Array)、CSP(Chip Size Package)などが挙げられる。また、プリント回路板にも本発明の封止用エポキシ樹脂成形材料は有効に使用できる。 As an electronic component device provided with an element sealed with an epoxy resin molding material for sealing obtained in the present invention, a semiconductor chip is mounted on a support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer. An electronic component device equipped with active elements such as transistors, diodes and thyristors, and passive elements such as capacitors, resistors and coils, and encapsulated with the epoxy resin molding material for sealing of the present invention Etc. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of a device such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the sealing epoxy resin of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Out Package), which is sealed by molding using a molding material. General resin-sealed type I such as lead package, TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), etc. A semiconductor chip connected to a tape carrier with a bump is sealed with a tape carrier package (TCP) sealed with an epoxy resin molding material of the present invention, wiring formed on a wiring board or glass, wire bonding, flip chip bonding COB (Chip) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder, etc., are sealed with the sealing epoxy resin molding material of the present invention On Board) Modules, hybrid ICs, multi-chip modules, devices mounted on the surface of the organic substrate with the wiring board connection terminals formed on the back, and the devices and the wiring formed on the organic substrate were connected by bump or wire bonding After, the epoxy resin molding material for sealing of the present invention Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a material. Moreover, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.
本発明の封止用エポキシ樹脂成形材料を用いて素子を封止する方法としては、低圧トランスファ成形法が最も一般的であるが、インジェクション成形法、圧縮成形法等を用いてもよい。 As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.
次に実施例により本発明を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
[本発明の封止用エポキシ樹脂成形材料の作製]
(実施例1〜17、参考例1〜9、比較例1〜13)
以下の成分をそれぞれ下記表1〜表3に示す質量部で配合し、混練温度80℃、混練時間10分の条件でロール混練を行い、実施例1〜17、参考例1〜9及び比較例1〜13の封止用エポキシ樹脂成形材料を作製した。なお表中の空欄は配合無しを表す。
[Production of sealing epoxy resin molding material of the present invention]
(Examples 1-17 , Reference Examples 1-9, Comparative Examples 1-13)
The components below are blended in parts by weight shown in Table 1 to Table 3, kneading temperature 80 ° C., subjected to kneading under the conditions of the kneading time of 10 min, Example 1-17, Reference Examples 1 to 9 and Comparative Examples 1 to 13 epoxy resin molding materials for sealing were produced. Note that the blank in the table indicates no blending.
(A)エポキシ樹脂としては、
エポキシ当量200、軟化点67℃のオルソクレゾールノボラック型エポキシ樹脂(エポキシ樹脂1、住友化学工業株式会社製商品名ESCN−190)、
エポキシ当量196、融点106℃のビフェニル型エポキシ樹脂(エポキシ樹脂2、ジャパンエポキシレジン株式会社製商品名YX−4000H)、
エポキシ当量242、融点118℃のチオジフェノール型エポキシ樹脂(エポキシ樹脂3、新日鐵化学株式会社製商品名YSLV−120TE)、
エポキシ当量241、軟化点96℃のビフェニレン骨格含有フェノール・アラルキル型エポキシ樹脂(エポキシ樹脂4、日本化薬株式会社製商品名CER−3000L)、
エポキシ当量238、軟化点52℃のフェノール・アラルキル樹脂のエポキシ化物(エポキシ樹脂5、日本化薬株式会社製商品名NC−2000L)
エポキシ当量375、軟化点80℃、臭素含有量48質量%のビスフェノールA型ブロム化エポキシ樹脂(エポキシ樹脂6)を使用した。(A) As an epoxy resin,
Orthocresol novolac epoxy resin having an epoxy equivalent of 200 and a softening point of 67 ° C. (epoxy resin 1, trade name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.),
Biphenyl type epoxy resin (epoxy resin 2, trade name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.) having an epoxy equivalent of 196 and a melting point of 106 ° C.,
Thiodiphenol type epoxy resin having an epoxy equivalent of 242 and a melting point of 118 ° C. (epoxy resin 3, trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.)
Biphenylene skeleton-containing phenol / aralkyl epoxy resin having an epoxy equivalent of 241 and a softening point of 96 ° C. (epoxy resin 4, Nippon Kayaku Co., Ltd., trade name CER-3000L),
Epoxy product of phenol aralkyl resin having an epoxy equivalent of 238 and a softening point of 52 ° C. (epoxy resin 5, product name NC-2000L manufactured by Nippon Kayaku Co., Ltd.)
A bisphenol A-type brominated epoxy resin (epoxy resin 6) having an epoxy equivalent of 375, a softening point of 80 ° C., and a bromine content of 48 mass% was used.
(B)硬化剤としては、
水酸基当量199、軟化点89℃のフェノール・アラルキル樹脂(硬化剤1、明和化成株式会社製商品名MEH−7851)、
水酸基当量176、軟化点70℃のフェノール・アラルキル樹脂(硬化剤2、三井化学株式会社製商品名ミレックスXLC)、
水酸基当量106、軟化点64℃のノボラック型フェノール樹脂(硬化剤3、明和化成株式会社製商品名H−4)を使用した。(B) As a curing agent,
Phenol aralkyl resin having a hydroxyl group equivalent of 199 and a softening point of 89 ° C. (curing agent 1, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.),
Phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (curing agent 2, trade name “Mirex XLC” manufactured by Mitsui Chemicals, Inc.)
A novolak-type phenol resin (curing agent 3, trade name H-4 manufactured by Meiwa Kasei Co., Ltd.) having a hydroxyl group equivalent of 106 and a softening point of 64 ° C. was used.
(C)硬化促進剤としては、トリフェニルホスフィンとp−ベンゾキノンとのベタイン型付加物(硬化促進剤1)、トリブチルホスフィンとp−ベンゾキノンとのベタイン型付加物(硬化促進剤2)を、(D)無機充てん剤としては平均粒径17.5μm、比表面積3.8m2/gの球状溶融シリカ使用した。(C) As a hardening accelerator, a betaine type adduct of triphenylphosphine and p-benzoquinone (curing accelerator 1), a betaine type adduct of tributylphosphine and p-benzoquinone (curing accelerator 2), ( D) As the inorganic filler, spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m 2 / g was used.
(E)成分のケイ素含有重合物としては、
重量平均分子量(Mw)2150、(E)ケイ素含有重合物中の全R 1 における置換または非置換のフェニル基の割合(Ph基の割合)75モル%、Ph基の割合をMwで除した値(Ph/Mw)0.0349のケイ素含有重合物
(ケイ素含有重合物1、東レ・ダウコーニング株式会社製商品名217FLAKE)、
Mw3700、Ph基の割合46モル%、Ph/Mw0.0124のケイ素含有重合物
(ケイ素含有重合物2、東レ・ダウコーニング株式会社製商品名233FLAKE)、
Mw5350、Ph基の割合67モル%、Ph/Mw0.0125のケイ素含有重合物
(ケイ素含有重合物3、東レ・ダウコーニング株式会社製商品名220FLAKE)、
Mw3500、Ph基の割合52モル%、Ph/Mw0.0149のケイ素含有重合物
(ケイ素含有重合物4、東レ・ダウコーニング株式会社製商品名SH6018)を使用した。
なお、ケイ素含有重合物1及び3は一般式(I)及び一般式(II)で示す構造を有し、ケイ素含有重合物2及び4は一般式(I)〜(III)で示す構造の全てを有する。
As the silicon-containing polymer of component (E),
Weight average molecular weight (Mw) 2150, (E) Percentage of substituted or unsubstituted phenyl groups (ratio of Ph groups) in all R 1 in the silicon-containing polymer 75% by mole, value obtained by dividing the percentage of Ph groups by Mw (Ph / Mw) 0.0349 silicon-containing polymer (silicon-containing polymer 1, trade name 217 FLAKE manufactured by Toray Dow Corning Co., Ltd.),
Mw3700, Ph group ratio 46 mol%, Ph / Mw 0.0124 silicon-containing polymer (silicon-containing polymer 2, trade name 233FLAKE manufactured by Toray Dow Corning Co., Ltd.),
Mw 5350, Ph group ratio 67 mol%, Ph / Mw 0.0125 silicon-containing polymer (silicon-containing polymer 3, product name 220FLAKE manufactured by Toray Dow Corning Co., Ltd.),
A silicon-containing polymer having a Mw of 3500, a Ph group ratio of 52 mol% and a Ph / Mw of 0.0149 (silicon-containing polymer 4, trade name SH6018 manufactured by Toray Dow Corning Co., Ltd.) was used.
The silicon-containing polymers 1 and 3 have the structures represented by the general formulas (I) and (II), and the silicon-containing polymers 2 and 4 have all the structures represented by the general formulas (I) to (III). Have
(E)成分以外、すなわち本発明達成するための好ましい範囲以外のケイ素含有重合物としては、
Mw850、Ph基の割合15モル%、Ph/Mw0.0177のケイ素含有重合物(ケイ素含有重合物5、東レ・ダウコーニング株式会社製商品名DC3037)、
Mw1350、Ph基の割合33モル%、Ph/Mw0.0244のケイ素含有重合物
(ケイ素含有重合物6、東レ・ダウコーニング株式会社製商品名DC3074)
Mw7900、フェニル基の割合34モル%、Ph/Mw0.0043のケイ素含有重合物(ケイ素含有重合物7、東レ・ダウコーニング株式会社製商品名249FLAKE)
室温における粘度400mPa・Sのフェニルメチルシリコーン(ケイ素含有重合物8、信越化学株式会社製商品名KF54)
エポキシ当量1660、軟化点80℃のポリシロキサン(ケイ素含有重合物9、東レ・ダウコーニング株式会社製商品名AY42−119)を使用した。
なお、ケイ素含有重合物5及び6は、一般式(I)〜(III)で示す各構造において、酸素原子と結合している水素原子がメチル基に置換された構造の全てを有し、ケイ素含有重合物7は、一般式(I)〜(III)で示す構造の全てを有し、ケイ素含有重合物8は、一般式(II)で示す構造のみを有し、ケイ素含有重合物9は、構造中にエポキシ基を含有する。As the silicon-containing polymer other than the component (E), that is, other than the preferred range for achieving the present invention,
Mw850, Ph group ratio 15 mol%, Ph / Mw 0.0177 silicon-containing polymer (silicon-containing polymer 5, product name DC3037 manufactured by Toray Dow Corning Co., Ltd.),
Silicon-containing polymer of Mw 1350, Ph group ratio 33 mol%, Ph / Mw 0.0244 (silicon-containing polymer 6, product name DC3074 manufactured by Toray Dow Corning Co., Ltd.)
Silicon-containing polymer having a Mw of 7900, a phenyl group ratio of 34 mol% and a Ph / Mw of 0.0043 (silicon-containing polymer 7, trade name 249FLAKE manufactured by Toray Dow Corning Co., Ltd.)
Phenylmethylsilicone having a viscosity of 400 mPa · S at room temperature (silicon-containing polymer 8, trade name KF54 manufactured by Shin-Etsu Chemical Co., Ltd.)
Polysiloxane having an epoxy equivalent of 1660 and a softening point of 80 ° C. (silicon-containing polymer 9, product name AY42-119 manufactured by Toray Dow Corning Co., Ltd.) was used.
The silicon-containing polymers 5 and 6 have all structures in which hydrogen atoms bonded to oxygen atoms are substituted with methyl groups in the structures represented by the general formulas (I) to (III). The containing polymer 7 has all of the structures represented by the general formulas (I) to (III), the silicon-containing polymer 8 has only the structure represented by the general formula (II), and the silicon-containing polymer 9 is The epoxy group is contained in the structure.
インデンオリゴマーとしては、東都化成株式会社製商品名I−100を使用した。
シラン化合物(a)としては、ビス−シクロペンチルジメトキシシラン(東レ・ダウコーニング株式会社製商品名Z6228)を使用した。
シラン化合物(b)としては、γ−グリシドキシプロピルトリメトキシシラン(シラン化合物(b)−1)、γ−アニリノプロピルトリメトキシシラン(シラン化合物(b)−2)、γ−メルカプトプロピルトリメトキシシラン(シラン化合物(b)−3)を使用した。
その他の添加成分としては、カルナバワックス、三酸化アンチモン、カーボンブラックを使用した。As an indene oligomer, Toto Kasei Co., Ltd. product name I-100 was used.
As the silane compound (a), bis-cyclopentyldimethoxysilane (trade name Z6228 manufactured by Toray Dow Corning Co., Ltd.) was used.
Examples of the silane compound (b) include γ-glycidoxypropyltrimethoxysilane (silane compound (b) -1), γ-anilinopropyltrimethoxysilane (silane compound (b) -2), γ-mercaptopropyltri Methoxysilane (silane compound (b) -3) was used.
As other additive components, carnauba wax, antimony trioxide, and carbon black were used.
[封止用エポキシ樹脂製形材料の評価]
実施例1〜17、参考例1〜9及び比較例1〜13で作製した封止用エポキシ樹脂成形材料の特性を、次の(1)〜(5)の各特性試験により評価した。評価結果を下記表1〜表3に示す。なお、封止用エポキシ樹脂成形材料の成形は、明記しない限りトランスファ成形機により、金型温度180℃、成形圧力6.9MPa、硬化時間90秒で成形した。また、必要に応じて後硬化は180℃で5時間の条件で行った。
(1)スパイラルフロー
EMMI−1−66に準じたスパイラルフロー測定用金型を用いて、封止用エポキシ成形材料を上記条件で成形し、流動距離(cm)を求めた。
(2)熱時硬度
封止用エポキシ樹脂成形材料を上記条件で直径50mm×厚さ3mmの円板に成形し、成形後直ちにショアD型硬度計((株)上島製作所製HD−1120(タイプD))を用いて測定した。
(3)室温曲げ弾性率及び260℃曲げ弾性率
封止用エポキシ樹脂成形材料を上記条件で10mm×70mm×3mmに成形、後硬化して試験片を作製し、A&D社製テンシロンを用い、JIS−K−6911に準拠した3点支持型曲げ試験を室温及び260℃の恒温槽内で行い、それぞれ室温曲げ弾性率(GPa)及び260℃曲げ弾性率(MPa)を求めた。
(4)耐リフロー性
8mm×10mm×0.4mmのシリコンチップを搭載した外形寸法20mm×14mm×2mmの80ピンフラットパッケージ(QFP)(リードフレーム材質:銅合金、ダイパッド部上面およびリード先端銀メッキ処理品)を、封止用エポキシ樹脂成形材料を用いて上記条件で成形、後硬化して作製し、85℃、85%RHの条件で168時間加湿した後、所定温度(235℃、245℃、255℃、265℃)、10秒の条件でリフロー処理を行い、パッケージ外部のクラックの有無を目視で、パッケージ内部の剥離発生の有無を超音波探傷装置(日立建機(株)製HYE−FOCUS)でそれぞれ観察し、試験パッケージ数(10)に対するクラック及び剥離発生パッケージ数の総和で評価した。
(5)難燃性
厚さ1/16インチ(約1.6mm)の試験片を成形する金型を用いて、封止用エポキシ樹脂成形材料を上記条件で成形して後硬化を行い、UL−94試験法に従って難燃性を評価した。
[Evaluation of epoxy resin molding material for sealing]
The characteristics of the epoxy resin molding materials for sealing produced in Examples 1 to 17, Reference Examples 1 to 9, and Comparative Examples 1 to 13 were evaluated by the following characteristic tests (1) to (5). The evaluation results are shown in Tables 1 to 3 below. The epoxy resin molding material for sealing was molded by a transfer molding machine at a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds unless otherwise specified. Further, if necessary, post-curing was performed at 180 ° C. for 5 hours.
(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.
(2) Hardness under heat The epoxy resin molding material for sealing is molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness meter (HD-1120 manufactured by Ueshima Seisakusho Co., Ltd.) D)).
(3) Room temperature flexural modulus and 260 ° C. flexural modulus The epoxy resin molding material for sealing was molded into 10 mm × 70 mm × 3 mm under the above conditions and post-cured to prepare a test piece. A three-point support bending test in accordance with -K-6911 was performed in a thermostatic chamber at room temperature and 260 ° C., and room temperature bending elastic modulus (GPa) and 260 ° C. bending elastic modulus (MPa) were obtained, respectively.
(4) Reflow resistance 80 mm flat package (QFP) with external dimensions of 20 mm x 14 mm x 2 mm mounted with 8 mm x 10 mm x 0.4 mm silicon chip (lead frame material: copper alloy, die pad top surface and lead tip silver plating Processed product) is molded and post-cured using the epoxy resin molding material for sealing, and is humidified for 168 hours under the conditions of 85 ° C. and 85% RH, and then at a predetermined temperature (235 ° C., 245 ° C.). Reflow treatment is performed for 10 seconds under the conditions of 255 ° C. and 265 ° C., the presence of cracks outside the package is visually checked, and the presence or absence of delamination inside the package is detected using an ultrasonic flaw detector (HYE- manufactured by Hitachi Construction Machinery Co., Ltd.). FOCUS) was observed, and the total number of cracks and delamination packages with respect to the number of test packages (10) was evaluated.
(5) Flame retardance Using a mold for molding a test piece having a thickness of 1/16 inch (about 1.6 mm), an epoxy resin molding material for sealing is molded under the above conditions and post-cured. UL Flame retardancy was evaluated according to the -94 test method.
表1〜表3から以下のことがわかった。
(E)成分の化合物を配合していない比較例1〜13は耐リフロー性が劣っている。直鎖状のポリシロキサンを配合した比較例12は難燃性に劣り、エポキシ基含有分岐状ポリシロキサンを配合した比較例13は曲げ弾性率が充分に低下できていないことがわかる。(E)成分の化合物の重量平均分子量が、本発明の範囲外である比較例9〜11は耐リフロー性に劣っており、比較例9及び10は難燃性にも劣っておりUL−94 V−0を達成していない。
From Tables 1 to 3, the following was found.
(E) Comparative Examples 1-13 which do not mix | blend the compound of a component are inferior in reflow resistance. It turns out that the comparative example 12 which mix | blended the linear polysiloxane is inferior in a flame retardance, and the comparative example 13 which mix | blended the epoxy group containing branched polysiloxane has not fully reduced the bending elastic modulus. Comparative Examples 9 to 11 in which the weight average molecular weight of the component (E) compound is outside the scope of the present invention are inferior in reflow resistance, and Comparative Examples 9 and 10 are also inferior in flame retardancy and UL-94. V-0 is not achieved.
これに対し、(E)成分の化合物を本発明の範囲内に配合し、(E)成分以外のケイ素含有重合物、シラン化合物(b)の配合組成が一部異なる以外は同一樹脂組成の比較例と比べ、実施例1〜17は耐リフロー性が良好で、全てUL−94 V−0を達成し、難燃性が良好で、また成形性も良好である。さらにはインデンオリゴマーを含む実施例12及び16、シラン化合物(a)をさらに含む実施例13及び17では耐リフロー性に特に優れている。 On the other hand, the compound of the component (E) is blended within the scope of the present invention, and the same resin composition is compared except that the compound composition of the silicon-containing polymer other than the component (E) and the silane compound (b) are partially different. Compared with the examples, Examples 1 to 17 have good reflow resistance, all achieve UL-94 V-0, good flame retardancy, and good moldability. Furthermore, Examples 12 and 16 containing an indene oligomer and Examples 13 and 17 further containing a silane compound (a) are particularly excellent in reflow resistance.
Claims (5)
(E)ケイ素含有重合物は、下記一般式(I)、下記一般式(II)、下記一般式(III)で示す構造のうちのいずれか2つまたは全ての構造のみからなり、
(E)ケイ素含有重合物の重量平均分子量が、1500以上7000以下である、
封止用エポキシ樹脂成形材料。
(式(IV)で、R 1 ’は炭素数5〜8のシクロアルキル基又はシクロアルケニル基を示し、R 2 はR 1 ’と同じ又は炭素数1〜6の炭化水素基を示し、R 3 は炭素数1〜6の炭化水素基を示し、R 1 ’〜R 3 で示す基の水素原子の一部が置換されていてもよく、pは1〜3の整数を示し、qは0〜3の整数を示す。) (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) inorganic filler , (E) silicon-containing polymer , and silane compound (a) represented by the following general formula (IV) Contains,
(E) The silicon-containing polymer consists of only two or all of the structures represented by the following general formula (I), the following general formula (II), and the following general formula (III) ,
(E) The weight average molecular weight of the silicon-containing polymer is 1500 or more and 7000 or less,
Epoxy resin molding material for sealing.
(In formula (IV), R 1 ′ represents a cycloalkyl group or cycloalkenyl group having 5 to 8 carbon atoms, R 2 represents the same as R 1 ′ or a hydrocarbon group having 1 to 6 carbon atoms, and R 3 Represents a hydrocarbon group having 1 to 6 carbon atoms, a part of hydrogen atoms of the groups represented by R 1 ′ to R 3 may be substituted, p represents an integer of 1 to 3, and q represents 0 to 0 Indicates an integer of 3.)
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JPH0723423B2 (en) * | 1986-09-19 | 1995-03-15 | 株式会社東芝 | Curable resin composition |
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JPH0453823A (en) * | 1990-06-21 | 1992-02-21 | Toray Ind Inc | Thermosetting resin composition |
JPH0733984A (en) * | 1993-07-16 | 1995-02-03 | Shin Etsu Chem Co Ltd | Room temperature curing organopolysiloxane composition |
JPH0881544A (en) * | 1994-09-13 | 1996-03-26 | Toshiba Chem Corp | Liquid resin sealing material and semiconductor device sealed therewith |
JPH08104795A (en) * | 1994-10-04 | 1996-04-23 | Toshiba Chem Corp | Liquid-resin sealing compound and sealed semiconductor device |
DE69913298T2 (en) * | 1998-06-09 | 2004-05-27 | Nitto Denko Corp., Ibaraki | EPOXY RESIN COMPOSITION FOR SEALING SEMICONDUCTORS AND THE SEMICONDUCTOR DEVICE THEREFORE |
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