JP2020094130A - Sealing resin composition and semiconductor device - Google Patents
Sealing resin composition and semiconductor device Download PDFInfo
- Publication number
- JP2020094130A JP2020094130A JP2018232976A JP2018232976A JP2020094130A JP 2020094130 A JP2020094130 A JP 2020094130A JP 2018232976 A JP2018232976 A JP 2018232976A JP 2018232976 A JP2018232976 A JP 2018232976A JP 2020094130 A JP2020094130 A JP 2020094130A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- compound
- nitrogen
- group
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 90
- 239000004065 semiconductor Substances 0.000 title claims abstract description 38
- 238000007789 sealing Methods 0.000 title abstract description 26
- -1 ester compound Chemical class 0.000 claims abstract description 146
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 69
- 239000003822 epoxy resin Substances 0.000 claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 61
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 26
- 239000011256 inorganic filler Substances 0.000 claims description 23
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 23
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 17
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 69
- 125000003118 aryl group Chemical group 0.000 description 27
- 239000005011 phenolic resin Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 22
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 18
- 150000002989 phenols Chemical class 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 13
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007822 coupling agent Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 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 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 238000000465 moulding Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 239000001993 wax 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
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- UZUNCLSDTUBVCN-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C(O)C=1C(C)(C)C1=CC=CC=C1 UZUNCLSDTUBVCN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000013872 montan acid ester Nutrition 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical group 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- 150000003739 xylenols Chemical class 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical compound C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- AMFYRKOUWBAGHV-UHFFFAOYSA-N 1h-pyrazolo[4,3-b]pyridine Chemical compound C1=CN=C2C=NNC2=C1 AMFYRKOUWBAGHV-UHFFFAOYSA-N 0.000 description 1
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 1
- BLBVJHVRECUXKP-UHFFFAOYSA-N 2,3-dimethoxy-1,4-dimethylbenzene Chemical group COC1=C(C)C=CC(C)=C1OC BLBVJHVRECUXKP-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- OWWNFGGOZYTYQL-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohex-3-ene-1-carboxylic acid Chemical compound OC(=O)C1CCC=CC1C(=O)OCC1OC1 OWWNFGGOZYTYQL-UHFFFAOYSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940088516 cipro Drugs 0.000 description 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- XOSYHSRXLVMOBA-UHFFFAOYSA-N cyclopenta-1,3-diene;phenol Chemical group C1C=CC=C1.C1C=CC=C1.OC1=CC=CC=C1 XOSYHSRXLVMOBA-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004206 montan acid ester Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、封止用樹脂組成物及び半導体装置に関する。 The present invention relates to a sealing resin composition and a semiconductor device.
コンピュータ、情報通信機器等は、近年ますます高性能化及び高機能化し、大量のデータを高速で処理するため、扱う信号が高周波数化する傾向にある。高周波数領域（例えば、２０ＧＨｚ以上）の信号を扱う場合、伝送損失が小さいことが望まれる。そして、この伝送損失を小さく抑える観点から、半導体装置の素子を封止する封止用樹脂組成物の硬化物においても、誘電正接の低い材料が望まれる。
ここで特許文献１には、エポキシ樹脂用硬化剤として、活性エステル樹脂を含有する熱硬化性樹脂組成物が開示されており、硬化物の誘電正接を低く抑えることができるとされている。
2. Description of the Related Art Computers, information communication devices, etc. have become more sophisticated and more sophisticated in recent years and process a large amount of data at high speed, so that the frequency of signals handled tends to increase. When handling a signal in a high frequency region (for example, 20 GHz or higher), it is desired that the transmission loss be small. From the viewpoint of suppressing this transmission loss to be small, a material having a low dielectric loss tangent is also desired in the cured product of the sealing resin composition for sealing the elements of the semiconductor device.
Here, Patent Document 1 discloses a thermosetting resin composition containing an active ester resin as a curing agent for epoxy resin, and it is said that the dielectric loss tangent of the cured product can be suppressed low.
また近年、半導体材料における次世代の基板材料として窒化ケイ素が用いられる傾向にある。そのため、半導体装置の素子を封止する封止用樹脂組成物の硬化物においても、窒化ケイ素に対する高い接着性が望まれる。
本開示は上記事情に鑑み、２０ＧＨｚにおける誘電正接を低く維持したまま、窒化ケイ素に対する接着力に優れる硬化物を形成可能な封止用樹脂組成物、及び、これにより封止した素子を備える半導体装置を提供することを課題とする。
Further, in recent years, silicon nitride tends to be used as a next-generation substrate material for semiconductor materials. Therefore, a cured product of a sealing resin composition for sealing an element of a semiconductor device is also required to have high adhesiveness to silicon nitride.
In view of the above circumstances, the present disclosure provides a sealing resin composition capable of forming a cured product having excellent adhesion to silicon nitride while maintaining a low dielectric loss tangent at 20 GHz, and a semiconductor device including an element sealed thereby. The challenge is to provide.
上記課題を解決するための手段には、以下の実施態様が含まれる。 Means for solving the above problems include the following embodiments.
［１］ エポキシ樹脂と、
活性エステル化合物及び窒素含有フェノール化合物を含む硬化剤と、
を含有する封止用樹脂組成物。
[1] Epoxy resin,
A curing agent containing an active ester compound and a nitrogen-containing phenol compound,
A resin composition for encapsulation containing:
［２］ 前記窒素含有フェノール化合物の水酸基当量が１００ｇ／ｅｑ以上である前記［１］に記載の封止用樹脂組成物。 [2] The encapsulating resin composition according to the above [1], wherein the hydroxyl group equivalent of the nitrogen-containing phenol compound is 100 g/eq or more.
［３］ 前記窒素含有フェノール化合物が窒素含有の複素環式化合物を含む、前記［１］又は［２］に記載の封止用樹脂組成物。 [3] The encapsulating resin composition according to the above [1] or [2], wherein the nitrogen-containing phenol compound contains a nitrogen-containing heterocyclic compound.
［４］ 前記窒素含有の複素環式化合物が、複素環骨格を構成する原子として、２つ以上の窒素原子を有する複素環式化合物を含む、前記［３］に記載の封止用樹脂組成物。 [4] The encapsulating resin composition according to the above [3], wherein the nitrogen-containing heterocyclic compound contains a heterocyclic compound having two or more nitrogen atoms as atoms constituting the heterocyclic skeleton. ..
［５］ 前記窒素含有フェノール化合物の含有率が、前記硬化剤の総量に対して、１５質量％以下である前記［１］〜［４］のいずれか１項に記載の封止用樹脂組成物。 [5] The encapsulating resin composition according to any one of [1] to [4], in which the content of the nitrogen-containing phenol compound is 15% by mass or less based on the total amount of the curing agent. ..
［６］ 無機充填材を更に含む、前記［１］〜［５］のいずれか１項に記載の封止用樹脂組成物。 [6] The encapsulating resin composition according to any one of [1] to [5], further including an inorganic filler.
［７］ 前記無機充填材の含有率が、封止用樹脂組成物中、６５体積％以上である前記［６］に記載の封止用樹脂組成物。 [7] The encapsulating resin composition according to the above [6], wherein the content of the inorganic filler is 65% by volume or more in the encapsulating resin composition.
［８］ 半導体素子と、前記半導体素子を封止してなる前記［１］〜［７］のいずれか１項に記載の封止用樹脂組成物の硬化物と、を含む半導体装置。 [8] A semiconductor device comprising a semiconductor element and a cured product of the encapsulating resin composition according to any one of [1] to [7], which is obtained by encapsulating the semiconductor element.
本開示によれば、２０ＧＨｚにおける誘電正接を低く維持したまま、窒化ケイ素に対する接着力に優れる硬化物を形成可能な封止用樹脂組成物、及び、これにより封止した素子を備える半導体装置が提供される。 According to the present disclosure, there is provided a sealing resin composition capable of forming a cured product having excellent adhesion to silicon nitride while maintaining a low dielectric loss tangent at 20 GHz, and a semiconductor device including an element sealed by the sealing resin composition. To be done.
本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本開示において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
In the present disclosure, the term “process” includes not only a process independent of other processes but also the process even if the process is not clearly distinguishable from the other processes as long as the purpose of the process is achieved. ..
In the present disclosure, the numerical range indicated by using "to" includes the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition unless otherwise specified.
−封止用樹脂組成物−
本開示の封止用樹脂組成物は、エポキシ樹脂と、活性エステル化合物及び窒素含有フェノール化合物を含む硬化剤と、を含有する。封止用樹脂組成物は、その他の添加剤を含んでいてもよい。
-Resin composition for sealing-
The encapsulating resin composition of the present disclosure contains an epoxy resin and a curing agent containing an active ester compound and a nitrogen-containing phenol compound. The encapsulating resin composition may contain other additives.
本開示の封止用樹脂組成物は、２０ＧＨｚにおける誘電正接を低く維持したまま、窒化ケイ素に対する接着力に優れる硬化物を形成可能である。その理由は必ずしも明らかではないが、以下のように考えられる。 The encapsulating resin composition of the present disclosure can form a cured product having excellent adhesion to silicon nitride while maintaining a low dielectric loss tangent at 20 GHz. The reason is not always clear, but it is considered as follows.
本開示の封止用樹脂組成物は、硬化剤として活性エステル化合物を含む。エポキシ樹脂の硬化剤として一般的に用いられるフェノール硬化剤等は、エポキシ樹脂との反応において２級水酸基を生じ易い。これに対して、硬化剤として活性エステル化合物を用いると、エポキシ樹脂との硬化反応では、２級水酸基の代わりにエステル基が生じる。エステル基は、２級水酸基に比べて極性が低く、分極し難い。そのため、２級水酸基を発生させるフェノール樹脂等の硬化剤を用いる場合に比べ、活性エステル化合物を用いる場合には、硬化物の誘電正接を低く抑えることができると考えられる。
一方で、活性エステル化合物を硬化剤として用いると、得られる硬化物は窒化ケイ素に対して密着性が低下することが明らかとなった。このように、硬化剤として活性エステル化合物を用いると、得られる硬化物の誘電正接を低く抑えることができるものの、窒化ケイ素に対する接着性が低下する、というトレードオフの関係にあることが分かった。
The encapsulating resin composition of the present disclosure contains an active ester compound as a curing agent. A phenol curing agent or the like generally used as a curing agent for an epoxy resin is likely to generate a secondary hydroxyl group in the reaction with the epoxy resin. On the other hand, when an active ester compound is used as the curing agent, an ester group is generated instead of the secondary hydroxyl group in the curing reaction with the epoxy resin. The ester group has a lower polarity than the secondary hydroxyl group and is difficult to polarize. Therefore, it is considered that when an active ester compound is used, the dielectric loss tangent of the cured product can be suppressed lower than when a curing agent such as a phenol resin that generates a secondary hydroxyl group is used.
On the other hand, it was revealed that when an active ester compound is used as a curing agent, the obtained cured product has reduced adhesion to silicon nitride. As described above, it was found that when an active ester compound is used as a curing agent, the dielectric loss tangent of the obtained cured product can be suppressed to a low level, but the adhesiveness to silicon nitride is reduced, which is a trade-off relationship.
これに対して、本開示の封止用樹脂組成物では、硬化剤として、活性エステル化合物に加えて、窒素含有フェノール化合物を含む。窒素含有フェノール化合物における窒素原子部位によって、窒化ケイ素基板に対する接着性が向上するものと考えられる。また、窒素含有フェノール化合物におけるフェノール部位のエポキシ樹脂に対する反応性の程度は明らかではないが、硬化物における誘電正接が低く維持されることから、活性エステル化合物とエポキシ樹脂との硬化反応を阻害していないものと考えられる。 In contrast, the encapsulating resin composition of the present disclosure contains a nitrogen-containing phenol compound as a curing agent in addition to the active ester compound. It is considered that the nitrogen atom site in the nitrogen-containing phenol compound improves the adhesion to the silicon nitride substrate. In addition, although the degree of reactivity of the phenol moiety of the nitrogen-containing phenol compound with the epoxy resin is not clear, since the dielectric loss tangent of the cured product is kept low, it inhibits the curing reaction between the active ester compound and the epoxy resin. It is considered not to exist.
［エポキシ樹脂］
封止用樹脂組成物は、エポキシ樹脂を含む。
本開示の封止用樹脂組成物に含まれるエポキシ樹脂の種類は、特に制限されない。
エポキシ樹脂として具体的には、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等のフェノール化合物及び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化合物からなる群より選ばれる少なくとも１種のフェノール性化合物と、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等の脂肪族アルデヒド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であるノボラック型エポキシ樹脂（フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等）；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド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トリフェニルメタン型フェノール樹脂をエポキシ化したものであるトリフェニルメタン型エポキシ樹脂；上記フェノール化合物及びナフトール化合物と、アルデヒド化合物とを酸性触媒下で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である共重合型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ等のジグリシジルエーテルであるジフェニルメタン型エポキシ樹脂；アラルキル置換、アルキル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；スチルベン系フェノール化合物のジグリシジルエーテルであるスチルベン型エポキシ樹脂；ビスフェノールＳ等のジグリシジルエーテルである硫黄原子含有エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテルであるエポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等の多価カルボン酸化合物のグリシジルエステルであるグリシジルエステル型エポキシ樹脂；アニリン、ジアミノジフェニルメタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したものであ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化合物の共縮合樹脂をエポキシ化したものであるジシクロペンタジエン型エポキシ樹脂；分子内のオレフィン結合をエポキシ化したものであるビニルシクロヘキセンジエポキシド、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、２−（３，４−エポキシ）シクロヘキシル−５，５−スピロ（３，４−エポキシ）シクロヘキサン−ｍ−ジオキサン等の脂環型エポキシ樹脂；パラキシリレン変性フェノール樹脂のグリシジルエーテルであるパラキシリレン変性エポキシ樹脂；メタキシリレン変性フェノール樹脂のグリシジルエーテルであるメタキシリレン変性エポキシ樹脂；テルペン変性フェノール樹脂のグリシジルエーテルであるテルペン変性エポキシ樹脂；ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるジシクロペンタジエン変性エポキシ樹脂；シクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるシクロペンタジエン変性エポキシ樹脂；多環芳香環変性フェノール樹脂のグリシジルエーテルである多環芳香環変性エポキシ樹脂；ナフタレン環含有フェノール樹脂のグリシジルエーテルであるナフタレン型エポキシ樹脂；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；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；フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等のアラルキル型フェノール樹脂をエポキシ化したものであるアラルキル型エポキシ樹脂；アラルキル型フェノール樹脂及びビフェノールなどが挙げられる。さらにはアクリル樹脂のエポキシ化物等もエポキシ樹脂として挙げられる。
上記の中でも、エポキシ樹脂としては、アラルキル型エポキシ樹脂、ビフェニル型エポキシ樹脂等が好ましい。
エポキシ樹脂は、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。
[Epoxy resin]
The sealing resin composition contains an epoxy resin.
The type of epoxy resin contained in the encapsulating resin composition of the present disclosure is not particularly limited.
Specific examples of the epoxy resin include at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolac type), which is obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of a certain phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst. Epoxy resin, orthocresol novolac type epoxy resin, etc.); Epoxy triphenylmethane type phenol resin obtained by condensing or co-condensing the above phenolic compound and an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst Triphenylmethane-type epoxy resin that is a epoxidized compound; Copolymer-type epoxy resin that is an epoxidized novolak resin obtained by co-condensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol A, a diphenylmethane type epoxy resin which is a diglycidyl ether such as bisphenol F; a biphenyl type epoxy resin which is a diglycidyl ether of an aralkyl-substituted, alkyl-substituted or unsubstituted biphenol; a stilbene type epoxy which is a diglycidyl ether of a stilbene-based phenol compound Resin: Sulfur atom-containing epoxy resin that is a diglycidyl ether such as bisphenol S; Epoxy resin that is a glycidyl ether of alcohols such as butanediol, polyethylene glycol, polypropylene glycol; Multivalent such as phthalic acid, isophthalic acid, tetrahydrophthalic acid Glycidyl ester type epoxy resin, which is a glycidyl ester of a carboxylic acid compound; glycidyl amine type epoxy resin, in which active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene and phenol Dicyclopentadiene type epoxy resin obtained by epoxidizing a co-condensed resin of a compound; vinyl cyclohexene diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylate, 2-(3,4-epoxy)siku A cycloaliphatic epoxy resin such as lohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane; a glycidyl ether of a para-xylylene-modified phenol resin, a para-xylylene-modified epoxy resin; a glycidyl ether of a meta-xylylene-modified phenol resin. Metaxylylene-modified epoxy resin; terpene-modified epoxy resin, which is a glycidyl ether of terpene-modified phenol resin; dicyclopentadiene-modified epoxy resin, which is a glycidyl ether of dicyclopentadiene-modified phenol resin; cyclopentadiene-modified, which is a glycidyl ether of cyclopentadiene-modified phenol resin Epoxy resin; Polycyclic aromatic ring-modified epoxy resin, which is a glycidyl ether of polycyclic aromatic ring-modified phenol resin; Naphthalene-type epoxy resin, which is a glycidyl ether of naphthalene ring-containing phenol resin; Halogenated phenol novolac-type epoxy resin; Hydroquinone-type epoxy resin Trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; epoxidation of aralkyl type phenol resin such as phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin Examples thereof include aralkyl type epoxy resins; aralkyl type phenol resins and biphenols. Further, epoxy compounds such as epoxidized products of acrylic resin can also be used.
Among the above, as the epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin and the like are preferable.
The epoxy resins may be used alone or in combination of two or more.
エポキシ樹脂のエポキシ当量（分子量／エポキシ基数）は、特に制限されない。成形性、耐リフロー性及び電気的信頼等の各種特性バランスの観点からは、１００ｇ／ｅｑ〜１０００ｇ／ｅｑであることが好ましく、１５０ｇ／ｅｑ〜５００ｇ／ｅｑであることがより好ましい。 The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of various property balances such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq.
エポキシ樹脂のエポキシ当量は、ＪＩＳ Ｋ ７２３６：２００９に準じた方法で測定される値とする。 The epoxy equivalent of the epoxy resin is a value measured by a method according to JIS K 7236:2009.
エポキシ樹脂が固体である場合、その軟化点又は融点は特に制限されない。成形性と耐リフロー性の観点からは４０℃〜１８０℃であることが好ましく、封止用樹脂組成物の調製の際の取扱い性の観点からは５０℃〜１３０℃であることがより好ましい。 When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of handleability when preparing the encapsulating resin composition.
エポキシ樹脂の融点又は軟化点は、示差走査熱量測定（ＤＳＣ）又はＪＩＳ Ｋ ７２３４：１９８６に準じた方法（環球法）で測定される値とする。 The melting point or softening point of the epoxy resin is a value measured by a differential scanning calorimetry (DSC) or a method (ring and ball method) according to JIS K 7234:1986.
封止用樹脂組成物中のエポキシ樹脂の含有率は、強度、流動性、耐熱性、成形性等の観点から０．５質量％〜５０質量％であることが好ましく、２質量％〜３０質量％であることがより好ましい。 The content of the epoxy resin in the encapsulating resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and 2% by mass to 30% by mass. % Is more preferable.
［硬化剤］
封止用樹脂組成物は、硬化剤を含む。
硬化剤は、活性エステル化合物及び窒素含有フェノール化合物を含む。封止用樹脂組成物は、活性エステル化合物及び窒素含有フェノール化合物以外の硬化剤を含んでもよい。
[Curing agent]
The encapsulating resin composition contains a curing agent.
Curing agents include active ester compounds and nitrogen-containing phenolic compounds. The encapsulating resin composition may contain a curing agent other than the active ester compound and the nitrogen-containing phenol compound.
（活性エステル化合物）
本開示における活性エステル化合物とは、エポキシ基と反応するエステル基を１分子中に１個以上有し、エポキシ樹脂の硬化作用を有する化合物をいう。
(Active ester compound)
The active ester compound in the present disclosure refers to a compound having one or more ester groups that react with an epoxy group in one molecule and having a curing action on an epoxy resin.
本開示の封止用樹脂組成物は、先述のとおり、硬化剤として活性エステル化合物を用いることによって、硬化物の誘電正接を低く抑えることができる。
また、硬化物中の極性基は硬化物の吸水性を高めるところ、硬化剤として活性エステル化合物を用いることによって硬化物の極性基濃度を抑え、硬化物の吸水性を抑制することができる傾向にある。そして、硬化物の吸水性を抑制すること、つまりは極性分子であるＨ２Ｏの含有量を抑制することにより、硬化物の誘電正接をさらに低く抑えることができると考えられる。硬化物の吸水率は、０％〜０．３５％が好ましく、０％〜０．３０％がより好ましく、０％〜０．２５％がさらに好ましい。ここで硬化物の吸水率は、プレッシャークッカー試験（１２１℃、２．１気圧、２４時間）によって求める質量増加率である。
As described above, the encapsulating resin composition of the present disclosure can suppress the dielectric loss tangent of a cured product to a low level by using an active ester compound as a curing agent.
Further, when the polar group in the cured product enhances the water absorption of the cured product, it tends to be possible to suppress the water absorption of the cured product by suppressing the concentration of the polar group of the cured product by using an active ester compound as a curing agent. is there. It is considered that the dielectric loss tangent of the cured product can be further suppressed by suppressing the water absorption of the cured product, that is, by suppressing the content of H 2 O which is a polar molecule. The water absorption of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and further preferably 0% to 0.25%. Here, the water absorption rate of the cured product is a mass increase rate obtained by a pressure cooker test (121° C., 2.1 atmospheric pressure, 24 hours).
活性エステル化合物は、エポキシ基と反応するエステル基を分子中に１個以上有する化合物であればその種類は特に制限されない。 The type of the active ester compound is not particularly limited as long as it is a compound having at least one ester group that reacts with an epoxy group in the molecule.
活性エステル化合物としては、フェノールエステル化合物、チオフェノールエステル化合物、Ｎ−ヒドロキシアミンエステル化合物、複素環ヒドロキシ化合物のエステル化物等が挙げられる。 Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.
活性エステル化合物としては、例えば、脂肪族カルボン酸及び芳香族カルボン酸の少なくとも１種と脂肪族ヒドロキシ化合物及び芳香族ヒドロキシ化合物の少なくとも１種とから得られるエステル化合物が挙げられる。脂肪族化合物を重縮合の成分とするエステル化合物は、脂肪族鎖を有することによりエポキシ樹脂との相溶性に優れる傾向にある。芳香族化合物を重縮合の成分とするエステル化合物は、芳香環を有することにより耐熱性に優れる傾向にある。 Examples of the active ester compound include ester compounds obtained from at least one kind of aliphatic carboxylic acid and aromatic carboxylic acid and at least one kind of aliphatic hydroxy compound and aromatic hydroxy compound. An ester compound having an aliphatic compound as a polycondensation component tends to have excellent compatibility with an epoxy resin because it has an aliphatic chain. An ester compound containing an aromatic compound as a polycondensation component tends to have excellent heat resistance because it has an aromatic ring.
活性エステル化合物の具体例としては、芳香族カルボン酸とフェノール性水酸基との縮合反応にて得られる芳香族エステルが挙げられる。中でも、ベンゼン、ナフタレン、ビフェニル、ジフェニルプロパン、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン酸等の芳香環の水素原子の２〜４個をカルボキシ基で置換した芳香族カルボン酸成分と、前記した芳香環の水素原子の１個を水酸基で置換した１価フェノールと、前記した芳香環の水素原子の２〜４個を水酸基で置換した多価フェノールとの混合物を原材料として、芳香族カルボン酸とフェノール性水酸基との縮合反応にて得られる芳香族エステルが好ましい。すなわち、上記芳香族カルボン酸成分由来の構造単位と上記１価フェノール由来の構造単位と上記多価フェノール由来の構造単位とを有する芳香族エステルが好ましい。 Specific examples of the active ester compound include aromatic esters obtained by condensation reaction of aromatic carboxylic acids and phenolic hydroxyl groups. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenyl sulfonic acid are substituted with a carboxy group, and a hydrogen atom of the aromatic ring described above. Of the aromatic carboxylic acid and the phenolic hydroxyl group using as a raw material a mixture of a monohydric phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 of the hydrogen atoms of the aromatic ring described above are substituted with a hydroxyl group. Aromatic esters obtained by condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monohydric phenol, and a structural unit derived from the polyhydric phenol is preferable.
活性エステル化合物の具体例としては、特開２０１２−２４６３６７号公報に記載されている、脂肪族環状炭化水素基を介してフェノール化合物が結節された分子構造を有するフェノール樹脂と、芳香族ジカルボン酸又はそのハライドと、芳香族モノヒドロキシ化合物とを反応させて得られる構造を有する活性エステル樹脂が挙げられる。当該活性エステル樹脂としては、下記の構造式（１）で表される化合物が好ましい。 Specific examples of the active ester compound include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group described in JP 2012-246367 A, an aromatic dicarboxylic acid or An active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound can be mentioned. As the active ester resin, a compound represented by the following structural formula (1) is preferable.
構造式（１）中、Ｒ１は炭素数１〜４のアルキル基であり、Ｘはベンゼン環、ナフタレン環、炭素数１〜４のアルキル基で置換されたベンゼン環若しくはナフタレン環、又はビフェニル基であり、Ｙはベンゼン環、ナフタレン環、又は炭素数１〜４のアルキル基で置換されたベンゼン環若しくはナフタレン環であり、ｋは０又は１であり、ｎは繰り返し数の平均を表し０．２５〜１．５である。 In Structural Formula (1), R 1 is an alkyl group having 1 to 4 carbon atoms, X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group. And Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average of the number of repetitions. 25 to 1.5.
構造式（１）で表される化合物の具体例としては、例えば、下記の例示化合物（１−１）〜（１−１０）が挙げられる。構造式中のｔ−Ｂｕは、ｔｅｒｔ−ブチル基である。 Specific examples of the compound represented by Structural Formula (1) include the following Exemplified Compounds (1-1) to (1-10). T-Bu in the structural formula is a tert-butyl group.
活性エステル化合物の別の具体例としては、特開２０１４−１１４３５２号公報に記載されている、下記の構造式（２）で表される化合物及び下記の構造式（３）で表される化合物が挙げられる。 Another specific example of the active ester compound is a compound represented by the following structural formula (2) and a compound represented by the following structural formula (3), which are described in JP-A-2014-114352. Can be mentioned.
構造式（２）中、Ｒ１及びＲ２はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基、又は炭素数１〜４のアルコキシ基であり、Ｚはベンゾイル基、ナフトイル基、炭素数１〜４のアルキル基で置換されたベンゾイル基又はナフトイル基、及び炭素数２〜６のアシル基からなる群から選ばれるエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｚのうち少なくとも１個はエステル形成構造部位（ｚ１）である。 In Structural Formula (2), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon atom. An benzoyl group or a naphthoyl group substituted with an alkyl group of 1 to 4 and an ester-forming structural site (z1) selected from the group consisting of an acyl group of 2 to 6 carbon atoms, or a hydrogen atom (z2), Z At least one of them is an ester-forming structural site (z1).
構造式（３）中、Ｒ１及びＲ２はそれぞれ独立に、水素原子、炭素数１〜４のアルキル基、又は炭素数１〜４のアルコキシ基であり、Ｚはベンゾイル基、ナフトイル基、炭素数１〜４のアルキル基で置換されたベンゾイル基又はナフトイル基、及び炭素数２〜６のアシル基からなる群から選ばれるエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｚのうち少なくとも１個はエステル形成構造部位（ｚ１）である。 In structural formula (3), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, or a carbon atom. An benzoyl group or a naphthoyl group substituted with an alkyl group of 1 to 4 and an ester-forming structural site (z1) selected from the group consisting of an acyl group of 2 to 6 carbon atoms, or a hydrogen atom (z2), Z At least one of them is an ester-forming structural site (z1).
構造式（２）で表される化合物の具体例としては、例えば、下記の例示化合物（２−１）〜（２−６）が挙げられる。 Specific examples of the compound represented by Structural Formula (2) include the following Exemplified Compounds (2-1) to (2-6).
構造式（３）で表される化合物の具体例としては、例えば、下記の例示化合物（３−１）〜（３−６）が挙げられる。 Specific examples of the compound represented by Structural Formula (3) include the following Exemplified Compounds (3-1) to (3-6).
活性エステル化合物としては、市販品を用いてもよい。活性エステル化合物の市販品としては、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物として「ＥＸＢ９４５１」、「ＥＸＢ９４６０」、「ＥＸＢ９４６０Ｓ」、「ＨＰＣ−８０００−６５Ｔ」（ＤＩＣ株式会社製）；芳香族構造を含む活性エステル化合物として「ＥＸＢ９４１６−７０ＢＫ」、「ＥＸＢ−８」、「ＥＸＢ−９４２５」（ＤＩＣ株式会社製）；フェノールノボラックのアセチル化物を含む活性エステル化合物として「ＤＣ８０８」（三菱ケミカル株式会社製）；フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「ＹＬＨ１０２６」（三菱ケミカル株式会社製）等が挙げられる。 A commercially available product may be used as the active ester compound. Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Corporation) as aromatic ester compounds containing a dicyclopentadiene type diphenol structure; "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Corporation) as an active ester compound containing a structure; "DC808" (Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac. "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be mentioned as an active ester compound containing a benzoylated product of phenol novolac.
活性エステル化合物は、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 active ester compounds may be used alone or in combination of two or more.
活性エステル化合物のエステル当量は、特に制限されない。成形性、耐リフロー性、電気的信頼性等の各種特性バランスの観点からは、１５０ｇ／ｅｑ〜４００ｇ／ｅｑが好ましく、１７０ｇ／ｅｑ〜３００ｇ／ｅｑがより好ましく、２００ｇ／ｅｑ〜２５０ｇ／ｅｑがさらに好ましい。 The ester equivalent of the active ester compound is not particularly limited. From the viewpoint of various characteristics balance such as moldability, reflow resistance, and electrical reliability, 150 g/eq to 400 g/eq are preferable, 170 g/eq to 300 g/eq are more preferable, and 200 g/eq to 250 g/eq are preferable. More preferable.
活性エステル化合物のエステル当量は、ＪＩＳ Ｋ ００７０：１９９２に準じた方法により測定される値とする。 The ester equivalent of the active ester compound is a value measured by a method according to JIS K 0070:1992.
エポキシ樹脂と活性エステル化合物との当量比（エステル基／エポキシ基）は、硬化物の誘電正接を低く抑える観点からは、０．７５以上が好ましく、０．８０以上がより好ましく、０．８５以上がさらに好ましい。
エポキシ樹脂と活性エステル化合物との当量比（エステル基／エポキシ基）は、活性エステル化合物の未反応分を少なく抑える観点からは、１．１０以下が好ましく、１．０５以下がより好ましく、１．０３以下がさらに好ましい。
The equivalent ratio of the epoxy resin and the active ester compound (ester group/epoxy group) is preferably 0.75 or more, more preferably 0.80 or more, and more preferably 0.85 or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. Is more preferable.
The equivalent ratio (ester group/epoxy group) of the epoxy resin and the active ester compound is preferably 1.10 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted content of the active ester compound. It is more preferably 03 or less.
硬化剤の総量に対する活性エステル化合物の含有率の下限値は、硬化物の誘電正接を低く抑える観点から、８５質量％以上であることが好ましく、８８質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。
硬化剤の総量に対する活性エステル化合物の含有率の上限値は、９８質量％以下であることが好ましく、９７質量％以下であることがより好ましく、９６質量％以下であることがさらに好ましい。
The lower limit of the content of the active ester compound with respect to the total amount of the curing agent is preferably 85% by mass or more, more preferably 88% by mass or more, and 90% by mass from the viewpoint of suppressing the dielectric loss tangent of the cured product. % Or more is more preferable.
The upper limit of the content of the active ester compound relative to the total amount of the curing agent is preferably 98% by mass or less, more preferably 97% by mass or less, and further preferably 96% by mass or less.
（窒素含有フェノール化合物）
本開示の硬化剤は、窒素含有フェノール化合物を含む。
窒素含有フェノール化合物とは、窒素原子を有する基と、ヒドロキシ基を有する芳香族基と、を一分子中に有する化合物を表す。窒素含有フェノール化合物は、１種単独で用いても、２種以上を組み合わせて用いてもよい。
(Nitrogen-containing phenol compound)
The curing agent of the present disclosure comprises a nitrogen-containing phenolic compound.
The nitrogen-containing phenol compound refers to a compound having a group having a nitrogen atom and an aromatic group having a hydroxy group in one molecule. The nitrogen-containing phenol compounds may be used alone or in combination of two or more.
窒素原子を有する基としては、特に制限されず、窒素含有の官能基であってもよく、窒素含有の複素環式化合物から任意の水素原子を一つ除いた基であってもよい。窒素含有の官能基及び窒素含有の複素環式化合物から水素原子を一つ除いた基は、窒素含有フェノール化合物１分子中に、１種の基を単独で用いても、２種以上の基を組み合わせて用いてもよい。 The group having a nitrogen atom is not particularly limited, and may be a nitrogen-containing functional group or a group obtained by removing one arbitrary hydrogen atom from a nitrogen-containing heterocyclic compound. A group obtained by removing one hydrogen atom from a nitrogen-containing functional group and a nitrogen-containing heterocyclic compound has two or more groups even if one group is used alone in one molecule of a nitrogen-containing phenol compound. You may use it in combination.
窒素含有の官能基としては、アミノ基；アミド基；シアノ基等が挙げられる。
窒素含有の複素環式化合物から任意の水素原子を一つ除いた基としては、窒素含有の脂環式化合物、窒素含有の芳香族化合物等から任意の水素原子を一つ除いた基が挙げられる。
窒素含有の脂環式化合物としては、ピロリジン、ピペリジン、モルホリン、ジアザビシクロウンデセン、ジアザビシクロノネン等が挙げられる。
窒素含有の芳香族化合物としては、ピリジン、メラミン、ジアゾール化合物（イミダゾール、ピラゾール等）、オキサジアゾール化合物（１，２，４−オキサジアゾール、１，２，５−オキサジアゾール、１，３，４−オキサジアゾール、１，２，３−オキサジアゾール等）、トリアジン化合物（１，２，３−トリアジン、１，２，４−トリアジン、１，３，５−トリアジン等）、トリアゾール化合物（１，２，３−トリアゾール、１，２，４−トリアゾール等）、ベンゾトリアゾール化合物（１，２，３−ベンゾトリアゾール、１，２，４−ベンゾトリアゾール等）などが挙げられる。
上記の中でも、窒素含有の芳香族化合物は、窒化ケイ素の基板に対する硬化物の接着性をより向上させる観点から、メラミン、トリアゾール化合物及びベンゾトリアゾール化合物からなる群より選ばれる少なくとも１種であることが好ましい。
Examples of the nitrogen-containing functional group include an amino group; an amide group; and a cyano group.
Examples of the group obtained by removing one arbitrary hydrogen atom from a nitrogen-containing heterocyclic compound include a group obtained by removing one arbitrary hydrogen atom from a nitrogen-containing alicyclic compound and a nitrogen-containing aromatic compound. ..
Examples of the nitrogen-containing alicyclic compound include pyrrolidine, piperidine, morpholine, diazabicycloundecene, diazabicyclononene and the like.
Examples of the nitrogen-containing aromatic compound include pyridine, melamine, diazole compounds (imidazole, pyrazole, etc.), oxadiazole compounds (1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3). , 4-oxadiazole, 1,2,3-oxadiazole, etc.), triazine compound (1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, etc.), triazole compound (1,2,3-triazole, 1,2,4-triazole, etc.), benzotriazole compounds (1,2,3-benzotriazole, 1,2,4-benzotriazole, etc.), and the like.
Among the above, the nitrogen-containing aromatic compound is at least one selected from the group consisting of melamine, a triazole compound, and a benzotriazole compound, from the viewpoint of further improving the adhesion of the cured product of the silicon nitride to the substrate. preferable.
ヒドロキシ基を有する芳香族基における芳香族基としては、特に制限されず、適宜公知の芳香族化合物から任意の水素原子を一つ除いた基を適用してよい。
ヒドロキシ基を有する芳香族基における芳香族基としては、ベンゼン、ナフタレン、トリアジン化合物（１，２，３−トリアジン、１，２，４−トリアジン、１，３，５−トリアジン等）などの芳香族化合物から任意の水素原子を一つ除いた基が挙げられる。
上記の中でも、ヒドロキシ基を有する芳香族基における芳香族基は、窒化ケイ素の基板に対する硬化物の接着性をより向上させる観点から、ベンゼンから任意の水素原子を一つ除いた基であることが好ましい。つまり、ヒドロキシ基を有する芳香族基は、フェノール基であることが好ましい。
The aromatic group in the aromatic group having a hydroxy group is not particularly limited, and a group obtained by removing one arbitrary hydrogen atom from a known aromatic compound may be applied as appropriate.
Examples of the aromatic group in the aromatic group having a hydroxy group include aromatic compounds such as benzene, naphthalene, and triazine compounds (1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, etc.). A group obtained by removing one arbitrary hydrogen atom from a compound can be mentioned.
Among the above, the aromatic group in the aromatic group having a hydroxy group is a group obtained by removing one arbitrary hydrogen atom from benzene from the viewpoint of further improving the adhesiveness of the cured product to the substrate of silicon nitride. preferable. That is, the aromatic group having a hydroxy group is preferably a phenol group.
上記の中でも、窒素含有フェノール化合物は、窒素含有の複素環式化合物を含むものであることが好ましい。窒素含有の複素環式化合物は、窒素原子を有する基として含まれていてもよく、また、ヒドロキシ基を有する芳香族基における芳香族基として含まれていてもよい。窒素含有の複素環式化合物は、窒素含有の芳香族化合物を含むものであることがより好ましい。
窒素含有フェノール化合物が窒素含有の複素環式化合物を含むと、これを含む封止用樹脂組成物を硬化物とした際に、窒化ケイ素の基板に対する硬化物の接着性がより向上する傾向にある。
Among the above, the nitrogen-containing phenol compound preferably contains a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound may be contained as a group having a nitrogen atom, or may be contained as an aromatic group in the aromatic group having a hydroxy group. More preferably, the nitrogen-containing heterocyclic compound contains a nitrogen-containing aromatic compound.
When the nitrogen-containing phenol compound contains a nitrogen-containing heterocyclic compound, the adhesiveness of the cured product to the substrate of silicon nitride tends to be further improved when a sealing resin composition containing the same is used as a cured product. ..
窒素含有の複素環式化合物における複素環骨格を構成する窒素原子の数は、特に制限されない。例えば、窒素含有の複素環式化合物は、複素環骨格を構成する原子として、２つ以上の窒素原子を有する複素環式化合物を含むことが好ましく、３つ以上の窒素原子を有する複素環式化合物を含むことがより好ましい。
窒素含有の複素環式化合物が、前記２つ以上の窒素原子を有する複素環式化合物を含むと、これを含む封止用樹脂組成物を硬化物とした際に、窒化ケイ素の基板に対して窒素含有フェノール化合物における複数の窒素原子が協同的に相互作用する傾向にある。そのため、窒化ケイ素の基板に対する硬化物の接着性がより向上する傾向にある。
The number of nitrogen atoms constituting the heterocyclic skeleton in the nitrogen-containing heterocyclic compound is not particularly limited. For example, the nitrogen-containing heterocyclic compound preferably contains a heterocyclic compound having two or more nitrogen atoms as atoms constituting the heterocyclic skeleton, and preferably a heterocyclic compound having three or more nitrogen atoms. It is more preferable to include
When the nitrogen-containing heterocyclic compound contains the heterocyclic compound having two or more nitrogen atoms, when the encapsulating resin composition containing the heterocyclic compound is used as a cured product, the nitrogen-containing heterocyclic compound is added to the substrate of silicon nitride. Multiple nitrogen atoms in nitrogen-containing phenolic compounds tend to interact cooperatively. Therefore, the adhesiveness of the cured product of the silicon nitride to the substrate tends to be further improved.
窒素含有フェノール化合物は、置換基を有していてもよい。
窒素含有フェノール化合物における置換基の位置は、ヒドロキシ基を有する芳香族基におけるヒドロキシ基の水素原子以外の水素原子が置換されているものであれば、特に制限されない。
窒素含有フェノール化合物における置換基としては、特に制限されず、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数７〜２０のアラルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜１４のアリール基、炭素数５〜１４のヘテロアリール基、ハロゲン原子（フッ素原子、ヨウ素原子、塩素原子等）などが挙げられる。置換基におけるアルキル基、アラルキル基及びアルコキシ基は、直鎖状、分岐鎖状、環状のいずれであってもよい。
窒素含有フェノール化合物における置換基が２つ以上存在する場合、隣接する位置に結合する複数の置換基は、互いに結合し、ヒドロキシ基を有する芳香族基における芳香族環、窒素原子を有する複素環式化合物等と、連結して環を形成してもよい。
The nitrogen-containing phenol compound may have a substituent.
The position of the substituent in the nitrogen-containing phenol compound is not particularly limited as long as the hydrogen atom other than the hydrogen atom of the hydroxy group in the aromatic group having a hydroxy group is substituted.
The substituent in the nitrogen-containing phenol compound is not particularly limited, and is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Examples include aryl groups having 6 to 14 carbon atoms, heteroaryl groups having 5 to 14 carbon atoms, and halogen atoms (fluorine atom, iodine atom, chlorine atom, etc.). The alkyl group, aralkyl group and alkoxy group in the substituent may be linear, branched or cyclic.
When there are two or more substituents in the nitrogen-containing phenol compound, the plurality of substituents bonded to adjacent positions are bonded to each other, and the aromatic ring in the aromatic group having a hydroxy group, the heterocyclic group having a nitrogen atom It may combine with a compound or the like to form a ring.
窒素原子を有する基とヒドロキシ基を有する芳香族基とが連結される位置は、特に制限されず、炭素原子上であっても窒素原子上であってもよい。
例えば、窒素原子を有する基がベンゾトリアゾール化合物から任意の水素原子を一つ除いた基である場合、窒素含有フェノール化合物は、ベンゾトリアゾール化合物における２位の窒素原子と、ヒドロキシ基を有する芳香族基における芳香族基上の２位の炭素原子と、が連結された構造であってもよい。
The position at which the nitrogen atom-containing group and the hydroxy group-containing aromatic group are linked is not particularly limited, and may be on a carbon atom or a nitrogen atom.
For example, when the group having a nitrogen atom is a group obtained by removing one arbitrary hydrogen atom from a benzotriazole compound, the nitrogen-containing phenol compound is an aromatic group having a nitrogen atom at the 2-position in the benzotriazole compound and a hydroxy group. It may be a structure in which the carbon atom at the 2-position on the aromatic group in is linked.
窒素原子を有する基とヒドロキシ基を有する芳香族基とは、連結基を介して連結されていてもよく、連結基を介さずに直接連結されていてもよい。窒素原子を有する基とヒドロキシ基を有する芳香族基とが連結基を介して連結される場合、連結基の種類は特に制限されず、炭素数１〜５のアルキレン基等が挙げられる。 The group having a nitrogen atom and the aromatic group having a hydroxy group may be linked via a linking group or may be linked directly without a linking group. When the group having a nitrogen atom and the aromatic group having a hydroxy group are linked via a linking group, the type of the linking group is not particularly limited, and examples thereof include an alkylene group having 1 to 5 carbon atoms.
窒素含有フェノール化合物は、合成品であっても、市販品であってもよい。
窒素含有フェノール化合物の市販品としては、日立化成株式会社製のＨＰＭ−Ｊ３；シプロ化成株式会社製のＳＥＥＳＯＲＢ７０９、ＳＥＥＳＯＲＢ７０７、ＳＥＥＳＯＲＢ７０６、ＳＥＥＳＯＲＢ７０４等；ＢＡＳＦジャパン株式会社製のＴｉｎｕｖｉｎ９２８等；サンケミカル株式会社製のサイアソーブＵＶ１１６４；株式会社ＡＤＥＫＡ社製のＥＰ−３９８０Ｓ、ＬＡ−３１などが挙げられる。
The nitrogen-containing phenol compound may be a synthetic product or a commercially available product.
Commercially available nitrogen-containing phenol compounds include HPM-J3 manufactured by Hitachi Chemical Co., Ltd.; SEESORB709, SEESORB707, SEESORB706, SEESORB704 manufactured by Cypro Chemical Co.; Tinuvin928 manufactured by BASF Japan Co.; Siasorb UV1164; EP-3980S, LA-31 manufactured by ADEKA CORPORATION and the like can be mentioned.
窒素含有フェノール化合物の水酸基当量は、１００ｇ／ｅｑ以上であることが好ましく、１１０ｇ／ｅｑ〜６００ｇ／ｅｑであることがより好ましく、１１５ｇ／ｅｑ〜５５０ｇ／ｅｑであることがさらに好ましい。 The hydroxyl group equivalent of the nitrogen-containing phenol compound is preferably 100 g/eq or more, more preferably 110 g/eq to 600 g/eq, and further preferably 115 g/eq to 550 g/eq.
窒素含有フェノール化合物の水酸基当量が１００ｇ／ｅｑ以上であると、窒素含有フェノール化合物の一分子中に水酸基が過度に存在しない傾向にある。そのため、封止用樹脂組成物を硬化物とした際に、硬化物中の架橋密度が過度に高くなり過ぎず、誘電正接の上昇がより抑制される傾向にある。 When the hydroxyl group equivalent of the nitrogen-containing phenol compound is 100 g/eq or more, hydroxyl groups tend not to be excessively present in one molecule of the nitrogen-containing phenol compound. Therefore, when the encapsulating resin composition is used as a cured product, the crosslink density in the cured product does not become excessively high, and an increase in dielectric loss tangent tends to be further suppressed.
窒素含有フェノール化合物の含有率は、前記硬化剤の総量に対して、１５質量％以下であることが好ましく、１質量％〜１２質量％であることがより好ましく、３質量％〜１０質量％であることがさらに好ましい。
窒素含有フェノール化合物の含有率が、前記硬化剤の総量に対して、１５質量％以下であると、封止用樹脂組成物を硬化物とした際に、前記硬化物における誘電正接の上昇がより抑制される傾向にある。
The content rate of the nitrogen-containing phenol compound is preferably 15% by mass or less, more preferably 1% by mass to 12% by mass, and more preferably 3% by mass to 10% by mass with respect to the total amount of the curing agent. It is more preferable that there is.
When the content of the nitrogen-containing phenol compound is 15% by mass or less with respect to the total amount of the curing agent, the dielectric loss tangent in the cured product is more increased when the encapsulating resin composition is used as a cured product. It tends to be suppressed.
窒素含有フェノール化合物の含有率は、前記活性エステル化合物の総量に対して、１５質量％以下であることが好ましく、１質量％〜１２質量％であることがより好ましく、３質量％〜１０質量％であることがさらに好ましい。
窒素含有フェノール化合物の含有率が、前記活性エステル化合物の総量に対して、１５質量％以下であると、封止用樹脂組成物を硬化物とした際に、前記硬化物における誘電正接の上昇が抑制される傾向にある。一方、窒素含有フェノール化合物の含有率が、前記活性エステル化合物の総量に対して、１質量％以上であると、誘電正接を維持したまま、窒化ケイ素に対する接着性に優れる硬化物が得られる傾向にある。
The content of the nitrogen-containing phenol compound is preferably 15% by mass or less, more preferably 1% by mass to 12% by mass, and more preferably 3% by mass to 10% by mass, based on the total amount of the active ester compound. Is more preferable.
When the content of the nitrogen-containing phenol compound is 15% by mass or less based on the total amount of the active ester compound, when the encapsulating resin composition is used as a cured product, the dielectric loss tangent of the cured product increases. It tends to be suppressed. On the other hand, when the content of the nitrogen-containing phenol compound is 1% by mass or more with respect to the total amount of the active ester compounds, a cured product having excellent adhesiveness to silicon nitride tends to be obtained while maintaining the dielectric loss tangent. is there.
（その他の硬化剤）
硬化剤は、活性エステル化合物及び窒素含有フェノール化合物以外のその他の硬化剤を含んでもよい。その他の硬化剤を含む場合、その他の硬化剤の種類は特に制限されず、封止用樹脂組成物の所望の特性等に応じて選択できる。その他の硬化剤としては、窒素原子を有さないフェノール硬化剤、酸無水物硬化剤、ポリメルカプタン硬化剤、ポリアミノアミド硬化剤、イソシアネート硬化剤、ブロックイソシアネート硬化剤等が挙げられる。
(Other curing agents)
The curing agent may include other curing agents other than the active ester compound and the nitrogen-containing phenol compound. When other curing agent is included, the type of the other curing agent is not particularly limited, and can be selected according to the desired characteristics of the encapsulating resin composition and the like. Examples of other curing agents include phenol curing agents having no nitrogen atom, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like.
窒素原子を有さないフェノール硬化剤として具体的には、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、置換又は非置換のビフェノール等の多価フェノール化合物；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、フェニルフェノール等のフェノール化合物及び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化合物からなる群より選ばれる少なくとも一種のフェノール性化合物と、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等のアルデヒド化合物と、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；上記フェノール性化合物と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル等と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；パラキシリレン変性フェノール樹脂、メタキシリレン変性フェノール樹脂；テルペン変性フェノール樹脂；上記フェノール性化合物と、ジシクロペンタジエンとから共重合により合成されるジシクロペンタジエン型フェノール樹脂及びジシクロペンタジエン型ナフトール樹脂；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；ビフェニル型フェノール樹脂；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド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トリフェニルメタン型フェノール樹脂；これら２種以上を共重合して得たフェノール樹脂などが挙げられる。これらのフェノール硬化剤は、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。 Specific examples of the phenol curing agent having no nitrogen atom include polyphenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A. And at least one phenolic compound selected from the group consisting of phenol compounds such as bisphenol F and phenylphenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde. A novolac-type phenol resin obtained by condensation or co-condensation of a. with an acidic catalyst; a phenol aralkyl resin, a naphthol aralkyl resin, or the like synthesized from the above phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or the like. Aralkyl-type phenol resin; para-xylylene-modified phenol resin, meta-xylylene-modified phenol resin; terpene-modified phenol resin; dicyclopentadiene-type phenol resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization from the above-mentioned phenolic compound and dicyclopentadiene Cyclopentadiene-modified phenol resin; polycyclic aromatic ring-modified phenol resin; biphenyl type phenol resin; obtained by condensing or co-condensing the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst. Triphenylmethane type phenol resin; a phenol resin obtained by copolymerizing two or more of these, and the like. These phenol curing agents may be used alone or in combination of two or more.
その他の硬化剤の官能基当量（フェノール硬化剤の場合は水酸基当量）は、特に制限されない。成形性、耐リフロー性、電気的信頼性等の各種特性バランスの観点からは、７０ｇ／ｅｑ〜１０００ｇ／ｅｑであることが好ましく、８０ｇ／ｅｑ〜５００ｇ／ｅｑであることがより好ましい。 The functional group equivalent of other curing agents (hydroxyl group equivalent in the case of a phenol curing agent) is not particularly limited. From the viewpoint of balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g/eq to 1000 g/eq, more preferably 80 g/eq to 500 g/eq.
その他の硬化剤の官能基当量（フェノール硬化剤の場合は水酸基当量）は、ＪＩＳ Ｋ ００７０：１９９２に準じた方法により測定される値とする。 Functional group equivalents of other curing agents (hydroxyl group equivalents in the case of phenol curing agents) are values measured by a method according to JIS K 0070:1992.
（硬化剤の性質）
硬化剤の軟化点又は融点は、特に制限されない。成形性と耐リフロー性の観点からは、４０℃〜１８０℃であることが好ましく、封止用樹脂組成物の製造時における取扱い性の観点からは、５０℃〜１３０℃であることがより好ましい。
(Properties of curing agent)
The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during production of the resin composition for sealing, it is more preferably 50°C to 130°C. ..
硬化剤の融点又は軟化点は、ＪＩＳ Ｋ ７２３４：１９８６及びＪＩＳ Ｋ ７２３３：１９８６に記載の単一円筒回転粘度計法により測定される値とする。 The melting point or softening point of the curing agent is a value measured by the single cylinder rotational viscometer method described in JIS K 7234:1986 and JIS K 7233:1986.
エポキシ樹脂とすべての硬化剤（活性エステル化合物、窒素含有フェノール化合物及びその他の硬化剤）との当量比、すなわちエポキシ樹脂中の官能基数に対する硬化剤中の官能基数の比（硬化剤中の官能基数／エポキシ樹脂中の官能基数）は、特に制限されない。それぞれの未反応分を少なく抑える観点からは、０．５〜２．０の範囲に設定されることが好ましく、０．６〜１．３の範囲に設定されることがより好ましい。成形性と耐リフロー性の観点からは、０．８〜１．２の範囲に設定されることがさらに好ましい。 Equivalent ratio of epoxy resin to all curing agents (active ester compounds, nitrogen-containing phenolic compounds and other curing agents), that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (the number of functional groups in the curing agent /Number of functional groups in epoxy resin) is not particularly limited. From the viewpoint of suppressing the amount of each unreacted component, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.
［無機充填材］
本開示の封止用樹脂組成物は、無機充填材を含有してもよい。無機充填材の種類は、特に制限されない。具体的には、溶融シリカ、結晶シリカ、ガラス、アルミナ、タルク、クレー、マイカ等の無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。
[Inorganic filler]
The encapsulating resin composition of the present disclosure may contain an inorganic filler. The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as fused silica, crystalline silica, glass, alumina, talc, clay and mica. You may use the inorganic filler which has a flame retardant effect. Examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, complex metal hydroxides such as complex hydroxide of magnesium and zinc, and zinc borate.
無機充填材の中でも、線膨張係数低減の観点からは溶融シリカ等のシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。無機充填材は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。無機充填材の形態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。 Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic fillers may be used alone or in combination of two or more. Examples of the form of the inorganic filler include non-powder, spherical beads, fibers and the like.
無機充填材が粒子状である場合、その平均粒径は、特に制限されない。例えば、平均粒径が０．２μｍ〜１００μｍであることが好ましく、０．５μｍ〜５０μｍであることがより好ましい。平均粒径が０．２μｍ以上であると、封止用樹脂組成物の粘度の上昇がより抑制される傾向がある。平均粒径が１００μｍ以下であると、充填性がより向上する傾向にある。無機充填材の平均粒径は、レーザー散乱回折法粒度分布測定装置により、体積平均粒径（Ｄ５０）として求める。 When the inorganic filler is particulate, the average particle size is not particularly limited. For example, the average particle size is preferably 0.2 μm to 100 μm, more preferably 0.5 μm to 50 μm. When the average particle diameter is 0.2 μm or more, increase in viscosity of the encapsulating resin composition tends to be further suppressed. When the average particle size is 100 μm or less, the filling property tends to be further improved. The average particle diameter of the inorganic filler is determined as a volume average particle diameter (D50) by a laser scattering diffraction particle size distribution measuring device.
封止用樹脂組成物に含まれる無機充填材の含有率は特に制限されない。
無機充填材の含有率は、封止用樹脂組成物中、６０体積％〜９０体積％であることが好ましく、６５体積％〜８５体積％であることがより好ましく、７０体積％〜８０体積％であることがさらに好ましい。
無機充填材の含有率が封止用樹脂組成物中の６０体積％以上であると、硬化物の熱膨張係数、熱伝導率、弾性率等の特性がより向上する傾向にある。
無機充填材の含有率が封止用樹脂組成物中の９０体積％以下であると、封止用樹脂組成物の粘度の上昇が抑制され、流動性がより向上して成形性がより良好になる傾向にある。
The content of the inorganic filler contained in the encapsulating resin composition is not particularly limited.
The content of the inorganic filler in the sealing resin composition is preferably 60% by volume to 90% by volume, more preferably 65% by volume to 85% by volume, and 70% by volume to 80% by volume. Is more preferable.
When the content of the inorganic filler is 60% by volume or more in the encapsulating resin composition, the properties such as the thermal expansion coefficient, thermal conductivity and elastic modulus of the cured product tend to be further improved.
When the content of the inorganic filler is 90% by volume or less in the encapsulating resin composition, the increase in viscosity of the encapsulating resin composition is suppressed, the fluidity is further improved, and the moldability is better. Tends to become.
［各種添加剤］
封止用樹脂組成物は、上述の成分に加えて、以下に例示するカップリング剤、イオン交換体、離型剤、難燃剤、着色剤、応力緩和剤等の各種添加剤を含んでもよい。封止用樹脂組成物は、以下に例示する添加剤以外にも必要に応じて当技術分野で周知の各種添加剤を含んでもよい。
[Various additives]
The encapsulating resin composition may include various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a coloring agent, and a stress relaxation agent, which are exemplified below, in addition to the above components. The encapsulating resin composition may include various additives well known in the art, if necessary, in addition to the additives exemplified below.
（カップリング剤）
封止用樹脂組成物は、カップリング剤を含んでもよい。樹脂成分と無機充填材との接着性を高める観点からは、封止用樹脂組成物はカップリング剤を含むことが好ましい。カップリング剤としては、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、ビニルシラン等のシラン系化合物、チタン系化合物、アルミニウムキレート化合物、アルミニウム／ジルコニウム系化合物などの公知のカップリング剤が挙げられる。
(Coupling agent)
The sealing resin composition may include a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane-based compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, titanium-based compounds, aluminum chelate compounds, aluminum/zirconium-based compounds. ..
封止用樹脂組成物がカップリング剤を含む場合、カップリング剤の量は、無機充填材１００質量部に対して０．０５質量部〜５質量部であることが好ましく、０．１質量部〜２．５質量部であることがより好ましい。カップリング剤の量が無機充填材１００質量部に対して０．０５質量部以上であると、フレームとの接着性がより向上する傾向にある。カップリング剤の量が無機充填材１００質量部に対して５質量部以下であると、パッケージの成形性がより向上する傾向にある。 When the encapsulating resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. More preferably, it is from 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
（イオン交換体）
封止用樹脂組成物は、イオン交換体を含んでもよい。封止用樹脂組成物は、封止される素子を備える半導体装置の耐湿性及び高温放置特性を向上させる観点から、イオン交換体を含むことが好ましい。イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、ハイドロタルサイト化合物、並びにマグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスからなる群より選ばれる少なくとも１種の元素の含水酸化物等が挙げられる。イオン交換体は、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。中でも、下記一般式（Ａ）で表されるハイドロタルサイトが好ましい。
(Ion exchanger)
The encapsulating resin composition may include an ion exchanger. The encapsulating resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and the high-temperature storage property of the semiconductor device including the element to be encapsulated. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples include hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth. The ion exchangers may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.
Ｍｇ（１−Ｘ）ＡｌＸ（ＯＨ）２（ＣＯ３）Ｘ／２・ｍＨ２Ｏ ……（Ａ）
（０＜Ｘ≦０．５、ｍは正の数）
Mg (1-X) Al X (OH) 2 (CO 3) X / 2 · mH 2 O ...... (A)
(0<X≦0.5, m is a positive number)
封止用樹脂組成物がイオン交換体を含む場合、その含有量は、ハロゲンイオン等のイオンを捕捉するのに充分な量であれば特に制限はない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．１質量部〜３０質量部であることが好ましく、１質量部〜１０質量部であることがより好ましい。 When the encapsulating resin composition contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to trap ions such as halogen ions. For example, it is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent).
（離型剤）
封止用樹脂組成物は、成形時における金型との良好な離型性を得る観点から、離型剤を含んでもよい。離型剤は特に制限されず、従来公知のものを用いることができる。具体的には、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。離型剤は、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。
(Release agent)
The encapsulating resin composition may include a release agent from the viewpoint of obtaining good releasability from the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agents may be used alone or in combination of two or more.
封止用樹脂組成物が離型剤を含む場合、その量は樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．０１質量部〜１０質量部が好ましく、０．１質量部〜５質量部がより好ましい。離型剤の量が樹脂成分１００質量部に対して０．０１質量部以上であると、離型性が充分に得られる傾向にある。１０質量部以下であると、より良好な接着性が得られる傾向にある。 When the encapsulating resin composition contains a releasing agent, the amount thereof is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent), More preferably, it is from 5 parts by mass to 5 parts by mass. When the amount of the release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the releasability tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.
（難燃剤）
封止用樹脂組成物は、難燃剤を含んでもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。具体的には、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む有機又は無機の化合物、金属水酸化物等が挙げられる。難燃剤は、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。
(Flame retardants)
The encapsulating resin composition may include a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardants may be used alone or in combination of two or more.
封止用樹脂組成物が難燃剤を含む場合、その量は、所望の難燃効果を得るのに充分な量であれば特に制限されない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して１質量部〜３０質量部であることが好ましく、２質量部〜２０質量部であることがより好ましい。 When the encapsulating resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (the total amount of the epoxy resin and the curing agent).
（着色剤）
封止用樹脂組成物は、着色剤を含んでもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、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。
(Colorant)
The encapsulating resin composition may include a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. The colorants may be used alone or in combination of two or more.
［封止用樹脂組成物の調製方法］
封止用樹脂組成物の調製方法は、特に制限されない。一般的な手法としては、所定の配合量の成分をミキサー等によって十分混合した後、ミキシングロール、押出機等によって溶融混練し、冷却し、粉砕する方法を挙げることができる。より具体的には、例えば、上述した成分の所定量を攪拌及び混合し、予め７０℃〜１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練し、冷却し、粉砕する方法を挙げることができる。
[Method for preparing encapsulating resin composition]
The method for preparing the encapsulating resin composition is not particularly limited. As a general method, there can be mentioned a method in which predetermined amounts of components are sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, cooled, and pulverized. More specifically, for example, a method of stirring and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like preheated to 70° C. to 140° C., cooling, and pulverizing. be able to.
封止用樹脂組成物は、常温常圧下（例えば、２５℃、大気圧下）において固体であることが好ましい。封止用樹脂組成物が固体である場合の形状は特に制限されず、粉状、粒状、タブレット状等が挙げられる。封止用樹脂組成物がタブレット状である場合の寸法及び質量は、パッケージの成形条件に合うような寸法及び質量となるようにすることが取り扱い性の観点から好ましい。 The encapsulating resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25° C. and atmospheric pressure). The shape of the encapsulating resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, and tablets. From the viewpoint of handleability, it is preferable that the size and mass of the encapsulating resin composition in the form of a tablet be such that it meets the molding conditions of the package.
−半導体装置−
本開示の一実施形態である半導体装置は、半導体素子と、前記半導体素子を封止してなる本開示の封止用樹脂組成物の硬化物と、を備える。
-Semiconductor device-
A semiconductor device according to an embodiment of the present disclosure includes a semiconductor element and a cured product of the encapsulating resin composition of the present disclosure obtained by encapsulating the semiconductor element.
半導体装置としては、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、有機基板等の支持部材に、半導体素子（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など）を搭載して得られた素子部を封止用樹脂組成物で封止したものが挙げられる。
より具体的には、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半導体素子の端子部とリード部とをワイヤボンディング、バンプ等で接続した後、封止用樹脂組成物を用いてトランスファ成形等によって、半導体素子を封止した構造を有する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素子を封止用樹脂組成物で封止した構造を有するＴＣＰ（Ｔａｐｅ Ｃａｒｒｉｅｒ Ｐａｃｋａｇｅ）；支持部材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素子を、封止用樹脂組成物で封止した構造を有する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等；裏面に配線板接続用の端子を形成した支持部材の表面に半導体素子を搭載し、バンプ又はワイヤボンディングにより半導体素子と支持部材に形成された配線とを接続した後、封止用樹脂組成物で半導体素子を封止した構造を有するＢＧＡ（Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ Ｓｉｚｅ Ｐａｃｋａｇｅ）、ＭＣＰ（Ｍｕｌｔｉ Ｃｈｉｐ Ｐａｃｋａｇｅ）などが挙げられる。また、プリント配線板においても封止用樹脂組成物を好適に使用することができる。
Semiconductor devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other supporting members, and semiconductor elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, resistors, etc.). , A passive element such as a coil) and the element portion obtained by mounting the element portion with a sealing resin composition.
More specifically, a semiconductor element is fixed on a lead frame, and a terminal portion of the semiconductor element such as a bonding pad and a lead portion are connected by wire bonding, bumps or the like, and then transferred using a sealing resin composition. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), and SOJ (Small Oval) SJ (Small Oval) that have a structure in which a semiconductor element is sealed by molding or the like. ), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and other general resin-encapsulated ICs; a semiconductor device having bumps connected to a tape carrier is encapsulated with a resin composition for encapsulation. TCP (Tape Carrier Package) having: COB (Chip On Package) having a structure in which a semiconductor element connected to wiring formed on a supporting member by wire bonding, flip chip bonding, solder or the like is sealed with a sealing resin composition. Board) module, hybrid IC, multi-chip module, etc.; a semiconductor element is mounted on the surface of a support member having terminals for connecting wiring boards formed on the back surface, and wiring formed on the semiconductor element and the support member by bumps or wire bonding. BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., which have a structure in which a semiconductor element is sealed with a sealing resin composition after connecting. Further, the resin composition for encapsulation can also be preferably used in printed wiring boards.
−半導体装置の製造方法−
本開示の半導体装置の製造方法は、特に制限されず、半導体素子を支持部材上に配置する工程と、前記半導体素子を本開示の封止用樹脂組成物で封止する工程と、を含んで製造されていてもよい。
-Semiconductor Device Manufacturing Method-
The method for manufacturing a semiconductor device of the present disclosure is not particularly limited, and includes a step of disposing a semiconductor element on a supporting member, and a step of sealing the semiconductor element with the sealing resin composition of the present disclosure. It may be manufactured.
上記各工程を実施する方法は特に制限されず、一般的な手法により行うことができる。また、半導体装置の製造に使用する支持部材及び半導体素子の種類は特に制限されず、半導体装置の製造に一般的に用いられる支持部材及び半導体素子を使用できる。 The method for carrying out each of the above steps is not particularly limited, and a general method can be used. Further, the types of the supporting member and the semiconductor element used for manufacturing the semiconductor device are not particularly limited, and the supporting member and the semiconductor element generally used for manufacturing the semiconductor device can be used.
本開示の封止用樹脂組成物を用いて電子部品を封止する方法は特に制限されず、用途に応じて選択することができる。例えば、トランスファー成型等の公知のモールド方法により行うことができる。電子部品装置の例としては、ＩＣ、ＬＳＩ、パワーデバイス等を挙げることができる。 The method of encapsulating an electronic component using the encapsulating resin composition of the present disclosure is not particularly limited and can be selected according to the application. For example, it can be performed by a known molding method such as transfer molding. Examples of electronic component devices include ICs, LSIs, power devices, and the like.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明は下記実施例により限定されるものではない。以下の実施例に示す材料、使用量、割合、処理手順等は、本開示の趣旨を逸脱しない限り適宜変更することができる。なお、特に断りがない限り「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples. Materials, usage amounts, ratios, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present disclosure. In addition, "part" means "part by mass" unless otherwise specified.
−封止用樹脂組成物の調製−
下記に示す成分を表１に示す配合（質量部）で混合し、実施例と比較例の封止用樹脂組成物を調製した。
-Preparation of sealing resin composition-
The components shown below were mixed in the composition (parts by mass) shown in Table 1 to prepare encapsulating resin compositions of Examples and Comparative Examples.
・エポキシ樹脂１：ビフェニルアラルキル型エポキシ樹脂、エポキシ当量２７５ｇ／ｅｑ（日本化薬株式会社、品名「ＮＣ-３０００」）
・エポキシ樹脂２：ビフェニル型エポキシ樹脂、エポキシ当量１９２ｇ／ｅｑ（三菱ケミカル株式会社、品名「ＹＸ−４０００」）
Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 275 g/eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
Epoxy resin 2: biphenyl type epoxy resin, epoxy equivalent 192 g/eq (Mitsubishi Chemical Corporation, product name "YX-4000")
・硬化剤１：ビフェニルアラルキル型フェノール樹脂（水酸基当量１９９ｇ／ｅｑ、エア・ウォーター株式会社、品名「ＨＥ２００Ｃ−１０」）
・硬化剤２：活性エステル化合物（ＤＩＣ株式会社、品名「ＥＸＢ−８」）
・硬化剤３：窒素含有フェノール化合物（メラミン変性フェノール樹脂、水酸基当量１２０ｇ／ｅｑ、日立化成株式会社製、品名「ＨＰＭ−Ｊ３」、複素環骨格を構成する原子として３つの窒素原子を有する。）
・硬化剤４：窒素含有フェノール化合物（ベンゾトリアゾール−フェノール系化合物、水酸基当量３２３ｇ／ｅｑ、シプロ化成株式会社製、品名「ＳＥＥＯＲＢ７０９」、複素環骨格を構成する原子として３つの窒素原子を有する。）
・硬化剤５：窒素含有フェノール化合物（ベンゾトリアゾール−フェノール系化合物、水酸基当量４４１ｇ／ｅｑ、ＢＡＳＦ社製、品名「Ｔｉｎｕｖｉｎ９２８」、複素環骨格を構成する原子として３つの窒素原子を有する。）
・硬化剤６：窒素含有フェノール化合物（トリアゾール−フェノール系化合物、水酸基当量５０９ｇ／ｅｑ、サンケミカル株式会社製、品名「サイアソーブＵＶ１１６４」、複素環骨格を構成する原子として３つの窒素原子を有する。）
-Curing agent 1: Biphenyl aralkyl type phenol resin (hydroxyl equivalent 199 g/eq, Air Water Co., Ltd., product name "HE200C-10")
-Curing agent 2: Active ester compound (DIC Corporation, product name "EXB-8")
-Curing agent 3: Nitrogen-containing phenol compound (melamine-modified phenol resin, hydroxyl group equivalent 120 g/eq, manufactured by Hitachi Chemical Co., Ltd., product name "HPM-J3", having three nitrogen atoms as atoms constituting the heterocyclic skeleton.)
-Curing agent 4: Nitrogen-containing phenol compound (benzotriazole-phenol compound, hydroxyl group equivalent 323 g/eq, manufactured by Cipro Kasei Co., Ltd., product name "SEEORB709", having three nitrogen atoms as atoms constituting a heterocyclic skeleton.)
Curing agent 5: nitrogen-containing phenol compound (benzotriazole-phenol compound, hydroxyl equivalent 441 g/eq, manufactured by BASF, product name "Tinuvin 928", having three nitrogen atoms as atoms constituting the heterocyclic skeleton)
-Curing agent 6: Nitrogen-containing phenol compound (triazole-phenol compound, hydroxyl group equivalent 509 g/eq, manufactured by Sun Chemical Co., product name "Ciasorb UV1164", having three nitrogen atoms as atoms constituting the heterocyclic skeleton.)
・硬化促進剤：トリフェニルホスフィンのｐ−ベンゾキノン付加物
・カップリング剤：Ｎ−フェニル−３−アミノプロピルトリメトキシシラン（信越化学工業社、品名「ＫＢＭ−５７３」）
・離型剤：モンタン酸エステルワックス（クラリアントジャパン株式会社、品名「ＨＷ−Ｅ」）
・着色剤：カーボンブラック（三菱ケミカル株式会社、品名「ＭＡ６００」）
・無機充填材：シリカフィラ（デンカ株式会社、品名「ＦＢ−９４５４ＦＣ」、平均粒径１８μｍ）
-Curing accelerator: p-benzoquinone adduct of triphenylphosphine-Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Release agent: montanic acid ester wax (Clariant Japan KK, product name "HW-E")
・Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
Inorganic filler: Silica filler (Denka Corporation, product name "FB-9454FC", average particle size 18 μm)
［封止用樹脂組成物の硬化物における評価］
表１に示す組成比で配合した各例の封止用樹脂組成物について、以下試験項目で評価した。評価結果を下記表１に示す。なお、硬化性樹脂組成物の成形は、明記しない限りトランスファ成形機により、金型温度１７５℃、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を１７５℃で６時間の条件で行った。
[Evaluation of cured product of sealing resin composition]
The following test items evaluated the encapsulating resin composition of each example blended in the composition ratio shown in Table 1. The evaluation results are shown in Table 1 below. The curable resin composition was molded by a transfer molding machine at a mold temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, unless otherwise specified. If necessary, post-curing was performed at 175° C. for 6 hours.
（比誘電率及び誘電正接）
封止用樹脂組成物をトランスファ成形機に仕込み、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で成形し、後硬化を１７５℃で６時間行い、棒状の硬化物（縦０．８ｍｍ、横０．６ｍｍ、厚さ９０ｍｍ）を得た。この硬化物を試験片として、空洞共振器（株式会社関東電子応用開発、「ＣＰ５６１」）及びネットワーク・アナライザー（キーサイトテクノロジー社、「ＰＮＡ Ｅ８３６４Ｂ」）を用いて、温度２５±１℃下、２０ＧＨｚでの比誘電率と誘電正接を測定した。
(Relative permittivity and loss tangent)
The sealing resin composition was charged into a transfer molding machine, molded under the conditions of a mold temperature of 180° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and post-curing was performed at 175° C. for 6 hours to obtain a rod-shaped cured product ( A length of 0.8 mm, a width of 0.6 mm, and a thickness of 90 mm) were obtained. Using this cured product as a test piece, using a cavity resonator (Kanto Electronics Co., Ltd. development, “CP561”) and a network analyzer (Keysight Technologies, Inc., “PNA E8364B”), at a temperature of 25±1° C., 20 GHz. The relative permittivity and the dielectric loss tangent were measured.
（熱時硬度）
各例で調製したエポキシ樹脂組成物を上記条件で直径５０ｍｍ×厚み３ｍｍの円板に成形し、成形後直ちにショアＤ型硬度計（高分子計器株式会社、アスカー、タイプＤデュロメータ）を用いて測定した。
(Hardness when heated)
The epoxy resin composition prepared in each example was molded into a disk having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, it was measured using a Shore D type hardness meter (Kobunshi Keiki Co., Ltd., Asker, type D durometer). did.
（２６０℃せん断接着力 （Ｐｄ−ＰＰＦ））
硬化性樹脂組成物を上記条件で、窒化ケイ素の基板上に、底面直径４ｍｍ、上面直径３ｍｍ、高さ４ｍｍのサイズで成形し、上記条件で後硬化した。その後、ボンドテスター（ノードソン・アドバンスト・テクノロジー株式会社、シリーズ４０００）を用い、銅板の温度を２６０℃に保ちながら、せん断速度５０μｍ／ｓでせん断接着力（ＭＰａ）を求めた。
(260°C shear adhesive strength (Pd-PPF))
The curable resin composition was molded on a silicon nitride substrate under the above conditions to have a bottom surface diameter of 4 mm, a top surface diameter of 3 mm, and a height of 4 mm, and post-cured under the above conditions. Then, using a bond tester (Nordson Advanced Technology Co., Ltd., Series 4000), the shear adhesive strength (MPa) was determined at a shear rate of 50 μm/s while maintaining the temperature of the copper plate at 260°C.
表１に示すように、実施例の封止用樹脂組成物は、比較例の封止用樹脂組成物に比べ、２０ＧＨｚにおける誘電正接が低く維持されたまま、窒化ケイ素の基板に対する接着性を高くすることがわかった。 As shown in Table 1, the encapsulating resin compositions of Examples have higher adhesion of silicon nitride to the substrate while maintaining a low dielectric loss tangent at 20 GHz, as compared with the encapsulating resin compositions of Comparative Examples. I found out that
Claims (8)
活性エステル化合物及び窒素含有フェノール化合物を含む硬化剤と、
を含有する封止用樹脂組成物。 Epoxy resin,
A curing agent containing an active ester compound and a nitrogen-containing phenol compound,
A resin composition for encapsulation containing:
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018232976A JP7238374B2 (en) | 2018-12-12 | 2018-12-12 | Encapsulating resin composition and semiconductor device |
| JP2022163504A JP2022186772A (en) | 2018-12-12 | 2022-10-11 | Encapsulating resin composition and semiconductor device |
| JP2024065758A JP2024091762A (en) | 2018-12-12 | 2024-04-15 | Resin composition for transfer molding and semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018232976A JP7238374B2 (en) | 2018-12-12 | 2018-12-12 | Encapsulating resin composition and semiconductor device |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022163504A Division JP2022186772A (en) | 2018-12-12 | 2022-10-11 | Encapsulating resin composition and semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020094130A true JP2020094130A (en) | 2020-06-18 |
| JP7238374B2 JP7238374B2 (en) | 2023-03-14 |
Family
ID=71086312
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018232976A Active JP7238374B2 (en) | 2018-12-12 | 2018-12-12 | Encapsulating resin composition and semiconductor device |
| JP2022163504A Pending JP2022186772A (en) | 2018-12-12 | 2022-10-11 | Encapsulating resin composition and semiconductor device |
| JP2024065758A Pending JP2024091762A (en) | 2018-12-12 | 2024-04-15 | Resin composition for transfer molding and semiconductor device |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022163504A Pending JP2022186772A (en) | 2018-12-12 | 2022-10-11 | Encapsulating resin composition and semiconductor device |
| JP2024065758A Pending JP2024091762A (en) | 2018-12-12 | 2024-04-15 | Resin composition for transfer molding and semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JP7238374B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012246367A (en) * | 2011-05-26 | 2012-12-13 | Dic Corp | Thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and buildup film |
| JP2012251133A (en) * | 2011-05-10 | 2012-12-20 | Ajinomoto Co Inc | Resin composition |
| JP2016008280A (en) * | 2014-06-25 | 2016-01-18 | 味の素株式会社 | Resin composition |
| JP2016089112A (en) * | 2014-11-10 | 2016-05-23 | 味の素株式会社 | Resin composition |
| JP2017171925A (en) * | 2017-04-20 | 2017-09-28 | 味の素株式会社 | Resin composition |
| JP2018111827A (en) * | 2009-11-26 | 2018-07-19 | 味の素株式会社 | Epoxy resin composition |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4984385B2 (en) * | 2004-10-18 | 2012-07-25 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
| JP4697521B2 (en) * | 2005-03-02 | 2011-06-08 | 日立化成工業株式会社 | Method for manufacturing metal foil, metal foil using the same, metal foil with resin, metal-clad laminate, printed wiring board, and printed wiring board manufacturing method |
| JP5196256B2 (en) * | 2008-08-28 | 2013-05-15 | Ｄｉｃ株式会社 | Epoxy resin composition and cured product thereof |
| JP5282643B2 (en) * | 2008-11-12 | 2013-09-04 | 東亞合成株式会社 | Adhesive composition, coverlay film and flexible copper-clad laminate using the same |
| JP2010143988A (en) * | 2008-12-17 | 2010-07-01 | Toagosei Co Ltd | Adhesive composition and cover-lay film and flexible copper-clad laminate using the same |
| TW201817807A (en) * | 2012-05-31 | 2018-05-16 | 日商味之素股份有限公司 | Resin composition |
| JP6028587B2 (en) * | 2013-01-18 | 2016-11-16 | 味の素株式会社 | Resin composition |
| WO2014157446A1 (en) * | 2013-03-29 | 2014-10-02 | 日本ゼオン株式会社 | Curable epoxy composition, film, multilayer film, prepreg, laminate, cured product, and composite body |
| JP6408847B2 (en) * | 2014-09-30 | 2018-10-17 | 積水化学工業株式会社 | Resin composition |
| JP6436173B2 (en) * | 2014-10-27 | 2018-12-12 | 日本ゼオン株式会社 | Curable epoxy composition, and film, laminated film, prepreg, laminate, cured product, and composite obtained using the same |
| JP2016125042A (en) * | 2015-01-08 | 2016-07-11 | 横浜ゴム株式会社 | Adhesive composition, light control panel comprising the same, method for producing the same, and optical imaging device |
| US20190031822A1 (en) * | 2016-03-28 | 2019-01-31 | Sekisui Chemical Co., Ltd. | Resin composition and multilayer substrate |
| JP6939687B2 (en) * | 2018-04-16 | 2021-09-22 | 味の素株式会社 | Resin composition |
-
2018
- 2018-12-12 JP JP2018232976A patent/JP7238374B2/en active Active
-
2022
- 2022-10-11 JP JP2022163504A patent/JP2022186772A/en active Pending
-
2024
- 2024-04-15 JP JP2024065758A patent/JP2024091762A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018111827A (en) * | 2009-11-26 | 2018-07-19 | 味の素株式会社 | Epoxy resin composition |
| JP2012251133A (en) * | 2011-05-10 | 2012-12-20 | Ajinomoto Co Inc | Resin composition |
| JP2012246367A (en) * | 2011-05-26 | 2012-12-13 | Dic Corp | Thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and buildup film |
| JP2016008280A (en) * | 2014-06-25 | 2016-01-18 | 味の素株式会社 | Resin composition |
| JP2016089112A (en) * | 2014-11-10 | 2016-05-23 | 味の素株式会社 | Resin composition |
| JP2017171925A (en) * | 2017-04-20 | 2017-09-28 | 味の素株式会社 | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2024091762A (en) | 2024-07-05 |
| JP2022186772A (en) | 2022-12-15 |
| JP7238374B2 (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2024026589A (en) | Sealing resin composition, electronic component device, and manufacturing method of electronic component device | |
| JP2022101587A (en) | Epoxy resin composition, curable resin composition, and electronic part device | |
| JP2024091744A (en) | Encapsulating resin composition, electronic component device, and method for producing electronic component device | |
| JP7388160B2 (en) | Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device | |
| JP7452028B2 (en) | Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device | |
| JP7635709B2 (en) | Encapsulating resin composition, electronic component device, and method for producing electronic component device | |
| JP7491223B2 (en) | Encapsulating resin composition, electronic component device, and method for producing electronic component device | |
| TWI854956B (en) | Epoxy resin composition and electronic component apparatus | |
| JP2020152825A (en) | Resin composition for sealing, electronic component device, and production method for electronic component device | |
| WO2020129249A1 (en) | Resin composition for sealing and electronic component device | |
| WO2020129248A1 (en) | Sealing resin composition and electronic component device | |
| JP2020122071A (en) | Sealing resin composition, electronic component device, and method for manufacturing same | |
| JP7396290B2 (en) | Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device | |
| JP7238374B2 (en) | Encapsulating resin composition and semiconductor device | |
| JP2021113253A (en) | Resin composition for sealing, electronic component equipment, and manufacturing method of electronic component equipment | |
| JP2022011184A (en) | Encapsulating resin composition and electronic component equipment | |
| JP2021084980A (en) | Sealing resin composition, electronic component device and method for producing electronic component device | |
| JP7487596B2 (en) | Encapsulating resin composition, electronic component device, and method for producing electronic component device | |
| JPWO2020065873A1 (en) | Manufacturing method of sealing resin composition, electronic component device and electronic component device | |
| JP2000129094A (en) | Epoxy resin molding material for sealing and electronic component device | |
| JP2004346226A (en) | Epoxy resin molding material for sealing, and electronic component apparatus | |
| JP2024081463A (en) | Sealing resin composition, electronic component device and method for producing electronic component device | |
| JP2022021901A (en) | A resin composition for encapsulation, an electronic component device, and a method for manufacturing the electronic component device. | |
| JP2024081462A (en) | Sealing resin composition, electronic component device and method for producing electronic component device | |
| JP2024081461A (en) | Sealing resin composition, electronic component device and method for producing electronic component device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20211008 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220804 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220809 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221011 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230131 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230213 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7238374 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |