JP4481672B2 - Fine particles for semiconductor sealing material and resin composition for semiconductor sealing - Google Patents
Fine particles for semiconductor sealing material and resin composition for semiconductor sealing Download PDFInfo
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- JP4481672B2 JP4481672B2 JP2004030902A JP2004030902A JP4481672B2 JP 4481672 B2 JP4481672 B2 JP 4481672B2 JP 2004030902 A JP2004030902 A JP 2004030902A JP 2004030902 A JP2004030902 A JP 2004030902A JP 4481672 B2 JP4481672 B2 JP 4481672B2
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- 239000004065 semiconductor Substances 0.000 title claims description 59
- 239000011342 resin composition Substances 0.000 title claims description 47
- 239000010419 fine particle Substances 0.000 title claims description 30
- 238000007789 sealing Methods 0.000 title claims description 14
- 239000003566 sealing material Substances 0.000 title description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 98
- 229920000620 organic polymer Polymers 0.000 claims description 40
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 230000003287 optical effect Effects 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000005538 encapsulation Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Chemical group 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000005033 polyvinylidene chloride Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000002245 particle Substances 0.000 description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 35
- 239000006185 dispersion Substances 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 35
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 239000000377 silicon dioxide Substances 0.000 description 28
- 125000000962 organic group Chemical group 0.000 description 19
- -1 polyethylene Polymers 0.000 description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 15
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008393 encapsulating agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 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 4
- 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 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000002040 relaxant effect Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- XEGLBSZEAJDYBS-UHFFFAOYSA-N 3-tert-butylperoxy-1-(tert-butylperoxymethyl)-1,5-dimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(COOC(C)(C)C)C1 XEGLBSZEAJDYBS-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- 229960001950 benzethonium chloride Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、半導体素子、特に光半導体素子の封止材に含有させる微粒子、および、該微粒子と樹脂とを含んでなる半導体封止用樹脂組成物に関する。
以下、本明細書において、樹脂組成物とは、最終商品である封止材のほか、封止材になる前の中間品をも指すことがある。
The present invention relates to a fine particle to be contained in a sealing element of a semiconductor element, particularly an optical semiconductor element, and a semiconductor sealing resin composition comprising the fine particle and a resin.
Hereinafter, in the present specification, the resin composition may refer to an intermediate product before becoming a sealing material in addition to a sealing material that is a final product.
従来から、ＬＳＩ、発光ダイオード（ＬＥＤ）、有機エレクトロルミネッセンス（有機ＥＬ）、太陽電池（ｐ型半導体、ｎ型半導体）等の半導体素子を封止する際に用いられる封止材の材料としては、通常、各種樹脂が用いられ、特に、光半導体に用いる封止材には透明樹脂が用いられている。該透明樹脂としては、一般に、ビスフェノール型エポキシ樹脂や脂環式エポキシ樹脂等が用いられている。封止材として供される樹脂組成物は、さらに、酸無水物系などの硬化剤をも含有してなり、硬化反応により硬化され、樹脂組成物硬化体（以下、単に「硬化体」と言うことがある。）として光半導体素子を封止する。
ところで、半導体素子の封止においては、前記樹脂組成物の硬化時の硬化収縮に起因する、あるいは、樹脂と半導体素子との線膨張係数の差（硬化反応時の温度から室温に戻る際の冷却収縮時に顕著である。）に起因する、半導体素子と硬化体との接着界面における歪みにより内部応力が発生するという問題がある。具体的には、この内部応力によって、半導体素子が劣化し、例えば、ＬＥＤなどの光半導体素子であればその輝度が大きく低下するという問題が生じる。そこで、このような内部応力を緩和・低減させるため、シリカ粒子等の線膨張係数の小さい無機系微粒子を新たな材料として添加することにより、硬化体の線膨張係数を小さくし、半導体素子の線膨張係数に近似させる方法が既に提案されている（例えば、特許文献１参照。）。
Conventionally, as a sealing material used for sealing semiconductor elements such as LSI, light emitting diode (LED), organic electroluminescence (organic EL), solar cell (p-type semiconductor, n-type semiconductor), Usually, various resins are used, and in particular, a transparent resin is used as a sealing material used for an optical semiconductor. As the transparent resin, generally, a bisphenol type epoxy resin, an alicyclic epoxy resin, or the like is used. The resin composition used as the sealing material further contains a curing agent such as an acid anhydride, is cured by a curing reaction, and is cured as a resin composition (hereinafter simply referred to as “cured body”). The optical semiconductor element is sealed.
By the way, in the sealing of the semiconductor element, it is caused by curing shrinkage at the time of curing of the resin composition, or a difference in linear expansion coefficient between the resin and the semiconductor element (cooling when returning from the temperature at the curing reaction to room temperature). There is a problem that internal stress is generated due to the distortion at the bonding interface between the semiconductor element and the cured body, which is caused by the constriction). Specifically, the semiconductor element deteriorates due to the internal stress. For example, in the case of an optical semiconductor element such as an LED, there is a problem that the luminance is greatly reduced. Therefore, in order to relieve and reduce such internal stress, by adding inorganic fine particles having a small linear expansion coefficient, such as silica particles, as a new material, the linear expansion coefficient of the cured body can be reduced, and the wire of the semiconductor element can be reduced. A method of approximating the expansion coefficient has already been proposed (for example, see Patent Document 1).
ところが、上記目的で添加したシリカ粒子は、樹脂（例えば、エポキシ樹脂）との親和性が低く、樹脂組成物中で容易に凝集し大きな凝集体（二次粒子）となりやすく、例えば、光半導体素子の封止においては、この凝集体と樹脂との界面で光が乱反射し、光透過性が著しく低下する（白濁化する）という問題がある。
そこで、本発明の解決しようとする課題は、上述した半導体素子と硬化体との接触界面における内部応力を小さくすることができるとともに、樹脂組成物中での分散性に優れ、さらに、例えば光半導体素子の封止に用いた場合であれば、高い光透過性と十分な輝度を確保することのできる硬化体を得させる、半導体封止材用微粒子、および、半導体封止用樹脂組成物を提供することにある。 Therefore, the problem to be solved by the present invention is that the internal stress at the contact interface between the semiconductor element and the cured body can be reduced, and the dispersibility in the resin composition is excellent. Provided is a semiconductor encapsulant fine particle and a semiconductor encapsulating resin composition that can provide a cured product capable of ensuring high light transmittance and sufficient luminance if used for device encapsulation. There is to do.
本発明者は、上記課題を解決するため鋭意検討を行った。その過程において、半導体（特に光半導体）封止材用微粒子としてシリカ粒子（シリカ系無機微粒子）を採用するにあたり、その表面に有機基を結合させ、該表面の少なくとも一部に有するようにした微粒子、および、該微粒子を含む樹脂組成物を用いると、上記課題を一挙に解決できることを見出し、それを確認して、本発明を完成した。
すなわち、本発明にかかる半導体封止材用微粒子は、シリカ粒子の表面の少なくとも一部に有機基が結合してなるものであることを特徴とする。
また、本発明にかかる半導体封止用樹脂組成物は、樹脂と上記本発明にかかる半導体封止材用微粒子とを含むものであることを特徴とする。
The present inventor has intensively studied to solve the above problems. In the process, when adopting silica particles (silica-based inorganic fine particles) as fine particles for semiconductor (especially optical semiconductor) encapsulant, fine particles that have organic groups bonded to the surface and have at least a part of the surface. And when the resin composition containing the fine particles was used, it was found that the above-mentioned problems could be solved at once, and it was confirmed that the present invention was completed.
That is, the fine particles for a semiconductor encapsulant according to the present invention are characterized in that an organic group is bonded to at least a part of the surface of the silica particles.
Moreover, the resin composition for semiconductor encapsulation according to the present invention comprises a resin and the fine particles for semiconductor encapsulation according to the present invention.
本発明によれば、半導体素子と硬化体との接触界面における内部応力を小さくすることができるとともに、樹脂組成物中での分散性に優れ、さらに、例えば光半導体素子の封止に用いた場合であれば、高い光透過性と十分な輝度を確保することのできる硬化体を得させる、半導体封止材用微粒子、および、半導体封止用樹脂組成物を提供することができる。 According to the present invention, the internal stress at the contact interface between the semiconductor element and the cured body can be reduced, the dispersibility in the resin composition is excellent, and, for example, when used for sealing an optical semiconductor element Then, the fine particle for semiconductor sealing materials and the resin composition for semiconductor sealing which can obtain the hardening body which can ensure high light transmittance and sufficient brightness | luminance can be provided.
以下、本発明にかかる半導体封止材用微粒子および半導体封止用樹脂組成物について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
本発明にかかる半導体封止材用微粒子（以下、「本発明の微粒子」と言うことがある。）は、粒子本体となるシリカ粒子の表面の少なくとも一部に有機基が結合してなる微粒子である。
ここで、シリカ粒子（シリカ系無機微粒子）とは、下記一般式：
−Ｓｉ−Ｏ−
で表される構造単位を繰り返し単位とする３次元架橋構造を有する粒子である。
Hereinafter, the fine particles for semiconductor encapsulating material and the resin composition for encapsulating a semiconductor according to the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and the present invention is not limited to the following examples. Modifications can be made as appropriate without departing from the spirit of the invention.
The fine particles for a semiconductor encapsulant according to the present invention (hereinafter sometimes referred to as “fine particles of the present invention”) are fine particles in which an organic group is bonded to at least a part of the surface of the silica particles as the particle body. is there.
Here, the silica particles (silica-based inorganic fine particles) are the following general formula:
-Si-O-
The particle | grains which have a three-dimensional crosslinked structure which makes the structural unit represented by a repeating unit.
上記有機基としては、特に限定はされないが、例えば、有機ポリマー残基やアルコキシ基、アルキル基、アルケニル基、アリール基等が好ましく挙げられる。これら有機基は、シリカ粒子表面への結合にあたり、１種のみ用いられても２種以上併用されていてもよく、特に限定はされない。
上記有機ポリマー残基としては、例えば、（メタ）アクリル系ポリマー残基、エポキシ系ポリマー残基、スチレン系ポリマー残基、酢酸ビニル系ポリマー残基、ポリエチレンやポリプロピレン等のオレフィン系ポリマー残基、ポリ塩化ビニル残基、ポリ塩化ビニリデン残基、ポリエチレンテレフタレート等のポリエステル残基、および、これらの共重合体のポリマー残基や、アミノ基、エポキシ基、ヒドロキシ基およびカルボキシル基等の官能基で一部変性させた（置換した）ポリマー残基等が挙げられるが、なかでも（メタ）アクリル系ポリマー残基やエポキシ系ポリマー残基が、半導体封止材用の樹脂との親和性が高い点で好ましい。なお、これら有機ポリマー残基は、シリカ粒子表面への結合にあたり、１種のみ用いられても２種以上併用されていてもよく、特に限定はされない。
Although it does not specifically limit as said organic group, For example, an organic polymer residue, an alkoxy group, an alkyl group, an alkenyl group, an aryl group etc. are mentioned preferably. These organic groups may be used alone or in combination of two or more for bonding to the surface of the silica particles, and are not particularly limited.
Examples of the organic polymer residue include (meth) acrylic polymer residues, epoxy polymer residues, styrene polymer residues, vinyl acetate polymer residues, olefin polymer residues such as polyethylene and polypropylene, poly Polyester residues such as vinyl chloride residue, polyvinylidene chloride residue, polyethylene terephthalate, etc., and polymer residues of these copolymers and some functional groups such as amino group, epoxy group, hydroxy group and carboxyl group Modified (substituted) polymer residues and the like can be mentioned. Among them, (meth) acrylic polymer residues and epoxy polymer residues are preferable in terms of high affinity with a resin for semiconductor encapsulant. . These organic polymer residues may be used alone or in combination of two or more for bonding to the surface of the silica particles, and are not particularly limited.
上記有機ポリマー残基の分子量、形状、組成および官能基の有無については、特に限定はなく、任意の有機ポリマー残基を使用することができる。
有機ポリマー残基の形状については、例えば、直鎖状、分岐状および架橋構造等の任意の形状のものを使用することができる。
上記アルコキシ基としては、例えば、下記一般式（１）：
−（ＯＲ） （１）
（但し、Ｒは、炭素数１から２０のアルキル基を表す。）
で表されるアルコキシ基からなる群より選ばれる少なくとも１つであることが好ましいが、なかでも、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基およびｎ−ブトキシ基等が、半導体封止材用の樹脂との親和性が高い点で好ましい。なお、これらアルコキシ基は、シリカ粒子表面への結合にあたり、１種のみ用いられても２種以上併用されていてもよく、特に限定はされない。
The molecular weight, shape, composition, and presence / absence of a functional group of the organic polymer residue are not particularly limited, and any organic polymer residue can be used.
About the shape of an organic polymer residue, the thing of arbitrary shapes, such as linear, branched, and a crosslinked structure, can be used, for example.
Examples of the alkoxy group include the following general formula (1):
-(OR) (1)
(However, R represents an alkyl group having 1 to 20 carbon atoms.)
It is preferable that at least one selected from the group consisting of alkoxy groups represented by the formula: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, etc. It is preferable in terms of high affinity with the resin for the material. These alkoxy groups may be used alone or in combination of two or more for bonding to the silica particle surface, and are not particularly limited.
上記アルキル基、アルケニル基、アリール基としては、例えば、下記一般式（２）：
−Ｒａ （２）
（但し、Ｒａは、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数６〜２０のアリール基のいずれかを表す。）
で表される群から選ばれる少なくとも１つであることが好ましいが、なかでも、メチル基、エチル基、ｎ−プロピル基、ビニル基、γ−メタクリロキシプロピル基、γ−アクリロキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基、γ−グリシドキシプロピル基、フェニル基等は、前述した親和性を特に高めることができ、シリカ粒子どうしの凝集を効果的に抑制できるために好ましい。なお、これらアルキル基、アルケニル基、アリール基は、シリカ粒子表面への結合にあたり、１種のみ用いられても２種以上併用されていてもよく、限定はされない。
Examples of the alkyl group, alkenyl group, and aryl group include the following general formula (2):
-R a (2)
(However, R a is optionally substituted alkyl group having 1 to 20 carbon atoms, which may have a substituent alkenyl group having 2 to 20 carbon atoms, substituted Or any of aryl groups having 6 to 20 carbon atoms.
It is preferably at least one selected from the group represented by the formula: Among them, a methyl group, ethyl group, n-propyl group, vinyl group, γ-methacryloxypropyl group, γ-acryloxypropyl group, β -(3,4-epoxycyclohexyl) ethyl group, γ-glycidoxypropyl group, phenyl group and the like are preferable because the above-described affinity can be particularly enhanced and aggregation of silica particles can be effectively suppressed. . These alkyl groups, alkenyl groups, and aryl groups may be used alone or in combination of two or more for bonding to the silica particle surface, and are not limited.
本発明の微粒子において、その表面に結合している有機基の含有割合は、特に限定はされないが、本発明の微粒子の粒子本体となるシリカ粒子に対して０．０１〜２００重量％であることが好ましく、より好ましくは０．０５〜１５０重量％、さらに好ましくは０．１〜１００重量％である。上記有機基の含有割合が０．０１重量％未満であると、半導体封止材用の樹脂中でのシリカ粒子の分散安定性が不十分になり、二次凝集が発生するおそれがあり、２００重量％を超えると、シリカ粒子の内部応力の緩和・減少の効果が十分に発揮されないおそれがある。
上記有機基として有機ポリマー残基が結合している場合、該有機ポリマー残基の含有割合は、本発明の微粒子の粒子本体となるシリカ粒子に対して１〜２００重量％であることが好ましく、より好ましくは５〜１５０重量％、さらに好ましくは１０〜１００重量％である。上記有機ポリマー残基の含有割合が１重量％未満であると、半導体封止材用の樹脂中でのシリカ粒子の分散安定性が不十分になり、二次凝集が発生するおそれがあり、２００重量％を超えると、シリカ粒子の内部応力の緩和・減少の効果が十分に発揮されないおそれがある。
In the fine particles of the present invention, the content ratio of the organic group bonded to the surface thereof is not particularly limited, but is 0.01 to 200% by weight with respect to the silica particles serving as the particle main body of the fine particles of the present invention. Is more preferable, 0.05 to 150% by weight, still more preferably 0.1 to 100% by weight. When the organic group content is less than 0.01% by weight, the dispersion stability of the silica particles in the resin for semiconductor encapsulant becomes insufficient, and secondary aggregation may occur. If it exceeds wt%, the effect of relaxing or reducing the internal stress of the silica particles may not be sufficiently exhibited.
When an organic polymer residue is bonded as the organic group, the content ratio of the organic polymer residue is preferably 1 to 200% by weight with respect to the silica particles serving as the particle body of the fine particles of the present invention, More preferably, it is 5-150 weight%, More preferably, it is 10-100 weight%. When the content of the organic polymer residue is less than 1% by weight, the dispersion stability of the silica particles in the resin for semiconductor encapsulant becomes insufficient, and secondary aggregation may occur. If it exceeds wt%, the effect of relaxing or reducing the internal stress of the silica particles may not be sufficiently exhibited.
上記有機基としてアルコキシ基が結合している場合、該アルコキシ基の含有割合は、本発明の微粒子の粒子本体となるシリカ粒子に対して０．０１〜１００重量％であることが好ましく、より好ましくは０．０５〜８０重量％、さらに好ましくは０．１〜５０重量％である。アルコキシ基の含有割合が、０．０１重量％未満であると、半導体封止材用の樹脂中でのシリカ粒子の分散安定性が不十分になり、二次凝集が発生するおそれがあり、１００重量％を超えると、シリカ粒子の内部応力の緩和・減少の効果が十分に発揮されないおそれがある。
上記有機基としてアルキル基、アルケニル基、アリール基から選ばれる少なくとも１種が結合している場合、該アルキル基、アルケニル基、アリール基の含有割合は、本発明の微粒子の粒子本体となるシリカ粒子に対して０．０１〜１００重量％であることが好ましく、より好ましくは０．０５〜８０重量％、さらに好ましくは０．１〜５０重量％である。アルキル基、アルケニル基、アリール基の含有割合が、０．０１重量％未満であると、半導体封止材用の樹脂中でのシリカ粒子の分散安定性が不十分になり、二次凝集が発生するおそれがあり、１００重量％を超えると、シリカ粒子の内部応力の緩和・減少の効果が十分に発揮されないおそれがある。
When an alkoxy group is bonded as the organic group, the content of the alkoxy group is preferably 0.01 to 100% by weight, more preferably based on the silica particles that are the particle body of the fine particles of the present invention. Is 0.05 to 80% by weight, more preferably 0.1 to 50% by weight. If the content of the alkoxy group is less than 0.01% by weight, the dispersion stability of the silica particles in the resin for semiconductor encapsulant becomes insufficient, and secondary aggregation may occur. If it exceeds wt%, the effect of relaxing or reducing the internal stress of the silica particles may not be sufficiently exhibited.
When at least one selected from an alkyl group, an alkenyl group, and an aryl group is bonded as the organic group, the content ratio of the alkyl group, alkenyl group, and aryl group is a silica particle that is the particle body of the fine particles of the present invention. The content is preferably 0.01 to 100% by weight, more preferably 0.05 to 80% by weight, and still more preferably 0.1 to 50% by weight. When the content ratio of the alkyl group, alkenyl group and aryl group is less than 0.01% by weight, the dispersion stability of the silica particles in the resin for semiconductor encapsulant becomes insufficient, and secondary aggregation occurs. If the amount exceeds 100% by weight, the effect of relaxing or reducing the internal stress of the silica particles may not be sufficiently exhibited.
本発明の微粒子は、例えば、下記１）〜３）で説明する方法等により調製することができる。以下では、シリカ粒子の表面に結合させる有機基の種類に応じて説明するが、他の有機基も結合させてよいとする。
１） 有機基として有機ポリマー残基が結合している場合。具体的には、以下の２つがある。
１−１）１分子当たりに少なくとも１個のポリシロキサン基を有し、かつ、該ポリシロキサン基中に少なくとも１つのＳｉ−ＯＲ２基（Ｒ２は、水素原子、または、アルキル基およびアシル基から選ばれる置換されていてもよい基であり、Ｓｉ−ＯＲ２基を１分子中に複数有する場合、複数のＲ２は互いに同一であっても異なっていてもよい。）を有する少なくとも１種の有機ポリマーを、該有機ポリマーのみで、あるいは、加水分解可能なアルコキシシランとともに、加水分解・縮合して得る方法。
The fine particles of the present invention can be prepared, for example, by the method described in the following 1) to 3). Below, although it demonstrates according to the kind of organic group couple | bonded with the surface of a silica particle, suppose that another organic group may be couple | bonded.
1) When an organic polymer residue is bonded as an organic group. Specifically, there are the following two.
1-1) It has at least one polysiloxane group per molecule, and at least one Si-OR 2 group (R 2 is a hydrogen atom or an alkyl group and an acyl group in the polysiloxane group) And when there are a plurality of Si-OR 2 groups in one molecule, a plurality of R 2 may be the same or different from each other. The organic polymer obtained by hydrolysis / condensation with the organic polymer alone or with a hydrolyzable alkoxysilane.
１−２）アルコキシシランのゾルゲル反応により合成されたシリカ粒子の表面シラノール基に、該シラノール基と反応し得る官能基（例えば、アルコキシ基、ヒドロキシ基、カルボキシル基、アミノ基およびエポキシ基等）を１分子当たりに少なくとも１個有する少なくとも１種の有機ポリマーを、結合させて得る方法。
２） 有機基としてアルコキシ基が結合している場合。具体的には、以下の２つがある。
２−１）アルコキシシランのゾルゲル反応により合成されたシリカ粒子の表面シラノール基をアルコール置換して得る方法。
1-2) Functional groups (for example, alkoxy group, hydroxy group, carboxyl group, amino group, and epoxy group) that can react with the silanol group are added to the surface silanol group of the silica particles synthesized by the sol-gel reaction of alkoxysilane. A method wherein at least one organic polymer having at least one molecule per molecule is bonded.
2) When an alkoxy group is bonded as an organic group. Specifically, there are the following two.
2-1) A method in which the surface silanol groups of silica particles synthesized by sol-gel reaction of alkoxysilane are substituted with alcohol.
２−２）ケイ酸塩から生成したシリカ粒子の表面シラノール基をアルコキシ基で置換されたオルガノゾル（例えば、日産化学社製のメタノールシリカゾルやＩＰＡ−シリカゾル等。）を用いて得る方法。
３） 有機基としてアルキル基、アルケニル基、アリール基から選ばれる少なくとも１種が結合している場合。具体的には、以下の２つがある。
３−１）アルコキシシランとして、下記一般式（３）：
Ｒｂ ｎＳｉ（ＯＲｃ）４−ｎ （３）
（但し、Ｒｂは、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数６〜２０のアリール基から選ばれる少なくとも１種の有機基を表す。Ｒｃは、水素原子、炭素数１〜５のアルキル基、炭素数２〜５のアシル基から選ばれる少なくとも１種の有機基を表す。ｎは１〜３の整数である。）
で示されるアルコキシシランを必須成分として少なくとも１種以上用いて加水分解・縮合反応して得る方法。
2-2) A method obtained by using organosol (for example, methanol silica sol or IPA-silica sol manufactured by Nissan Chemical Co., Ltd.) in which the surface silanol groups of silica particles generated from silicate are substituted with alkoxy groups.
3) When at least one selected from an alkyl group, an alkenyl group, and an aryl group is bonded as an organic group. Specifically, there are the following two.
3-1) As alkoxysilane, the following general formula (3):
R b n Si (OR c ) 4-n (3)
(However, Rb has a C1-C20 alkyl group which may have a substituent, a C2-C20 alkenyl group which may have a substituent, and a substituent. It represents at least one organic group selected from aryl groups having 6 to 20 carbon atoms, and R c is at least selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Represents one organic group, n is an integer from 1 to 3)
A method obtained by hydrolysis / condensation reaction using at least one alkoxysilane represented by formula (1) as an essential component.
３−２）アルコキシシランのゾルゲル反応により合成されたシリカ粒子の表面シラノール基と上記一般式（３）で示されるアルコキシシランを反応させて、アルキル基、アルケニル基、アリール基から選ばれる少なくとも１種を導入する方法。
上記１）〜３）の調製方法において、シリカ粒子を得る場合等に用いるアルコキシシランとしては、下記一般式（４）：
Ｒｂ ｎＳｉ（ＯＲｃ）４−ｎ （４）
（但し、Ｒｂは、置換基を有していてもよい炭素数１〜２０のアルキル基、置換基を有していてもよい炭素数２〜２０のアルケニル基、置換基を有していてもよい炭素数６〜２０のアリール基から選ばれる少なくとも１種の有機基を表す。Ｒｃは、水素原子、炭素数１〜５のアルキル基、炭素数２〜５のアシル基から選ばれる少なくとも１種の有機基を表す。ｎは０〜３の整数である。）
で示されるアルコキシシランが用いられ、例えば、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、テトラアセトキシシラン等の、上記一般式（４）でｎ＝０の４官能性シラン；メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン、メチルトリアセトキシシラン、ビニルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３，４−エポキシブチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等の、上記一般式（４）でｎ＝１の３官能性シラン；ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン等の、上記一般式（４）でｎ＝２の２官能性シラン；トリメチルメトキシシラン、トリメチルフェノキシシラン等の、上記一般式（４）でｎ＝３の１官能性シラン；などを挙げることができる。これらは１種のみ用いられても２種以上併用されていてもよく、特に限定はされない。
3-2) At least one selected from an alkyl group, an alkenyl group, and an aryl group by reacting the surface silanol group of silica particles synthesized by the sol-gel reaction of alkoxysilane with the alkoxysilane represented by the general formula (3). How to introduce.
In the preparation methods of 1) to 3) above, the alkoxysilane used for obtaining silica particles or the like is represented by the following general formula (4):
R b n Si (OR c ) 4-n (4)
(However, Rb has a C1-C20 alkyl group which may have a substituent, a C2-C20 alkenyl group which may have a substituent, and a substituent. It represents at least one organic group selected from aryl groups having 6 to 20 carbon atoms, and R c is at least selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Represents one organic group, n is an integer from 0 to 3)
For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraacetoxysilane, and the like, a tetrafunctional silane in which n = 0 in the above general formula (4); Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, methyltriacetoxysilane, vinyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrieth Trifunctional silane of the above general formula (4) and n = 1, such as xysilane; Bifunctional silane of the above general formula (4) and n = 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxysilane A monofunctional silane in which n = 3 in the general formula (4), such as trimethylmethoxysilane and trimethylphenoxysilane; These may be used alone or in combination of two or more, and are not particularly limited.
また、シリカ粒子を得る場合においては、アルコキシシランの他に、封止材用樹脂硬化体の屈折率を調整することを目的として、他の金属アルコキシド、例えば、アルコキシチタン、アルコキシアルミニウムおよびアルコキシジルコニウム等を導入して用いることもでき、特に、光半導体素子の封止用途を考慮する場合は、上記他の金属酸化物等は、上記硬化体の透明性を失わない範囲で導入することが好ましい。
上記シリカ粒子の形状は、例えば、球状、針状、板状、鱗片状および破砕粒状など、特に限定はされない。
本発明の微粒子は、その平均粒子径が０．１μｍ以下であることが好ましく、より好ましくは０．０８μｍ以下、さらに好ましくは０．０６μｍ以下である。上記平均粒子径が０．１μｍを超える場合は、樹脂組成物を硬化させて得られる硬化体の光透過性が著しく低下する（白化する）おそれがある。
In the case of obtaining silica particles, in addition to alkoxysilane, other metal alkoxides such as alkoxytitanium, alkoxyaluminum, alkoxyzirconium and the like are used for the purpose of adjusting the refractive index of the cured resin for sealing material. In particular, when considering the sealing application of the optical semiconductor element, it is preferable to introduce the other metal oxides and the like as long as the transparency of the cured body is not lost.
The shape of the silica particles is not particularly limited, for example, a spherical shape, a needle shape, a plate shape, a scale shape, and a crushed particle shape.
The fine particles of the present invention preferably have an average particle size of 0.1 μm or less, more preferably 0.08 μm or less, and still more preferably 0.06 μm or less. When the average particle diameter exceeds 0.1 μm, the light transmittance of a cured product obtained by curing the resin composition may be significantly reduced (whitened).
本発明の微粒子は、各種半導体のなかでも、特に光半導体のための封止材用の材料として好適に用いることができる。
本発明にかかる半導体封止用樹脂組成物（以下、「本発明の樹脂組成物」と称することがある。）は、樹脂と上記本発明にかかる半導体封止材用微粒子とを含んでなる樹脂組成物である。
本発明の樹脂組成物は、以下に詳述するような各種成分により構成されてなるものであって、通常、液状、粉末状、あるいは粉末状のものを打錠したタブレット状などとして取り扱われる。
The fine particles of the present invention can be suitably used as a sealing material for optical semiconductors among various semiconductors.
The resin composition for semiconductor encapsulation according to the present invention (hereinafter sometimes referred to as “resin composition of the present invention”) is a resin comprising the resin and the fine particles for semiconductor encapsulation according to the present invention. It is a composition.
The resin composition of the present invention is composed of various components as described in detail below, and is usually handled as a liquid, a powder, or a tablet obtained by tableting a powder.
一般に、半導体封止用の樹脂組成物に用い得る上記樹脂としては、エポキシ樹脂、ポリイミド樹脂、アクリル樹脂およびフェノール樹脂等が挙げられるが、なかでも、半導体が光半導体である場合の樹脂組成物には、透明性を有する樹脂（透明樹脂）が用いられ、該透明樹脂としてはエポキシ樹脂が好ましい。
上記エポキシ樹脂としては、ビスフェノール型エポキシ樹脂、脂環式エポキシ樹脂およびノボラック型エポキシ樹脂等が、優れた透明性を有するため好ましく用いられるが、光半導体封止用としては、ビスフェノールＡ型エポキシ樹脂および脂環式エポキシ樹脂がより好ましい。脂環式エポキシ樹脂としては、アリシリックジエポキシアセタール、アリシリックジエポキシアジペート、アリシリックジエポキシカルボキシレートおよびビニルシクロヘキセンジオキシド等が好ましく用いられる。上記列挙したエポキシ樹脂を使用する場合は、必要に応じて、その他のエポキシ樹脂（上記列挙した以外のエポキシ樹脂）を併用することもできる。その他のエポキシ樹脂を用いる場合は、通常、使用するエポキシ樹脂全体の５０重量％以下で配合して用いることが好ましい。
In general, examples of the resin that can be used for a resin composition for semiconductor encapsulation include epoxy resin, polyimide resin, acrylic resin, and phenol resin. Among them, the resin composition in the case where the semiconductor is an optical semiconductor is used. Is a transparent resin (transparent resin), and the transparent resin is preferably an epoxy resin.
As the epoxy resin, a bisphenol type epoxy resin, an alicyclic epoxy resin, a novolac type epoxy resin, and the like are preferably used because they have excellent transparency. An alicyclic epoxy resin is more preferable. Preferred examples of the alicyclic epoxy resin include alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide. When using the epoxy resins listed above, other epoxy resins (epoxy resins other than those listed above) can be used in combination as necessary. When other epoxy resins are used, it is usually preferable to use them by blending at 50% by weight or less of the entire epoxy resin to be used.
上記エポキシ樹脂としては、一般には、エポキシ当量１００〜１０００、軟化点１２０℃以下のものを使用することが好ましく、常温で液状であるものを用いても、常温で固形のものを用いてもよく、特に限定はされない。
本発明の樹脂組成物において、上記本発明の微粒子の配合割合は、特に限定はされないが、本発明の樹脂組成物全体に対して１０〜８０重量％であることが好ましく、より好ましくは２０〜７０重量％、さらに好ましくは３０〜６０重量％である。上記配合割合が１０％重量未満であると、硬化体の線膨張係数が十分小さくならず、内部応力の緩和・減少の効果が小さくなるおそれがあり、８０重量％を超えると、線膨張係数は小さくなるが、硬化体が硬脆くなるおそれがある。
In general, it is preferable to use an epoxy resin having an epoxy equivalent of 100 to 1000 and a softening point of 120 ° C. or lower. The epoxy resin may be liquid at room temperature or solid at room temperature. There is no particular limitation.
In the resin composition of the present invention, the blending ratio of the fine particles of the present invention is not particularly limited, but is preferably 10 to 80% by weight, more preferably 20 to 20% by weight with respect to the entire resin composition of the present invention. 70% by weight, more preferably 30 to 60% by weight. If the blending ratio is less than 10% by weight, the linear expansion coefficient of the cured product may not be sufficiently small, and the effect of relaxation / reduction of internal stress may be reduced. If the blending ratio exceeds 80% by weight, the linear expansion coefficient is Although it becomes small, there exists a possibility that a hardening body may become hard and brittle.
本発明の樹脂組成物においては、上記樹脂および本発明の微粒子以外に、例えば該樹脂の種類に応じて、硬化剤や硬化触媒を適宜配合することができる。
上記硬化剤としては、例えば、酸無水物系硬化剤、アミン系硬化剤、フェノール系硬化剤などを用いることができ、なかでも上記樹脂がエポキシ樹脂である場合は、酸無水物系硬化剤を用いることが好ましい。
酸無水物系硬化剤としては、分子量１４０〜２００程度のものが好ましく、具体的には、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸等の無色ないし淡黄色の酸無水物が挙げられる。これらは１種のみ用いても２種以上を併用してもよい。
In the resin composition of the present invention, in addition to the resin and the fine particles of the present invention, for example, a curing agent or a curing catalyst can be appropriately blended depending on the type of the resin.
As the curing agent, for example, an acid anhydride curing agent, an amine curing agent, a phenol curing agent, and the like can be used. In particular, when the resin is an epoxy resin, an acid anhydride curing agent is used. It is preferable to use it.
As the acid anhydride-based curing agent, those having a molecular weight of about 140 to 200 are preferable, and specifically, colorless or colorless such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like. Pale yellow acid anhydride is mentioned. These may be used alone or in combination of two or more.
硬化剤を用いる場合、その配合割合は、特に限定されないが、上記樹脂１００重量部に対して４０〜２００重量部であることが好ましく、より好ましくは５０〜１５０重量部、さらに好ましくは６０〜１００重量部である。硬化剤の配合割合が、上記範囲外であると、半導体封止用の樹脂組成物を十分に硬化させることができないおそれがある。
上記硬化触媒としては、例えば、三級アミン、四級アンモニウム塩、イミダゾール化合物、ホウ素化合物および有機金属錯塩などを用いることができ、なかでも上記樹脂がエポキシ樹脂である場合は、イミダゾール化合物が好ましい。硬化触媒を用いる場合、その配合割合は特に限定はされず、適宜必要量設定すればよい。
In the case of using a curing agent, the blending ratio is not particularly limited, but it is preferably 40 to 200 parts by weight, more preferably 50 to 150 parts by weight, and still more preferably 60 to 100 parts by weight based on 100 parts by weight of the resin. Parts by weight. If the blending ratio of the curing agent is out of the above range, the resin composition for semiconductor encapsulation may not be sufficiently cured.
As the curing catalyst, for example, a tertiary amine, a quaternary ammonium salt, an imidazole compound, a boron compound, an organometallic complex salt, or the like can be used. In particular, when the resin is an epoxy resin, an imidazole compound is preferable. When a curing catalyst is used, the blending ratio is not particularly limited, and a necessary amount may be set appropriately.
本発明の樹脂組成物は、上記各種成分（樹脂、微粒子、硬化剤および硬化触媒）以外にも、必要に応じて、染料、変性剤、変色防止剤、離型剤、反応性あるいは非反応性希釈剤などの従来公知の他の添加成分を適宜配合してなるものであってもよい。なお、これら他の添加成分の配合量は、本発明の樹脂組成物の特性が著しく損なわれない程度であれば特に限定はされない。
本発明の樹脂組成物を用いて半導体素子（特に光半導体素子）を封止するにあたっては、その方法・手段は特に限定はされず、例えば、トランスファー成形や注型塔の公知のモールド方法などを挙げることができ、半導体素子（特に光半導体素子）を本発明の樹脂組成物の硬化体からなる封止樹脂層によって効果的に封止した半導体装置（特に光半導体装置）が得られる。
The resin composition of the present invention is not limited to the above-described various components (resin, fine particles, curing agent, and curing catalyst), and if necessary, a dye, a modifier, a discoloration inhibitor, a release agent, a reactive or non-reactive property. It may be formed by appropriately blending other conventionally known additive components such as a diluent. In addition, the compounding quantity of these other additional components will not be specifically limited if it is a grade which the characteristic of the resin composition of this invention is not impaired remarkably.
In sealing a semiconductor element (especially an optical semiconductor element) using the resin composition of the present invention, the method and means thereof are not particularly limited. For example, a known molding method for transfer molding or casting tower is used. A semiconductor device (particularly an optical semiconductor device) in which a semiconductor element (particularly an optical semiconductor element) is effectively sealed with a sealing resin layer made of a cured product of the resin composition of the present invention can be obtained.
本発明の樹脂組成物は、各種半導体素子のなかでも、特に光半導体素子の封止用として好適に用いることができ、また、封止の必要な、あるいは、封止しておくことが好ましい各種装置および基材部分等にも好適に用いることができる。 Among the various semiconductor elements, the resin composition of the present invention can be suitably used particularly for sealing an optical semiconductor element, and various kinds that require or are preferably sealed. It can be suitably used for the apparatus and the base material part.
以下に、実施例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下では、便宜上、「リットル」を単に「Ｌ」と、「重量％」を「ｗｔ％」と記すことがある。
〔合成例１〕 重合性ポリシロキサン（Ｓ−１）の合成
撹拌機、温度計および冷却管を備えた３００ｍＬの四つ口フラスコに、テトラメトキシシラン１４４．５ｇ、γ−メタクリロキシプロピルトリメトキシシラン２３．６ｇ、水１９ｇ、メタノール３０．０ｇ、アンバーリスト１５（ローム・アンド・ハース・ジャパン社製の陽イオン交換樹脂）５．０ｇを入れ、６５℃で２時間撹拌し、反応させた。反応混合物を室温まで冷却した後、冷却管に代えて、蒸留塔およびこれに接続させた冷却管および流出口を設け、常圧下、８０℃まで２時間かけて昇温し、メタノールが流出しなくなるまで同温度で保持した。さらに、２７ｋＰａの圧力下、９０℃の温度で、メタノールが流出しなくなるまで同温度で保持し、反応をさらに進行させた。再び、室温まで冷却した後、アンバーリスト１５を濾別し、数平均分子量が１，８００の重合性ポリシロキサン（Ｓ−１）を得た。
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. Hereinafter, for convenience, “liter” may be simply referred to as “L”, and “wt%” may be referred to as “wt%”.
[Synthesis Example 1] Synthesis of polymerizable polysiloxane (S-1) In a 300 mL four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 g of tetramethoxysilane and γ-methacryloxypropyltrimethoxysilane 23.6 g, 19 g of water, 30.0 g of methanol, and 5.0 g of Amberlyst 15 (cation exchange resin manufactured by Rohm and Haas Japan) were added and stirred at 65 ° C. for 2 hours for reaction. After the reaction mixture is cooled to room temperature, a distillation column, a cooling tube connected to the distillation column and an outlet are provided in place of the cooling tube, and the temperature is raised to 80 ° C. over 2 hours under normal pressure, so that methanol does not flow out. Until the same temperature. Further, the reaction was allowed to proceed further under a pressure of 27 kPa at a temperature of 90 ° C. until the methanol no longer flowed out. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain polymerizable polysiloxane (S-1) having a number average molecular weight of 1,800.
〔合成例２〕 有機ポリマー（Ｐ−１）の合成
撹拌機、滴下口、温度計、冷却管およびＮ２ガス導入口を備えた１Ｌのフラスコに、有機溶剤としてトルエン２００ｇを入れ、Ｎ２ガスを導入し、撹拌しながらフラスコ内温を１１０℃まで加熱した。次いで、合成例１で得られた重合性ポリシロキサン（Ｓ−１）２０ｇ、メチルメタクリレート１６０ｇ、２−ヒドロキシエチルメタクリレート２０ｇ、２，２’−アゾビスイソブチロニトリル６ｇを混合した溶液を滴下口より２時間かけて滴下した。滴下後も同温度で１時間撹拌し続けた後、１，１’−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロへキサン０．４ｇを３０分おきに２回添加し、さらに２時間加熱して共重合を行い、数平均分子量が１２，０００の有機ポリマー（Ｐ−１）のトルエン溶液を得た。
[Synthesis Example 2] Synthesis of organic polymer (P-1) In a 1 L flask equipped with a stirrer, a dripping port, a thermometer, a condenser tube and an N 2 gas inlet, 200 g of toluene as an organic solvent was added, and N 2 gas was added. The flask was heated to 110 ° C. with stirring. Next, a solution prepared by mixing 20 g of the polymerizable polysiloxane (S-1) obtained in Synthesis Example 1, 160 g of methyl methacrylate, 20 g of 2-hydroxyethyl methacrylate, and 6 g of 2,2′-azobisisobutyronitrile was added to the dropping port. More dropwise over 2 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 0.4 g of 1,1′-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane was added twice every 30 minutes. The mixture was further heated for 2 hours for copolymerization to obtain a toluene solution of an organic polymer (P-1) having a number average molecular weight of 12,000.
〔合成例３〕 有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）の合成
撹拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１Ｌの四つ口フラスコに、酢酸ブチル４００ｇ、メタノール１００ｇを入れておき、内温を２０℃に調整した。次いで、フラスコ内を撹拌しながら、合成例２で得られた有機ポリマー（Ｐ−１）のトルエン溶液１２ｇ、テトラメトキシシラン６０ｇ、酢酸ブチル４０ｇの混合液（原料液Ａ）を滴下口イから、２５％アンモニア水４０ｇ、メタノール４０ｇの混合液（原料液Ｂ）を滴下口ロから、１時間かけて滴下した。滴下後、同温度で２時間撹拌を続けた。その後、１５ｋＰａの圧力下、フラスコ内の温度を１００℃まで昇温し、アンモニア、水、メタノール、トルエンおよび酢酸ブチルを固形分濃度が３０ｗｔ％になるまで留去することにより、有機ポリマー残基結合シリカ粒子が酢酸ブチルに分散した分散体（Ｚ−１）を得た。該粒子の平均粒子径は０．０３０μｍであった。
[Synthesis Example 3] Synthesis of organic polymer residue-bonded silica particle dispersion (Z-1) In a 1 L four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B), and a thermometer. In addition, 400 g of butyl acetate and 100 g of methanol were added, and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed solution (raw material liquid A) of 12 g of the toluene solution of the organic polymer (P-1) obtained in Synthesis Example 2, 60 g of tetramethoxysilane, and 40 g of butyl acetate was added from the dropping port i. A mixed liquid (raw material liquid B) of 40 g of 25% aqueous ammonia and 40 g of methanol was added dropwise over 1 hour from the dropping port. After dropping, stirring was continued for 2 hours at the same temperature. Thereafter, the temperature in the flask is raised to 100 ° C. under a pressure of 15 kPa, and ammonia, water, methanol, toluene and butyl acetate are distilled off until the solid content concentration becomes 30 wt%, thereby bonding organic polymer residues. A dispersion (Z-1) in which silica particles were dispersed in butyl acetate was obtained. The average particle diameter of the particles was 0.030 μm.
〔合成例４〕 シリカ粒子分散体（Ｚ−２）の合成
撹拌機、２つの滴下口（滴下口イおよび滴下口ロ）、温度計を備えた１Ｌの四つ口フラスコに、酢酸ブチル４００ｇ、メタノール１００ｇを入れておき、内温を２０℃に調整した。ついでフラスコ内を撹拌しながら、酢酸ブチル溶液４０ｇ、テトラメトキシシラン６０ｇ、酢酸ブチル４０ｇの混合液（原料液Ａ）を滴下口イから、２５％アンモニア水４０ｇ、メタノール４０ｇの混合液（原料液Ｂ）を滴下口ロから、１時間かけて滴下した。滴下後、同温度で２時間撹拌を続けた。その後、１５ｋＰａの圧力下、フラスコ内の温度を１００℃まで昇温し、アンモニア、水、メタノールおよび酢酸ブチルを固形分濃度が３０ｗｔ％になるまで留去することにより、シリカ粒子が酢酸ブチルに分散した分散体（Ｚ−２）を得た。該粒子の平均粒子径は０．０３５μｍであった。
[Synthesis Example 4] Synthesis of Silica Particle Dispersion (Z-2) Into a 1 L four-necked flask equipped with a stirrer, two dropping ports (dropping port A and dropping port B), a thermometer, 400 g of butyl acetate, 100 g of methanol was added and the internal temperature was adjusted to 20 ° C. Next, while stirring the inside of the flask, a mixed liquid (raw material liquid A) of 40 g of butyl acetate solution, 60 g of tetramethoxysilane, and 40 g of butyl acetate was added from the dripping port a. ) Was added dropwise from the dropping port over 1 hour. After dropping, stirring was continued for 2 hours at the same temperature. Thereafter, the temperature in the flask is raised to 100 ° C. under a pressure of 15 kPa, and ammonia, water, methanol and butyl acetate are distilled off until the solid content concentration becomes 30 wt%, whereby silica particles are dispersed in butyl acetate. A dispersion (Z-2) was obtained. The average particle diameter of the particles was 0.035 μm.
〔合成例５〕 シラノール基と反応可能な有機ポリマー（Ｐ−２）の合成
撹拌機、滴下口、温度計、冷却管およびＮ２ガス導入口を備えた１Ｌのフラスコに、有機溶剤としてトルエン２００ｇを入れ、Ｎ２ガスを導入し、撹拌しながらフラスコ内温を１１０℃まで加熱した。ついでγ−メタクリロキシプロピルトリメトキシシラン２０ｇ、メチルメタクリレート１８０ｇ、２，２’−アゾビスイソブチロニトリル６ｇを混合した溶液を滴下口より２時間かけて滴下した。滴下後も同温度で１時間撹拌し続けた後、１，１’−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロへキサン０．４ｇを３０分おきに２回添加し、さらに２時間加熱して共重合を行い、数平均分子量が１３，０００の有機ポリマー（Ｐ−２）のトルエン溶液を得た。
[Synthesis Example 5] Synthesis of organic polymer (P-2) capable of reacting with silanol group In a 1 L flask equipped with a stirrer, a dropping port, a thermometer, a cooling pipe and an N 2 gas inlet, 200 g of toluene as an organic solvent And N 2 gas was introduced, and the temperature inside the flask was heated to 110 ° C. while stirring. Then, a solution prepared by mixing 20 g of γ-methacryloxypropyltrimethoxysilane, 180 g of methyl methacrylate, and 6 g of 2,2′-azobisisobutyronitrile was dropped from the dropping port over 2 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 0.4 g of 1,1′-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane was added twice every 30 minutes. The mixture was further heated for 2 hours for copolymerization to obtain a toluene solution of an organic polymer (P-2) having a number average molecular weight of 13,000.
〔合成例６〕 有機ポリマー残基結合シリカ粒子分散体（Ｚ−３）の合成
撹拌機、温度計および冷却管を備えた３００ｍＬの四つ口フラスコに、合成例４で得られたシリカ粒子分散体（Ｚ−２）１００ｇと、合成例５で得られた有機ポリマー（Ｐ−２）のトルエン溶液１０ｇを入れ、１１０℃で２時間加熱した。
その後、１５ｋＰａの圧力下、フラスコ内の温度を１００℃で、メタノール、トルエンおよび酢酸ブチルを固形分濃度が３０ｗｔ％になるまで留去することにより、有機ポリマー残基結合シリカ粒子が酢酸ブチルに分散した分散体（Ｚ−３）を得た。該粒子の平均粒子径は０．０３４μｍであった。
[Synthesis Example 6] Synthesis of organic polymer residue-bonded silica particle dispersion (Z-3) Silica particle dispersion obtained in Synthesis Example 4 was placed in a 300 mL four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. The body (Z-2) 100g and the toluene solution 10g of the organic polymer (P-2) obtained by the synthesis example 5 were put, and it heated at 110 degreeC for 2 hours.
Then, under a pressure of 15 kPa, the temperature in the flask is 100 ° C., and methanol, toluene and butyl acetate are distilled off until the solid content concentration becomes 30 wt%, whereby the organic polymer residue-bonded silica particles are dispersed in butyl acetate. A dispersion (Z-3) was obtained. The average particle diameter of the particles was 0.034 μm.
〔合成例７〕 シラノール基と反応可能な有機ポリマー（Ｐ−３）の合成
撹拌機、滴下口、温度計、冷却管およびＮ２ガス導入口を備えた１Ｌのフラスコに、有機溶剤としてトルエン２００ｇを入れ、Ｎ２ガスを導入し、撹拌しながらフラスコ内温を１１０℃まで加熱した。次いで、メチルメタクリレート１９０ｇ、２−ヒドロキシエチルメタクリレート２０ｇ、２，２’−アゾビスイソブチロニトリル６ｇを混合した溶液を滴下口より２時間かけて滴下した。滴下後も同温度で１時間撹拌し続けた後、１，１’−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロへキサン０．４ｇを３０分おきに２回添加し、さらに２時間加熱して共重合を行い、数平均分子量が１３，５００の有機ポリマー（Ｐ−３）のトルエン溶液を得た。
[Synthesis Example 7] Synthesis of an organic polymer (P-3) capable of reacting with a silanol group 200 g of toluene as an organic solvent was added to a 1 L flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and an N 2 gas inlet. And N 2 gas was introduced, and the temperature inside the flask was heated to 110 ° C. while stirring. Next, a solution in which 190 g of methyl methacrylate, 20 g of 2-hydroxyethyl methacrylate, and 6 g of 2,2′-azobisisobutyronitrile were mixed was dropped from the dropping port over 2 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 0.4 g of 1,1′-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane was added twice every 30 minutes. The mixture was further heated for 2 hours for copolymerization to obtain a toluene solution of an organic polymer (P-3) having a number average molecular weight of 13,500.
〔合成例８〕 有機ポリマー残基結合シリカ粒子分散体（Ｚ−４）の合成
撹拌機、温度計および冷却管を備えた３００ｍＬの四つ口フラスコに、合成例４で得られたシリカ粒子分散体（Ｚ−２）１００ｇと、合成例７で得られた有機ポリマー（Ｐ−３）のトルエン溶液１０ｇを入れ、１１０℃で２時間加熱した。その後、１５ｋＰａの圧力下、フラスコ内の温度を１００℃で、水、メタノール、トルエンおよび酢酸ブチルを固形分濃度が３０ｗｔ％になるまで留去することにより、有機ポリマー残基結合シリカ粒子が酢酸ブチルに分散した分散体（Ｚ−４）を得た。該粒子の平均粒子径は０．０３８μｍであった。
[Synthesis Example 8] Synthesis of organic polymer residue-bonded silica particle dispersion (Z-4) Silica particle dispersion obtained in Synthesis Example 4 was placed in a 300 mL four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. The body (Z-2) 100g and the toluene solution 10g of the organic polymer (P-3) obtained by the synthesis example 7 were put, and it heated at 110 degreeC for 2 hours. Then, under a pressure of 15 kPa, the temperature in the flask is 100 ° C., and water, methanol, toluene and butyl acetate are distilled off until the solid content concentration becomes 30 wt%. Dispersion (Z-4) dispersed in was obtained. The average particle size of the particles was 0.038 μm.
〔合成例９〕 アルコキシ基結合シリカ粒子分散体（Ｚ−５）の合成
１Ｌのナス型フラスコに、日産化学社製のメタノールシリカゾル（平均粒子径０．０２０μｍ、メタノール溶液３０％）１５０ｇと酢酸ブチル１５０ｇを投入した後、ロータリーエバポレーターを使って、１５ｋＰａの圧力下、フラスコ内の温度を１００℃で、メタノールおよび酢酸ブチルを固形分濃度３０ｗｔ％になるまで留去することにより、メトキシ基結合シリカ粒子が酢酸ブチルに分散した分散体（Ｚ−５）を得た。該粒子の平均粒子径は０．０２０μｍであった。
〔合成例１０〕 有機基結合シリカ粒子分散体（Ｚ−６）の合成
撹拌機、滴下口、温度計、冷却管を備えた１Ｌのフラスコに、水酸化ナトリウム水溶液（０．０２４重量％）４５０ｇを入れ、塩化ベンゼトニウム９ｇを加えて室温で溶解させた。次に、メチルトリメトキシシラン９０ｇを滴下口より２時間かけて滴下し、そのまま３時間攪拌を行った後、さらに滴下口よりトリメチルフェノキシシラン１０ｇを３０分かけて滴下し、そのまま１時間攪拌を行うことにより、メチル基が結合したシリカ粒子の水分散体が得られた。続いて、反応液にメタノール１０００ｇを加えてシリカ粒子を凝集させた後、遠心分離により固液分離を行い、水、メタノールを除去した。得られたケーキを攪拌機を備えた１Ｌのフラスコに移し、メチルイソブチルケトン１０００ｇを加えて３時間攪拌を行い、シリカ粒子をメチルイソブチルケトンに分散させた。続いて、固形分濃度が３０重量％になるまでメチルイソブチルケトンの濃縮を行い、メチル基結合シリカ粒子がメチルイソブチルケトンに分散した分散体（Ｚ−６）を得た。該粒子の平均粒子径は０．０２５μｍであった。
[Synthesis Example 9] Synthesis of alkoxy group-bonded silica particle dispersion (Z-5) In a 1 L eggplant-shaped flask, 150 g of methanol silica sol (average particle size 0.020 μm, methanol solution 30%) manufactured by Nissan Chemical Co., Ltd. and butyl acetate After adding 150 g, methoxy group-bonded silica particles are distilled off using a rotary evaporator at a pressure of 15 kPa at a temperature of 100 ° C. and methanol and butyl acetate are distilled off to a solid content concentration of 30 wt%. Dispersion (Z-5) dispersed in butyl acetate was obtained. The average particle diameter of the particles was 0.020 μm.
[Synthesis Example 10] Synthesis of organic group-bonded silica particle dispersion (Z-6) 450 g of sodium hydroxide aqueous solution (0.024 wt%) was added to a 1 L flask equipped with a stirrer, a dripping port, a thermometer, and a cooling tube. And 9 g of benzethonium chloride was added and dissolved at room temperature. Next, 90 g of methyltrimethoxysilane was added dropwise over 2 hours from the dropping port, and the mixture was stirred as it was for 3 hours. Then, 10 g of trimethylphenoxysilane was added dropwise over 30 minutes from the dropping port, and the mixture was stirred as it was for 1 hour. As a result, an aqueous dispersion of silica particles having a methyl group bonded thereto was obtained. Subsequently, 1000 g of methanol was added to the reaction solution to aggregate the silica particles, and then solid-liquid separation was performed by centrifugation to remove water and methanol. The obtained cake was transferred to a 1 L flask equipped with a stirrer, 1000 g of methyl isobutyl ketone was added and stirred for 3 hours, and silica particles were dispersed in methyl isobutyl ketone. Subsequently, methyl isobutyl ketone was concentrated until the solid content concentration became 30% by weight to obtain a dispersion (Z-6) in which methyl group-bonded silica particles were dispersed in methyl isobutyl ketone. The average particle diameter of the particles was 0.025 μm.
〔合成例１１〕 有機基結合シリカ粒子分散体（Ｚ−７）の合成
撹拌機、滴下口、温度計、冷却管を備えた１Ｌのフラスコに、水酸化ナトリウム水溶液（０．０２４重量％）４５０ｇを入れ、塩化ベンゼトニウム９ｇを加えて室温で溶解させた。次に、ビニルトリメトキシシラン９０ｇを滴下口より２時間かけて滴下し、そのまま３時間攪拌を行った後、さらに滴下口よりトリメチルフェノキシシラン１０ｇを３０分かけて滴下し、そのまま１時間攪拌を行うことにより、メチル基およびビニル基が結合したシリカ粒子の水分散体が得られた。続いて、反応液にメタノール１０００ｇを加えてシリカ粒子を凝集させた後、遠心分離により固液分離を行い、水、メタノールを除去した。得られたケーキを攪拌機を備えた１Ｌのフラスコに移し、メチルイソブチルケトン１０００ｇを加えて３時間攪拌を行い、シリカ粒子をメチルイソブチルケトンに分散させた。続いて、固形分濃度が３０重量％になるまでメチルイソブチルケトンの濃縮を行い、メチル基およびビニル基が結合したシリカ粒子がメチルイソブチルケトンに分散した分散体（Ｚ−７）を得た。該粒子の平均粒子径は０．０３０μｍであった。
[Synthesis Example 11] Synthesis of organic group-bonded silica particle dispersion (Z-7) 450 g of sodium hydroxide aqueous solution (0.024 wt%) was added to a 1 L flask equipped with a stirrer, a dripping port, a thermometer, and a cooling pipe. And 9 g of benzethonium chloride was added and dissolved at room temperature. Next, 90 g of vinyltrimethoxysilane was added dropwise from the dropping port over 2 hours and stirred as it was for 3 hours, and then 10 g of trimethylphenoxysilane was further dropped from the dropping port over 30 minutes and stirred as it was for 1 hour. As a result, an aqueous dispersion of silica particles having a methyl group and a vinyl group bonded thereto was obtained. Subsequently, 1000 g of methanol was added to the reaction solution to aggregate the silica particles, and then solid-liquid separation was performed by centrifugation to remove water and methanol. The obtained cake was transferred to a 1 L flask equipped with a stirrer, 1000 g of methyl isobutyl ketone was added and stirred for 3 hours, and silica particles were dispersed in methyl isobutyl ketone. Subsequently, methyl isobutyl ketone was concentrated until the solid content concentration became 30% by weight to obtain a dispersion (Z-7) in which silica particles bonded with methyl groups and vinyl groups were dispersed in methyl isobutyl ketone. The average particle diameter of the particles was 0.030 μm.
＜実施例１＞
有機ポリマー合成例３で得られた結合シリカ粒子分散体（Ｚ−１）１００ｇ、エポキシ当量１８５のビスフェノールＡ型エポキシ樹脂（液状樹脂）１０ｇおよび４−メチルヘキサヒドロ無水フタル酸９ｇを混合し、酢酸ブチルを減圧して留去することにより、有機ポリマー残基結合シリカ粒子含有エポキシ樹脂を得た。その後、硬化触媒として２−エチル−４−メチルイミダゾール０．０５ｇを添加し、封止材用樹脂組成物（１）を得た。
この封止材用樹脂組成物（１）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで８７％であった。
<Example 1>
100 g of the bonded silica particle dispersion (Z-1) obtained in organic polymer synthesis example 3, 10 g of bisphenol A type epoxy resin (liquid resin) having an epoxy equivalent of 185 and 9 g of 4-methylhexahydrophthalic anhydride are mixed, and acetic acid is mixed. Butyl was distilled off under reduced pressure to obtain an epoxy resin containing organic polymer residue-bonded silica particles. Thereafter, 0.05 g of 2-ethyl-4-methylimidazole was added as a curing catalyst to obtain a resin composition for sealing material (1).
The light transmittance of the cured product obtained by thermosetting the resin composition for sealing material (1) at 120 ° C. was 87% at a thickness of 4 cm.
＜実施例２＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例６で得られた有機ポリマー残基結合シリカ粒子分散体（Ｚ−３）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（２）を得た。
この封止材用樹脂組成物（２）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで８５％であった。
＜実施例３＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例８で得られた有機ポリマー残基結合シリカ粒子分散体（Ｚ−４）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（３）を得た。
<Example 2>
In Example 1, 100 g of the organic polymer residue-bonded silica particle dispersion (Z-3) obtained in Synthesis Example 6 was used instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1). In the same manner as in Example 1, a resin composition for sealing material (2) was obtained.
The light transmittance of the cured product obtained by thermosetting the resin composition for sealing material (2) at 120 ° C. was 85% at a thickness of 4 cm.
<Example 3>
In Example 1, 100 g of the organic polymer residue-bonded silica particle dispersion (Z-4) obtained in Synthesis Example 8 was used instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1). In the same manner as in Example 1, a resin composition for sealing material (3) was obtained.
この封止材用樹脂組成物（３）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで８３％であった。
＜実施例４＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例９で得られたメトキシ基結合シリカ粒子分散体（Ｚ−５）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（４）を得た。
この封止材用樹脂組成物（４）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで８０％であった。
The light transmittance of the cured product obtained by thermosetting this resin composition for sealing material (3) at 120 ° C. was 83% at a thickness of 4 cm.
<Example 4>
In Example 1, instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1), 100 g of the methoxy group-bonded silica particle dispersion (Z-5) obtained in Synthesis Example 9 was used. In the same manner as in Example 1, a resin composition for sealing material (4) was obtained.
The light transmittance of the cured product obtained by thermosetting this resin composition for sealing material (4) at 120 ° C. was 80% at a thickness of 4 cm.
＜実施例５＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例１０で得られたメチル基結合シリカ粒子分散体（Ｚ−６）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（５）を得た。
この封止材用樹脂組成物（５）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで９０％であった。
＜実施例６＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例１１で得られたメチル基およびビニル基が結合したシリカ粒子分散体（Ｚ−７）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（６）を得た。
<Example 5>
In Example 1, instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1), 100 g of the methyl group-bonded silica particle dispersion (Z-6) obtained in Synthesis Example 10 was used. In the same manner as in Example 1, a resin composition for sealing material (5) was obtained.
The light transmittance of the cured product obtained by thermosetting this resin composition for sealing material (5) at 120 ° C. was 90% at a thickness of 4 cm.
<Example 6>
In Example 1, instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1), 100 g of the silica particle dispersion (Z-7) bonded with the methyl group and vinyl group obtained in Synthesis Example 11 was used. Except having used, it carried out similarly to Example 1, and obtained the resin composition for sealing materials (6).
この封止材用樹脂組成物（６）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで９２％であった。
＜比較例１＞
実施例１において、有機ポリマー残基結合シリカ粒子分散体（Ｚ−１）１００ｇの代わりに、合成例４で得られたシリカ粒子分散体（Ｚ−２）１００ｇを用いた以外は、実施例１と同様にして、封止材用樹脂組成物（ｃ１）を得た。
この封止材用樹脂組成物（ｃ１）を１２０℃で熱硬化して得られた硬化体の光透過率は、厚み４ｃｍで２０％であった。
The light transmittance of the cured product obtained by thermosetting this resin composition for sealing material (6) at 120 ° C. was 92% at a thickness of 4 cm.
<Comparative Example 1>
Example 1 except that 100 g of the silica particle dispersion (Z-2) obtained in Synthesis Example 4 was used instead of 100 g of the organic polymer residue-bonded silica particle dispersion (Z-1) in Example 1. In the same manner as above, a resin composition for sealing material (c1) was obtained.
The light transmittance of the cured product obtained by thermosetting the resin composition for sealing material (c1) at 120 ° C. was 20% at a thickness of 4 cm.
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